Dr.
Ulrich Daiminger
Engelhard & Natural Gas
Engelhard Corporation
A surface and materials science company
that develops technologies to improve
customers’ products and processes
Engelhard Corporation
Core Surface
Materials
Competencies Chemistry
Science
Kaolin Size Platinum Thermal Stability
Alumina Shape Palladium Acidity
Silica Hardness Charge
Mica Porosity Rhodium Transparency
Zeolites Pore Size Cobalt Activity
Hydrophobicity Gloss
Nickel
Titanium
Specialized
Engineered
Chemical
Materials
Formulations
Engelhard Corporation
Engineered Specialized
Materials Chemical
Formulations
Markets
Automotive • Petrochemical • Agriculture • Oil Refining • Fine Chemicals • Paper
Plastics • Cosmetics • Air Quality • Construction • Packaging • Coatings
Engelhard around the world
• 6,420 People
• More than 100 locations
• 2000 Sales: $5.5 Billion
• 2000 Earnings: $247 Million
Products & Processes in the Natural Gas Markets
• Reaction (catalysts)
– Fischer-Tropsch (Gas-to-Liquids)
– Hydrogenation catalysts
– ......
• Separation (adsorption)
– Nitrogen rejection (Molecular GatesTM)
– CO2 rejection (Molecluar GatesTM)
– LNG mol sieve protection (Sorbead®)
– (acid gas) dehydration (Sorbead®)
– Hydrocarbon recovery units (SordecoTM, Sorbead)
Molecular GatesTM: Separations
• N2 Rejection
Deliverable
• CO2 Removal
• N2 & NGL
• CO2 & NGL
• Argon Purification
• Claus HC
• H2S enrichment
• C2/C2=
• Air Separation
Theoretical
• Xylenes Separation
Molecular GatesTM: Process Fundamentals
• PSA (pressure swing adsorption)
• size exclusion
C 3.8 A
C N N
N
N 3.6 A
C C
Molecular GatesTM: unique pore size control
4.2
CH3OH
largest molecule
4 C2H6
adsorbed
C2H4 CO
CH4
3.8 Ar
N2
Pore diameter, Å
3.6
O2
3.4
CO2
3.2
H2
2.8
effective sizes taken from Breck, D.W. Zeolite Molecular Sieves, 1974.
H2O
2.6
200 220 240 260 280 300 320 340 360 380
Temperature, °C
Molecular GatesTM: N2 rejection / market
40
Composition 30
Cryogenics
(% N2)
20 Molecular
Gate
10
0
0 20 40 60 80
Capacity
(MMSCFD)
Molecular GatesTM: N2 rejection / basic flow sheet
Enriched CH4 C1,C2,C3
1.3 - 3.0 bar a 1 bar pressure drop
PRODUCT
FEED
8 -55 bar
PSA
N2
C1
C2
0.5 bar a 1.3 bar a
C3
C4+ TAIL GAS
CO2 N2, C4+
H2O CO2, H2O
Lost HCs
Molecular GatesTM: N2 rejection / Hamilton Creek unit
• located in
SW Colorado
• operation un-attended
• 9-bed PSA
• skid-mounted
• feed:
– 18% N2
– 0.2 MM SCFD
• product
– 3-6% N2
Molecular GatesTM: N2 rejection / experience
Hamilton Creek On-Stream Factors - 99% Availability
100%
• reasons for
90%
down-time
80%
– electronics
70%
60% – compressor
50% – valves
40% – ...
