US010760011B2

( 12 ) United States Patent ( 10) Patent No.: US 10,760,011 B2

Al - Ghamdi (45) Date of Patent : Sep. 1 , 2020
(54) SYSTEM FOR CONVERSION OF CRUDE 4,180,453 A 12/1979 Franck et al .
OIL TO PETROCHEMICALS AND FUEL 5,906,728 A 5/1999 Iaccino et al .
PRODUCTS INTEGRATING VACUUM GAS 5,980,732 A 11/1999 Gillis
5,981,818 A 11/1999 Purvis et al .
OIL HYDROCRACKING AND STEAM 6,166,279 A 12/2000 Schwab et al .
CRACKING 6,210,561 B1 4/2001 Bradow et al .
6,538,168 B1 3/2003 Schwab et al .
( 71 ) Applicant: Saudi Arabian Oil Company , Dhahran 7,550,642 B2 6/2009 Powers
(SA) 7,938,952 B2 5/2011 Coylar et al.
8,394,900 B2 3/2013 Abhari
8,529,753 B2 9/2013 Niu et al .
(72 ) Inventor : Mohammed Saeed Al -Ghamdi , 8,540,870 B2 9/2013 McGehee et al .
Dammam (SA ) 8,722,950 B2 5/2014 Hal et al .
8,754,277 B2 6/2014 Vijayakumari et al.
( 73 ) Assignee : SAUDI ARABIAN OIL COMPANY, 8,936,716 B2 1/2015 Hoehn et al .
Dhahran (SA ) 8,940,950 B2 1/2015 Ellrich et al .
9,273,256 B2 3/2016 Gillis et al .
9,452,955 B2 9/2016 Sieli et al .
( * ) Notice: Subject to any disclaimer, the term of this 9,464,240 B2 10/2016 Bridges et al.
patent is extended or adjusted under 35 9,550,707 B2 1/2017 Schrod et al .
U.S.C. 154 ( b ) by 0 days. 9,650,580 B2 5/2017 Merdrignac et al .
9,856,425 B2 1/2018 Ward et al .
( 21 ) Appl . No .: 16 /555,794 9,862,898 B2 * 1/2018 Ward C10G 35/00
9,920,263 B2 3/2018 Klein et al .
2004/0054247 Al 3/2004 Powers
( 22 ) Filed : Aug. 29, 2019 2007/0090018 A1 4/2007 Keusenkothen et al .
2007/0232846 A1 10/2007 Baumgartner et al .
( 65 ) Prior Publication Data 2008/0194900 A1 * 8/2008 Bhirud C10G 65/16
585/648
US 2020/0109338 A1 Apr. 9 , 2020 2010/0056839 Al 3/2010 Ramachandran et al .
( Continued )
Related U.S. Application Data
FOREIGN PATENT DOCUMENTS
( 63 ) Continuation of application No. 15 / 817,128 , filed on
Nov. 17 , 2017 , now Pat . No. 10,472,579 . CA 2674212 C 4/2015
CN 103374395 B 7/2015
( 60 ) Provisional application No. 62/ 424,883 , filed on Nov. (Continued )
21 , 2016, provisional application No. 62/450,018 ,
filed on Jan. 24 , 2017 , provisional application No.
62/ 450,043 , filed on Jan. 24 , 2017 , provisional OTHER PUBLICATIONS
application No. 62/ 450,031 , filed on Jan. 24 , 2017 , PCT/US2017/ 062563, International Search Report arid Written
provisional application No. 62/ 450,062 , filed on Jan. Opinion dated Jan. 26 , 2018 , 14 pages .
24, 2017
( 51 ) Int . Cl . Primary Examiner Randy Boyer
C10G 55/06 ( 2006.01 )
B01D 3/14 ( 2006.01 ) (74 ) Attorney, Agent, or Firm Abelman , Frayne and
C10G 7700 ( 2006.01 ) Schwab
C10G 47/02 ( 2006.01 )
(52) U.S. CI . ( 57 ) ABSTRACT
CPC C10G 55/06 ( 2013.01 ) ; B01D 3/14
(2013.01 ) ; C10G 7700 (2013.01 ) ; C10G 47/02 Process scheme configurations are disclosed that enable
( 2013.01 ) ; CIOG 2300/104 ( 2013.01 ) ; CIOG conversion of crude oil feeds with several processing units
2300/1051 (2013.01 ) ; CI0G 2300/1055 in an integrated manner into petrochemicals. The designs
(2013.01 ) ; CIOG 2300/1059 ( 2013.01 ) ; CIOG utilize minimum capital expenditures to prepare suitable
2400/20 (2013.01) feedstocks for the steam cracker complex . The integrated
(58) Field of Classification Search process for converting crude oil to petrochemical products
CPC B01J 2219/00006
See application file for complete search history. including olefins and aromatics, and fuel products, includes
mixed feed steam cracking and gas oil steam cracking. Feeds
( 56 ) References Cited to the mixed feed steam cracker include light products and
naphtha from hydroprocessing zones within the battery
U.S. PATENT DOCUMENTS limits , recycle streams from the C3 and C4 olefins recovery
steps , and raffinate from a pyrolysis gasoline aromatics
3,472,909 A 10/1969 Raymond extraction zone within the battery limits . Feeds to the gas oil
3,702,292 A 11/1972 Burich steam cracker include unconverted oil intermediates from
3,842,138 A 10/1974 Chahvekilian et al. vacuum gas oil hydrotreating.
3,855,113 A 12/1974 Gould
3,898,299 A 8/1975 Jones
4,065,379 A 12/1977 Soonawala et al .
4,115,467 A 9/1978 Fowler 13 Claims , 11 Drawing Sheets
 US 10,760,011 B2
Page 2

( 56 ) References Cited
U.S. PATENT DOCUMENTS
2010/0087692 A1 4/2010 Yoshimura et al .
2010/0168487 A1 7/2010 Sawyer et al .
2010/0285950 A1 11/2010 Mao
2011/0042269 A1 2/2011 Kuechler et al .
2011/0119994 A1 5/2011 Hogendoorn et al.
2011/0174682 A1 7/2011 Iaccino
2013/0237714 Al 9/2013 Vijayakurnari et al .
2013/0245295 Al 9/2013 Westrenen
2013/0248419 Al 9/2013 Abba et al .
2014/0081061 A1 3/2014 Stanley et al.
2016/0115400 A1 4/2016 Sun et al .
2016/0137933 A1 * 5/2016 Ward C10G 51/00
208/60
2016/0368838 A1 12/2016 Ward et al .
2016/0369180 A1 12/2016 Ward et al .
2016/0369188 A1 * 12/2016 Housmans C10G 67/0445
2016/0369190 A1 * 12/2016 Ward C10G 67/00
2017/0009155 Al 1/2017 Oprins
FOREIGN PATENT DOCUMENTS
CN 103374395 B 7/2015
GB 1301019 A 12/1972
WO 2014177424 A2 11/2014
WO 2016071776 A2 5/2016
WO 2017014976 A1 1/2017
* cited by examiner
U.S. Patent Sep. 1 , 2020 Sheet 1 of 11 US 10,760,011 B2
100 156 154

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U.S. Patent Sep. 1 , 2020 Sheet 2 of 11 US 10,760,011 B2

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U.S. Patent Sep. 1 , 2020 Sheet 3 of 11 US 10,760,011 B2

210 -208
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U.S. Patent Sep. 1 , 2020 Sheet 4 of 11 US 10,760,011 B2

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U.S. Patent Sep. 1 , 2020 Sheet 5 of 11 US 10,760,011 B2

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U.S. Patent Sep. 1 , 2020
? Sheet 6 of 11 US 10,760,011 B2

156 -154
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FIG . 6
U.S. Patent Sep. 1 , 2020 Sheet 7 of 11 US 10,760,011 B2
330
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338 342
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FIG . 7
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U.S. Patent Sep. 1 , 2020 Sheet 8 of 11 US 10,760,011 B2

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U.S. Patent Sep. 1 , 2020
? Sheet 9 of 11 US 10,760,011 B2

152 272 210

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U.S. Patent Sep. 1 , 2020 Sheet 10 of 11 US 10,760,011 B2

156 -154
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U.S. Patent Sep. 1 , 2020 Sheet 11 of 11 US 10,760,011 B2

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 US 10,760,011 B2
1 2
SYSTEM FOR CONVERSION OF CRUDE chemicals and fuel product from a crude oil feed . The
OIL TO PETROCHEMICALS AND FUEL integrated process includes an initial separation step to
PRODUCTS INTEGRATING VACUUM GAS separate from a crude oil feed in an atmospheric distillation
OIL HYDROCRACKING AND STEAM zone at least a fraction comprising straight run naphtha and
CRACKING 5 lighter components, one or more middle distillate fractions,
RELATED APPLICATIONS and an atmospheric residue fraction. A vacuum gas oil
fraction is separated from the atmospheric residue fraction in
This application is a Continuation of U.S. patent appli a vacuum distillation zone . In a distillate hydroprocessing
cation Ser. No. 15 / 817,128 filed Nov. 17 , 2017 , which ( “ DHP ” ) zone , such as a diesel hydrotreater, at least a
claims priority to U.S. Provisional Patent Application No. 10 portion of the middle distillates are processed to produce a
62 /424,883 filed Nov. 21 , 2016 , U.S. Provisional Patent naphtha fraction and a diesel fuel fraction . The vacuum gas
Application No. 62 /450,018 filed Jan. 24 , 2017 , U.S. Pro oil fraction ( and optionally all or a portion of an atmospheric
visional Patent Application No. 62 /450,031 filed Jan. 24 , gas oil fraction , or all or a portion of a heavy atmospheric
2017 , U.S. Provisional Patent Application No. 62/ 450,043 gas oil fraction ) is processed in a gas oil hydrocracking zone .
filed Jan. 24 , 2017 , and U.S. Provisional Patent Application 15 Unconverted oil is processed in a gas oil steam cracking
No. 62/ 450,062 filed Jan. 24 , 2017 , the contents of which are zone . The fraction ( s) from the atmospheric distillation with
all incorporated herein by reference in their entireties. straight run naphtha and lighter components, and an aro
matics extraction zone raffinate, are processed in a mixed
BACKGROUND OF THE INVENTION feed steam cracking zone . The products from the mixed feed
20 steam cracking zone and the gas oil steam cracking zone
Field of the Invention include integrated or separate mixed product stream ( s) com
The inventions disclosed herein relate to an integrated prising H2 , methane, ethane, ethylene, mixed C3s and mixed
C4s ; pyrolysis gasoline stream ( s ); and pyrolysis oil
process and system for converting crude oil to petrochemi
cals and fuel products. stream (s ).
25 From the mixed product stream (s ) C3s and the mixed C4s ,
Description of Related Art petrochemicals ethylene, propylene and butylenes are recov
ered . Ethane and non - olefinic C3s are recycled to the mixed
The lower olefins ( i.e. , ethylene, propylene, butylene and feed steam cracking zone , and non - olefinic C4s are recycled
butadiene) and aromatics ( i.e. , benzene, toluene and xylene ) to the mixed feed steam cracking zone or to a separate
are basic intermediates which are widely used in the petro 30 processing zone for production of additional petrochemicals.
chemical and chemical industries . Thermal cracking, or Pyrolysis gasoline is treated in a py - gas hydroprocessing
steam pyrolysis, is a major type of process for forming these zone to produce hydrotreated pyrolysis gasoline. The
materials, typically in the presence of steam , and in the hydrotreated pyrolysis gasoline is routed to the aromatics
absence of oxygen . Typical feedstocks for steam pyrolysis extraction zone to recover aromatic products and the aro
can include petroleum gases , such as ethane, and distillates 35 matics extraction zone raffinate that is recycled to the mixed
such as naphtha, kerosene and gas oil . The availability of feed steam cracking zone .
these feedstocks is usually limited and requires costly and Still other aspects , embodiments , and advantages of these
energy - intensive process steps in a crude oil refinery . exemplary aspects and embodiments, are discussed in detail
A very significant portion of ethylene production relies on below . Moreover, it is to be understood that both the
naphtha as theandfeedstock
lower paraffin higher .aromatics
Howevercontent
, heavythan
naphtha has a
light naph 40 foregoing information and the following detailed description
are merely illustrative examples of various aspects and
tha, making it less suitable as feedstock in the production of embodiments, and are intended to provide an overview or
ethylene without upgrading. Heavy naphtha can vary in the framework for understanding the nature and character of the
amount of total paraffins and aromatics based on its source . claimed aspects and embodiments . The accompanying
Paraffins content can range between about 27-70 % , naph 45 drawings are included to provide illustration and a further
thenes content can range between about 15-60% , and the understanding of the various aspects and embodiments, and
aromatics content can range between about 10-36 % ( volume are incorporated in and constitute a part of this specification .
basis ) .
Many chemicals producers are limited by the supply and The drawings, together with the remainder of the specifica
quality of feed from nearby refiners due to reliance on oil tion , serve to explain principles and operations of the
refinery by-products as feed. Chemicals producers are also 50 described and claimed aspects and embodiments.
limited by the high cost of oil refining and its associated BRIEF DESCRIPTION OF THE DRAWINGS
fuels markets, which may negatively influence the economic
value of refinery sourced feeds.Higher global fuel efficiency The invention will be described in further detail below
standards for automobiles and trucks will reduce fuels
demand and narrow refinery margins, and may complicate 55 and with reference to the attached drawings in which the
the economics of fuels and chemicals supply and / or markets. same or similar elements are referred to by the same number,
A need remains in the art for improved processes for and where :
converting crude oil to basic chemical intermediates such as FIG . 1 schematically depicts operations upstream of a
lower olefins and aromatics. In addition , a need remains in steam cracker complex in embodiments of processes for
the art for new approaches that offer higher value chemical 60 producing
production opportunities with greater leverage on econo
petrochemicals and fuel product;
FIG . 2 schematically depicts operations downstream of
mies of scale . and including a steam cracker complex in embodiments of
processes for producing petrochemicals and fuel product;
SUMMARY FIG . 3 schematically depicts operations downstream of
65 and including a steam cracker complex in embodiments of
In accordance with one or more embodiments, the inven processes for producing petrochemicals integrating metath
tion relates to an integrated process for producing petro esis ;
 US 10,760,011 B2
3 4
FIG . 4 schematically depicts operations downstream of tures thereof. The crude petroleum mixtures can be whole
and including a steam cracker complex in embodiments of range crude oil or topped crude oil . As used herein , “ crude
processes for producing petrochemicals and fuel products oil” also refers to such mixtures that have undergone some
integrating mixed butanol production; pre -treatment such as water - oil separation; and / or gas - oil
FIG . 5 schematically depicts operations downstream of 5 separation ; and/ or desalting; and / or stabilization . In certain
and including a steam cracker complex in embodiments of embodiments, crude oil refers to any of such mixtures
processes for producing petrochemicals and fuel products having an API gravity (ASTM D287 standard ), of greater
integrating metathesis and mixed butanol production; than or equal to about 20 ° , 30 ° , 32 ° , 34 ° , 36 ° , 38 ° , 40 ° , 42 °
FIG . 6 schematically depicts operations upstream of a or 44º .
steam cracker complex in further embodiments of processes 10 The acronym “ AXL ” as used herein refers to Arab Extra
for producing petrochemicals and fuel product; Light crude oil , characterized by an API gravity of greater
FIG . 7 schematically depicts a single reactor hydrocrack than or equal to about 38 ° , 40 ° , 42 ° or 44 ° , and in certain
ing zone ; embodiments in the range of about 38 ° -46 ° , 38 ° -44 ° , 38º
FIG . 8 schematically depicts a series - flow hydrocracking 42 ° , 380-40.5 ° , 390-46 ° , 39 ° -44 ° , 399-42 ° or 39 ° -40.5º .
zone with recycle ; 15 The acronym “ AL ” as used herein refers to Arab Light
FIG . 9 schematically depicts a two - stage hydrocracking crude oil , characterized by an API gravity of greater than or
zone with recycle ; equal to about 30 ° , 32 ° , 34 ° , 36 ° or 38 ° , and in certain
FIG . 10 schematically depicts operations downstream of embodiments in the range of about 30 ° -38 ° , 30 ° -36 ° , 30 °
and including a steam cracker complex in further embodi 350 , 32 ° -38 ° , 32 ° -36 ° , 320-35 ° , 33 ° -38 ° , 33º - 36 ° or 330-35º .
ments of processes for producing petrochemicals and fuel 20 The acronym “ LPG ” as used herein refers to the well
product; known acronym for the term “ liquefied petroleum gas , ” and
FIG . 11 schematically depicts operations in further generally is a mixture of C3 - C4 hydrocarbons. In certain
embodiments of processes for producing petrochemicals and embodiments , these are also referred to as “ light ends."
fuel products integrating metathesis ; and The term “ naphtha ” as used herein refers to hydrocarbons
FIGS . 12 and 13 schematically depict operations 25 boiling in the range of about 20-205 , 20-193 , 20-190 ,
upstream of a steam cracker complex in still further embodi 20-180 , 20-170 , 32-205 , 32-193 , 32-190 , 32-180 , 32-170 ,
ments of processes for producing petrochemicals and fuel 36-205 , 36-193 , 36-190 , 36-180 or 36-170 ° C.
product. The term “ light naphtha ” as used herein refers to hydro
carbons boiling in the range of about 20-110 , 20-100 , 20-90 ,
DESCRIPTION 30 20-88 , 32-110 , 32-100 , 32-90 , 32-88 , 36-110 , 36-100 , 36-90
or 36-88 ° C.
Process scheme configurations are disclosed that enable The term “ heavy naphtha ” as used herein refers to hydro
conversion of crude oil feeds with several processing units carbons boiling in the range of about 90-2 90-193 ,
in an integrated manner into petrochemicals. The designs 90-190 , 90-180 , 90-170 , 93-205 , 93-193 , 93-190 , 93-180 ,
utilize minimum capital expenditures to prepare suitable 35 93-170 , 100-205 , 100-193 , 100-190 , 100-180 , 100-170 , 110
feedstocks for the steam cracker complex. The integrated 205 , 110-193 , 110-190 , 110-180 or 110-170 ° C.
process for converting crude oil to petrochemical products In certain embodiments naphtha, light naphtha and / or
including olefins and aromatics, and fuel products, includes heavy naphtha refer to such petroleum fractions obtained by
mixed feed steam cracking and gas oil steam cracking. Feeds crude oil distillation , or distillation of intermediate refinery
to the mixed feed steam cracker include light products and 40 processes as described herein .
naphtha from hydroprocessing zones within the battery The modifying term “ straight run ” is used herein having
limits , recycle streams from the C3 and C4 olefins recovery its well - known meaning, that is , describing fractions derived
steps , and raffinate from a pyrolysis gasoline aromatics directly from the atmospheric distillation unit , optionally
extraction zone within the battery limits . Feeds to the gas oil subjected to steam stripping, without other refinery treat
steam cracker include unconverted oil intermediates from 45 ment such as hydroprocessing, fluid catalytic cracking or
vacuum gas oil hydrotreating. steam cracking. An example of this is “ straight run naphtha”
The phrase “ a major portion” with respect to a particular and its acronym “ SRN ” which accordingly refers to “ naph
stream or plural streams means at least about 50 wt % and tha " defined above that is derived directly from the atmo
up to 100 wt % , or the same values of another specified unit. spheric distillation unit , optionally subjected to steam strip
The phrase “ a significant portion ” with respect to a 50 ping , as is well known .
particular stream or plural streams means at least about 75 The term “ kerosene ” as used herein refers to hydrocar
wt % and up to 100 wt % , or the same values of another bons boiling in the range of about 170-280 , 170-270 , 170
specified unit. 260 , 180-280 , 180-270 , 180-260 , 190-280 , 190-270 , 190
The phrase " a substantial portion ” with respect to a 260 , 193-280 , 193-270 or 193-260 ° C.
particular stream or plural streams means at least about 90 , 55 The term “ light kerosene ” as used herein refers to hydro
95 , 98 or 99 wt % and up to 100 wt % , or the same values carbons boiling in the range of about 170-250 , 170-235 ,
of another specified unit. 170-230 , 170-225 , 180-250 , 180-235 , 180-230 , 180-225 ,
The phrase “ a minor portion” with respect to a particular 190-250 , 190-235 , 190-230 or 190-225º C.
stream or plural streams means from about 1 , 2 , 4 or 10 wt The term “ heavy kerosene” as used herein refers to
% , up to about 20 , 30 , 40 or 50 wt % , or the same values of 60 hydrocarbons boiling in the range of about 225-280 , 225
another specified unit . 270 , 225-260 , 230-280 , 230-270 , 230-260 , 235-280 , 235
The term “ crude oil ” as used herein refers to petroleum 270 , 235-260 or 250-280º C.
extracted from geologic formations in its unrefined form . The term “ atmospheric gas oil ” and its acronym “ AGO ”
Crude oil suitable as the source material for the processes as used herein refer to hydrocarbons boiling in the range of
herein include Arabian Heavy , Arabian Light, Arabian Extra 65 about 250-370 , 250-360 , 250-340 , 250-320 , 260-370 , 260
Light, other Gulf crudes, Brent, North Sea crudes, North and 360 , 260-340 , 260-320 , 270-370 , 270-360 , 270-340 or 270
West African crudes, Indonesian, Chinese crudes, or mix 320 ° C.
 US 10,760,011 B2
5 6
The term “ heavy atmospheric gas oil ” and its acronym greater than that of a hypothetical localized structure ( e.g. ,
“ H - AGO ” as used herein in certain embodiments refer to the Kekule structure ). The most common method for determin
heaviest cut of hydrocarbons in the AGO boiling range ing aromaticity of a given hydrocarbon is the observation of
including the upper 3-30 ° C. range ( e.g. , for AGO having a diatropicity in its 1H NMR spectrum , for example the
range of about 250-360 ° C. , the range of H - AGO includes an 5 presence of chemical shifts in the range of from 7.2 to 7.3
initial boiling point from about 330-357 ° C. and an end ppm for benzene ring protons .
boiling point of about 360 ° C. ) . The terms " naphthenic hydrocarbons ” or “ naphthenes ” or
The term “medium atmospheric gas oil ” and its acronym " cycloalkanes ” are used herein having their established
" M - AGO ” as used herein in certain embodiments in con meanings and accordingly relates to types of alkanes that
junction with H -AGO to refer to the remaining AGO after 10 have one or more rings of carbon atoms in the chemical
H - AGO is removed , that is , hydrocarbons in the AGO structure of their molecules .
boiling range excluding the upper about 3-30 ° C. range ( e.g. , The term “ wild naphtha ” is used herein to refer to naphtha
for AGO having a range of about 250-360 ° C. , the range of products derived from hydroprocessing units such as distil
M - AGO includes an initial boiling point of about 250 ° C. late hydroprocessing units , diesel hydroprocessing units
and an end boiling point of from about 330-357 ° C. ) . 15 and / or gas oil hydroprocessing units.
In certain embodiments , the term “ diesel” is used with The term “ unconverted oil” and its acronym “ UCO , ” is
reference to a straight run fraction from the atmospheric used herein having its known meaning, and refers to a highly
distillation unit. In embodiments in which this terminology paraffinic fraction from a hydrocracker with a low nitrogen,
is used , the diesel fraction refers to medium AGO range sulfur and nickel content and including hydrocarbons having
hydrocarbons and in certain embodiments also in combina- 20 an initial boiling point corresponding to the end point of the
tion with heavy kerosene range hydrocarbons . AGO range hydrocarbons, in certain embodiments the initial
The term “ atmospheric residue ” and its acronym “ AR ” as
boiling point in the range of about 340-370 ° C. , for instance
used herein refer to the bottom hydrocarbons having an about 340 , 360 or 370 ° C. , and an end point in the range of
initial boiling point corresponding to the end point of the about 510-560 ° C. , for instance about 540 , 550 or 560 ° C.
AGO range hydrocarbons, and having an end point based on 25 UCO is also known in the industry by other synonyms
the characteristics of the crude oil feed . including " hydrowax . "
The term “ vacuum gas oil” and its acronym “ VGO " as The term “ C # hydrocarbons” or “ C # ” , is used herein
used herein refer to hydrocarbons boiling in the range of having its well -known meaning, that is , wherein “ # ” is an
about 370-550 , 370-540 , 370-530 , 370-510 , 400-550 , 400 integer value , and means hydrocarbons having that value of
540 , 400-530 , 400-510 , 420-550 , 420-540 , 420-530 or 420- 30
carbon atoms. The term “ C # + hydrocarbons” or “ C # + ”
510 ° C. refers to hydrocarbons having that value or more carbon
The term “ light vacuum gas oil ” and its acronym “LVGO ” atoms . The term " C # - hydrocarbons ” or “ C # -” refers to
as used herein refer hydrocarbons boiling in the range of hydrocarbons having that value or less carbon atoms. Simi
about 370-425 , 370-415 , 370-405 , 370-395 , 380-425 , 390 larly, ranges are also set forth , for instance, C1 - C3 means a
425 or 400-425 ° C. 35 mixture comprising C1 , C2 and C3 .
The term " heavy vacuum gas oil ” and its acronym The term “ petrochemicals ” or “ petrochemical products ”
" HVGO ” as used herein refer to hydrocarbons boiling in the refers to chemical products derived from crude oil that are
range of about 425-550 , 425-540 , 425-530 , 425-510 , 450 not used as fuels. Petrochemical products include olefins and
550 , 450-540 , 450-530 or 450-510 ° C. aromatics that are used as a basic feedstock for producing
The term “ vacuum residue ” and its acronym “ VR ” as used 40 chemicals and polymers. Typical olefinic petrochemical
herein refer to the bottom hydrocarbons having an initial products include , but are not limited to , ethylene, propylene,
boiling point corresponding to the end point of the VGO butadiene, butylene- 1, isobutylene , isoprene, cyclopentadi
range hydrocarbons, and having an end point based on the ene and styrene. Typical aromatic petrochemical products
characteristics of the crude oil feed . include, but are not limited to , benzene , toluene , xylene, and
The term “ fuels” refers to crude oil -derived products used 45 ethyl benzene .
as energy carriers. Fuels commonly produced by oil refin The term “ olefin ” is used herein having its well-known
eries include, but are not limited to , gasoline, jet fuel, diesel meaning, that is , unsaturated hydrocarbons containing at
fuel, fuel oil and petroleum coke. Unlike petrochemicals, least one carbon - carbon double bond . In plural , the term
which are a collection of well -defined compounds, fuels “ olefins ” means a mixture comprising two or more unsatu
typically are complex mixtures of different hydrocarbon 50 rated hydrocarbons containing at least one carbon - carbon
compounds. double bond . In certain embodiments , the term “ olefins ”
The terms “ kerosene fuel ” or “ kerosene fuel products ” relates to a mixture comprising two or more of ethylene,
refer to fuel products used as energy carriers, such as jet fuel propylene, butadiene, butylene - 1, isobutylene, isoprene and
or other kerosene range fuel products ( and precursors for cyclopentadiene.
producing such jet fuel or other kerosene range fuel prod- 55 The term “ BTX ” as used herein refers to the well -known
ucts ) . Kerosene fuel includes but is not limited to kerosene acronym for benzene, toluene and xylenes.
fuel products meeting Jet A or Jet A - 1 jet fuel specifications. The term “ make -up hydrogen ” is used herein with refer
The terms “ diesel fuel” and “ diesel fuel products ” refer to ence to hydroprocessing zones to refer to hydrogen require
fuel products used as energy carriers suitable for compres ments of the zone that exceed recycle from conventionally
sion -ignition engines ( and precursors for producing such 60 integrated separation vessels ; in certain embodiments as
fuel products ). Diesel fuel includes but is not limited to used herein all or a portion of the make -up hydrogen in any
ultra - low sulfur diesel compliant with Euro V diesel stan given hydroprocessing zone or reactor within a zone is from
dards. gases derived from the steam cracking zone ( s ) in the inte
The term “ aromatic hydrocarbons” or “ aromatics ” is very grated processes and systems .
well known in the art. Accordingly, the term “ aromatic 65 The term " crude to chemicals conversion " as used herein
hydrocarbon ” relates to cyclically conjugated hydrocarbons refers to conversion of crude oil into petrochemicals includ
with a stability ( due to delocalization ) that is significantly ing but not limited to lower olefins such as ethylene,
 US 10,760,011 B2
7 8
propylene, butylenes (including isobutylene), butadiene, From the mixed product stream ( s) C3s and the mixed C4s ,
MTBE , butanols, benzene, ethylbenzene, toluene, xylenes, petrochemicals ethylene, propylene and butylenes are recov
and derivatives of the foregoing. ered . Ethane and non - olefinic C3s are recycled to the mixed
The term " crude to chemicals conversion ratio ” as used feed steam cracking zone , and non - olefinic C4s are recycled
herein refers to the ratio , on a mass basis , of the influent 5 to the mixed feed steam cracking zone or to a separate
crude oil before desalting, to petrochemicals. processing zone for production of additional petrochemicals .
The term “ crude C4” refers to the mixed C4 effluent from Pyrolysis gasoline is treated in a py - gas hydroprocessing
a steam cracking zone . zone to produce hydrotreated pyrolysis gasoline . The
The term " C4 Raffinate 1 ” or “ C4 Raff- 1 ” refers to the hydrotreated pyrolysis gasoline is routed to the aromatics
mixed C4s stream leaving the butadiene extraction unit, that 10 extraction zone to recover aromatic products and the aro
is , mixed C4s from the crude C4 except butadiene . matics extraction zone raffinate that is recycled to the mixed
The term “ C4 Raffinate 2 ” or “ C4 Raff- 2 ” refers to the feed steam cracking zone .
mixed C4s stream leaving the MTBE unit, that is , mixed C4s Ethane and non - olefinic C3s and C4s are recovered , with
from the crude C4 except butadiene and isobutene. ethane and non - olefinic C3s recycled to the steam cracking
The term “ C4 Raffinate 3” or “ C4 Raff - 3 ” refers to the 15 complex, and non - olefinic C4s recycled to the steam crack
mixed C4s stream leaving the C4 distillation unit, that is , ing complex or passed to a separate processing zone for
mixed C4s from the crude C4 except butadiene , isobutene, production of additional petrochemicals such as propylene
and butane - 1 . and / or mixed butanol liquids. Pyrolysis gasoline is treated in
The terms " pyrolysis gasoline” and its abbreviated form a py - gas hydroprocessing zone to produce hydrotreated
" py - gas ” are used herein having their well- known meaning, 20 pyrolysis gasoline , which is routed to an aromatics extrac
that is , thermal cracking products in the range of C5 to C9 , tion complex to recover aromatic petrochemicals and a
for instance having an end boiling point of about 204.4 ° C. raffinate, including pyrolysis gasoline raffinate that is
( 400 ° F. ) , in certain embodiments up to about 148.9 ° C. recycled to the steam cracking complex .
( 300 ° F. ) . FIGS . 1 and 2 schematically depict embodiments of
The terms “ pyrolysis oil ” and its abbreviated form “ py- 25 processes and systems for conversion of crude oil to petro
oil ” are used herein having their well-known meaning , that chemicals and fuel products, including a mixed feed steam
is , a heavy oil fraction, C10 + , that is derived from steam cracking zone and a gas oil steam cracking zone . Generally,
cracking FIG . 1 shows operations upstream of the mixed feed steam
The terms “ light pyrolysis oil” and its acronym “LPO ” as cracking zone (“ MFSC ” ) 230 and the gas oil steam cracking
used herein in certain embodiments refer to pyrolysis oil 30 zone 250 while FIG . 2 shows operations downstream of the
having an end boiling point of about 440 , 450 , 460 or 470 ° crude oil conversion zone and including the mixed feed
C. steam cracking zone 230 and the gas oil steam cracking zone
The terms “ heavy pyrolysis oil” and its acronym “ HPO " 250 .
as used herein in certain embodiments refer to pyrolysis oil The mixed feed steam cracking zone and the gas oil steam
having an initial boiling point of about 440 , 450 , 460 or 470 ° 35 cracking zone are shown for simplicity in a single schematic
C. block 230/250 in FIGS . 2 , 3 , 4 and 5 .
In general, the integrated process for producing petro In the description herein , both the mixed feed steam
chemicals and fuel products from a crude oil feed includes cracking zone 230 and the gas oil steam cracking zone 250
an initial separation step to separate from a crude oil feed in are collectively referred to as the “ steam cracker complex ”
an atmospheric distillation zone at least a first atmospheric 40 230/250 in certain instances , although a person having
distillation zone fraction comprising straight run naphtha; a ordinary skill in the art will appreciate that the different
second atmospheric distillation zone fraction comprising at steam cracking zones contain different furnaces and associ
least a portion of middle distillates , and a third atmospheric ated exchangers, with certain products from each combined
distillation zone fraction comprising atmospheric residue. A for further downstream operations. In certain embodiments
first vacuum distillation zone fraction comprising vacuum 45 quench systems and fractionation units can be combined . In
gas oil is separated from the third atmospheric distillation additional embodiments separate quench systems and frac
zone fraction in a vacuum distillation zone . In a distillate tionation units can be used for each of the mixed feed steam
hydroprocessing ( “ DHP' ) zone , such as a diesel cracking zone 230 and the gas oil steam cracking zone 250 .
hydrotreater, at least a portion of the second atmospheric With reference to FIG . 1 , a crude oil feed 102 , in certain
distillation zone fraction is processed to produce at least a 50 embodiments AXL or AL , is separated into fractions in a
first DHP fraction and a second DHP fraction , wherein the crude complex 100 , typically including an atmospheric
first DHP fraction comprises naphtha and the second DHP distillation zone (“ ADU " ) 110 , a saturated gas plant 150 and
fraction is used for diesel fuel production. The first vacuum a vacuum distillation zone (“ VDU ” ) 160. The crude oil feed
distillation zone fraction ( and optionally all or a portion of 102 , in certain embodiments having LPG and light naphtha
an atmospheric gas oil fraction, or all or a portion of a heavy 55 removed , is separated into fractions in the atmospheric
atmospheric gas oil fraction ) is processed in a gas oil distillation zone 110. As shown in FIG . 1 , light products, for
hydrocracking zone to produce naphtha, middle distillates, instance, light hydrocarbons with fewer than six carbons, are
and unconverted oil . Unconverted oil is processed in a gas passed to a mixed feed steam cracking zone 230. In par
oil steam cracking zone . ticular, C2 - C4 hydrocarbons 152 including ethane, propane
At least the first atmospheric distillation zone fraction and 60 and butanes are separated from the light ends and LPG 112
a pyrolysis gasoline raffinate from an aromatics extraction from the atmospheric distillation zone 110 via the saturated
zone are processed in a mixed feed steam cracking zone . The gas plant 150. Optionally, other light products are routed to
products from the mixed feed steam cracking zone and the the saturated gas plant 150 , shown in dashed lines as stream
gas oil steam cracking zone include integrated or separate 156 , such as light gases from refinery units within the
mixed product stream ( s) comprising H2 , methane, ethane , 65 integrated system , and in certain embodiments light gases
ethylene, mixed C3s and mixed C4s; pyrolysis gasoline from outside of the battery limits . The separated C2 - C4
stream ( s ); and pyrolysis oil stream ( s ). hydrocarbons 152 are routed to the mixed feed steam
 US 10,760,011 B2
9 10
cracking zone 230. Off -gases 154 from the saturated gas naphtha 184 is routed through the crude complex 100 , alone ,
plant 150 and off - gases 208 from the mixed feed steam or in combination with other wild naphtha fractions from
cracking zone 230 and gas oil steam cracking zone 250 are within the integrated process . In embodiments in which the
removed and recovered as is typically known , for instance to wild naphtha 184 is routed through the crude complex 100 ,
contribute to a fuel gas (“ FG ” ) system . 5 all or a portion of the liquefied petroleum gas produced in
Straight run naphtha 136 from the atmospheric distillation the vacuum gas oil hydroprocessing zone can be passed with
zone 110 is passed to the mixed feed steam cracking zone the wild naphtha. In certain embodiments, all , a substantial
230. In certain embodiments, all , a substantial portion or a portion, a significant portion or a major portion of the wild
significant portion of the straight run naphtha 136 is routed
to the mixed feed steam cracking zone 230. Remaining 10 naphtha 230 (
184 is routed to the mixed feed steam cracking zone
directly or through the crude complex 100 ) .
naphtha (if any ) can be added to a gasoline pool . In addition , In certain embodiments ( as denoted by dashed lines ) , all ,
in certain embodiments the straight run naphtha stream 136 a substantial portion , a significant portion or a major portion
contains naphtha from other sources as described herein and of the third middle distillate fraction
sometimes referred to as wild naphtha, for instance, naphtha vacuum gas oil hydroprocessing zone 126 in
is routed to the
combination with
range hydrocarbons from one or more of the integrated 15 the vacuum gas oil stream 162 ; any portion that is not passed
distillate , gas oil and / or residue hydroprocessing units .
Middle distillates are used to produce diesel and / or kero to the vacuum gas oil hydroprocessing zone can be routed to
sene , and additional feed to the mixed feed steam cracking the gas oil steam cracking zone 250 without hydroprocess
zone 230. In the embodiments shown in FIG . 1 , at least three ing . In further embodiments (as denoted by dashed lines ) ,
different middle distillate cuts are processed for production 20 all , a substantial portion, a significant portion or a major
of fuel products and petrochemicals ( via the steam cracker ). portion of the third middle distillate fraction 126 is routed to
In one example using the arrangement shown in FIG . 1 , a the gas oil steam cracking zone 250 without hydroprocess
first atmospheric distillation zone middle distillate fraction ing , and any portion that is not passed to the gas oil steam
116 , in certain embodiments referred to as a kerosene cracking zone 250 is routed to the vacuum gas oil hydro
fraction , contains light kerosene range hydrocarbons, a 25 processing zone .
second atmospheric distillation zone middle distillate frac An atmospheric residue fraction 114 from the atmospheric
tion 122 , in certain embodiments referred to as a diesel distillation zone 110 is further separated in the vacuum
fraction, contains heavy kerosene range hydrocarbons and distillation zone 160. Vacuum gas oil 162 from the vacuum
medium AGO range hydrocarbons, and a third atmospheric distillation zone 160 is routed to the vacuum gas oil hydro
distillation zone middle distillate fraction 126 , in certain 30 cracking zone 320. In certain embodiments, vacuum gas oil
embodiments referred to as an atmospheric gas oil fraction , 162 can bypass the vacuum gas oil hydrocracking zone 320
contains heavy AGO range hydrocarbons. In another and be routed to the gas oil steam cracking zone 250 (not
example using the arrangement shown in FIG . 1 , a first shown The heaviest fraction 168 from the vacuum distil
middle distillate fraction 116 contains kerosene range hydro lation zone 160 , vacuum residue, can be sent to a fuel oil
carbons, a second middle distillate fraction 122 contains 35 ( “ FO ” ) pool and / or optionally processed in a residue treat
medium AGO range hydrocarbons and a third middle dis ment zone 800 , shown in dashed lines . In certain embodi
tillate fraction 126 contains heavy AGO range hydrocar ments, a minor portion of the atmospheric residue fraction
bons . In another example using the arrangement shown in 114 can bypass the vacuum distillation zone 160 ( not shown)
FIG . 1 , a first middle distillate fraction 116 contains light and is routed to the optional residue treating zone 800 and / or
kerosene range hydrocarbons and a portion of heavy kero- 40 the gas oil steam cracking zone 250 ( not shown) .
sene range hydrocarbons, a second middle distillate fraction The vacuum gas oil hydrocracking zone 320 can operate
122 contains a portion of heavy kerosene range hydrocar under mild, moderate or severe hydrocracking conditions ,
bons and a portion of medium AGO range hydrocarbons and and generally produces a hydrocracked naphtha fraction
a third middle distillate fraction 126 contains a portion of 326 , the diesel fuel fraction 322 , and an unconverted oil
medium AGO range hydrocarbons and heavy AGO range 45 fraction 324. The diesel fuel fraction 322 is recovered as
hydrocarbons. fuel, for instance , compliant with Euro V diesel standards,
For example, a first middle distillate fraction 116 can be and can be combined with the diesel fuel fraction 182 from
processed in a kerosene sweetening process 170 to produce the diesel hydrotreating zone 180. In certain embodiments ,
kerosene fuel product 172 , for instance , jet fuel compliant all , a substantial portion, a significant portion or a major
with Jet Aor Jet A - 1 specifications, and optionally other fuel 50 portion of the total vacuum gas oil 162 is routed to the
products (not shown ). In certain embodiments herein , all or vacuum gas oil hydrocracking zone 320. The remainder (if
a portion of the first middle distillate fraction 116 is not used any ) can be routed directly to the gas oil steam cracking zone
for fuel production, but rather is used as a feed for distillate 250 , bypassing the vacuum gas oil hydrocracking zone . In
hydroprocessing so as to produce additional feed for the addition to vacuum gas oil and optionally atmospheric gas
mixed feed steam cracking zone 230 . 55 oil , in certain embodiments the hydrocracking zone 320 can
A second middle distillate fraction 122 is processed in a also process atmospheric and / or vacuum gas oil range
distillate hydroprocessing zone such as a diesel hydrotreat products from an optional vacuum residue treatment zone
ing zone 180 , to produce wild naphtha 184 and a diesel fuel 800 .
fraction 182 , for instance, compliant with Euro V diesel All , a substantial portion , a significant portion or a major
standards. In additional embodiments, all or a portion of the 60 portion of the hydrocracked naphtha fraction 326 from the
first middle distillate fraction 116 can be treated with the vacuum gas oil hydrocracking zone 320 is routed to the
second middle distillate fraction 122 , as denoted by dashed mixed feed steam cracking zone 230. Remaining wild naph
lines . tha ( if any) can be added to a gasoline pool . In certain
All or a portion of the wild naphtha 184 is routed to the embodiments , the naphtha fraction 326 is routed through the
mixed feed steam cracking zone 230 ; any portion that is not 65 crude complex 100. In embodiments in which the hydroc
passed to the mixed feed steam cracking zone 230 can be racked naphtha fraction 326 is routed through the crude
routed to the gasoline pool . In certain embodiments, the wild complex 100 , all or a portion of the liquefied petroleum gas
 US 10,760,011 B2
11 12
produced in the gas oil hydrocracking zone 320 can be certain embodiments all or a portion of the residual C4s can
passed with the hydrocracked naphtha fraction 326 . be diverted . Separation of the ethylene 202 , propylene 204
All , a substantial portion or a significant portion of the and the mixed C4s stream 206 occurs in a suitable arrange
unconverted oil fraction 324 from the vacuum gas oil ment of known separation steps for separating steam crack
hydrocracking zone 320 is routed to the gas oil steam 5 ing zone effluents, including compression stage ( s ) , depro
cracking zone 250. The remainder ( if any ) can be recycled panizer, debutanizer, demethanizer and deethanizer.
and cracked to extinction and / or bled from the system and / or All , a substantial portion or a significant portion of the
passed to the optional vacuum residue treating zone . pyrolysis gasoline 212 from the steam cracker complex
In certain embodiments, at least a major portion of a 230/250 is fed to a py - gas hydrotreatment and recovery
vacuum residue fraction 168 from the vacuum distillation 10 center 600/620 . In certain embodiments, select hydrocar
zone 160 is passed to the optional vacuum residue treatment bons having 5-12 carbons are recovered from untreated
zone 800. In certain embodiments, all , a substantial portion, pyrolysis gasoline and the remainder is subsequently
a significant portion or a major portion of the total vacuum hydrotreated for aromatics recovery. In a py - gas hydrotreat
residue 168 is routed to the optional vacuum residue treat ing unit, diolefins and olefins in the pyrolysis gasoline are
ment zone 800. The remainder (if any ) is routed to the fuel 15 saturated .
oil pool ( not shown ). In addition, in certain embodiments, a Hydrotreated pyrolysis gasoline from the py -gas
minor portion of the atmospheric residue fraction 114 can hydrotreating unit in certain embodiments having C5s
bypass the vacuum distillation zone 160 ( not shown ) and be removed and recycled to the mixed feed steam cracking
routed to the optional vacuum residue treatment zone 800. In zone 230 instead of or in conjunction with C5s from the
certain embodiments, all or a portion of a pyrolysis oil 20 aromatics extraction zone 620 ) is routed to the aromatics
stream 218 from the steam cracker complex, for instance , extraction zone 620. The py - gas hydrotreating zone 600 and
shown as stream 902 , can be processed in the optional the aromatics extraction zone 620 are shown for simplicity
vacuum residue treatment zone 800 . in a single schematic block 600/620 in FIGS . 2 , 3 , 4 and 5 .
With reference to FIG . 2 , the mixed feed steam cracking The aromatics extraction zone 620 includes, for instance ,
zone 230 and the gas oil steam cracking zone 250 operate to 25 one or more extractive distillation units , and operates to
convert their respective feeds into ethylene 202 , propylene separate the hydrotreated pyrolysis gasoline into an aromat
204 , mixed C4s 206 , pyrolysis gasoline 212 , pyrolysis oil ics stream 622 containing high -purity benzene, toluene,
218 , and off -gases 208 that can be passed to an integrated xylenes and C9 aromatics , which are recovered for chemical
fuel gas system . Further, hydrogen 210 is recovered from the markets. C5 raffinate 606 and non - aromatics 646 ( for
cracked products and can be recycled to hydrogen users 30 instance, C6 - C9 ) are recycled to the mixed feed steam
within the complex limits . Not shown are the ethane and cracking zone 230. In certain embodiments, all , a substantial
propane recycle, which are typical in steam cracking opera portion or a significant portion of the C5 raffinate 606 and
tions , although it is appreciated that in certain embodiments non - aromatics 646 are passed the mixed feed steam
all or a portion of the ethane and propane can be diverted . cracking zone 230. A heavy aromatics stream 642 ( for
In certain embodiments, all , a substantial portion, a signifi- 35 instance, C10 - C12 ) can be used as an aromatic solvent, an
cant portion or a major portion of ethane is recycled to the octane boosting additive or as a cutter stock into a fuel oil
mixed feed steam cracking zone 230 , and all , a substantial pool . In certain embodiments ethylbenzene 628 can be
portion , a significant portion or a major portion of propane recovered .
is mixed feed steam cracking zone 230. In certain embodi In certain embodiments, pyrolysis oil 218 can be blended
ments hydrogen for all hydrogen users in the integrated 40 into the fuel oil pool . In additional embodiments, pyrolysis
process and system is derived from hydrogen 210 recovered oil 218 can be fractioned (not shown ) into light pyrolysis oil
from the cracked products, and no outside hydrogen is and heavy pyrolysis oil . For instance, light pyrolysis oil can
required once the process has completed start- up and be blended with the first middle distillate stream 116 and / or
reached equilibrium . In further embodiments excess hydro the second middle distillate stream 122 , for processing to
gen can be recovered . 45 produce diesel fuel product and / or additional feed to the
For simplicity , operations in an olefins recovery train are mixed feed steam cracking zone 230. In further embodi
not shown, but are well known and are considered part of the ments light pyrolysis oil derived from pyrolysis oil 218 can
mixed feed steam cracking zone 230 and gas oil steam be processed in the vacuum gas oil hydrocracking zone 320 .
cracking zone 250 as described herein with respect to FIGS . In additional embodiments, light pyrolysis oil derived from
2 , 3 , 4 and 5 . 50 pyrolysis oil 218 can be blended into the fuel oil pool . In
The mixed C4s stream 206 containing a mixture of C4s further embodiments, light pyrolysis derived from pyrolysis
from the steam cracker complex 230/250 , known as crude oil 218 can be processed in the residue treating zone 800. In
C4s , is routed to a butadiene extraction unit 500 to recover certain embodiments, all , a substantial portion, a significant
a high purity 1,3 -butadiene product 502. A first raffinate 504 portion or a major portion of light pyrolysis oil derived from
( " C4 - Raff - 1 ”) containing butanes and butenes is passed to a 55 pyrolysis oil 218 can be passed to one or both of the diesel
selective hydrogenation unit ( “ SHU ” ) and methyl tertiary hydrotreating zone 180 and / or the vacuum gas oil hydroc
butyl ether (“MTBE ” ) unit , SHU and MTBE zone 510 , racking zone 320 ; any remainder can be blended into the fuel
where it is mixed with high purity fresh methanol 512 from oil pool. Heavy pyrolysis oil can be blended into the fuel oil
outside battery limits to produce methyl tertiary butyl ether pool , used as a carbon black feedstock and / or processed in
514 . 60 the optional residue treating zone 800. In certain embodi
A second raffinate 516 (“ C4 Raff- 2 ” ) from the SHU and ments, all , a substantial portion , a significant portion or a
MTBE zone 510 is routed to a C4 distillation unit 520 for major portion of the pyrolysis oil 218 ( light and heavy) can
separation into a 1 - butene product stream 522 and an alkane be processed in the optional residue treating zone 800 .
stream 524 (a third raffinate “ C4 Raff -3 ” ) containing FIG . 3 schematically depicts further embodiments of
residual C4s , all , a substantial portion, a significant portion 65 processes and systems for conversion of crude oil to petro
or a major portion of which is recycled to the mixed feed chemicals and fuel products, with metathesis conversion of
steam cracking zone 230 although it is appreciated that in C4 and C5 olefins to produce additional propylene. The
 US 10,760,011 B2
13 14
process operates as described with respect to FIG . 1 cracking operations. In this embodiment, an additional step
upstream of the steam cracking operations. is provided to convert a mixture of butenes into mixed
Downstream of the steam cracking operations, the buta butanols suitable as a gasoline blending oxygenate and for
diene extraction train can optionally operate in a manner octane enhancement. Suitable processes to convert a mixture
similar to that in FIG . 1 shown as the third C4 raffinate 5 of butenes into mixed butanols are described in one or more
stream 524 from a diverter (in dashed lines ) from the C4 of commonly owned patent publications
distillation unit 520 directly to the mixed feed steam crack US20160115107A1 , US20150225320A1 ,
ing zone 230 . US20150148572A1 , US20130104449A1 ,
In a metathesis mode of operation, a mixed C4 raffinate US20120245397A1 and commonly owned U.S. Pat. Nos .
stream 532 ( “ C4 Raff 3 " ) from the C4 distillation unit 520 10 9,447,346B2 , 9,393,540B2 , 9,187,388B2 , 8,558,036B2 , all
and C5 raffinate 540 from the py - gas hydrotreatment and of which are incorporated by reference herein in their
recovery center 600/620 are routed to a metathesis unit 530 entireties. In certain embodiments, a particularly effective
for metathesis conversion to additional propylene 534. In conversion process known as “ SuperButolTM ” technology is
certain embodiments , all, a substantial portion , a significant integrated, which is a one - step process that converts a
portion or a major portion of the cracked C5s from the 15 mixture of butenes into mixed butanol liquids.
py - gas hydrotreater can be routed to the metathesis unit 530 Downstream of the steam cracking operations, the buta
prior to aromatics extraction . As indicated, a portion 536 of diene extraction train can optionally operate in a manner
the ethylene product 202 can be routed to the metathesis unit similar to that in FIG . 2 shown as the stream 524 from a
530. In additional embodiments, ethylene for the metathesis diverter ( in dashed lines ) from the C4 distillation unit 520
unit 530 is supplied from outside the complex limits , instead 20 directly to the mixed feed steam cracking zone 230. A mixed
of or in addition to the portion 536 of the ethylene product butanols production zone 550 is integrated for selective
202 . recovery of various alkene and diene pyrolysis chemicals
Selective recovery of various alkene and diene pyrolysis having four carbons, and in certain processing arrangements
chemicals having four carbons, and metathesis conversion to hydrating a portion of those C4's in a butanol production
produce additional propylene, is achieved using a metathesis 25 unit ( such as a “ SuperButo1TM ” unit) to produce high value
unit 530. A stream 538 containing a mixture of mostly fuel additives .
saturated C4/ C5 from the metathesis unit 530 is recycled to For instance, the mixed butanols production zone 550
the mixed feed steam cracking unit 230 . operates to convert butenes to butanols from undervalued
As in FIG . 2 , in the configuration of FIG . 3 , pyrolysis refinery/petrochemical mixed olefin streams. The butanols
gasoline 212 from the steam cracker complex 230/250 is 30 provide an alternative option for oxygenates in gasoline
routed to the py - gas hydrotreatment and recovery center blends . The crude C4 processing center 550 includes the
600/620 ; C6 - C9 aromatics stream 622 , BTX , is recovered conversion reaction of butenes to butanols , for instance, in
for chemical ma ts ; C6 - C9 non - aromatics stream 646 is one or more high pressure catalytic reactors followed by
recycled to the mixed feed steam cracking zone 230 ; and the gravity separation of butenes and butanols from water, and
heavy aromatics stream 642 ( for instance , C10 - C12 prod- 35 subsequent separation of the butanols product from butenes
ucts ) is recovered . In certain embodiments ethylbenzene 628 by distillation . Process stages include butenes and water
can be recovered . In addition, in a metathesis mode of make-up and recycle , butanol reaction , high pressure sepa
operation , a C5 raffinate is routed to the metathesis unit 530 , ration , low pressure separation , debutenizer distillation
shown as stream 540. Optionally C5 raffinate is recycled to ( product column) and an aqueous distillation column.
the mixed feed steam cracking zone 230 (as in the embodi- 40 FIG . 4 depicts embodiments in which a C4 raffinate
ments of FIG . 2 ) via stream 606 , shown in dashed lines in stream 552 containing butenes from the C4 distillation unit
FIG . 3. In certain embodiments (not shown) , all or a portion 520 routed to the mixed butanols production zone 550 to
of the cracked C5s from the py - gas hydrotreater can be convert the mixture of butenes into mixed butanol liquids
routed to the metathesis unit 530 prior to aromatics extrac 554. In certain embodiments, all , a substantial portion, a
tion . 45 significant portion or a major portion of stream 552 is routed
In the configuration depicted in FIG . 3 , an optional to the butanol production unit 550. Alkanes 556 are recycled
diverter is shown , indicated as a diverter and stream in to the mixed feed steam cracking zone 230 .
dashed lines , to bypass the metathesis conversion process , to As in FIGS . 1 and 2 in the configuration of FIG . 4 ,
therefore divert all , a substantial portion , a significant por pyrolysis gasoline 212 from the steam cracker complex
tion or a major portion of the third C4 raffinate stream 524 50 230/250 is routed to the py - gas hydrotreatment and recovery
to the mixed feed steam cracking zone 230. In a metathesis center 600/620 ; C6 - C9 aromatics stream 622 are recovered
mode , flow can be directed to the metathesis conversion unit for chemical markets, C5 raffinate 606 and non -aromatics
530. In further alternative modes , flow of the third C4 646 ( for instance , C6 - C9 ) can be recycled to the mixed feed
raffinate stream 524 can be directed to the mixed feed steam steam cracking zone 230 , and the heavy aromatics stream
cracking zone 230 and the metathesis conversion unit 530. 55 642 ( for instance , C10 - C12 products ) is recovered . In certain
In this manner, a producer can vary the quantity of feed to embodiments ethylbenzene 628 can be recovered .
tailor the desired outputs. Accordingly, 0-100 % of the third In the configuration depicted in FIG . 4 , an optional
C4 raffinate stream 524 can be routed to the metathesis diverter is shown , indicated as a diverter and stream in
conversion unit 530 , and the remainder (if any) is directed dashed lines, to bypass the process for conversion of a
to the mixed feed steam cracking zone 230. The quantity can 60 mixture of butenes into mixed butanols, to therefore divert
be determined , for instance , based upon demand for ethyl all , a substantial portion, a significant portion or a major
ene , demand for propylene , and / or minimum ranges for portion of the C4 Raff - 3 524 to the mixed feed steam
which the unit is operated depending on design capacity. cracking zone 230. In a mixed butanol liquid mode of
FIG . 4 schematically depicts further embodiments of operation, flow can be directed to the mixed butanols
processes and systems for conversion of crude oil to petro- 65 production zone 550 for conversion of a mixture of butenes
chemicals and fuel products. The process operates as into mixed butanols . In further alternative modes, flow of the
described with respect to FIG . 1 upstream of the steam C4 Raff - 3 524 can be directed to the mixed feed steam
 US 10,760,011 B2
15 16
cracking zone 230 and the mixed butanols production zone to the mixed feed steam cracking zone 230. An optional
550. In this manner , a producer can vary the quantity of feed valve also can be provided to direct flow of the C4 Raff - 3 to
to tailor the desired outputs . Accordingly, 0-100 % of the one or both of the metathesis conversion unit 530 and / or the
third C4 raffinate stream 524 can be routed to mixed mixed butanols production zone 550 for conversion of a
butanols production zone 550 , and the remainder ( if any) is 5 mixture of butenes into mixed butanols. In further alterna
directed to the mixed feed steam cracking zone 230. The tive modes , flow of the C4 Raff - 3 524 can be directed to each
quantity can be determined, for instance , based upon of the mixed feed steam cracking zone 230 , the metathesis
demand for ethylene, demand for mixed butanols , and / or conversion unit 530 (as stream 532 ) , and the mixed butanols
minimum ranges for which the unit is operated depending on production zone 550 ( as stream 552 ) . In this manner, a
design capacity. 10 producer can vary the quantity of feed to tailor the desired
FIG . 5 schematically depicts further embodiments of outputs. Accordingly, all , a substantial portion, a significant
processes and systems for conversion of crude oil to petro portion or a major portion of the third C4 raffinate stream
chemicals and fuel products. In this embodiment, additional can be routed to the metathesis conversion unit 530 , and the
step ( s ) of metathesis conversion of C4 and C5 olefins to remainder (if any) is directed to the mixed feed steam
produce additional propylene, and / or conversion of a mix- 15 cracking zone 230 and / or the mixed butanols production
ture of butenes into mixed butanols suitable as a gasoline zone 550. In certain embodiments, all , a substantial portion,
blending oxygenate and for octane enhancement, are inte a significant portion or a major portion of the third C4
grated. The process operates as described with respect to raffinate stream is routed to the metathesis conversion unit
FIG . 1 upstream of the steam cracking operations. 530 , and the remainder (if any) is directed to the mixed feed
Downstream of the steam cracking operations, the buta- 20 steam cracking zone 230. In further embodiments, all , a
diene extraction train can optionally operate in a manner substantial portion, a significant portion or a major portion
similar to that in FIG . 2 shown as the stream 524 from a of the third C4 raffinate stream is routed to the metathesis
diverter ( in dashed lines) from the C4 distillation unit 520 conversion unit 530 , and the remainder (if any ) is directed
directly to the mixed feed steam cracking zone 230 as an to the mixed butanols production zone 550 for production of
optional mode of operation. The configuration in FIG . 5 25 mixed butanols. In further embodiments, all , a substantial
integrates selective recovery of various alkene and diene portion, a significant portion or a major portion of the third
pyrolysis chemicals having four carbons, metathesis con C4 raffinate stream is routed to the mixed butanols produc
version to produce additional propylene, and / or conversion tion zone 550 for production of mixed butanols , and the
of a mixture of butenes into mixed butanols suitable as a remainder (if any) is directed to both the mixed feed steam
gasoline blending oxygenate and for octane enhancement. 30 cracking zone 230 and the metathesis conversion unit 530 .
FIG . 5 depicts a stream 552 containing butenes from the In further embodiments, all , a substantial portion, a signifi
C4 distillation step ( "C4 Raff - 3 ” ) that can be routed to a cant portion or a major portion of the third C4 raffinate
mixed butanols production zone 550 for conversion of the stream is routed to the mixed butanols production zone 550
mixture of butenes into mixed butanol liquids 554. Alkanes for production of mixed butanols, and the remainder (if any )
556 are recycled to the mixed feed steam cracking zone 230. 35 is directed to the mixed feed steam cracking zone 230. In
In addition , a portion 532 of the 2 -butene rich raffinate - 3 further embodiments, all , a substantial portion, a significant
from the C4 distillation unit 520 is passed to a metathesis portion or a major portion of the third C4 raffinate stream is
unit 530 for metathesis conversion to additional propylene routed to the mixed butanols production zone 550 for
534. As indicated, a portion 536 of the ethylene product 202 production of mixed butanols, and the remainder (if any) is
can be routed to the metathesis unit 530. In additional 40 directed to the metathesis conversion unit 530. The quantity
embodiments, ethylene for the metathesis unit 530 is sup can be determined, for instance , based upon demand for
plied from outside the complex limits , instead of or in ethylene, demand for propylene, demand for mixed
addition to the portion 536 of the ethylene product 202. A butanols, and / or minimum ranges for which the unit is
stream 538 , having a mixture of mostly saturated C4 / C5 operated depending on design capacity.
from metathesis unit , is recycled to the mixed feed steam 45 FIGS . 6 and 10 schematically depict embodiments of
cracking zone 230 . processes and systems for conversion of crude oil to petro
As in FIG . 2 , in the configuration of FIG . 5 , pyrolysis chemicals and fuel products including a mixed feed steam
gasoline 212 from the steam cracker complex 230/250 is cracking zone 230 and a gas oil steam cracking zone 250 .
routed to the py - gas hydrotreatment and recovery center A crude oil feed 102 is passed to a crude complex 100 ,
600/620 ; C6 - C9 aromatics stream 622 , BTX , is recovered 50 which generally includes an atmospheric distillation zone
for chemical markets; non - aromatics 646 ( for instance , 110 , a saturated gas plant 150 and a vacuum distillation zone
C6 - C9 ) is recycled to the mixed feed steam cracking zone 160. The atmospheric distillation unit and vacuum distilla
230 , and the heavy aromatics stream 642 ( for instance , tion unit are used in well -known arrangements .
C10 - C12 products) is recovered . In certain embodiments Intermediate streams obtained from the feed 102 via
ethylbenzene 628 can be recovered . The raffinate stream 540 55 separation in the crude complex 100 include : off- gas 154 ,
can be routed to the metathesis unit 530 , as shown , and /or obtained within the crude complex 100 via the saturated gas
optionally recycled to the mixed feed steam cracking zone plant 150 , and the sweet off -gas can be sent to the fuel gas
230 as shown in dashed lines, stream 606. In certain embodi system or to the steam cracker complex ; a light ends stream
ments (not shown ), all or a portion of the cracked C5s from 152 , obtained within the crude complex 100 via the saturated
the py - gas hydrotreater can be routed to the metathesis unit 60 gas plant 150 , and which is passed to the mixed feed steam
530 prior to aromatics extraction . cracking zone 230 ; one or more straight run naphtha
In the configuration depicted in FIG . 5 , an optional stream ( s ), in this embodiment a light naphtha stream 138
diverter is shown, indicated as a diverter and stream in and a heavy naphtha stream 140 , which are passed to the
dashed lines, to bypass the metathesis conversion process mixed feed steam cracking zone 230 ; a first middle distillate
and the process for conversion of a mixture of butenes into 65 stream 116 that is passed to a kerosene sweetening zone 170 ,
mixed butanols, to therefore divert all , a substantial portion, such as a mercaptan oxidation zone ; a second middle
a significant portion or a major portion of the C4 Raff - 3 524 distillate stream 122 that is passed to a diesel hydrotreating
 US 10,760,011 B2
17 18
zone 180 ; a third middle distillate stream 126 that can be wppm . In certain embodiments two or more desalters are
passed to the gas oil hydrocracking zone 320 , the gas oil included to achieve a target salt content of less than or equal
steam cracking zone 250 , or both the gas oil hydrocracking to about 3 wppm .
zone 320 and the gas oil steam cracking zone 250 ; an In one embodiment of a crude complex 100 herein , feed
atmospheric residue fraction 114 that is passed to the 5 102 is preheated before entering a desalting unit , for
vacuum distillation zone 160 ; a light vacuum gas oil stream instance, to a temperature ( ° C. ) in the range of about
164 and a heavy vacuum gas oil stream 166 from the 105-165 , 105-150 , 105-145 , 120-165 , 120-150 , 120-145 ,
vacuum distillation zone 160 that are passed to the vacuum 125-165 , 125-150 , 125-145 , and in certain embodiments
gas oil hydrocracking zone 320 ; and a vacuum residue about 135. Suitable desalters are designed to remove salt
stream 168 from the vacuum distillation zone 160 , all or a 10 down to a typical level of about 0.00285 kg/m ( 1 lb / 1000
portion of which can optionally be passed to a residue bbl ) in a single stage . In certain embodiments , plural preheat
treating zone 800 , and / or to a fuel oil pool . In certain and desalting trains are employed. The desalter operating
embodiments the third middle distillate stream 126 is routed pressure can be based on a pressure margin above crude and
water mixture vapor pressure at desalter operating tempera
to both the gas oil hydrocracking zone 320 and the gas oil 15 ture to ensure liquid phase operation , for instance in the
steam cracking zone 250. For instance, the third middle range of about 2.75-4.15 , 2.75-3.80 , 2.75-3.65 , 3.10-4.15 ,
distillate stream 126 can be two separate temperature frac 3.10-3.80 , 3.10-3.65 , 3.25-4.15 , 3.25-3.80 , 3.25-3.65 and in
tions of an atmospheric gas oil stream from the crude certain embodiments about 3.45 barg.
complex 100 , including heavy AGO that is passed to the gas The atmospheric distillation zone 110 can employ frac
oil hydrocracking zone 320 , and medium AGO ( if not 20 tionated products and pumparounds to provide enough heat
contained in the second middle distillate fraction 122 ) that for desalting. In certain embodiments, the desalter operating
bypasses the gas oil hydrocracking zone 320 and is directly temperature can be controlled by a diesel pumparound swing
routed to the gas oil steam cracking zone 250 without heat exchanger. In certain embodiments, desalter brine pre
hydrocracking. In another arrangement, the third middle heats desalter make - up water in a spiral type heat exchanger
distillate stream 126 can be divided based on volume or 25 to minimize fouling and achieve rundown cooling against
mass flow , for instance , with a diverter. cooling water before the brine is routed to the wastewater
The intermediate streams from the crude complex 100 are system .
used in an efficient manner in the integrated process and In certain embodiments , desalted crude is preheated
system herein . The light ends stream 152 , and the straight before entering a preflash tower, to a temperature ( ° C. ) in
run naphtha stream ( s ), in this embodiment light naphtha 138 30 the range of about 180-201 , 185-196 , or 189-192 . The
and heavy naphtha 140 , are routed to the mixed feed steam preflash tower removes LPG and light naphtha from the
cracking zone 230 as feed for conversion into light olefins crude before it enters the final preheat exchangers . The
and other valuable petrochemicals. Either or both of the preflash tower minimizes the operating pressure of the
straight run naphtha streams, light naphtha 138 and heavy preheat train to maintain liquid phase operation at the crude
naphtha 140 , can optionally be steam - stripped in a side 35 furnace pass valves and also reduces the requisite size of the
stripper prior to routing to the mixed feed steam cracking main crude column .
zone 230 . In one example of a suitable crude distillation system , a
Components of the crude complex not shown but which crude furnace vaporizes materials at or below a certain cut
are well- known can include feed /product and pump -around point, for instance , at a temperature ( ° C. ) in the range of
heat exchangers, crude charge heaters , crude tower ( s ) , prod- 40 about 350-370 , 355-365 or 360 ( 680 ° F. ) , before the crude
uct strippers, cooling systems , hot and cold overhead drum enters the flash zone of the crude tower . The furnace is
systems including re - contactors and off - gas compressors , designed for a suitable outlet temperature , for instance , at a
and units for water washing of overhead condensing sys temperature ( ° C . ) in the range of about 338-362 , 344-354 or
tems . The atmospheric distillation zone 110 can include 348.9 ( 660 ° F. ) . Crude column flash zone conditions are at
well -known design features. Furthermore, in certain 45 a temperature ( ° C. ) in the range about 328-374 , 328-355 ,
embodiments, all or portions of the naphtha, kerosene and 337-374 , 327-355 , or 346.1 ( 655 ° F. ) , and a pressure (barg )
atmospheric gas oil products from the atmospheric distilla in the range of about 1.35-1.70 , 1.35-1.60 , 1.44-1.70 , 1.44
tion column are steam - stripped in side strippers, and atmo 1.60 or 1.52 .
spheric residue is steam -stripped in a reduced - size can In certain embodiments the crude tower contains 59 trays
section inside the bottom of the atmospheric distillation 50 and produces six cuts , with draw temperatures for each
column. product as follows: light naphtha, 104.4 ° C. (220 ° F. )
The feed to the atmospheric distillation zone 110 is (overhead vapor); heavy naphtha, 160.6 ° C. (321 ° F. ) (sid
primarily the crude feed 102 , although it shall be appreciated edraw ); kerosene, 205 ° C. ( 401 ° F. ) ( sidedraw ); diesel,
that wild naphtha, LPGs and off -gas streams from the diesel 261.7 ° C. ( 503 ° F. ) ( sidedraw ); AGO , 322.2 ° C. ( 612 ° F. )
hydrotreating zone 180 , the vacuum gas oil hydrocracking 55 (sidedraw ); atmospheric residue, 340.6 ° C. ( 645 ° F. ) (bot
zone 320 , and in certain embodiments from an optional toms ) . The heavy naphtha draw includes a reboiled side
residue treating zone , can be routed to the atmospheric stripper against diesel pumparound , and is controlled to a
distillation zone 110 where they are fractionated before 185 ° C. ( 365 ° F. ) D86 end point. The kerosene draw includes
being passed to the cracking complex. A desalting unit (not a steam stripper at 14.54 kg/m3 ( 5.1 lb steam per bbl ) ; the
shown ) is typically included upstream of the distillation 60 draw rate is limited on the back end by freeze point. The
zone 110. A substantial amount of the water required for diesel draw includes a steam stripper at 14.54 kg/m3 ( 5.1 lb
desalting can be obtained from a sour water stripper within steam per bbl ) , and this draw is controlled to a 360 ° C. ( 680 °
the integrated process and system . F. ) D86 95 % point. The AGO draw includes a steam stripper
The desalting unit refers to a well-known arrangement of at 14.82 kg/m² ( 5.2 lb steam per bbl) , which sets the
vessels for desalting of crude oil , and as used herein is 65 overflash at 2 vol % on crude. The crude tower also contains
operated to reduce the salt content to a target level , for 3 pumparounds for top , diesel , and AGO . Diesel pump
instance, to a level of less than or equal to about 10 , 5 , or 3 around provides heat to the heavy naphtha stripper reboiler
 US 10,760,011 B2
19 20
and debutanizer reboiler along with controlling desalter plant 150 include : an off -gas stream 154 , containing C1 - C2
operating temperature via swing heat. The bottoms stream of alkanes that is passed to the fuel gas system and / or the steam
the atmospheric column is steam stripped at 28.5 kg /m3 ( 10 cracker complex ; and a light ends stream 152 , containing
lb steam /bbl). C2 + , that is passed to the mixed feed steam cracking unit
The atmospheric residue fraction 114 from the atmo 5 230 .
spheric distillation zone 110 is further distilled in the In certain embodiments, a suitable saturated gas plant 150
vacuum distillation zone 160 , which fractionates the atmo includes amine and caustic washing of liquid feed, and
spheric residue fraction 114 into vacuum gas oil fractions , amine treatment of vapor feed , before subsequent steps . The
shown as a light vacuum gas oil stream 164 and a heavy crude tower overhead vapor is compressed and recontacted
vacuum gas oil stream 166 , and a vacuum residue stream 10 with naphtha before entering an amine scrubber for H2S
168. Vacuum gas oil from streams 164 and 166 is routed to removal and is then routed to the steam cracker complex.
the vacuum gas oil hydrocracking zone 320. The vacuum Recontact naphtha is debutanized to remove LPGs which are
residue stream 168 can be routed to a fuel oil pool ( such as amine washed and routed to the steam cracker complex . The
a high sulfur fuel oil pool ) , or in certain embodiments, debutanized naphtha is routed separately from the heavy
passed to a residue treating zone 800 . 15 naphtha to the steam cracker complex. As is known, light
The vacuum distillation zone 160 can include well -known naphtha absorbs C4 and heavier hydrocarbons from the
design features , such as operation at reduced pressure levels vapor as it travels upward through an absorber / debutanizer.
(mm Hg absolute pressure ), for instance , in the range of Off -gas from the absorber / debutanizer is compressed and
about 30-40 , 32-36 or 34 , which can be maintained by steam sent to a refinery fuel gas system . A debutanizer bottoms
ejectors or mechanical vacuum pumps . Vacuum bottoms can 20 stream is sent to the mixed feed steam cracker as an
be quenched to minimize coking , for instance , via exchange additional source of feed .
against crude at a temperature ( ° C. ) in the range of about As shown, the first middle distillate fraction 116 is pro
334-352 , 334-371 , 338-352 , 338-371 or 343.3 ( 650 ° F. ) . cessed in a kerosene sweetening zone 170 to remove
Vacuum distillation can be accomplished in a single stage or unwanted sulfur compounds, as is well- known. Treated
in plural stages . In certain embodiments, the atmospheric 25 kerosene is recovered as a kerosene fuel product 172 , for
residue fraction 114 is heated in a direct fired furnace and instance , jet fuel compliant with Jet A or Jet A - 1 specifica
charged to vacuum fractionator at a temperature ( ° C . ) in the tions , and optionally other fuel products. In certain embodi
range of about 390-436 , 390-446 , 380-436 , 380-446 or ments herein , all or a portion of the first middle distillate
400-425 . fraction 116 is not used for fuel production, but rather is used
In one embodiment, the atmospheric residue is heated to 30 as a feed for distillate hydroprocessing so as to produce
a temperature ( ° C . ) in the range of about 399-420 , 399-430 , additional feed for the mixed feed steam cracking zone 230 .
389-420 , 389-430 or 409.4 (769 ° F. ) in the vacuum furnace For instance , a suitable kerosene sweetening zone 170 can
to achieve flash zone conditions of a temperature ( ° C . ) in the include, but is not limited to , systems based on MeroxTM
range of about 392-412 , 392-422 , 382-412 , 382-422 or technology (Honeywell UOP, US ) , Sweetn’K technology
401.7 ( 755 ° F. ) and pressure levels (mm Hg absolute pres- 35 (Axens, IFP Group Technologies, FR) or ThiolexTM tech
sure) in the range of about 30-40 , 32-36 or 34. The vacuum nology (Merichem Company, US ) . Processes of these types
column is designed for a theoretical cut point temperature ( ° are well - established commercially and appropriate operating
C. ) in the range of about 524-551 , 524-565 , 511-551 , conditions are well known to produce fuel product 172 and
511-565 or 537.8 ( 1000 ° F. ) , by removing light VGO and disulfide oils as by -products. In certain kerosene sweetening
heavy VGO from the vacuum residue. The overhead vacuum 40 technologies, impregnated carbon is utilized as catalyst to
system can include two parallel trains of jet ejectors each promote conversion to disulfide oil . In certain embodiments,
including three jets . A common vacuum pump is used at the common treatment of sour water from the kerosene sweet
final stage . In one embodiment, the vacuum tower is sized ening zone 170 and other unit operations is employed to
for a 0.35 C - Factor and about a 14.68 lpm/m² (0.3 gpm / ft?) maximize process integration .
wetting rate at the bottom of the wash zone . Wash zone slop 45 For example , one arrangement of a kerosene sweetening
wax is recycled to the vacuum furnace to minimize fuel oil zone includes caustic wash of the kerosene feed for residual
production. Vacuum bottoms are quenched via exchange H2S removal, employing an electrostatic coalescer ( for
against crude to minimize coking at a temperature ( ° C . ) in instance using 10 degrees Baumé). The reactor vessel con
the range of about 334-352 , 334-371 , 338-352 , 338-371 or taining an effective quantity of activated carbon catalyst
343.3 ° C. ( 650 ° F. ) . 50 utilizes air in conjunction with the caustic solution to affect
The saturated gas plant 150 generally comprises a series the oxidation of mercaptan to disulfides. Caustic is separated
of operations including fractionation and in certain systems from treated kerosene in the bottom section of the reactor.
absorption and fractionation , as is well known , with an After water washing , kerosene product passes upwards
objective to process light ends to separate fuel gas range through one of two parallel salt filters to remove free water
components from LPG range components suitable as a 55 and some soluble water. The kerosene product passes down
steam cracker feedstock . The light ends that are processed in ward through one of two parallel clay filters for removal of
one or more saturated gas plants within embodiments of the solids , moisture, emulsions and surfactants, so as to ensure
integrated system and process herein are derived from the that the kerosene product meets haze , color stability and
crude distillation , such as light ends and LPG . In addition , water separation specifications, for instance , compliant with
other light products can optionally be routed to the saturated 60 Jet A specifications.
gas plant 150 , shown in dashed lines as stream 156 , such as The second middle distillate fraction 122 is processed in
light gases from refinery units within the integrated system , a diesel hydrotreating zone 180 in the presence of an
and in certain embodiments light gases from outside of the effective amount of hydrogen obtained from recycle within
battery limits . For instance , stream 156 can contain off -gases the diesel hydrotreating zone 180 and make -up hydrogen
and light ends from the diesel hydrotreating zone 180 , the 65 186. In certain embodiments, all or a portion of the make -up
gas oil hydrocracking zone 320 and / or from the py - gas hydrogen 186 is derived from the steam cracker hydrogen
hydrotreating zone 600. The products from the saturated gas stream 210 from the olefins recovery train 270. A suitable
 US 10,760,011 B2
21 22
hydrotreating zone 180 can include , but is not limited to , within the diesel hydrotreating zone 180 , are well known
systems based on technology commercially available from and are considered part of the diesel hydrotreating zone 180 .
Honeywell UOP, US ; Chevron Lummus Global LLC In certain embodiments, the diesel hydrotreating zone 180
( CLG) , US ; Axens, IFP Group Technologies, FR ; Haldor operating conditions include :
Topsoe A / S , DK ; or joint technology from KBR , Inc , US , 5 a reactor inlet temperature ( ° C. ) in the range of from
and Shell Global Solutions , US . about 296-453 , 296-414 , 296-395 , 336-453 , 336-414 , 336
The diesel hydrotreating zone 180 operates under condi 395a , reactor
355-453 , 355-414 , 355-395 or 370-380 ;
outlet temperature ( ° C. ) in the range of from
tions effective for removal of a significant amount of the about 319-487 , 319-445 , 319-424 , 361-487 , 361-445 , 361
sulfur and other known contaminants, for instance, to meet
necessary sulfur specifications for the diesel fuel fraction 10 424a , start
382-487 , 382-445 , 382-424 or 400-406 ;
of run ( SOR) reaction temperature ( ° C. ) , as a
182 , such as diesel fuel compliant with Euro V diesel weighted average
standards. In addition , a hydrotreated naphtha fraction 184 from about 271-416bed, 271-379
temperature ( WABT ), in the range of
, 271-361 , 307-416 , 307-379 ,
( sometimes referred to as wild naphtha) is recovered from 307-361 , 325-416 , 325-379 , 325-361 or 340-346 ;
the diesel hydrotreating zone 180 , which is routed to the 15 an end of run (EOR) reaction temperature ( ° C. ) , as a
mixed feed steam cracking zone 230 as one of plural steam WABT, in the range of from about 311-476 , 311-434 ,
cracking feed sources . Effluent off- gases are recovered from 311-414 , 352-476 , 352-434 , 352-414 , 373-476 , 373-434 ,
the diesel hydrotreating zone 180 and are passed to the 373-414 or 390-396 ;
olefins recovery train , the saturated gas plant as part of the a reaction inlet pressure ( barg) in the range of from about
other gases stream 156 , and / or directly to a fuel gas system . 20 48-72 , 48-66 , 48-63 , 54-72 , 54-66 , 54-63 , 57-72 , 57-66 or
Liquefied petroleum gas can be recovered from the diesel 57-63 ;
hydrotreating zone 180 and routed to the mixed feed steam a reaction outlet pressure (barg ) in the range of from about
cracking zone, the olefins recovery train and / or the saturated 44-66 , 44-60 , 44-58 , 49-66 , 49-60 , 49-58 , 52-66 , 52-60 or
gas plant. In certain embodiments, the hydrotreated naphtha 52-58 ;
fraction 184 is routed through the crude complex 100 , alone , 25 a hydrogen partial pressure (barg ) (outlet) in the range of
or in combination with other wild naphtha fractions from from about 32-48 , 32-44 , 32-42 , 36-48 , 36-44 , 36-42 , 38-48 ,
within the integrated process . In embodiments in which 38-44 or 38-42 ;
hydrotreated naphtha fraction 184 is routed through the a hydrogen treat gas feed rate ( standard liters per liter of
crude complex 100 , all or a portion of the liquefied petro hydrocarbon feed , SLt/Lt) up to about 400 , 385 , 353 or 337 ,
leum gas produced in the diesel hydrotreating zone 180 can 30 in certain embodiments from about 256-385 , 256-353 , 256
be passed with the hydrotreated naphtha fraction 184. In 337 , 289-385 , 289-353 , 289-337 , 305-385 , 305-353 or 305
certain embodiments , all , a substantial portion or a signifi 337 ;
cant portion of the wild naphtha 184 is routed to the mixed a hydrogen quench gas feed rate ( SLt/Lt) up about 100 ,
feed steam cracking zone 230 ( directly or through the crude 85 , 78 or 75 , in certain embodiments from about 57-85 ,
complex 100 ) . 35 57-78 , 57-75 , 64-85 , 64-78 , 64-75 , 68-85 , 68-78 or 68-75 ;
The diesel hydrotreating zone 180 can optionally process and
other fractions from within the complex ( not shown ). In a make -up hydrogen feed rate (SLt/Lt) up to about 110 ,
embodiments in which a kerosene sweetening zone 170 is 108 , 100 or 95 , in certain embodiments from about 70-108 ,
used , all or a portion of the disulfide oil can be additional 70-100 , 70-95 , 80-108 , 80-100 , 80-95 , 85-108 , 85-100 or
feed to the diesel hydrotreating zone 180. Further, all or a 40 85-95 .
portion of the first middle distillate fraction 116 can be An effective quantity of hydrotreating catalyst is provided
additional feed to the diesel hydrotreating zone 180. Addi in the diesel hydrotreating zone 180 , including those pos
tionally, all or a portion of distillates from the vacuum gas sessing hydrotreating functionality and which generally con
oil hydrocracking zone 320 , and / or all or a portion of tain one or more active metal component of metals or metal
distillates from the optional vacuum residue treatment zone , 45 compounds (oxides or sulfides) selected from the Periodic
can be routed to the diesel hydrotreating zone 180. Any Table of the Elements IUPAC Groups 6-10 . In certain
portion of distillates not routed to the diesel hydrotreating embodiments, the active metal component is one or more of
zone 180 can be passed to the crude complex 100 or routed Co , Ni , W and Mo. The active metal component is typically
to the mixed feed steam cracking zone 230. Further, all or a deposited or otherwise incorporated on a support, such as
portion of light pyrolysis oil can be routed to the diesel 50 amorphous alumina , amorphous silica alumina , zeolites , or
hydrotreating zone 180 . combinations thereof. The catalyst used in the diesel
The diesel hydrotreating zone 180 can contain one or hydrotreating zone 180 can include one or more catalyst
more fixed -bed, ebullated -bed , slurry -bed, moving bed , con selected from Co/ Mo , Ni/ Mo , Ni/ W , and Co /Ni/Mo. Com
tinuous stirred tank ( CSTR) or tubular reactors , in series binations of one or more of Co/ Mo , Ni /Mo , Ni /W and
and / or parallel arrangement. In certain embodiments, the 55 Co /Ni/Mo, can also be used . The combinations can be
diesel hydrotreating zone 180 contains a layered bed reactor composed of different particles containing a single active
with three catalyst beds and having inter -bed quench gas , metal species , or particles containing multiple active spe
and employs a layered catalyst system with the layer of cies . In certain embodiments, Co/ Mo hydrodesulfurization
hydrodewaxing catalyst positioned between beds of catalyst is suitable . Effective liquid hourly space velocity
hydrotreating catalyst . Additional equipment, including 60 values (h- ?), on a fresh feed basis relative to the hydrotreat
exchangers, furnaces, feed pumps, quench pumps , and com ing catalysts , are in the range of from about 0.1-10.0 ,
pressors to feed the reactor( s ) and maintain proper operating 0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 , 0.3-2.0 , 0.5-10.0 , 0.5-5.0 ,
conditions , are well known and are considered part of the 0.5-2.0 or 0.8-1.2 . Suitable hydrotreating catalysts used in
diesel hydrotreating zone 180. In addition , equipment the diesel hydrotreating zone 180 have an expected lifetime
including pumps , compressors , high temperature separation 65 in the range of about 28-44, 34-44 , 28-38 or 34-38 months.
vessels , low temperature separation vessels and the like to In certain embodiments , an effective quantity of hydrode
separate reaction products and provide hydrogen recycle waxing catalyst is also added . In such embodiments, effec
 US 10,760,011 B2
23 24
tive hydrodewaxing catalysts include those typically used overall complex and improve the economic threshold of
for isomerizing and cracking paraffinic hydrocarbon feeds to cracking heavy feeds . This application of a gas oil hydroc
improve cold flow properties, such as catalysts comprising racking zone. as a chemical yield control mechanism , is
Ni , W , or molecular sieves or combinations thereof. Catalyst uncommon in the industry, where fuels products are typi
comprising Ni/ W , zeolite with medium or large pore sizes , 5 cally the product objectives.
or a combination thereof are suitable , along with catalyst Hydrocracking processes are used commercially in a large
comprising aluminosilicate molecular sieves such as zeolites number of petroleum refineries . They are used to process a
with medium or large pore sizes . Effective commercial variety of feeds boiling above the atmospheric gas oil range
zeolites include for instance ZSM - 5 , ZSM - 11 , ZSM - 12 , ( for example, in the range of about 370 to 520 ° C. ) in
ZSM - 22 , ZSM - 23 , ZSM 35 , and zeolites of type beta and Y. 10 conventional hydrocracking units and boiling above the
Hydrodewaxing catalyst is typically supported on an oxide vacuum gas oil range ( for example , above about 520 ° C.) in
support such as A1203 , SiO2 , ZrO2, zeolites , zeolite -alu residue hydrocracking units. In general, hydrocracking pro
mina, alumina - silica , alumina - silica - zeolite , activated car cesses split the molecules of the feed into smaller, i.e. ,
bon, and mixtures thereof. Effective liquid hourly space lighter, molecules having higher average volatility and eco
velocity values (catalyst
hydrodewaxing h ='), on, are
a fresh feed basis relative to the
in the range of from about
15 nomic value . Additionally, hydrocracking processes typi
cally improve the quality of the hydrocarbon feedstock by
0.1-12.0 , 0.1-8.0 , 0.1-4.0 , 0.5-12.0 , 0.5-8.0 , 0.5-4.0 , 1.0 increasing the hydrogen - to - carbon ratio and by removing
12.0 , 1.0-8.0 , 1.0-4.0 or 1.6-2.4 . Suitable hydrodewaxing organosulfur and organonitrogen compounds. The signifi
catalysts used in the diesel hydrotreating zone 180 have an cant economic benefit derived from hydrocracking pro
expected lifetime in the range of about 28-44 , 34-44 , 28-38 20 cesses has resulted in substantial development of process
or 34-38 months. improvements and more active catalysts.
In high capacity operations, two or more parallel trains of Three major hydrocracking process schemes include
reactors are utilized . In such embodiments, the flow in the single - stage once through hydrocracking, series - flow hydro
diesel hydrotreating zone 180 is split after the feed pump cracking with or without recycle, and two - stage recycle
into parallel trains, wherein each train contains feed / effluent 25 hydrocracking. Single - stage once through hydrocracking is
heat exchangers, feed heater, a reactor and the hot separator. the simplest of the hydrocracker configuration and typically
Each reactor contains three catalyst beds with inter -bed occurs at operating conditions that are more severe than
quench gas . A layered catalyst system is used with the layer hydrotreating processes, and less severe than conventional
of hydrodewaxing catalyst positioned between beds of higher pressure hydrocracking processes . It uses one or more
hydrotreating catalyst . The trains recombine after the hot 30 reactors for both treating steps and cracking reaction , so the
separators. Tops from the hot separators are combined and catalyst must be capable of both hydrotreating and hydro
passed to a cold separator. Bottoms from the hot separators cracking. This configuration is cost effective, but typically
and from the cold separator are passed to a product stripper results in relatively low product yields ( for example, a
to produce stabilized ultra -low sulfur diesel and wild naph maximum conversion rate of about 50 wt % ) . Single stage
tha. Tops from the cold separator are subjected to absorption 35 hydrocracking is often designed to maximize mid -distillate
and amine scrubbing. Recycle hydrogen is recovered , and yield over a single or dual catalyst systems . Dual catalyst
passed ( along with make- up hydrogen ) to the reaction zone systems can be used in a stacked- bed configuration or in two
as treat gas and quench gas . different reactors . The effluents are passed to a fractionator
The light vacuum gas oil stream 164 and heavy vacuum column to separate the H2S , NH3 , light gases ( C1 - C4) ,
gas oil stream 166 (or full range VGO , not shown) are 40 naphtha and diesel products, boiling in the temperature
processed in a gas oil hydrocracking zone 320 in the range including and below atmospheric gas oil range frac
presence of an effective amount of hydrogen obtained from tions ( for instance in the temperature range of 36-370 ° C. ) .
recycle within the gas oil hydrocracking zone 320 and The hydrocarbons boiling above the atmospheric gas oil
make-up hydrogen 302. In certain embodiments, all or a range ( for instance 370 ° C. ) are typically unconverted oils .
portion of the make -up hydrogen 302 is derived from the 45 Any portion of these unconverted oils that are not recycled
steam cracker hydrogen stream 210 from the olefins recov are drawn from a bottoms fraction in a gas oil hydrocracking
ery train 270. In certain embodiments ( shown in dashed lines zone 320 as a hydrogen - rich bleed stream and is effectively
in FIG . 6 ) , all or a portion of the heavy middle distillate integrated as feed to the gas oil steam cracking zone 250 as
fraction, such as a portion of the third middle distillate described herein . In certain embodiments , unconverted oils
fraction 126 , e.g. , atmospheric gas oil from the atmospheric 50 can be processed in a lube oil production unit ( not shown ).
distillation zone 110 , can be treated in the gas oil hydroc The gas oil hydrocracking zone 320 operates under mild ,
racking zone . The heavy middle distillate fraction can moderate or severe hydrocracking conditions, and generally
include a full range atmospheric gas oil , or a fraction thereof produces off -gas and light ends (not shown ), a wild naphtha
such as heavy atmospheric gas oil . Further, a portion of the stream 326 , a diesel fuel fraction 322 , and an unconverted oil
third middle distillate fraction 126 can be routed to the gas 55 fraction 324. Effluent off -gases are recovered from the gas
oil hydrocracking zone 320 , while the remainder bypasses oil hydrocracking zone 320 and are passed to the olefins
gas oil hydrocracking zone 320 and is directly routed to the recovery train , the saturated gas plant as part of the other
gas oil steam cracking zone 250 without hydroprocessing. In gases stream 156 , and / or directly to a fuel gas system .
certain embodiments , all, a substantial portion , a significant Liquefied petroleum gas can be recovered from the gas oil
portion or a major portion of the combined vacuum gas oil , 60 hydrocracking zone 320 and routed to the mixed feed steam
streams 164 and 166 , is routed to the vacuum gas oil cracking zone, the olefins recovery train and / or the saturated
hydrocracking zone 320 ; the remainder of vacuum gas oil (if gas plant. The naphtha fraction 326 is routed to the mixed
any) can be routed directly to the gas oil steam cracking zone feed steam cracking zone 230. In certain embodiments, the
250 , bypassing the vacuum gas oil hydrocracking zone . naphtha fraction 326 is routed through the crude complex
In accordance with the process herein , the severity of the 65 100 , alone , or in combination with other wild naphtha
gas oil hydrocracking operation can be used to moderate the fractions from within the integrated process . In embodi
relative yield of olefin and aromatic chemicals from the ments in which naphtha fraction 326 is routed through the
 US 10,760,011 B2
25 26
crude complex 100 , all or a portion of the liquefied petro mina , amorphous silica alumina, zeolites , or combinations
leum gas produced in the gas oil hydrocracking zone 320 can thereof. In certain embodiments, alone or in combination
be passed with the naphtha fraction 326. The unconverted oil with the above metals , Pt group metals such as Pt and / or Pd ,
fraction 324 is routed to the gas oil steam cracking zone 250 . may be present as a hydrogenation component, generally in
The diesel fuel fraction 322 is recovered as fuel, for instance , 5 an amount of about 0.1-2 wt % based on the weight of the
compliant with Euro V diesel standards, and can be com catalyst. Suitable hydrocracking catalyst have an expected
bined with the diesel fuel fraction 182 from the diesel lifetime in the range of about 18-30 , 22-30 , 18-26 or 22-26
hydrotreating zone 180 . months.
Vacuum gas oil hydrocracking zone 320 can operate Exemplary products from the gas oil hydrocracking zone
under mild , moderate or severe conditions, depending on 10 320 include 27-99, 27-90, 27-82, 27-80, 27-75, 27-52,
factors including the feedstock and the desired degree of 27-48 , 30-99 , 30-90 , 30-82 , 30-80 , 30-75 , 30-52 , 30-48 ,
conversion . Such conditions are effective for removal of a 48-99 , 48-90 , 48-82 , 48-80 , 48-75 , 48-52 , 78-99 , 78-90 ,
significant amount of the sulfur and other known contami 78-85 , 80-90 or 80-99 wt % of effluent ( relative to the feed
nants, and for conversion of the feed ( s ) into a major pro
portion ofhydrocracked products and minor proportions of 15 tothetheatmospheric
gas oil hydrocracking zone 320) boiling at or below
residue end boiling point, such as 370 ° C. ,
off -gases, light ends and unconverted product that is passed including LPG , kerosene, naphtha , and atmospheric gas oil
to the gas oil steam cracking zone 250 .
For instance, a suitable vacuum gas oil hydrocracker zone range components. The remaining bottoms fraction is the
320 can include , but is not limited to , systems based on unconverted oil fraction , all or a portion of which can be
technology commercially available from Honeywell UOP, 20 effectively integrated as feed to the gas oil steam cracking
US ; Chevron Lummus Global LLC ( CLG) , US ; Axens, IFP zone 250 as described herein .
Group Technologies, FR ; or Shell Global Solutions , US . FIG . 7 schematically depicts embodiments of a once
The gas oil hydrocracking zone 320 can contain one or through single reactor hydrocracking zone 330 including a
more fixed -bed , ebullated -bed , slurry -bed , moving bed , con reaction zone 332 and a fractionating zone 342 , which can
tinuous stirred tank ( CSTR) or tubular reactors, in series 25 as a mild conversion or partial conversion hydrocracker.
and / or parallel arrangement. Additional equipment, includ Reaction zone 332 generally includes one or more inlets
ing exchangers, furnaces, feed pumps, quench pumps, and in fluid communication with a source of initial feedstock 334
compressors to feed the reactor ( s ) and maintain proper
operating conditions, are well known and are considered and a source of hydrogen gas 338. One or more outlets of
reaction zone 332 that discharge effluent stream 340 is in
part of the, including
equipment gas oil hydrocracking zone ,320.
pumps, compressors high Intemperature
addition, 30 fluid communication with one or more inlets of the frac
separation vessels , low temperature separation vessels and tionating zone 342 ( typically including one or more high
the like to separate reaction products and provide hydrogen pressure and / or low pressure separation stages therebetween
recycle within the gas oil hydrocracking zone 320 , are well for recovery of recycle hydrogen, not shown) .
known and are considered part of the gas oil hydrocracking Fractionating zone 342 includes one or more outlets for
35 discharging
zone 320 . gases 344 , typically H2 , H2S , NH3 , and light
Series - flow hydrocracking with or without recycle is one hydrocarbons ( C7 - C ) ; one or more outlets for recovering
of the most commonly used configuration. It uses one product 346 , such as middle distillates naphtha and diesel
reactor ( containing both treating and cracking catalysts ) or products boiling in the temperature range including and
two or more reactors for both treating and cracking reaction 40 below atmospheric gas oil range fractions ( for instance in
steps . In a series - flow configuration the entire hydrocracked the temperature range of 36-370 ° C. ) ; and one or more
product stream from the first reaction zone , including light outlets for discharging bottoms 348 including hydrocarbons
gases ( typically C - C4, H2S , NH3 ) and all remaining hydro boiling above the atmospheric gas oil range ( for instance
carbons, are sent to the second reaction zone . Unconverted 370 ° C. ) . In certain embodiments, the temperature cut point
bottoms from the fractionator column are recycled back into 45 for bottoms 348 ( and correspondingly the end point for the
the first reactor for further cracking. This configuration products 346 ) is a range corresponding to the upper tem
converts heavy crude oil fractions such as vacuum gas oil , perature limit of the desired gasoline , kerosene and / or diesel
into light products and has the potential to maximize the product boiling point ranges for downstream operations.
yield of naphtha, kerosene and or diesel range hydrocarbons, In operation of the once - through single reactor hydroc
depending on the recycle cut point used in the distillation 50 racking zone 330 , a feedstock stream 334 and a hydrogen
section . stream 338 are charged to the reaction zone 332. Hydrogen
Two - stage recycle hydrocracking uses two reactors and stream 338 is an effective quantity of hydrogen to support
unconverted bottoms from the fractionation column are the requisite degree of hydrocracking, feed type , and other
passed to the second reactor for further cracking. Since the factors, and can be any combination including , recycle
first reactor accomplishes both hydrotreating and hydroc- 55 hydrogen 336 from optional gas separation subsystems ( not
racking, the feed to second reactor is virtually free of shown ) associated with reaction zone 332 , and / or derived
ammonia and hydrogen sulfide . This permits the use of high from fractionator gas stream 344 and make-up hydrogen
performance zeolite catalysts which are susceptible to poi 302 , if necessary . In certain embodiments, a reaction zone
soning by sulfur or nitrogen compounds. can contain multiple catalyst beds and can receive one or
Effective hydrocracking catalyst generally contain about 60 more quench hydrogen streams between the beds (not
5-40 wt % based on the weight of the catalyst , of one or more shown ).
active metal component of metals or metal compounds The reaction effluent stream 340 contains converted,
( oxides or sulfides ) selected from the Periodic Table of the partially converted and unconverted hydrocarbons. Reaction
Elements IUPAC Groups 6-10 . In certain embodiments , the effluent stream 340 is passed to fractionating zone 342
active metal component is one or more of Mo , W , Co or Ni . 65 (optionally after one or more high pressure and low pressure
The active metal component is typically deposited or oth separation stages to recover recycle hydrogen ), generally to
erwise incorporated on a support, such as amorphous alu recover gas and liquid products and by -products 344 , 346 ,
 US 10,760,011 B2
27 28
and separate a bottoms fraction 348. This stream 348 is an end of run (EOR) reaction temperature, as a WABT, in
routed to the gas oil steam cracking zone 250 as described the range of from about 338-516 , 338-471 , 338-450 , 382
herein . 516 , 382-471 , 382-450 , 400-516 , 400-471 , 400-450 or 422
Gas stream 344 , typically containing H2 , H2S , NH3 , and 430 ;
light hydrocarbons (CZ - C4 ) , is discharged and recovered and 5 a reaction inlet pressure ( barg ) in the range of from about
can be further processed . Effluent off -gases are passed to the 108-161 , 108-148 , 108-141 , 121-161 , 121-148 , 121-141 ,
olefins recovery train , the saturated gas plant as part of the 128-161 , 128-148 , 128-141 or 131-137 ;
other gases stream 156 , and / or directly to a fuel gas system . a reaction outlet pressure (barg ) in the range of from about
Liquefied petroleum gas can be recovered and routed to the 10 100-150 , 100-137 , 100-130 , 112-150 , 112-137 , 112-130 ,
mixed feed steam cracking zone , the olefins recovery train 118-150 , 118-137 or 118-130 ;
and / or the saturated gas plant. One or more cracked product a hydrogen partial pressure ( barg ) (outlet) in the range of
streams 346 are discharged via appropriate outlets of the from about 77-116 , 77-106 , 77-101 , 87-116 , 87-106 , 87-101 ,
fractionator and can be further processed and / or blended in 92-116 , 92-106 , 92-101 or 94-98 ;
downstream refinery operations to produce gasoline , kero 15 a hydrogen treat gas feed rate ( SLt/Lt) up to about 530 ,
sene and / or diesel fuel, or other petrochemical products. 510 , 470 or 450 , in certain embodiments from about 340
In certain embodiments (not shown ), fractionating zone 510 , 340-470 , 340-450 , 382-510 , 382-470 , 382-450 , 400
342 can operate as a flash vessel to separate heavy compo 510 , 400-470 , 400-450 or 410-440 ;
nents at a suitable cut point, for example, a range corre a hydrogen quench gas feed rate ( SLt/Lt) up to about 470 ,
sponding to the upper temperature range of the desired 20 427 , 391 or 356 , in certain embodiments from about 178
gasoline , kerosene and / or diesel products for downstream 427 , 178-214 , 178-356 , 214-321 or 178-391 ;
operations. In certain embodiments, a suitable cut point is in make - up hydrogen rate ( SLt/Lt) up to about 225 , 215 , 200
the range of 350 to 450 ° C. , 360 to 450 ° C. , 370 to 450 ° C. , or 190 , in certain embodiments from about 143-215 , 143
350 to 400 ° C. , 360 to 400 ° C. , 370 to 400 ° C. , 350 to 380 ° 200 , 143-190 , 161-215 , 161-200 , 161-190 , 170-215 , 170
C. , or 360 to 380 ° C. The stream above that cut point is 25 200 or 170-190 ; and
routed to the gas oil steam cracking zone 250 as described liquid hourly space velocity values (h - 1 ), on a fresh feed
herein . basis relative to the hydrocracking catalysts , are in the range
For instance, a suitable once -through single reactor of from about 0.1-10.0 , 0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 ,
hydrocracking zone 330 can include, but is not limited to , 30 0.3-2.0 , 0.4-10.0 , 0.4-5.0 or 0.5-3.0 .
systems based on technology comme mercially available from Under the above conditions and catalyst selections , exem
plary products from the once - through single reactor hydro
Honeywell UOP, US ; Chevron Lummus Global LLC cracking zone 330 operating in a mild hydrocracking mode
( CLG) , US ; Axens, IFP Group Technologies, FR ; or Shell of operation include 27 27-48 , 30-50 or 30-52 wt % of
Global Solutions , US. effluent ( relative to the feed to the gas oil hydrotreating zone
The reactor arrangement in the once - through single reac 35 330
tor hydrocracking zone 330 can contain one or more fixed point) ,boiling at or below the atmospheric residue end boiling
bed , ebullated -bed, slurry -bed, moving bed, continuous and atmospheric370gas° C.oil, including
such as LPG , kerosene, naphtha,
range components. The remaining
stirred tank (CSTR) , or tubular reactors, which can be in bottoms fraction is the unconverted oil fraction, all or a
parallel arrangement. The once - through single reactor portion of which can be effectively integrated as feed to the
hydrocracking zone 330 can operate in a mild hydrocracking 40 gas oil steam cracking zone 250 as described herein.
mode of operation or a partial conversion mode of operation . In certain embodiments, operating conditions for the
Additional equipment, including exchangers, furnaces, feed reactor( s ) in hydrocracking zone 330 using a once - through
pumps, quench pumps , and compressors to feed the ( single stage without recycle ) configuration and operating in
reactor( s ) and maintain proper operating conditions , are well a partial conversion mode include:
known and are considered part of the once -through single 45 a reactor inlet temperature ( ° C. ) in the range of from
reactor hydrocracking zone 330. In addition , equipment, about 340-502 , 340-460 , 340-440 , 372-502 , 372-460 , 372
including pumps, compressors , high temperature separation 440 , 394-502 , 394-460 , 394-440 or 412-420 ;
vessels , low temperature separation vessels and the like to a reactor outlet temperature ( ° C. ) in the range of from
separate reaction products and provide hydrogen recycle about 350-516 , 350-471 , 350-450 , 382-516 , 382-471 , 382
within the once -through single reactor hydrocracking zone 50 450a , start
400-516 , 400-471
of run ( SOR) ,reaction
400-450temperature
or 422-430,; as a weighted
330 , are well known and are considered part of the once average bed temperature ( WABT), in the range of from
through single reactor hydrocracking zone 330 . about 310-475 , 310-435 , 310-415 , 350-475 , 350-435 , 350
In certain embodiments, operating conditions for the
reactor( s ) in hydrocracking zone 330 using a once - through 55 415an, 370-475 , 370-435 , 370-415 or 390-397 ;
end of run (EOR) reaction temperature , as a WABT, in
( single stage without recycle ) configuration and operating in the range of from about 338-516 , 338-471 , 338-450 , 382
a mild hydrocracking mode include : 516 , 382-471 , 382-450 , 400-516 , 400-471 , 400-450 or 422
a reactor inlet temperature ( ° C. ) in the range of from 430 ;
about 329-502 , 329-460 , 329-440 , 372-502 , 372-460 , 372 a reaction inlet pressure ( barg) in the range of from about
440 , 394-502 , 394-460 , 394-440 or 412-420 ; 60 100-165 , 100-150 , 100-140 , 120-165 , 120-140 , 130-165 ,
a reactor outlet temperature ( ° C. ) in the range of from 130-150 , or 130-140 ;
about 338-516 , 338-471 , 338-450 , 382-516 , 382-471 , 382 a reaction outlet pressure (barg ) in the range of from about
450 , 400-516 , 400-471 , 400-450 or 422-430 ; 92-150 , 92-137 , 92-130 , 112-150 , 112-127 , 112-130 , 118
a start of run ( SOR) reaction temperature, as a weighted 140 , 118-130 ;
average bed temperature (WABT ), in the range of from 65 a hydrogen partial pressure (barg ) (outlet) in the range of
about 310-475 , 310-435 , 310-415 , 350-475 , 350-435 , 350 from about 80-120 , 80-106 , 80-101 , 90-120 , 90-106 ,
415 , 370-475 , 370-435 , 370-415 or 390-397 ; 90-101 , 100-120 , or 100-115 ;
 US 10,760,011 B2
29 30
a hydrogen treat gas feed rate ( SLt/Lt) up to about 677 , product 346 , such as middle distillates naphtha and diesel
615 , 587 or 573 , in certain embodiments from about 503 products boiling in the temperature range including and
615 , 503-587 , 503-573 , 531-615 , 531-587 , 531-573 , 545 below atmospheric gas oil range fractions ( for instance in
615 , 545-587 , or 545-573 ; the temperature range of 36-370 ° C. ) ; and one or more
a hydrogen quench gas feed rate ( SLt/Lt) up to about 614 , 5 outlets for discharging bottoms 348 including hydrocarbons
558 , 553 or 520 , in certain embodiments from about 457 boiling above the atmospheric gas oil range ( for instance
558 , 457-533 , 457-520 , 482-558 , 482-533 , 482-520 , 495 about 370 ° C. ) , from which a bleed stream 368 is obtained
558 , 495-533 , or 495-520 ; in processes that do not operate with 100% recycle. In
make -up hydrogen rate ( SLt/Lt) up to about 305 , 277 , 264 certain embodiments , the temperature cut point for bottoms
or264252 , in certain
, 204-252 embodiments
, 216-277 , 216-264from about, 228-277
, 216-252 204-277,, 204-
228 10 348 ( and correspondingly the end point for the products 346)
264 , or 228-252 , and is a range corresponding to the upper temperature limit of
liquid hourly space velocity values ( h = ' ), on a fresh feed the desired gasoline , kerosene and / or diesel product boiling
basis relative to the hydrocracking catalysts , are in the range point ranges for downstream operations.
of from about 0.1-10.0 , 0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 , 15 feedstock streamof334
In operation the series flow hydrocracking zone 350 , a
and a hydrogen stream 338 are charged
0.3-2.0 , 0.4-10.0 , 0.4-5.0 , 0.4-2.0 or 0.5-3.0 .
Under the above conditions and catalyst selections , exem to the first reaction zone 352. Hydrogen stream 338 is an
plary products from the once - through single reactor hydro effective quantity of hydrogen to support the requisite
cracking zone 330 operating as a partial conversion hydro degree of hydrocracking, feed type, and other factors, and
cracker include 48-82 , 50-80, 48-75 , or 50-75 wt % of 20 can be any combination including, recycle hydrogen 336
effluent ( relative to the feed to the gas oil hydrotreating zone from optional gas separation subsystems (not shown) asso
330 ) boiling at or below the atmospheric residue end boiling ciated with reaction zones 352 and 358 , and /or derived from
point, such as 370 ° C. , including LPG , kerosene, naphtha, fractionator gas stream 344 and make -up hydrogen 302. In
and atmospheric gas oil range components. The remaining certain embodiments, a reaction zone can contain multiple
bottoms fraction is the unconverted oil fraction , all or a 25 catalyst beds and can receive one or more quench hydrogen
portion of which can be effectively integrated as feed to the streams between the beds ( not shown ).
gas oil steam cracking zone 250 as described herein . First reaction zone 352 operates under effective condi
FIG . 8 schematically depicts another embodiment of a tions
series flow hydrocracking zone 350 , which operates as passedfortoproduction of reaction effluent stream 354 which is
series - flow hydrocracking system with recycle to the first 30 or more high pressurereaction
the second
and low
zone 358 ( optionally after one
pressure separation stages to
reactor zone , the second reactor zone , or both the first and recover recycle hydrogen ), optionally
second reactor zones . In general, series flow hydrocracking tional hydrogen stream 356. Second along
zone 350 includes a first reaction zone 352 a second
with an addi
reaction zone 358
reaction zone 358 and a fractionating zone 342 . operates under conditions effective for production of the
First reaction zone 352 generally includes one or more 35 reaction effluent stream 360 , which contains converted,
inlets in fluid communication with a source of initial feed partially converted and unconverted hydrocarbons.
stock 334 , a source of hydrogen gas 338 , and in certain The reaction effluent stream 360 is passed to fractionating
embodiments recycle stream 364a comprising all or a por zone 342 , generally to recover gas and liquid products and
tion of the fractionating zone 342 bottoms stream 348 and by -products 344 , 346 , and separate a bottoms fraction 348 .
optionally a portion of fractionating zone 342 product 40 A portion of the bottoms fraction 348 , stream 368 is routed
stream 362. One or more outlets of the first reaction zone to the gas oil steam cracking zone 250 as described herein .
352 that discharge effluent stream 354 is in fluid communi Gas stream 344 , typically containing H2 , H2S , NH3 , and
cation with one or more inlets of the second reaction zone light hydrocarbons (C -C4 ) , is discharged and recovered and
358. In certain embodiments, the effluents 354 are passed to can be further processed . Effluent off -gases are passed to the
the second reaction zone 358 without separation of any 45 olefins recovery train , the saturated gas plant as part of the
excess hydrogen and light gases . In optional embodiments, other gases stream 156 , and / or directly to a fuel gas system .
one or more high pressure and low pressure separation Liquefied petroleum gas can be recovered and routed to the
stages are provided between the first and second reaction mixed feed steam cracking zone , the olefins recovery train
zones 352 , 358 for recovery of recycle hydrogen (not and / or the saturated gas plant. One or more cracked product
shown ). 50 streams 346 are discharged via appropriate outlets of the
The second reaction zone 358 generally includes one or fractionator and can be further processed and / or blended in
more inlets in fluid communication with one or more outlets downstream refinery operations to produce gasoline , kero
of the first reaction zone 352 , optionally a source of addi sene and / or diesel fuel, or other petrochemical products. In
tional hydrogen gas 356 , and in certain embodiments a certain embodiments, a diesel fraction 362 derived from the
recycle stream 364b comprising all or a portion of the 55 one or more cracked product streams 346 can be integrated
fractionating zone 342 bottoms stream 348 and optionally a with the recycle streams to the reactors . This integration
portion of fractionating zone 342 product stream 362. One adds to the flexibility of the configuration between produc
or more outlets of the second reaction zone 358 that dis tion of diesel fuel or petrochemicals from the product
charge effluent stream 360 is in fluid communication with streams 346 .
one or more inlets of the fractionating zone 342 (optionally 60 In certain embodiments ( not shown ), fractionating zone
having one or more high pressure and low pressure separa 342 can operate as a flash vessel to separate heavy compo
tion stages in between the second reaction zone 358 and the nents at a suitable cut point, for example, a range corre
fractionating zone 342 for recovery of recycle hydrogen, not sponding to the upper temperature range of the desired
shown ). gasoline , kerosene and / or diesel products for downstream
Fractionating zone 342 includes one or more outlets for 65 operations. In certain embodiments, a suitable cut point is in
discharging gases 344 , typically H , H2S , NH3 , and light the range of 350 to 450 ° C. , 360 to 450 ° C. , 370 to 450 ° C. ,
hydrocarbons (C -C4) ; one or more outlets for recovering 350 to 400 ° C. , 360 to 400 ° C. , 370 to 400 ° C. , 350 to 380 °
 US 10,760,011 B2
31 32
C. , or 360 to 380º C. The stream above that cut point is a reaction outlet pressure (barg ) in the range of from about
routed to the gas oil steam cracking zone 250 as described 92-150 , 92-137 , 92-130 , 112-150 , 112-127 , 112-130 , 118
herein . 140 , 118-130 ;
All or a portion of the fractionator bottoms stream 348 a hydrogen partial pressure (barg ) (outlet) in the range of
from the reaction effluent is recycled to the first or second 5 from about 80-120 , 80-106 , 80-101 , 90-120 , 90-106 ,
reaction zones 352 and /or 358 ( streams 364a and /or 364b) . 90-101, 100-120 , or 100-115 ;
In certain embodiments , a portion of the fractionator bot 607a , hydrogen treat gas feed rate ( SLt/Lt) up to about 668 ,
580 or 566 , in certain embodiments from about 497
toms from the reaction effluent is removed as bleed stream
368. Bleed stream 368 can be about 0-10 vol % , 1-10 vol % , 10 607607 , 497-580 , 497-566 , 525-607 , 525-580 , 525-566 , 538
1-5 vol % or 1-3 vol % of the fractionator bottoms 348. This , 538-580 , or 538-566 ;
stream 368 is routed to the gas oil steam cracking zone 250 744 ,hydrogen
a quench gas feed rate (SLt/Lt) up to about 819 ,
711 or 694 , in certain embodiments from about 609
as described herein . 744 , 609-711 , 609-694 , 643-744 , 643-711 , 643-694 , 660
Accordingly, all or a portion of the fractionator bottoms 744 , 660-711 , or 660-694 ;
stream 348 is recycled to the second reaction zone 358 as 15 make - up hydrogen rate ( SLt/Lt) up to about 271 , 246 , 235
stream 364b , the first reaction zone 352 as stream 364a , or or 224 , in certain embodiments from about 182-246 , 182
both the first and second reaction zones 352 and 358. For 235 , 182-224 , 192-246 , 192-235 , 192-224 , 203-246 , 203
instance, stream 364a recycled to zone 352 comprises 0 to 235 , or 203-224 ; and
100 vol % , in certain embodiments 0 to about 80 vol % , and liquid hourly space velocity values (h- 1 ) , on a fresh feed
in further embodiments 0 to about 50 vol % of stream 348 , 20 basis relative to the hydrocracking catalysts , are in the range
and stream 364b recycled to zone 358 comprises 0 to 100 vol of from about 0.1-10.0 , 0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 ,
% , in certain embodiments 0 to about 80 vol % , and in 0.3-2.0 , 0.4-10.0 , 0.4-5.0 , 0.4-2.0 or 0.5-1.5 .
further embodiments 0 to about 50 vol % of stream 348. In In certain embodiments, operating conditions for the
certain embodiments , in which the recycle is at or second reactor( s ) in hydrocracking zone 350 using once
approaches 100 vol % , recycle of the unconverted oil 25 through series configuration operating in a partial conver
increases the yield of products suitable as feed to the mixed sion mode of operation include :
feed steam cracking zone 230 . In certain embodiments, partial conversion hydrocracking
For instance, a suitable series flow hydrocracking zone using once - through configuration operating conditions
350 can include , but is not limited to , systems based on include:
technology commercially available from Honeywell UOP , 30 a reactor inlet temperature ( ° C. ) in the range of from
US ; Chevron Lummus Global LLC ( CLG) , US ; Axens, IFP about 340-502 , 340-460 , 340-440 , 372-502 , 372-460 , 372
Group Technologies, FR ; or Shell Global Solutions , US . 440 , 394-502 , 394-460 , 394-440 or 412-420 ;
The reactor arrangement in the series flow hydrocracking a reactor outlet temperature ( ° C. ) in the range of from
zone 350 can contain one or more fixed -bed, ebullated- bed , about 350-516 , 350-471 , 350-450 , 382-516 , 382-471 , 382
slurry -bed , moving bed , continuous stirred tank (CSTR) , or 35 450 , 400-516 , 400-471 , 400-450 or 422-430 ;
tubular reactors , which can be in parallel arrangement. a start of run ( SOR) reaction temperature, as a weighted
Additional equipment, including exchangers, furnaces, feed average bed temperature ( WABT ), in the range of from
pumps , quench pumps, and compressors to feed the about 310-475 , 310-435 , 310-415 , 350-475 , 350-435 , 350
reactor( s ) and maintain proper operating conditions , are well 415 , 370-475 , 370-435 , 370-415 or 390-397 ;
known and are considered part of the series flow hydroc- 40 an end of run (EOR) reaction temperature , as a WABT, in
racking zone 350. In addition, equipment, including pumps, the range of from about 338-516 , 338-471 , 338-450 , 382
compressors, high temperature separation vessels , low tem 516 , 382-471 , 382-450 , 400-516 , 400-471 , 400-450 or 422
perature separation vessels and the like to separate reaction 430 ;
products and provide hydrogen recycle within the series a reaction inlet pressure (barg ) in the range of from about
flow hydrocracking zone 350 , are well known and are 45 90-150 , 90-130 , 90-140 , 110-150 , 110-130 , 110-145 , or
considered part of the series flow hydrocracking zone 350 . 130-150 ;
In certain embodiments, operating conditions for the first a reaction outlet pressure (barg ) in the range of from about
reactor ( s) in hydrocracking zone 350 using once - through 85-140 , 85-127 , 100-140 , 112-130 , 112-140 , or 118-130 ;
series configuration operating in a partial conversion mode hydrogen partial pressure ( barg ) ( outlet) in the range of
of operation include : 50 from about 80-130 , 80-120 , 80-101 , 90-130 , 90-120 ,
a reactor inlet temperature ( ° C. ) in the range of from 90-101 , 100-130 , or 100-115 ;
about 340-502 , 340-460 , 340-440 , 372-502 , 372-460 , 372 a hydrogen treat gas feed rate ( SLt/Lt) up to about 890 ,
440 , 394-502 , 394-460 , 394-440 or 412-420 ; 803 , 767 or 748 , in certain embodiments from about 657
a reactor outlet temperature ( ° C. ) in the range of from 803 , 657-767 , 657-748 , 694-803 , 694-767 , 694-748 , 712
about 350-516 , 350-471 , 350-450 , 382-516 , 382-471 , 382- 55 803 , 712-767 , or 712-748 ;
450 , 400-516 , 400-471 , 400-450 or 422-430 ; a hydrogen quench gas feed rate (SLt /Lt) up to about 850 ,
a start of run ( SOR) reaction temperature, as a weighted 764 , 729 or 712 , in certain embodiments from about 625
average bed temperature (WABT ), in the range of from 764 , 625-729 , 625-712 , 660-764 , 660-729 , 660-712 , 677
about 310-475 , 310-435 , 310-415 , 350-475 , 350-435 , 350 764 , 677-729 , or 677-712 ;
415 , 370-475 , 370-435 , 370-415 or 390-397 ; 60 make - up hydrogen rate ( SLt/Lt) up to about 372 , 338 , 323
an end of run (EOR ) reaction temperature, as a WABT, in or 309 , in certain embodiments from about 250-338 , 250
the range of from about 338-516 , 338-471 , 338-450 , 382 323 , 250-309 , 264-338 , 264-323 , 264-309 , 279-338 , 279
516 , 382-471 , 382-450 , 400-516 , 400-471 , 400-450 or 422 323 , or 279-309 ; and
430 ; liquid hourly space velocity values (h- ? ), on a fresh feed
a reaction inlet pressure (barg ) in the range of from about 65 basis relative to the hydrocracking catalysts , are in the range
100-165 , 100-150 , 100-140 , 120-165 , 120-140 , 130-165 , of from about 0.1-10.0 , 0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 ,
130-150 , or 130-140 ; 1.0-5.0 , 2.0-4.0 or 1.0-3.0 .
 US 10,760,011 B2
33 34
Under the above conditions and catalyst selections , exem certain embodiments, a reaction zone can contain multiple
plary products from the series - flow hydrocracking zone 350 catalyst beds and can receive one or more quench hydrogen
operating as a partial conversion hydrocracker using once streams between the beds (not shown ).
through configuration include 48-82 , 50-80 , 48-75 or 50-75 First reaction zone 372 operates under effective condi
wt % of effluent (relative to the feed to the hydrocracking 5 tions for production of reaction effluent stream 374 which is
zone 350 boiling at or below the atmospheric residue end passed to the fractionating zone 342 (optionally after one or
boiling point, such as 370 ° C. , including LPG , kerosene, more high pressure and low pressure separation stages to
naphtha, and atmospheric gas oil range components. The recover recycle hydrogen ) generally to recover gas and
remaining bottoms fraction is the unconverted oil fraction , liquid products and by -products, and separate a bottoms
all or a portion ofwhich can be effectively integrated as feed 10 fraction .
to the gas oil steam cracking zone 250 as described herein . Gas stream 344 , typically containing H , H2S , NH3 , and
FIG . 9 schematically depicts another embodiment of an
integrated hydrocracking unit operation, a two - stage with light hydrocarbons (C1 - C4 ) , is discharged and recovered and
recycle hydrocracking zone 370 , which operates as two can be further processed . Effluent off -gases are passed to the
stage hydrocracking system with recycle. In general, hydro- 15 olefins recovery train , the saturated gas plant as part of the
cracking zone 370 includes a first reaction zone 372 , a other gases stream 156 , and / or directly to a fuel gas system .
second reaction zone 382 and a fractionating zone 342 . Liquefied petroleum gas can be recovered and routed to the
First reaction zone 372 generally includes one or more mixed feed steam cracking zone , the olefins recovery train
inlets in fluid communication with a source of initial feed and / or the saturated gas plant. One or more cracked product
stock 334 and a source of hydrogen gas 338. One or more 20 streams 346 are discharged via appropriate outlets of the
outlets of the first reaction zone 372 that discharge effluent fractionator and can be further processed and / or blended in
stream 374 are in fluid communication with one or more downstream refinery operations to produce gasoline , kero
inlets of the fractionating zone 342 ( optionally having one or sene and / or diesel fuel, or other petrochemical products. In
more high pressure and low pressure separation stages certain embodiments, a diesel fraction 376 derived from the
therebetween for recovery of recycle hydrogen, not shown) . 25 one or more cracked product streams 346 can be integrated
Fractionating zone 342 includes one or more outlets for with the feed to the second stage reactor 382. This integra
discharging gases 344 , typically H2S , NH3 , and light hydro tion adds to the flexibility of the configuration between
carbons (C -C4 ) ; one or more outlets for recovering product production of diesel fuel or petrochemicals from the product
346 , such as naphtha and diesel products boiling in the streams 346 .
temperature range including and below atmospheric gas oil 30 In certain embodiments ( not shown ), fractionating zone
range fractions ( for instance in the temperature range of 342 can operate as a flash vessel to separate heavy compo
36-370 ° C. ) ; and one or more outlets for discharging bot nents at a suitable cut point, for example, a range corre
toms 348 including hydrocarbons boiling above the atmo sponding to the upper temperature range of the desired
spheric gas oil range ( for instance about 370 ° C.), from gasoline , kerosene and / or diesel products for downstream
which a bleed stream 368 is obtained in processes that do not 35 operations. In certain embodiments, a suitable cut point is in
operate with 100% recycle. In certain embodiments, the the range of 350 to 450 ° C. , 360 to 450 ° C. , 370 to 450 ° C. ,
temperature cut point for bottoms 348 ( and correspondingly 350 to 400 ° C. , 360 to 400 ° C. , 370 to 400 ° C. , 350 to 380 °
the end point for the products 346 ) is a range corresponding C. , or 360 to 380º C. The stream above that cut point is
to the upper temperature limit of the desired gasoline , routed to the gas oil steam cracking zone 250 as described
kerosene and / or diesel product boiling point ranges for 40 herein .
downstream operations. All or a portion of the fractionator bottoms stream 348
The fractionating zone 342 bottoms outlet is in fluid from the reaction effluent is passed to the second reaction
communication with the one or more inlets of the second zone 382 as stream 348a . In certain embodiments, all or a
reaction zone 382 for recycle stream 348a derived from the portion of the bottoms stream 348 is recycled to the second
bottoms stream 348. Recycle stream 348a can be all or a 45 reaction zone 382 as stream 348a , the first reaction zone 372
portion of the bottoms stream 348. In certain optional as stream 348b , or both the first and second reaction zones
embodiments ( as indicated by dashed lines in FIG . 9 ) , a 372 and 382. For instance , stream 348b which is recycled to
portion 348b is in fluid communication with one or more zone 372 comprises 0 to 100 vol % , 0 to about 80 vol % , or
inlets of the first reaction zone 372 . O to about 50 vol % of stream 348 , and stream 348a which
Second reaction zone 382 generally includes one or more 50 is recycled to zone 382 comprises 0 to 100 vol % , 0 to about
inlets in fluid communication with the fractionating zone 80 vol % , or 0 to about 50 vol % of stream 348. In certain
342 bottoms outlet portion 348a of bottoms 348 , and a embodiments, in which the recycle is at or approaches 100
source of hydrogen gas 384. One or more outlets of the vol % , recycle of the unconverted oil increases the yield of
second reaction zone 382 that discharge effluent stream 386 products suitable as feed to the mixed feed steam cracking
are in fluid communication with one or more inlets of the 55 zone 230 .
fractionating zone 342 ( optionally having one or more high In certain embodiments, a portion of the fractionator
pressure and low pressure separation stages therebetween bottoms from the reaction effluent is removed as bleed
for recovery of recycle hydrogen , not shown ). stream 368. Bleed stream 368 can be about 0-10 vol % , 1-10
In operation of the two - stage hydrocracking zone 370 , a vol % , 1-5 vol % or 1-3 vol % of the fractionator bottoms
feedstock stream 334 and a hydrogen stream 338 are charged 60 348 .
to the first reaction zone 372. Hydrogen stream 338 is an Second reaction zone 382 operates under conditions
effective quantity of hydrogen to support the requisite effective for production of the reaction effluent stream 386 ,
degree of hydrocracking, feed type, and other factors, and which contains converted , partially converted and uncon
can be any combination including, recycle hydrogen 336 verted hydrocarbons. The second stage the reaction effluent
from optional gas separation subsystems ( not shown) asso- 65 stream 386 is passed to the fractionating zone 342 , option
ciated with reaction zones 372 and 382 , and /or derived from ally through one or more gas separators to recovery recycle
fractionator gas stream 344 and make -up hydrogen 302. In hydrogen and remove certain light gases
 US 10,760,011 B2
35 36
For instance , a suitable two - stage hydrocracking zone 370 In certain embodiments, operating conditions for the
can include , but is not limited to , systems based on tech reactor ( s ) in the first stage reaction zone of the two - stage
nology commercially available from Honeywell UOP, US ; hydrocracking zone 370 include :
Chevron Lummus Global LLC ( CLG) , US ; Axens, IFP a reactor inlet temperature ( ° C. ) in the range of from
Group Technologies, FR ; or Shell Global Solutions , US . 5 about 340-502 , 340-460 , 340-440 , 372-502 , 372-460 , 372
The reactor arrangement in the two -stage with recycle 440 , 394-502 , 394-460 , 394-440 or 412-420 ;
hydrocracking zone 370 can contain one or more fixed -bed , about a reactor outlet temperature ( ° C. ) in the range of from
350-516 , 350-471 , 350-450 , 382-516 , 382-471 , 382
ebullated- bed , slurry - bed, moving bed, continuous stirred 450 , 400-516
tank (CSTR) , or tubular reactors , which can be in parallel 10 a start of run , 400-471 , 400-450 or 422-430 ;
arrangement. Additional equipment, including exchangers, average bed temperature ( SOR) reaction temperature , as a weighted
furnaces, feed pumps, quench pumps, and compressors to ( WABT ) , in the range of from
about 310-475 , 310-435 , 310-415 , 350-475 , 350-435 , 350
feed the reactor ( s ) and maintain proper operating conditions , 415
are well known and are considered part of the two -stage , 370-475 , 370-435 , 370-415 or 390-397 ;
an end of run (EOR) reaction temperature , as a WABT, in
hydrocracking zone 370. In addition , equipment, including 15 the range of from about 338-516, 338-471, 338-450 , 382
pumps, compressors , high temperature separation vessels , 516 , 382-471 , 382-450 , 400-516 , 400-471 , 400-450 or 422
low temperature separation vessels and the like to separate 430 ;
reaction products and provide hydrogen recycle within the a reaction inlet pressure ( barg) in the range of from about
two - stage hydrocracking zone 370 , are well known and are 80-145 , 80-100 , 80-131 , 80-120 , 120-145 , 100-145 , or 130
considered part of the two - stage hydrocracking zone 370 . 20 145 ;
In certain embodiments, operating conditions for the first a reaction outlet pressure ( barg ) in the range of from about
stage reactor ( s) in hydrocracking zone 370 using a two - stage 75-137 , 75-130 , 90-130 , 100-137 , 100-122 , or 112-137 ;
with recycle configuration operating in a full conversion a hydrogen partial pressure (barg ) (outlet) in the range of
mode of operation include : from about 90-145 , 90-106 , 90-120 , 100-145 , 100-106 , or
a reactor inlet temperature ( ° C. ) in the range of from 25 100-120 ;
about 340-502 , 340-460 , 340-440 , 372-502 , 372-460 , 372 a hydrogen treat gas feed rate ( SLt/Lt) up to about 910 ,
440 , 394-502 , 394-460 , 394-440 or 412-420 ; 823 , 785 or 767 , in certain embodiments from about 673
a reactor outlet temperature ( ° C. ) in the range of from 823 , 673-785 , 673-767 , 711-823 , 711-785 , 711-767 , 729
about 350-516 , 350-471 , 350-450 , 382-516 , 382-471 , 382 823 , 729-785 , or 729-767 ;
450 , 400-516 , 400-471 , 400-450 or 422-430 ; 30 a hydrogen quench gas feed rate (SLt/Lt) up to about 980 ,
a start of run ( SOR) reaction temperature, as a weighted 882 , 842 or 822 , in certain embodiments from about 721
average bed temperature (WABT ), in the range of from 882 , 721-842 , 721-822 , 761-882 , 761-842 , 761-822 , 781
about 310-475 , 310-435 , 310-415 , 350-475 , 350-435 , 350 882 , 78 or 781-822 ;
415 , 370-475 , 370-435 , 370-415 or 390-397 ; make - up hydrogen rate ( SLt/Lt) up to about 451 , 410 , 392
an end of run ( EOR ) reaction temperature, as a WABT, in 35 or 374 , in certain embodiments from about 303-410 , 303
the range of from about 338-516 , 338-471 , 338-450 , 382 392 , 303-374 , 321-410 , 321-392 , 321-374 , 338-410 , 338
516 , 382-471 , 382-450 , 400-516 , 400-471 , 400-450 or 422 392 , or 338-374 ; and liquid hourly space velocity values
430 ; ( h = '), on a fresh feed basis relative to the hydrocracking
a reaction inlet pressure (barg ) in the range of from about catalysts, are in the range of from about 0.1-10.0 , 0.1-5.0 ,
100-180 , 100-160 , 100-141 , 121-180 , 121-160 , 121-141 , 40 0.1-2.0 , 0.3-10.0 , 0.3-5.0 , 1.0-5.0 , 2.0-4.0 or 1.0-3.0 .
128-180 , 128-160 , 128-141 or 131-180 ; Under the above conditions and catalyst selections , exem
a reaction outlet pressure (barg ) in the range of from about plary products from the hydrocracking zone 370 operating
90-170 , 90-137 , 90-130 , 112-170 , 112-137 , 112-130 , 118 as a two - stage hydrocracker (with recycle) in a full conver
150 , 118-137 or 118-170 ; sion mode include 78-99 , 78-90 , 78-85 , 80-90 or 80-99 wt
a hydrogen partial pressure (barg ) (outlet) in the range of 45 % of effluent ( relative to the feed to the hydrocracking zone
from about 90-137 , 90-106 , 90-120 , 100-137 , 100-106 , or 370 ) boiling at or below the atmospheric residue end boiling
100-120 ; point, such as 370 ° C. , including LPG , kerosene, naphtha,
a hydrogen treat gas feed rate ( SLt/Lt) up to about 1050 , and atmospheric gas oil range components. The remaining
940 , 898 or 876 , in certain embodiments from about 769 bottoms fraction is the unconverted oil fraction , all or a
940 , 769-898 , 769-876 , 812-940 , 812-898 , 812-876 , 834- 50 portion of which can be effectively integrated as feed to the
940 , 834-898 , or 834-876 ; gas oil steam cracking zone 250 as described herein .
a hydrogen quench gas feed rate (SLt/Lt) up to about In certain embodiments, 0-100 wt % of the vacuum
1100 , 980 , 935 or 913 , in certain embodiments from about residue stream 168 can be processed in a residue treatment
801-980 , 801-935 , 801-913 , 846-980 , 846-935 , 846-913 , center 800 ( shown in dashed lines as an optional embodi
868-980 , 868-935 , or 868-913 ; 55 ment ). In additional embodiments, 0-100 wt % of the
make -up hydrogen rate ( SLt/Lt) up to about 564 , 512,490 pyrolysis oil from the steam cracker complex can be routed
or 468 , in certain embodiments from about 378-512 , 378 to the residue treatment center 800. The residue treatment
490 , 378-468 , 401-512 , 401-490 , 401-468 , 423-512 , 423 center 800 can include , but is not limited to , one or more of :
490 , or 423-468 ; and a catalytic hydrogen addition process , such as a residue
liquid hourly space velocity values ( h = ' ), on a fresh feed 60 hydrocracking system ; a thermal coking process, such as a
basis relative to the hydrocracking catalysts, are in the range delayed coker; and / or a solvent deasphalting process . In
of from about 0.1-10.0 , 0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 , certain embodiments, the residue treatment center 800 pro
0.3-2.0 , 0.4-10.0 , 0.4-5.0 , 0.4-2.0 or 0.5-1.5 . duces one or more of a distillate fraction 808 , a heavy
In certain embodiments, operating conditions for the fraction 806 , and / or a bottoms fraction 804. The distillate
second stage reactor ( s) in hydrocracking zone 370 using a 65 fraction 808 can include, for instance , one or more middle
two - stage with recycle configuration operating in a full distillate streams boiling in the temperature range including
conversion mode of operation include : and below atmospheric gas oil range fractions ( for instance
 US 10,760,011 B2
37 38
in the temperature range of 36-370 ° C. ) , or including and described below ; C4 raffinate 524 from the 1 -butene recov
below medium atmospheric gas oil range fractions . Note ery zone 520 described below ; wild naphtha 184 from the
that when the residue treatment center 800 is solvent deas diesel hydrotreating zone 180 described above (in certain
phalting , a distillate fraction 808 is not produced . Portions of embodiments via the crude complex ); wild naphtha 326
the distillate fraction 808 can be used as feed to the mixed 5 from the gas oil hydrocracking zone 320 described above (in
feed steam cracking zone 230 , feed to one or more of the certain embodiments via the crude complex ); a raffinate
integrated hydroprocessing zones , and / or used for produc stream 646 from the aromatics extraction zone 620
tion of fuel components. All or a portion of the heavy described below ; in certain embodiments a C5 cut derived
fraction 806 can include , for instance, one or more streams from the pyrolysis gasoline described below ; and optionally,
of treated heavy range hydrocarbons boiling above the 10 propane stream 228 ( from outside battery limits ) . In certain
atmospheric gas oil range ( for instance 370 ° C. ) , or above embodiments , the mixed feed steam cracking zone 230 can
the medium atmospheric gas oil range ; or deasphalted oil in accept alternate feeds from other sources, for instance , other
a solvent deasphalting unit . Portions of the heavy fraction
806 can be used as feed to the gas oil steam cracking zone naphtha range feeds that may become available from outside
250 , feed to one or more of the integrated hydroprocessing 15 of the battery limits .
The products from the mixed feed steam cracking zone
zones , recovered as unconverted oil product, used for lube
oil production in a base oil production zone , and / or incor 230 include: a quenched cracked gas stream 232 containing
porated in a fuel oil pool . The bottoms fraction 804 can mixed C1 - C4 paraffins and olefins that is routed to the
include , for instance, pitch in a residue hydrocracking sys olefins recovery zone 270 ; a raw pyrolysis gasoline stream
tem, petroleum coke in a delayed coker, or asphalt in a 20 234 that is routed to a py- gas hydrotreating zone 600 to
solvent deasphalting unit ) . produce hydrotreated pyrolysis gasoline 604 as feed to the
Embodiments of systems and processes incorporating aromatics extraction zone 620 , and C5s 606 ; and a pyrolysis
certain vacuum residue hydroprocessing zones are disclosed fuel oil stream 236 .
in U.S. patent application Ser. No. 15 / 817,133 filed on Nov. The mixed feed steam cracking zone 230 operates under
17 , 2017 , entitled “ Process and System for Conversion of 25 parameters effective to crack the feed into desired products
Crude Oil to Petrochemicals and Fuel Products Integrating including ethylene, propylene, butadiene, and mixed
Vacuum Residue Hydroprocessing ,” and U.S. patent appli butenes. Pyrolysis gasoline and pyrolysis oil are also recov
cation Ser. No. 15 / 817,136 filed on Nov. 17 , 2017 , entitled ered. In certain embodiments, the steam cracking furnace ( s)
“ Process and System for Conversion of Crude Oil to Pet are operated at conditions effective to produce an effluent
rochemicals and Fuel Products Integrating Vacuum Residue 30 having a propylene- to - ethylene weight ratio of from about
Conditioning and Base Oil Production ,” which are com 0.3-0.8 , 0.3-0.6 , 0.4-0.8 or 0.4-0.6 .
monly owned and are incorporated by reference herein in The mixed feed steam cracking zone 230 generally com
their entireties. Embodiments of systems and processes prises one or more trains of furnaces. For instance , a typical
incorporating solvent deasphalting are disclosed in U.S. arrangement includes reactors that can operate based on
patent application Ser. No. 15 / 817,140 filed on Nov. 17 , 35 well- known steam pyrolysis methods, that is , charging the
2017 , entitled “ Process and System for Conversion of Crude thermal cracking feed to a convection section in the presence
Oil to Petrochemicals and Fuel Products Integrating Solvent of steam to raise the temperature of the feedstock, and
Deasphalting of Vacuum Residue , ” which is commonly passing the heated feed to the pyrolysis reactor containing
owned and is incorporated by reference herein in its entirety. furnace tubes for cracking. In the convection section , the
Embodiments of systems and processes incorporating ther- 40 mixture is heated to a predetermined temperature, for
mal coking are disclosed in U.S. patent application Ser. No. example , using one or more waste heat streams or other
15 / 817,143 filed on Nov. 17 , 2017 , entitled “ Process and suitable heating arrangement.
System for Conversion of Crude Oil to Petrochemicals and The feed mixture is heated to a high temperature in a
Fuel Products Integrating Delayed Coking of Vacuum Resi convection section and material with a boiling point below
due , ” which is commonly owned and is incorporated by 45 a predetermined temperature is vaporized . The heated mix
reference herein in its entirety. ture (in certain embodiments along with additional steam) is
The mixed feed steam cracking zone 230 , which operates passed to the pyrolysis section operating at a further elevated
as a high severity or low severity thermal cracking process, temperature for short residence times , such as 1-2 seconds or
generally converts LPG , naphtha and heavier hydrocarbons less, effectuating pyrolysis to produce a mixed product
primarily into a mixed product stream 232 containing mixed 50 stream . In certain embodiments separate convection and
C1 - C4 paraffins and olefins. In certain embodiments, the radiant sections are used for different incoming feeds to the
mixed feed steam cracking zone 230 processes straight -run mixed feed steam cracking zone 230 with conditions in each
liquids from the crude unit, ethane and / or propane ( from optimized for the particular feed .
outside battery limits and / or recycled ) and various recycle In certain embodiments, steam cracking in the mixed feed
streams from chemical production and recovery areas within 55 steam cracking zone 230 carried out using the following
the integrated process and system . A suitable mixed feed conditions : a temperature ( ° C . ) in the convection section in
steam cracking zone 230 can include, but is not limited to , the range of about 400-600 , 400-550 , 450-600 or 500-600 ;
systems based on technology commercially available from a pressure ( barg ) in the convection section in the range of
Linde AG , DE ; TechnipFMC plc , UK ; Chicago Bridge & about 4.3-4.8 , 4.3-4.45 , 4.3-4.6 , 4.45-4.8 , 4.45-4.6 or 4.6
Iron Company N.V. ( CB & I ) , NL , or KBR , Inc , US . 60 4.8 ; a temperature ( ° C. ) in the pyrolysis section in the range
For instance , plural feeds to the mixed feed steam crack of about 700-950 , 700-900 , 700-850 , 750-950 , 750-900 or
ing zone 230 include : light ends 152 , light naphtha 138 and 750-850 ; a pressure ( barg ) in the pyrolysis section in the
heavy naphtha 140 (or a full range straight run naphtha 136 range of about 1.0-1.4 , 1.0-1.25 , 1.25-1.4 , 1.0-1.15 , 1.15-1.4
as shown in other embodiments ) from the crude complex or 1.15-1.25 ; a steam - to -hydrocarbon ratio in the in the
100 ; a LPG stream 634 from a transalkylation zone 630 ; a 65 convection section in the range of about 0.3 : 1-2 : 1 , 0.3 :1
recycle stream 282 from the methylacetylene /propadiene 1.5 : 1 , 0.5 : 1-2 : 1 , 0.5 : 1-1.5 : 1 , 0.7 : 1-2 : 1 , 0.7 : 1-1.5 : 1 , 1 : 1-2 : 1
(MAPD ) saturation and propylene recovery Zone 280 or 1 : 1-1.5 : 1 ; and a residence time ( seconds ) in the pyrolysis
 US 10,760,011 B2
39 40
section in the range of about 0.05-1.2 , 0.05-1 , 0.1-1.2 , 0.1-1 , olefins recovery zone 270 , a raw pyrolysis gasoline stream
0.2-1.2 , 0.2-1 , 0.5-1.2 or 0.5-1 . 254 that is routed to a py - gas hydrotreating zone 600 to
In operation of the mixed feed steam cracking zone 230 , provide additional feed 604 to the aromatics extraction zone
effluent from the cracking furnaces is quenched , for 620 , and a pyrolysis fuel oil stream 256 .
instance , using transfer line exchangers, and passed to a 5 The gas oil steam cracking zone 250 operates under
quench tower. The light products, quenched cracked gas parameters effective to crack the feed into desired products
stream 232 , are routed to the olefins recovery zone 270 . including ethylene, propylene, butadiene, and mixed
Heavier products are separated in a hot distillation section . butenes. Pyrolysis gasoline and pyrolysis oil are also recov
A raw pyrolysis gasoline stream is recovered in the quench ered . In certain embodiments, the steam cracking furnace (s )
system . Pyrolysis oil 236 is separated at a primary fraction- 10 in the gas oil steam cracking zone 250 are operated at
ator tower before the quench tower. conditions effective to produce an effluent having a propyl
In operation of one embodiment of the mixed feed steam ene -to - ethylene weight ratio of from about 0.3-0.8 , 0.3-0.6 ,
cracking zone 230 , the feedstocks are mixed with dilution 0.4-0.8 or 0.4-0.6 .
steam to reduce hydrocarbon partial pressure and then are In one embodiment of the gas oil steam cracking zone
preheated . The preheated feeds are fed to tubular reactors 15 250 , the feedstock is preheated and mixed with a dilution
mounted in the radiant sections of the cracking furnaces. The steam to reduce hydrocarbon partial pressure in a convection
hydrocarbons undergo free - radical pyrolysis reactions to section . The steam -hydrocarbon mixture is heated further
form light olefins ethylene and propylene, and other by and fed to tubular reactors mounted in the radiant sections of
products . In certain embodiments, dedicated cracking fur the cracking furnaces . The hydrocarbons undergo free
naces are provided with cracking tube geometries optimized 20 radical pyrolysis reactions to form light olefins, ethylene and
for each of the main feedstock types, including ethane, propylene, and other by -products.
propane, and butanes/naphtha. Less valuable hydrocarbons, In certain embodiments, steam cracking in the gas oil
such as ethane, propane , C4 raffinate, and aromatics raffi steam cracking zone 250 is carried out using the following
nate , produced within the integrated system and process , are conditions : a temperature ( ° C . ) in the convection section in
recycled to extinction in the mixed feed steam cracking zone 25 the range of about 300-450 or 300-400 ; a pressure ( barg) in
230 . the convection section in the range of about 7.2-9.7 , 7.2-8.5 ,
In certain embodiments, cracked gas from the furnaces is 7.2-7.7 , 7.7-8.5 , 7.7-9.7 or 8.5-9.7 ; a temperature ( ° C. ) in
cooled in transfer line exchangers ( quench coolers ), for the pyrolysis section in the range of about 700-850 , 700-800 ,
example , producing 1800 psig steam suitable as dilution 700-820 , 750-850 , 750-800 or 750-820 ; a pressure ( barg) in
steam . Quenched cracked gas enters a primary fractionator 30 the pyrolysis section in the range of about 0.9-1.2 , 0.9-1.4 ,
associated with the mixed feed steam cracking zone 230 for 0.9-1.6 , 1.2-1.4 , 1.2-1.6 or 1.4-1.6 ; a steam - to -hydrocarbon
removal of pyrolysis fuel oil bottoms from lighter compo ratio in the in the convection section in the range of about
nents . The primary fractionator enables efficient recovery of 0.75 : 1-2 : 1 , 0.75 : 1-1.5 : 1 , 0.85 : 1-2 : 1 , 0.9 : 1-1.5 : 1 , 0.9 : 1-2 : 1 ,
pyrolysis fuel oil . Pyrolysis fuel oil is stripped with steam in 1 : 1-2 : 1 or 1 : 1-1.5 : 1 ; and a residence time ( seconds ) in the
a fuel oil stripper to control product vapor pressure , and 35 pyrolysis section in the range of about 0.02-1 , 0.02-0.08 ,
cooled . In addition , secondary quench can be carried out by 0.02-0.5 , 0.1-1 , 0.1-0.5 , 0.2-0.5 , 0.2-1 , or 0.5-1 .
direct injection of pyrolysis fuel oil as quench oil into liquid In certain embodiments, cracked gas from the gas oil
furnace effluents . The stripped and cooled pyrolysis fuel oil steam cracking zone 250 furnaces is quenched in transfer
can be sent to a fuel oil pool or product storage . The primary line exchangers by producing, for instance, 1800 psig steam .
fractionator overhead is sent to a quench water tower; 40 Quenched gases are stripped with steam in a primary frac
condensed dilution steam for process water treating, and raw tionator. Lighter gases are recovered as the overhead prod
pyrolysis gasoline , are recovered . Quench water tower over uct ; a side - draw stream contains pyrolysis fuel oil . The
head is sent to the olefins recovery zone 270 , particularly the primary fractionator bottoms product is pyrolysis tar, which
first compression stage . Raw pyrolysis gasoline is sent to a is cooled and sent to product storage . Pyrolysis fuel oil from
gasoline stabilizer to remove any light ends and to control 45 the primary fractionator is stripped with steam in the pyroly
vapor pressure in downstream pyrolysis gasoline processing. sis fuel oil stripper, which separates pyrolysis gasoline as the
A closed- loop dilution steam /process water system is overhead and pyrolysis fuel oil as the bottoms product.
enabled , in which dilution steam is generated using heat Gasoline in the primary fractionator overhead is condensed
recovery from the primary fractionator quench pumparound and combined with gasoline from the pyrolysis fuel oil
loops . The primary fractionator enables efficient recovery of 50 stripper before being sent to a gasoline stabilizer. The
pyrolysis fuel oil due to energy integration and pyrolysis fuel gasoline stabilizer removes light products in the overhead ,
oil content in the light fraction stream . while the stabilizer bottoms are sent to the py - gas
The gas oil steam cracking zone 250 is operated under hydrotreater. C4 and lighter gases in the primary fractionator
conditions effective for conversion its feeds into light ole overhead are compressed, for instance , in two stages of
fins, pyrolysis gasoline and pyrolysis oil . As described 55 compression, before entering an absorber, depropanizer and
herein feeds to the gas oil steam cracking zone 250 include debutanizer .
vacuum gas oil range products from the vacuum gas oil Compression of C4 and lighter gases from both the mixed
hydroprocessing zone , such as unconverted oil 324 from the feed steam cracking zone 230 and the gas oil steam cracking
VGO hydrocracking zone 320 , and in certain embodiments zone 250 can be carried out in certain embodiments in a
all or a portion of the third middle distillate stream 126 , for 60 common step , to reduce capital and operating costs associ
instance, in the atmospheric gas oil range . In certain embodi ated with compression, thereby increasing efficiencies in the
ments , the gas oil steam cracking zone 250 can accept integrated process herein . Accordingly, both the C4 and
alternate feeds from other sources , for instance , other gas oil lighter gas stream 232 and the C4 and lighter gas stream 252
range feeds that may become available from outside of the are passed to the olefins recovery zone 270 .
battery limits . Products from the gas oil steam cracking zone 65 In certain embodiments, cracked gas from the furnaces of
250 include a quenched cracked gas stream 252 containing both the mixed feed steam cracking zone 230 and the gas oil
mixed C1 - C4 paraffins and olefins that is routed to the steam cracking zone 250 are subjected to common steps for
 US 10,760,011 B2
41 42
quenching, recovery of pyrolysis gasoline, recovery of (propylene, mixed binary refrigerant) for cryogenic separa
pyrolysis oil , and recovery of C4 and lighter gases . For tion . A front -end depropanizer optimizes the chilling train
instance, in one embodiment, the cracked gas from the and demethanizer loading. The depropanizer separates C3
furnaces of both steam cracking zones are combined cooled and lighter cracked gases as an overhead stream , with C4s
in transfer line exchangers ( quench coolers ) , for example, 5 and heavier hydrocarbons as the bottoms stream . The depro
producing 1800 psig steam suitable as dilution steam . panizer bottoms are routed to the debutanizer, which recov
Quenched cracked gas enters a primary fractionator for ers a crude C4s stream 206 and any trace pyrolysis gasoline ,
removal of pyrolysis fuel oil bottoms from lighter compo which can be routed to the py - gas hydrotreating zone 600
nents . The primary fractionator enables efficient recovery of (not shown ).
pyrolysis fuel oil . Pyrolysis fuel oil is stripped with steam in 10 The depropanizer overhead passes through a series of
a fuel oil stripper to control product vapor pressure and acetylene conversion reactors , and is then fed to the
cooled . In addition , secondary quench can be carried out by demethanizer chilling train , which separates a hydrogen -rich
direct injection of pyrolysis fuel oil as quench oil into liquid product via a hydrogen purification system , such as pressure
furnace effluents. The stripped and cooled pyrolysis fuel oil
can be sent to a fuel oil pool or product storage. The primary 15 implemented
swing adsorption. Front -end acetylene hydrogenation is
to optimize temperature control, minimize
fractionator overhead is sent to a quench water tower;
condensed dilution steam for process water treating, and raw green oil formation and simplify ethylene product recovery
pyrolysis gasoline , are recovered . Quench water tower over by eliminating a C2 splitter pasteurization section that is
head is sent to the olefins recovery zone 270 , particularly the otherwise typically included in product recovery. In addi
first compression stage . Raw pyrolysis gasoline is sent to a 20 tion , hydrogen purification via pressure swing adsorption
gasoline stabilizer to remove any light ends and to control eliminates the need for a methanation reactor that is other
vapor pressure in downstream pyrolysis gasoline processing. wise typically included in product recovery.
A closed- loop dilution steam /process water system is The demethanizer recovers methane in the overhead for
enabled , in which dilution steam is generated using heat fuel gas , and C2 and heavier gases in the demethanizer
recovery from the primary fractionator quench pumparound 25 bottoms are routed to the deethanizer. The deethanizer
loops . The primary fractionator enables efficient recovery of separates ethane and ethylene overhead which feeds a C2
pyrolysis fuel oil due to energy integration and pyrolysis fuel splitter. The C2 splitter recovers ethylene product 202 , in
oil content in the light fraction stream . certain embodiments polymer -grade ethylene product, in the
The mixed product stream 232 effluent from the mixed overhead . Ethane 272 from the C2 splitter bottoms is
feed steam cracking zone 230 and the mixed product stream 30 recycled to the mixed feed steam cracking zone 230. Deetha
252 effluent from the gas oil steam cracking zone 250 are nizer bottoms contain C3s from which propylene product
shown as combined streams 220. Stream 220 is routed to an 204 , in certain embodiments polymer -grade propylene prod
olefins recovery zone 270. For instance , light products from uct , is recovered as the overhead of a C3 splitter, with
the quenching step , C4- , H , and H2S , are contained in the
mixed product stream 220 that is routed to the olefins 35 propane 282 from the C3 splitter bottoms recycled to the
recovery zone 270. Products include : hydrogen 210 that is mixed feed steam cracking zone 230 .
used for recycle and / or passed to users ; fuel gas 208 that is A methyl acetylene / propadiene (MAPD ) saturation and
passed to a fuel gas system ; ethane 272 that is recycled to the propylene recovery zone 280 is provided for selective
mixed feed steam cracking zone 230 ; ethylene 202 that is hydrogenation to convert methyl acetylene /propadiene, and
recovered as product; a mixed C3 stream 286 that is passed 40 to recover propylene from a mixed C3 stream 286 from the
to a methyl acetylene/propadiene saturation and propylene olefins recovery zone 270. The mixed C3 286 from the
recovery zone 280 ; and a mixed C4 stream 206 that is passed olefins recovery zone 270 contains a sizeable quantity of
to a butadiene extraction zone 500 . propadiene and propylene. The methyl acetylene /propadiene
The olefins recovery zone 270 operates to produce on saturation and propylene recovery zone 280 enables produc
specification light olefin ( ethylene and propylene) products 45 tion of propylene 204 , which can be polymer -grade propyl
from the mixed product stream 220. For instance , cooled gas ene in certain embodiments .
intermediate products from the steam cracker is fed to a The methyl acetylene /propadiene saturation and propyl
cracked gas compressor, caustic wash zone , and one or more ene recovery zone 280 receives hydrogen 284 and mixed C3
separation trains for separating products by distillation . In 286 from the olefins recovery zone 270. Products from the
certain embodiments two trains are provided. The distilla- 50 methyl acetylene/propadiene saturation and propylene
tion train includes a cold distillation section , wherein lighter recovery zone 280 are propylene 204 which is recovered,
products such as methane, hydrogen , ethylene, and ethane and the recycle C3 stream 282 that is routed to the steam
are separated in a cryogenic distillation / separation opera cracking zone 230. In certain embodiments, hydrogen 284 to
tion . The mixed C2 stream from the steam cracker contains saturate methyl acetylene and propadiene is derived from
acetylenes that are hydrogenated to produce ethylene in an 55 hydrogen 210 obtained from the olefins recovery zone 270 .
acetylene selective hydrogenation unit . This system can also A stream 206 containing a mixture of C4s , known as
include ethylene, propane and / or propylene refrigeration crude C4s , from the olefins recovery zone 270 , is routed to
facilities to enable cryogenic distillation . a butadiene extraction zone 500 to recover a high purity
In one embodiment, mixed product stream 232 effluent 1,3 -butadiene product 502 from the mixed crude C4s . In
from the mixed feed steam cracking zone 230 and the mixed 60 certain embodiments (not shown ) , a step of hydrogenation
product stream 252 effluent from the gas oil steam cracking of the mixed C4 before the butadiene extraction zone 500
zone 250 are passed through three to five stages of com can be integrated to remove acetylenic compounds, for
pression . Acid gases are removed with caustic in a caustic instance, with a suitable catalytic hydrogenation process
wash tower . After an additional stage of compression and using a fixed bed reactor. 1,3 - butadiene 502 is recovered
drying, light cracked gases are chilled and routed to a 65 from the hydrogenated mixed C4 stream by extractive
depropanizer. In certain embodiments light cracked gases distillation using, for instance , n -methyl -pyrrolidone ( NMP )
are chilled with a cascaded two - level refrigeration system or dimethylformamide (DMF ) as solvent. The butadiene
 US 10,760,011 B2
43 44
extraction zone 500 also produces a raffinate stream 504 of about 70-95 % , 75-95 % , 85-95 % or 90-95 % on a weight
containing butane /butene, which is passed to a methyl basis . Effluent from the primary reactor is routed to a
tertiary butyl ether zone 510 . reaction column where reactions are completed. In certain
In one embodiment, in operation of the butadiene extrac embodiments, exothermic heat of the reaction column and
tion zone 500 , the stream 206 is preheated and vaporized 5 the primary reactor can optionally be used to supplement the
into a first extractive distillation column, for instance having column reboiler along with provided steam . The reaction
two sections . NMP or DMF solvent separates the 1,3 column bottoms contains methyl tertiary butyl ether, trace
butadiene from the other C4 components contained in amounts, for instance, less than 2 % , of unreacted methanol,
stream 504. Rich solvent is flashed with vapor to a second and heavy products produced in the primary reactor and
extractive distillation column that produces a high purity 10 reaction column . Reaction column overhead contains unre
1,3 -butadiene stream as an overhead product. Liquid solvent acted methanol and non -reactive C4 raffinate . This stream is
from the flash and the second distillation column bottoms
water washed to
are routed to a primary solvent recovery column. Bottoms to the 1 -butene recovery remove unreacted methanol and is passed
liquid is circulated back to the extractor and overhead liquid zone 520 as the C4 raffinate 516 .
is passed to a secondary solvent recovery or solvent polish- 15 Recovered methanol is removed from the wash water in a
methanol recovery column and recycled to the primary
ing column. Vapor overhead from the recovery columns reactor .
combines with recycle butadiene product into the bottom of The C4 raffinate stream 516 from the methyl tertiary butyl
the extractor to increase concentration of 1,3 -butadiene. The
1,3 -butadiene product 502 can be water washed to remove ether zone 510 is passed to a separation zone 520 for
any trace solvent. In certain embodiments, the product purity 20 butene-1 recovery. In certain embodiments, upstream of the
(wt % ) is 97-99.8 , 97.5-99.7 or 98-99.6 of 1,3 -butadiene ; methyl tertiary butyl ether zone 510 , or between the methyl
and 94-99 , 94.5-98.5 or 95-98 of the 1,3 -butadiene content tertiary butyl ether zone 510 and separation zone 520 for
(wt % ) of the feed is recovered . In addition to the solvent butene - 1 recovery , a selective hydrogenation zone can also
such as DMF, additive chemicals are blended with the be included (not shown) . For instance, in certain embodi
solvent to enhance butadiene recovery. In addition, the 25 ments, raffinate from the methyl tertiary butyl ether zone 510
extractive distillation column and primary solvent recovery is selectively hydrogenated in a selective hydrogenation unit
columns are reboiled using high pressure steam ( for to produce butene - 1 . Other co -monomers and paraffins are
instance, 600 psig ) and circulating hot oil from the aromatics also co- produced . The selective hydrogenation zone oper
extraction zone 620 as heat exchange fluid . ates in the presence of an effective amount of hydrogen
A methyl tertiary butyl ether zone 510 is integrated to 30 obtained from recycle within the selective hydrogenation
produce methyl tertiary butyl ether 514 and a second C4 zone and make -up hydrogen ; in certain embodiments, all or
raffinate 516 from the first C4 raffinate stream 504. In certain a portion of the make -up hydrogen for the selective hydro
embodiments C4 Raffinate 1 504 is subjected selective genation zone is derived from the steam cracker hydrogen
hydrogenation to selectively hydrogenate any remaining stream 210 from the olefins recovery train 270. For instance ,
dienes and prior to reacting isobutenes with methanol to 35 a suitable selective hydrogenation zone can include , but is
produce methyl tertiary butyl ether. not limited to , systems based on technology commercially
Purity specifications for recovery of a 1 -butene product available from Axens, IFP Group Technologies, FR ; Haldor
stream 522 necessitate that the level of isobutylene in the Topsoe A / S , DK ; Clariant International Ltd , CH ; Chicago
second C4 raffinate 516 be reduced . In general, the first C4 Bridge & Iron Company N.V. (CB & I ) , NL ; Honeywell UOP,
raffinate stream 504 containing mixed butanes and butenes , 40 US ; or Shell Global Solutions , US .
and including isobutylene, is passed to the methyl tertiary For selective recovery of a 1 - butene product stream 522 ,
butyl ether zone 510. Methanol 512 is also added, which and to recover a recycle stream 524 that is routed to the
reacts with isobutylene and produces methyl tertiary butyl mixed feed steam cracking zone 230 , and / or in certain
ether 514. For instance , methyl tertiary butyl ether product embodiments described herein routed to a metathesis zone ,
and methanol are separated in a series of fractionators, and 45 one or more separation steps are used . For example,
routed to a second reaction stage . Methanol is removed with 1 -butene can be recovered using two separation columns,
water wash and a final fractionation stage . Recovered metha where the first column recovers olefins from the paraffins
nol is recycled to the fixed bed downflow dehydrogenation and the second column separates 1 -butene from the mixture
reactors . In certain embodiments described below with including 2 -butene, which is blended with the paraffins from
respect to FIG . 11 , additional isobutylene can be introduced 50 the first column and recycled to the steam cracker as a
to the methyl tertiary butyl ether zone 510 , for instance , recycle stream 524 .
derived from a metathesis conversion unit. In certain embodiments , the C4 raffinate stream 516 from
In operation of one embodiment of the methyl tertiary the methyl tertiary butyl ether zone 510 is passed to a first
butyl ether zone 510 , the raffinate stream 504 , contains splitter, from which from isobutane, 1 -butene, and n -butane
35-45 % , 37-42.5 % , 38-41 % or 39-40 % isobutylene by 55 are separated from heavier C4 components. Isobutane ,
weight. This component is removed from the C4 raffinate 1 -butene, and n -butane are recovered as overhead , con
516 to attain requisite purity specifications, for instance , densed in an air cooler and sent to a second splitter. Bottoms
greater than or equal to 98 wt % for the 1 - butene product from the first splitter, which contains primarily cis- and
stream 522 from the butene - 1 recovery zone 520. Methanol trans - 2 - butene can be added to the recycle stream 524 , or in
512 , in certain embodiments high purity methanol having a 60 certain embodiments described herein passed to a metathesis
purity level of greater than or equal to 98 wt % from outside unit . In certain arrangements, the first splitter overhead
battery limits , and the isobutylene contained in the raffinate enters the mid -point of the second splitter. Isobutane product
stream 504 and in certain embodiments isobutylene 544 526 can optionally be recovered in the overhead ( shown in
from metathesis ( shown in dashed lines as an optional feed ), dashed lines ) , 1 - butene product 522 is recovered as a
react in a primary reactor. In certain embodiments the 65 sidecut , and n - butane is recovered as the bottoms stream .
primary reactor is a fixed bed downflow dehydrogenation Bottoms from both splitters is recovered as all or a portion
reactor and operates for isobutylene conversion in the range of recycle stream 524 .
 US 10,760,011 B2
45 46
The raw pyrolysis gasoline streams 234 and 254 from the tive . Two parallel first- stage reactors can be used in certain
steam crackers are treated and separated into treated naphtha embodiments to allow for regeneration in a continuous
and other fractions. In certain embodiments , all , a substan process without shutdown . In certain embodiments, the
tial portion or a significant portion of the pyrolysis gasoline first -stage reactor contains three catalyst beds with cooled
streams 234 and 254 are passed to the py - gas hydrotreating 5 first stage separator liquid recycled as quench material
zone 600. The raw pyrolysis gasoline streams 234 and 254 between each bed . First - stage effluent is stabilized and
are processed in a py - gas hydrotreating zone 600 in the separated in a column operating under slight vacuum to
presence of an effective amount of hydrogen obtained from reduce temperature. In certain embodiments C5 from the
recycle within the py - gas hydrotreating zone 600 and make C6 + is drawn , followed by a deoctanizer to remove C9 + and
up hydrogen 602. Effluent fuel gas is recovered and , for 10 produce a C6 - C8 heart naphtha cut . The column operates
instance , passed to a fuel gas system . In certain embodi under slight vacuum to limit temperature. The first stage
ments , all or a portion of the make -up hydrogen 602 is product is stripped to remove hydrogen , H2S , and other light
derived from the steam cracker hydrogen stream 210 from ends. In certain embodiments , the stripped first stage product
the olefins recovery train 270. For instance, a suitable py - gas
hydrotreating zone 600 can include, but is not limited to , 15 tois depentanized to remove cracked C5 , for instance,as feed
a metathesis unit. A second stage reactor operates in vapor
systems based on technology commercially available from
Honeywell UOP, US ; Chevron Lummus Global LLC phase and removes sulfur and saturates olefins. The second
( CLG) , US ; Axens, IFP Group Technologies , FR ; Haldor stage product is stripped to remove hydrogen , H2S , and
Topsoe A / S , DK ; or Chicago Bridge & Iron Company N.V. other light ends. In certain embodiments, both reactors are
( CB & I ) , NL . 20 multi -bed and use product recycle to control reactor tem
The py - gas hydrotreating zone 600 is operated under perature rise.
conditions , and utilizes catalyst ( s ) , that can be varied over a In certain embodiments , the first reaction stage of the
relatively wide range. These conditions and catalyst ( s ) are py - gas hydrotreating zone 600 operating conditions include :
selected for effective hydrogenation for saturation of certain a reactor inlet temperature ( ° C. ) in the range of from
olefin and diolefin compounds, and if necessary for 25 about 80-135 , 80-125 , 80-115 , 95-135 , 95-125 , 95-115 ,
hydrotreating to remove sulfur and / or nitrogen containing 100-135 , 100-125 , 100-115 or 107-111 ;
compounds . In certain embodiments, this is carried out in at a reactor outlet temperature ( ° C. ) in the range of from
least two catalytic stages , although other reactor configura about 145-230 , 145-206 , 145-200 , 165-230 , 165-206 , 165
tions can be utilized . Accordingly, py - gas hydrotreating zone 200 , 175-230 , 175-206 , 175-200 or 184-188 ;
600 subjects the pyrolysis gasoline streams 234 and 254 to 30 a start of run ( SOR) reaction temperature ( ° C. ) , as a
hydrogenation to produce hydrotreated pyrolysis gasoline weighted average bed temperature ( WABT ), in the range of
604 effective as feed to the aromatics extraction zone 620 . from about 75-125 , 75-115 , 75-110 , 90-125 , 90-115 , 90-110 ,
Effluent off- gases are recovered from the py - gas hydrotreat 95-125 , 95-115 , 95-110 or 99-10
ing zone 600 and are passed to the olefins recovery train , the an end of run (EOR) reaction temperature ( ° C. ) , as a
saturated gas plant as part of the other gases stream 156 , 35 WABT, in the range of from about 124-195 , 124-180 ,
and / or directly to a fuel gas system . Liquefied petroleum gas 124-170 , 140-195 , 140-180 , 140-170 , 150-195 , 150-180 ,
can be recovered from the py - gas hydrotreating zone 600 150-170 or 158-163 ;
and routed to the mixed feed steam cracking zone , the a reaction inlet pressure ( barg ) in the range of from about
olefins recovery train and / or the saturated gas plant. 25-40 , 25-35 , 25-33 , 28-40 , 28-35 , 28-33 , 30-40 , 30-35 or
In the py - gas hydrotreating zone 600 , diolefins in the feed 40 30-33 ;
and olefins in the C6 + portion of the feed are saturated to a reaction outlet pressure (barg ) in the range of from about
produce a naphtha stream 604 , a C5 + feed to the aromatics 23-35 , 23-33 , 23-31 , 25-35 , 25-33 , 25-31 , 28-35 , 28-33 or
extraction zone . In certain embodiments, a depentanizing -28-31 ;
step associated with the py - gas hydrotreating zone 600 a hydrogen partial pressure (barg ) (outlet) in the range of
separates all or a portion of the C5s , for instance , as 45 from about 15-25 , 15-22 , 15-21 , 18-25 , 18-22 , 18-21 , 19-25
additional feed 606 to the mixed feed steam cracking zone or 19-22 ;
230 and / or as feed to a metathesis unit 530 (as shown, for a hydrogen treat gas feed rate ( SLt/Lt) up to about 180 ,
instance , in FIG . 3 , FIG . 5 or FIG . 11 ) . In other embodi 165 or 156 , in certain embodiments from about 120-180 ,
ments, a depentanizing step associated with the aromatics 120-165 , 120-156 , 134-180 , 134-165 , 134-156 , 140-180 ,
extraction zone 620 separates all or a portion of the C5s from 50 140-165 or 140-156 ;
the hydrotreated naphtha stream 604 , for instance , as addi a liquid quench feed ratio ( Lt quench /Lt feed ) up to about
tional feed to the mixed feed steam cracking zone 230 and / or 0.8 , 0.7,0.6 or 0.5 , and in certain embodiments in the range
as feed to a metathesis unit 530 . of from about 0.35-0.6 , 0.35-0.55 , 0.35-0.5 , 0.4-0.6 , 0.4
In certain embodiments, pyrolysis gasoline is processed in 0.55 , 0.4-0.5 , 0.45-0.6 , 0.45-0.55 or 0.45-0.5 ; and
a first reaction stage for hydrogenation and stabilization . 55 a make -up hydrogen feed rate (SLt/Lt) up to about 60 , 55 ,
Diolefins are saturated selectively in the first reaction stage , 47 or 45 , in certain embodiments from about 34-55 , 34-47 ,
and remaining olefins are saturated in the second reaction 34-45 , 40-55 , 40-47 , 40-45 , 42-55 , 42-47 or 42-45 .
stage along with converting feed sulfur into hydrogen sul In certain embodiments, the second reaction stage of the
fide . The pyrolysis gasoline can be treated in a cold py - gas hydrotreating zone 600 operating conditions include :
hydrotreating unit , therefore reducing the level of aromatics 60 a reactor inlet temperature ( ° C. ) in the range of from
saturation . about 225-350 , 225-318 , 225-303 , 255-350 , 255-318 , 255
In an example of an effective py - gas hydrotreating zone 303 , 270-350 , 270-318 , 270-303 or 285-291 ;
600 , raw pyrolysis gasoline is passed through a coalescer a reactor outlet temperature ( ° C. ) in the range of from
before entering a feed surge drum . The first stage reactor about 289-445 , 289-405 , 289-386 , 328-445 , 328-405 , 328
operates in mixed phase and selectively hydrogenates diole- 65 386 , 345-445 , 345-405 , 345-386 or 364-370 ;
fins to mono -olefins and unsaturated aromatics to side - chain a start of run ( SOR) reaction temperature ( ° C. ) , as a
saturated aromatics. Pd- based catalyst materials are effec weighted average bed temperature ( WABT ), in the range of
 US 10,760,011 B2
47 48
from about 217-336 , 217-306 , 217-291 , 245-336 , 245-306 , Hydrotreated pyrolysis gasoline 604 is routed to the
245-291 , 260-336 , 260-306 , 260-291 or 274-280 ; aromatics extraction zone 620. In certain embodiments to
an end of run (EOR) reaction temperature ( ° C. ) , as a maximize production of petrochemicals, all , a substantial
WABT, in the range of from about 325-416 , 325-380 , portion or a significant portion of the hydrotreated pyrolysis
325-362 , 305-416 , 305-380 , 305-362 , 325-416 , 325-380 , 5 gasoline 604 is passed to the aromatics extraction zone 620 .
325-362 or 340-346 ;
a reaction inlet pressure ( barg) in the range of from about In modes of operation in which production of gasoline is the
objective some of the hydrotreated pyrolysis gasoline 604 is
25-37 , 25-34 , 25-32 , 28-37 , 28-34 , 28-32 , 29-37 , 29-34 or passed to a gasoline pool ( not shown ).
29-32 ;
a reaction outlet pressure (barg ) in the range of from about 10 oneTheor aromatics extraction zone 620 includes, for instance ,
23-35 , 23-32 , 23-30 , 26-35 , 26-32 , 26-30 , 28-35 , 28-32 or separate the hydrotreated distillation
more extractive
pyrolysis
units , and operates to
gasoline into high - purity
28-30 ;
benzene , toluene , xylenes and C9 aromatics
a hydrogen partial pressure ( barg ) ( outlet) in the range of FIG . 10 , a benzene stream 624 , a mixed xylenes . As depicted in
from about 6-10 , 6-9 , 7-10 or 7-9 ; stream 626
a hydrogen treat gas feed rate ( SLt/Lt) up to about 135 , 15 and a raffinate stream 646 are recovered from the aromatics
extraction zone 620 , with the raffinate stream 646 routed to
126 , 116 or 110 , in certain embodiments from about 84-126 ,
84-116 , 84-110 , 95-126 , 95-116 , 95-110 , 100-126 , 100-116 the mixed feed steam cracking zone 230 as additional feed .
or 100-110 ; and In addition , a toluene stream 636 and C9 + aromatics stream
a make -up hydrogen feed rate ( SLt /Lt) up to about 30 , 27 638 are passed from the aromatics extraction zone 620 to a
or 24 , in certain embodiments from about 18-30 , 18-27 , 20 toluene and C9 + transalkylation zone 630 for production of
18-24 , 21-30 , 21-27 , 21-24 , 22-30 , 22-27 or 22-24 . additional benzene and xylenes, recycled as stream 640 to
An effective quantity of catalyst possessing selective the aromatics extraction zone 620. In certain embodiments
hydrogenation functionality is provided , which generally ethylbenzene can be recovered (not shown ). Heavy aromat
contain one or more active metal component of metals or ics 642 are also recovered from the aromatics extraction
metal compounds (oxides or sulfides ) selected from Co , Mo , 25 zone 620 .
Pt , Pd, Fe , or Ni . The active metal component is typically In certain embodiments of operation of the aromatics
deposited or otherwise incorporated on a support, such as extraction zone 620 , aromatics are separated from the feed
amorphous alumina , amorphous silica alumina, zeolites , or by extractive distillation using, for instance , n - formylmor
combinations thereof. Exemplary selective hydrogenation pholine (NFM ), as an extractive solvent. Benzene, toluene,
catalyst predominantly use Pd as the active metal component 30 mixed xylenes and C9 + aromatics are separated via distil
on alumina support, including those commercially available lation . Benzene and mixed xylenes are recovered as product
under the trade name Olemax® 600 and Olemax® 601 . streams 624 and 626 , and toluene 636 and C9 + aromatics
Effective liquid hourly space velocity values ( h- '), on a 638 are sent to the toluene and C9 + transalkylation zone
fresh feed basis relative to the first stage pyrolysis gasoline 630. The transalkylation zone product stream 640 containing
reactor catalyst, are in the range of from about 0.1-10.0 , 35 benzene and mixed xylenes is returned to the recovery
0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 , 0.3-2.0 , 0.5-10.0 , 0.5-5.0 , section of the aromatics extraction zone 620. A paraffinic
0.5-2.0 or 0.9-1.44 . Suitable catalysts used in the first stage raffinate stream 646 is recycled as feed to the mixed feed
pyrolysis gasoline reactor have an expected lifetime in the steam cracking zone 230. In certain embodiments, the
range of about 18-30 , 22-30 , 18-26 or 22-26 months. paraffinic raffinate stream 646 is in direct fluid communica
An effective quantity of second stage pyrolysis gasoline 40 tion with the mixed feed steam cracking zone 230 , that is ,
reactor catalyst is provided , including those having hydro the stream is not subject to further catalytic processing prior
genation functionality and which generally contain one or to the steam cracking step.
more active metal component of metals or metal compounds Selection of solvent, operating conditions , and the mecha
( oxides or sulfides ) selected from the Periodic Table of the nism of contacting the solvent and feed permit control over
Elements IUPAC Groups 6-10 . In certain embodiments , the 45 the level of aromatic extraction . For instance , suitable sol
active metal component is one or more of Co , Ni , W and Mo. vents include n - formylmorpholine, furfural, N -methyl-2
The active metal component is typically deposited or oth pyrrolidone, dimethylformamide, dimethylsulfoxide, phe
erwise incorporated on a support, such as amorphous alu nol , nitrobenzene, sulfolanes, acetonitrile, furfural, or
mina, amorphous silica alumina, zeolites , or combinations glycols , and can be provided in a solvent to oil ratio of up
thereof. In certain embodiments , the catalyst used in the first 50 to about 20 : 1 , in certain embodiments up to about 4 : 1 , and
stage pyrolysis gasoline reactor includes one or more cata in further embodiments up to about 2 : 1 . Suitable glycols
lyst selected from Co /Mo , Ni /Mo , Ni/ W , and Co /Ni/Mo . include diethylene glycol, ethylene glycol, triethylene gly
Combinations of one or more of Co /Mo , Ni/ Mo , Ni /W and col , tetraethylene glycol and dipropylene glycol . The extrac
Co /NiMo / , can also be used . For example, a combination of tion solvent can be a pure glycol or a glycol diluted with
catalyst particles commercially available under the trade 55 from about 2-10 wt % water. Suitable sulfolanes include
names Olemax® 806 and Olemax® 807 can be used , with hydrocarbon - substituted sulfolanes (e.g. , 3 -methyl sulfo
active metal components of Co and Ni /Mo . The combina lane) , hydroxy sulfolanes ( e.g. , 3 - sulfolanol and 3 -methyl
tions can be composed of different particles containing a 4 -sulfolanol ), sulfolanyl ethers ( e.g. , methyl - 3 - sulfolanyl
single active metal species , or particles containing multiple ether ), and sulfolanyl esters ( e.g. , 3 -sulfolanyl acetate ) .
active species . Effective liquid hourly space velocity values 60 The aromatic separation apparatus can operate at a tem
( h- ?), on a fresh feed basis relative to the first stage pyrolysis perature in the range of from about 40-200 , 40-150 , 60-200 ,
gasoline reactor catalyst, are in the range of from about 60-150 , 86-200 or 80-150 ° C. The operating pressure of the
0.1-10.0 , 0.1-5.0 , 0.1-2.0 , 0.3-10.0 , 0.3-5.0 , 0.3-2.0 , 0.5 aromatic separation apparatus can be in the range of from
10.0 , 0.5-5.0 , 0.5-2.0 or 0.8-1.2 . Suitable catalysts used in about 1-20 , 1-16 , 3-20 , 3-16 , 5-20 or 5-16 barg . Types of
the second stage pyrolysis gasoline reactor have an expected 65 apparatus useful as the aromatic separation apparatus in
lifetime in the range of about 18-30 , 22-30 , 18-26 or 22-26 certain embodiments of the system and process described
months. herein include extractive distillation columns.
 US 10,760,011 B2
49 50
In one embodiment of operation of the aromatics extrac tional embodiments , either or both of the pyrolysis oil
tion zone 620 , the feed contains primarily C6 + components , streams 236 and 256 can be fractioned (not shown) into light
and is fractionated into a “ heart cut” of C6 - C8 , and a heavy pyrolysis oil and heavy pyrolysis oil . For instance , light
C9 + fraction . The C6 - C8 cut is routed to the extractive pyrolysis oil can be blended with one or more of the middle
distillation system where aromatics are separated from non 5 distillate streams, so that 0-100 % of light pyrolysis oil
aromatics ( saturates) via solvent distillation . The raffinate derived from either or both of the pyrolysis oil streams 236
(non -aromatics ) from the C6 - C8 is removed and recycled and 256 is processed to produce diesel fuel product and / or
back to the cracking complex as a feedstock . The aromatics additional feed to the mixed feed steam cracking zone 230 .
are soluble in the solvent and are carried from the bottom of In another embodiment 0-100% of lightpyrolysis oil derived
the extractive distillation column to the solvent stripper 10 from either or both of the pyrolysis oil streams 236 , 256 can
where they are stripped from the solvent, to recover aro be processed in the gas oil hydrocracking zone 320. In
matics extract and lean solvent which is recycled back to the certain embodiments, all , a substantial portion , a significant
extractive distillation column . The mixed aromatics extract portion or a major portion of light pyrolysis oil can be passed
is routed to a series of fractionation columns ( a benzene to one or both of the diesel hydrotreating zone 180 and / or the
column, a toluene column and a xylene column) where each 15 vacuum gas oil hydroprocessing zone ; any remainder can be
aromatic species is successively removed , for instance, as blended into the fuel oil pool . Heavy pyrolysis oil can be
benzene stream 624 and mixed xylenes stream 626. The blended into the fuel oil pool as a low sulfur component,
heavy C9 + fraction is further separated into C9 and C10 + and / or used as a carbon black feedstock . In further embodi
material. The toluene and C9 products are routed to the ments, 0-100 % of light pyrolysis oil and / or 0-100 % of heavy
toluene and C9 + transalkylation zone 630 where they are 20 pyrolysis oil derived from either or both of the pyrolysis oil
reacted to form additional benzene and mixed xylenes. This streams 236 , 256 can be processed in the optional residue
stream is recycled back to the fractionation portion of the treating zone 800. In certain embodiments, all , a substantial
aromatics extraction zone 620 to recover the benzene and portion, a significant portion or a major portion of the
mixed xylenes as well as to recycle the unconverted toluene pyrolysis oil streams 236 , 256 ( light and heavy ) can be
and C9 aromatics. The transalkylation effluent does not 25 processed in the optional residue treating zone 800 .
require re - extraction in the solvent distillation section and FIG . 11 depicts embodiments including integration of a
therefore is routed to the inlet of the benzene column . In metathesis zone 530. The process of FIG . 11 operates
certain embodiments toluene can be recycled to extinction , according to the description with respect to FIGS . 6 and 10 ,
or approaching extinction . C10 and heavier aromatics are or any of the other embodiments herein , in all other aspects .
removed as product 642. In certain embodiments ethylben- 30 For instance, a suitable metathesis zone 530 can include, but
zene can be recovered . is not limited to , systems based on technology commercially
The toluene and C9 + transalkylation zone 630 operates available from Chicago Bridge & Iron Company N.V.
under conditions effective to disproportionate toluene and (CB&I), NL .
C9 + aromatics into a mixed stream 640 containing benzene, Feedstocks to the metathesis zone 530 include : a portion
mixed xylenes and heavy aromatics . Product ratio of ben- 35 536 of the ethylene product 202 ; a C4 Raffinate - 3 stream 532
zene and xylene can be adjusted by selection of catalyst, from the 1 - butene recovery zone 520 , and the olefinic C5 cut
feedstock and operating conditions. The transalkylation 606 from the py - gas hydrotreating zone 600. The C4 Raf
zone 630 receives as feed the toluene stream 636 and the finate - 3 stream 532 is 0-100 % of the total C4 Raffinate - 3
C9 + aromatics stream 638 from the aromatics extraction from the 1 - butene recovery zone 520 ; any remaining portion
zone 620. A small quantity of hydrogen 632 , in certain 40 524 can be recycled to the mixed feed steam cracking zone
embodiments which is obtained all or in part from the 230. Products from the metathesis zone 530 include a
hydrogen stream 210 derived from the olefins recovery zone propylene product stream 534 and a stream 542 , having a
270 , is supplied for transalkylation reactions . Side cracking mixture of mostly saturated C4/ C5 from a metathesis unit
reactions occur producing fuel gas stream , for instance , that is recycled to the mixed feed steam cracking zone . In
passed to the fuel gas system , and LPG stream 634 that is 45 certain embodiments, isobutylene 544 can also be recovered
recycled to mixed feed steam cracking zone . A small ( shown in dashed lines ) and routed to the methyl tertiary
amount, such as 0.5-3 wt % of the total feed to the aromatics butyl ether zone 510. In embodiments that operate without
extraction, of heavy aromatics are produced due to conden separation of isobutylene, it is included within stream 542 .
sation reactions and are passed to the mixed stream 640 for In an example of a metathesis zone 530 used in the
recovery with other heavy aromatics . 50 integrated process herein , the C4 Raffinate - 3 stream 532
In operation of one embodiment of the toluene and C9 + from the separation zone 520 and the C5 olefins stream 606
transalkylation zone 630 , toluene and C9 aromatics are from the py - gas hydrotreating zone 600 ( or the aromatics
reacted with hydrogen under mild conditions to form a extraction zone) pass through a guard bed to remove t -butyl
mixture of C6 - C11 aromatics. The mixed aromatic product catechol and are mixed with a molar excess of fresh and
stream 640 is recycled back to the aromatics extraction zone 55 recycled ethylene. The reactor feed passes through another
620 where the benzene and mixed xylenes are recovered as guard bed to remove other trace contaminants, is heated in
products. C7 and C9 aromatics are recycled back as feed to a furnace and enters the disproportionation (metathesis )
the transalkylation zone 630 , and the C10 + fraction is reactor, where propylene is formed . The reactions reach
removed from the aromatics extraction zone 620 as heavy equilibrium conversion. The metathesis reactor effluent con
aromatics stream 642. The disproportionation reactions 60 tains a mixture of propylene , ethylene, and butenes /butanes,
occur in the presence of an effective quantity of hydrogen. and some C5 and heavier components from by - product
A minimal amount of hydrogen is consumed by cracking reactions. C4 olefins isomerize in the disproportionation
reactions under reactor conditions. Purge gas is recycled reactor and react with ethylene to form additional propylene.
back to the cracking complex for component recovery . In certain embodiments, disproportionation of C5 olefins
In certain embodiments, pyrolysis oil streams 236 and 65 yields isobutylene by -product for production of additional
256 can be blended into the fuel oil pool as a low sulfur MTBE . Cooled reactor effluent enters a deethylenizer, which
component, and / or used as carbon black feedstock . In addi recycles overhead ethylene to the disproportionation reactor.
 US 10,760,011 B2
51 52
Deethylenizer bottoms are passed to a depropylenizer, which as to derive most or all of the utility hydrogen from within
recovers grade propylene product as overhead . Propylene the battery limits . In certain embodiments there is zero
product purity is > 99.5 mol % ( polymer grade ). In certain external hydrogen use , in which make -up hydrogen is only
embodiments depropylenizer bottoms enter a deisobutylen required to initiate the operations; when the reactions reach
izer, which recovers isobutylene as overhead for additional 5 equilibrium , the hydrogen derived from the mixed feed
feedstock to the MTBE zone 510. Deisobutylenizer bottoms steam cracking and gas oil steam cracking products provides
are mixed with a recycle stream to dilute the olefin concen sufficient hydrogen to maintain the hydrogen requirements
tration , the mixture is heated and mixed with hydrogen , and of the hydrogen users in the integrated process. In further
routed to a total hydrogenation reactor, which saturates any embodiments, there is a net hydrogen gain , so that hydrogen
remaining C4/ C5 or heavier olefins and thereby enhances 10 can be added , for instance , to the fuel gas that is used to
light olefin yields . Cooled reactor effluent is recycled as operate the various heating units within the integrated pro
feedstock to the mixed feed steam cracking zone 230 . cess .
FIG . 12 depicts embodiments in which kerosene sweet Furthermore, the integrated process described herein
ening is in an optional unit , that is , the first middle distillate offers useful outlets for the off- gases and light ends from the
fraction 116 can be routed either through the kerosene 15 hydroprocessing units . For instance, the stream 156 that is
sweetening zone 170 or routed to the distillate hydrotreating passed to the saturated gas plant 150 of the crude complex
zone 180. The process of FIG . 12 operates according to the 100 can contain off- gases and light ends from the hydro
description with respect to FIGS . 6 and 10 , or any of the processing units, such as the diesel hydrotreating zone 180 ,
other embodiments herein , in all other aspects . the gas oil hydrocracking zone 320 and / or from the py - gas
During periods in which maximizing the fuel fraction 172 20 hydrotreating zone 600. In other embodiments, in combina
is desired , the first middle distillate fraction 116 can be tion with or as an alternative to the passing these off -gases
routed to the kerosene sweetening zone 170. During periods and light ends to stream 156 , all or a portion can be routed
in which the feedstock to the mixed feed steam cracking to the mixed feed steam cracking unit 230. For instance, C2s
zone 230 is to be maximized , the first middle distillate can be separated from the mixture of methane, hydrogen and
fraction 116 can be routed to the distillate hydrotreating zone 25 C2s using a cold distillation section ( “ cold box ” ) including
180 , so as to produce additional hydrotreated naphtha 184 . cryogenic distillation /separation operations, which can be
In additional alternative embodiments, the first middle dis integrated with any or all of the mixed feed steam cracking
tillate fraction 116 can be divided (on a volume or weight unit 230 , the saturated gas plant 150 and / or the olefins
basis , for example, with a diverter) so that a portion is passed recovery zone 270. Methane and hydrogen can be passed to
to the distillate hydrotreating zone 180 and the remaining 30 a fuel gas system or to an appropriate section of the olefins
portion is passed to the kerosene sweetening zone 170 . recovery zone 270 , such as the hydrogen purification sys
FIG . 13 depicts embodiments in which kerosene sweet tem . In still further embodiments, in combination with or as
ening is eliminated . Accordingly, the embodiments of an alternative the passing these off - gases and light ends to
FIG . 13 , two middle distillate fractions are used . In this stream 156 and / or routing them to the mixed feed steam
embodiment, a first middle distillate fraction 124 is routed to 35 cracking unit 230 , all or a portion can be routed to an
the distillate hydrotreating zone 180 , and a second middle appropriate section of the olefins recovery zone 270 , such as
distillate fraction 134 may be similar to the third middle the depropanizer, or combining the gases with the depro
distillate fraction 126 described in other embodiments panizer overheads.
herein . In one example using the arrangement shown in FIG . The unique configurations presented herein set forth a
13 , the first middle distillate fraction 124 contains kerosene 40 level of integration , of streams and units that allows the use
range hydrocarbons and medium AGO range hydrocarbons , of gas oil steam crackers in an economically efficient man
and the second atmospheric distillation zone middle distil ner. The configurations support and enhance chemical con
late fraction 134 contains heavy AGO range hydrocarbons. version using integrated processes with crude oil as a feed .
In another example using the arrangement shown in FIG . 13 , Hence , not only do these configurations permit lower capital
the first middle distillate fraction 124 contains kerosene 45 expenditure relative to conventional approaches of chemical
range hydrocarbons and a portion of medium AGO range production from fuels or refinery by -products, but it also
hydrocarbons and the second middle distillate fraction 134 exhibits an economical use of the gas oil cracker (through
contains a portion of medium AGO range hydrocarbons and the integration ). Accordingly, despite the use of crude oil as
heavy AGO range hydrocarbons. The process of FIG . 13 the feed , the processes herein are comparable to other
operates according to the description with respect to FIGS . 50 options currently common in the industry such as ethane
6 and 10 , or any of the other embodiments herein , in all other crackers that benefit from availability of ethane as a feed .
aspects . Embodiments described herein provide the ability to
Advantageously, process dynamics of the configurations achieve a crude to chemical conversion ratio in the range of,
and the integration of units and streams attain a very high for instance, up to 80 , 50 or 45 wt % , and in certain
level of integration ofutility streams between the mixed feed 55 embodiments in the range of about 39-45 wt % . In certain
steam cracking and other process units , result in increased embodiments the chemical conversion ratio is at least about
efficiencies and reduced overall operating costs . For 39 wt % , and in certain embodiments in the range of about
instance, the hydrogen can be tightly integrated so that the 39-80 , 39-50 or, 39-45 wt % . It should be appreciated that
net hydrogen demand from outside of the battery limits is this crude to chemicals conversion ratio can vary depending
minimized or even eliminated . In certain embodiments, the 60 on criteria such as feed , selected technology, catalyst selec
overall hydrogen utilization from outside of the battery tion and operating conditions for the individual unit opera
limits is less than about 40 , 30 , 15 , 10 or 5 wt % hydrogen tions .
based on the total hydrogen required by the hydrogen users In some embodiments , individual unit operations can
in the integrated process . Hydrogen is recovered from the include a controller to monitor and adjust the product slate
olefins recovery train , and is supplied to the hydrogen users 65 as desired . A controller can direct parameters within any of
in the system , including the diesel hydrotreater, the gas oil the individual unit operations the apparatus depending upon
hydrotreater, the py - gas hydrotreater, and transalkylation , so the desired operating conditions , which may , for example, be
 US 10,760,011 B2
53 54
based on customer demand and / or market value . A controller Although the computer system is described above by way
can adjust or regulate valves , feeders or pumps associated of example as one type of computer system upon which
with one or more unit operations based upon one or more various aspects of the processes herein can be practiced , it
signals generated by operator data input and / or automati should be appreciated that the invention is not limited to
cally retrieved data . 5 being implemented in software, or on the computer system
Such controllers provide a versatile unit having multiple as exemplarily described . Indeed , rather than implemented
modes of operation, which can respond to multiple inputs to on, for example , a general purpose computer system , the
increase the flexibility of the recovered product. The con controller, or components or subsections thereof, can alter
troller can be implemented using one or more computer natively be implemented as a dedicated system or as a
systems which can be, for example, a general-purpose 10 dedicated programmable logic controller (PLC) or in a
computer. Alternatively, the computer system can include distributed control system . Further, it should be appreciated
specially -programmed , special -purpose hardware , for that one or more features or aspects of the processes can be
example, an application - specific integrated circuit ( ASIC ) or implemented in software , hardware or firmware , or any
controllers intended for a particular unit operation within a combination thereof. For example, one or more segments of
refinery. 15 an algorithm executable by a controller can be performed in
The computer system can include one or more processors separate computers, which in turn , can be in communication
typically connected to one or more memory devices , which through one or more networks.
can comprise , for example, any one or more of a disk drive In some embodiments, one or more sensors and /or flow
memory, a flash memory device, a RAM memory device, or meters can be included at locations throughout the process ,
other device for storing data . The memory is typically used 20 which are in communication with a manual operator or an
for storing programs and data during operation of the automated control system to implement a suitable process
system . For example, the memory can be used for storing modification in a programmable logic controlled process. In
historical data relating to the parameters over a period of one embodiment, a process includes a controller which can
time , as well as operating data. Software , including pro be any suitable programmed or dedicated computer system ,
gramming code that implements embodiments of the inven- 25 PLC , or distributed control system . The flow rates of certain
tion, can be stored on a computer readable and / or writeable product streams can be measured , and flow can be redirected
nonvolatile recording medium , and then typically copied as necessary to meet the requisite product slate .
intomemory wherein it can then be executed by one or more Factors that can result in various adjustments or controls
processors . Such programming code can be written in any of include customer demand of the various hydrocarbon prod
a plurality of programming languages or combinations 30 ucts , market value of the various hydrocarbon products,
thereof. feedstock properties such as API gravity or heteroatom
Components of the computer system can be coupled by content, and product quality ( for instance, gasoline and
one or more interconnection mechanisms, which can include middle distillate indicative properties such as octane number
one or more busses , for instance , between components that for gasoline and cetane number for middle distillates ) .
are integrated within a same device, and/or a network , for 35 The disclosed processes and systems create new outlets
instance, between components that reside on separate dis for direct conversion of crude oil , for instance, light crudes
crete devices . The interconnection mechanism typically such as Arab Extra Light (AXL ) or Arab Light (AL ) crude
enables communications, for instance , data and instructions, oil . Additionally, the disclosed processes and systems offer
to be exchanged between components of the system . novel configurations that, compared to known processes and
The computer system can also include one or more input 40 systems , requires lower capital expenditure relative to con
devices, for example, a keyboard, mouse , trackball, micro ventional approaches of chemical production from fuels or
phone , touch screen , and other man - machine interface refinery by -products and that utilize refining units and an
devices as well as one or more output devices, for example, integrated chemicals complex . The disclosed processes and
a printing device , display screen , or speaker. In addition , the systems substantially increase the proportion of crude oil
computer system can contain one or more interfaces that can 45 that is converted to high purity chemicals that traditionally
connect the computer system to a communication network , command high market prices . Complications resulting from
in addition or as an alternative to the network that can be advancing the threshold of commercially proven process
formed by one or more of the components of the system . capacities are minimized or eliminated using the processes
According to one or more embodiments of the processes and systems described herein .
described herein , the one or more input devices can include 50 The disclosed processes and systems utilize different
sensors and / or flow meters for measuring any one or more commercially proven units arranged in novel configurations.
parameters of the apparatus and/ or unit operations thereof. These novel configurations enable production of refined
Alternatively, one or more of the sensors , flow meters , products and petrochemical products including olefins, aro
pumps , or other components of the apparatus can be con matics , MTBE , and butadiene . The disclosed processes and
nected to a communication network that is operatively 55 systems allow chemicals producers to de -couple from fuel
coupled to the computer system . Any one or more of the markets and have more freedom to increase chemical yields
above can be coupled to another computer system or com as a fraction of crude rate , as compared to traditional
ponent to communicate with the computer system over one chemical production using refinery intermediates or by
or more communication networks . Such a configuration products as feedstock . Also , the disclosed processes and
permits any sensor or signal-generating device to be located 60 systems substantially increase the proportion of crude oil
at a significant distance from the computer system and / or that is converted to high purity chemicals that traditionally
allow any sensor to be located at a significant distance from command high market prices.
any subsystem and / or the controller, while still providing The disclosed processes and systems provide alternatives
data therebetween . Such communication mechanisms can be for chemicals production that have lower capital investment
affected by utilizing any suitable technique including but not 65 relative to conventional routes that utilize refining units and
limited to those utilizing wired networks and / or wireless an integrated chemicals complex . Moreover, the disclosed
networks and protocols. processes and systems offer the flexibility of simultaneously
 US 10,760,011 B2
55 56
producing fuel products and chemical products. The ratio of ing at least a portion of middle distillates from the feed ,
chemicals to residual fuels can be modulated by process and a third ADU fraction comprising atmospheric resi
operations to address changing fuels and chemical market due;
opportunities . In certain embodiments, the process configu a vacuum distillation unit (VDU) operable to receive and
rations are flexible to enable processing of crude oil , such as 5
separate the third ADU fraction , and discharge a first
Arab Light or Arab Extra Light, to provide superior pro VDU fraction comprising vacuum gas oil ;
duction of chemical products, while minimizing the produc
tion of refined fuel products. The configurations offer the a distillate hydroprocessing (DHP) zone operable to
flexibility to structure operations to adjust the ratio of receive and convert middle distillates from the second
petrochemicals to refined products in order to achieve opti- 10 ADU fraction into a first DHP fraction and a second
mum operations and allows shifting the production ratio of DHP fraction , wherein the first DHP fraction comprises
chemicals to fuels, thereby adjusting to market conditions. naphtha and the second DHP fraction is used for diesel
For example, in vacuum gas oil hydroprocessing, as fuel production ;
severity increases, the yield of UCO decreases as the naph
tha yield increases, although for the most part the distillate 15 a gas oil hydrocracking ( GOHCK) zone operable to
yield does change as much because wild naphtha product is receive and treat vacuum gas oil from the first VDU
the result of distillate cracking . The UCO product is chemi fraction and produce a first GOHCK fraction contain
cally restructured through ring opening reactions to become ing naphtha range components, and an unconverted
much more paraffinic in nature , and remains a gas oil boiling fraction ;
range product. By modulating severity of vacuum gas oil 20
hydroprocessing , the shift is between naphtha and UCO a steam cracking zone comprising (a ) a mixed feed steam
relative product rates . The olefin yield of naphtha in the cracking ( MFSC ) zone operable to receive and ther
steam cracker is superior to UCO ; while the heavy product mally crack naphtha from the first ADU fraction and a
yield (mixed C4s and pyrolysis gasoline) from UCO is C6 - C9 non - aromatics raffinate stream derived from an
superior to naphtha. Therefore, a key advantage of modu- 25 aromatics extraction zone, and ( b ) a gas oil steam
lating the vacuum gas oil hydroprocessing conversion is to cracking ( GOSC) zone operable to receive and ther
economically and dynamically address changing market mally crack the unconverted fraction , wherein the
conditions for olefin and aromatic products, which may steam cracking zone is operable to produce a mixed
swing dramatically . product stream containing mixed C1 - C4 paraffins and
Each of the processing units are operated at conditions 30 olefins, a pyrolysis gas stream , and a pyrolysis oil
typical for such units, which conditions can be varied based stream ;
on the type of feed to maximize, within the capability of the
unit's design , the desired products. Desired products can a naphtha hydroprocessing zone operable to receive and
include fractions suitable as feedstock to the mixed feed treat the pyrolysis gas stream and produce a
steam cracking zone 230 or gas oil steam cracking zone 250 , 35 hydrotreated pyrolysis gas stream ; and
or fractions suitable for use as fuel products. Likewise , the aromatics extraction zone operable to receive and
processing units employ appropriate catalyst( s) depending separate the hydrotreated pyrolysis gas stream into one
upon the feed characteristics and the desired products. or more aromatic products streams, and the C6 - C9
Certain embodiments of these operating conditions and non -aromatics raffinate stream .
catalysts are described herein , although it shall be appreci- 40
ated that variations are well known in the art and are within 2. The system as in claim 1 , wherein the MFSC zone is
the capabilities of those skilled in the art. operable to receive and thermally crack naphtha from the
For the purpose of the simplified schematic illustrations first DHP fraction, naphtha from the first GOHCK fraction ,
and descriptions herein , accompanying components that are or both naphtha from the first DHP fraction and naphtha
conventional in crude centers, such as the numerous valves , 45 from the first GOHCK fraction .
temperature sensors , preheater (s ), desalting operation (s ), 3. The system as in claim 1 , wherein the naphtha
and the like are not shown .
In addition , accompanying components that are in con hydrotreating zone is operable to produce a C5s stream , and
ventional hydroprocessing units such as , for example , wherein the MFSC zone is operable to receive and thermally
hydrogen recycle sub -systems, bleed streams, spent catalyst 50 crack the C5s stream .
discharge sub - systems , and catalyst replacement sub -sys 4. The system as in claim 1 , wherein the ADU is further
tems the like are not shown . operable to receive and separate naphtha from the first DHP
Further, accompanying components that are in conven fraction , naphtha from the first GOHCK fraction , or both
tional thermal cracking systems such as steam supplies, coke naphtha from the first DHP fraction and naphtha from the
removal sub -systems, pyrolysis sections , convection sec- 55 first GOHCK fraction .
tions and the like are not shown .
The method and system of the present invention have to 5.separate The system as in claim 1 , wherein the ADU is operable
been described above and in the attached drawings; how that is heaviera further ADU fraction including heavy AGO
than the second ADU fraction and lighter than
ever, modifications will be apparent to those of ordinary skill
in the art and the scope of protection for the invention is to 60 the third ADU fraction, and wherein the GOHCK zone is
operable to receive and convert the further ADU fraction .
be defined by the claims that follow .
The invention claimed is : 6. The system as in claim 1 , wherein the ADU is operable
1. An integrated system for producing petrochemicals and to separate a further ADU fraction including heavy AGO
fuel products comprising: that is heavier than the second ADU fraction and lighter than
an atmospheric distillation unit ( ADU ) operable to receive 65 the third ADU fraction, and wherein the GOSC zone is
and separate a feed, and discharge a first ADU fraction operable to receive and thermally crack the further ADU
comprising naphtha, a second ADU fraction compris fraction .
 US 10,760,011 B2
57 58
7. The system as in claim 1 , wherein the ADU is operable 11. The system as in claim 9 , further comprising a mixed
to separate a further ADU fraction including kerosene that is butanols production zone operable to receive and convert a
heavier than the first ADU fraction and lighter than the mixture of butenes from the C4 distillation unit into a mixed
second ADU fraction , and the system further comprising a butanol product stream .
kerosene sweetening zone operable to receive and treat the 5
further ADU fraction . 12. The system as in claim 9 , wherein the naphtha
8. The system as in claim 7 , wherein the ADU is operable hydrotreating zone is operable to produce a C5s stream , and
to separate a further ADU fraction including heavy AGO further comprising a metathesis reaction zone operable to
that is heavier than the second ADU fraction and lighter than receive and convert all or a portion of the C5s stream into a
the third ADU fraction , and wherein (a ) the GOSC zone is 10 propylene stream , and a C4 /C5 raffinate stream , and wherein
operable to receive and thermally crack the additional ADU the MFSC zone is operable to receive and thermally crack
fraction, or ( b ) the GOHCK zone is operable to receive and the C4 /C5 raffinate stream .
convert the additional ADU fraction .
9. The system as in claim 1 , further comprising: 13. The system as in claim 9 , wherein the naphtha
an olefins recovery train operable to receive and separate hydrotreating zone is operable to produce a C5s stream , and
the mixed product stream into a fuel gas stream , an 15 further comprising a metathesis reaction zone operable to
ethylene stream , a mixed C3s stream , and a mixed C4s receive and convert all or a portion of the C5s stream into a
stream , and propylene stream , and a C4 / C5 raffinate stream ; and a mixed
a C4 distillation unit operable to receive and separate a butanols production zone operable to receive and convert a
portion of C4s recovered from the mixed product
stream into an olefinic stream and a non - olefinic 20 mixture of butenes from the C4 distillation unit into a mixed
stream . butanol product stream and an alkanes stream ; wherein the
10. The system as in claim 9 , wherein the MFSC zone is MFSC zone is operable to receive and thermally crack the
operable to receive and thermally crack the non - olefinic non -olefinic stream and the C4 /C5 raffinate stream .
stream .