30%
20%
10%
0%
22-Sep22-Oct21-Nov21-Dec20-Jan19-Feb21-Mar20-Apr20-May19-Jun19-Jul18-Aug17-Sep17-Oct
Molecular Gates: CO2 removal
• same basic principle / different adsorbent
• first commercial unit to commissioned May, 2002
– Tidelands, CA
• cost lower/comparable to traditional amine- + glycol-units and:
– no amines
– ease of operation
– modular installation possible
– no eco-concerns (amines, glycol)
Tidelands, CA
– Tidelands, CA
– 1 MM SCFD
– CO2in: 18%,
CO2out < 1%
– 3 vessel design
Sorbead® - overview
• Applications
– protection layer
– (acid gas) dehydration
– Hydrocarbon dew-pointing
• Principle
– preferred adsorption
– TSA (Temperature swing
adsorption)
• references
– 200+
Protection layer: Sorbead® WS
• Properties
– water stable (WS)
– adsorption capacity
• Use
– protection (buffer layer) against
liquid water carry over in: Sorbead® WS
– LNG mol sieve units
– HRU units
• references (not comprehensive)
– LNG Bonny Island, Nigeria
– Woodside Energies, Australia
water carry-over
• water carry-over leads to:
– „high“ water concentrations
– high local heat of adsorption
– high local temperatures
– shattering of beads
• consequences
– channeling / poor flow distribution
– high ∆P
– increased dew point
– decreased capacity
• solution
– Sorbead® WS
competitive analysis: water stable silica gel
Sbd WS PRC • Sorbead® WS manufactured using
Form Beads Beads unique process that imparts water
TReg for 16h °C 160 160
stability
Surface
m²/g 650 244
Area
VP cm³/g 0,40 0,60 • Competition uses heat treatment
dP nm 2,70 9,00 which destroys micro and meso
Crush Strength N 100 < 100 N
Waterstability % 100 100 pores, surface area and adsorption
Bulk Density g/l 0,70 0,50 capacity
Attrition % 0,02 0,15
Water isotherm
25°C
• Sorbead® WS contributes to
10% r.H % 4,9 2,0
20% r.H. % 8,2 3,0 adsorption, competitive products
40% r.H. % 18,0 4,3 relatively inert (like support balls),
60% r.H. % 29,0 6,4
80% r.H. % 34,0 10,0 therefore higher costs
Sorbead®: experience at work
• production of Sorbead® started 1952
in Nienburg, Germany
(according to Mobil license)
• continuous process improvements
and product developments
• plant certified according to DIN ISO
14000 and QS9000 (necessary for
automotive industry)
glycol carry over
• glycol carry over from glycol drying unit
(TEG) can lead to:
– fouling/clogging of down-stream heat-
exchanger in cryogenic gas separation
– degradation of down-stream mol sieve
• consequences
– downtime (lost capacity)
– higher OPEX
• solution
– AF125 (wide porous)
(Acid gas) Dehydration
• When to use:
– acid gas: commercial experience
up to 12% H2S (Sulphur River, Tx)
– under ground storage
• What to use
– Sorbead H / Sorbead+
– protective layer WS
Sorbead H
(Acid gas) Dehydration: generic flow sheet
Feed Cooling Gas Bypass
Gas
Regen Gas
2
1
A B
4 Air Cooler
F After Filter
3 Heater
Fuelgas Sales Gas
7 Stock Tank 6 LP-Separator 5 HP-Separator
Hydrocarbon recovery units (HRU)
• similar to dehydration
• adsorbent: Sorbead H
• SordecoTM technology
HRU: principle
Flow Direction
C4 C5 C6+ H2O
C3 C4 C5 C6+
H2O
C2 C3 C4 C5
C6+
Length of Cycle
HRU: experience
• 200+ references
• membrane protection, peak-shaving units (UGS),
pipeline spec.
• life times 10+ years observed
• performance /
main factors for deteriorating performance
and effecting life time
• many different (tower) designs known
• loading (own loading team, world wide) / start-up
• trouble shooting
• sampling
HRU case study: Grissik (I)
• location: Grissik, Indonesia / capacity: 300 MMSCFD / 30% CO2
• original set-up:
inlet sep. → membrane CO2 sep. → MDEA → TEG → sales gas
• problem:
membrane capacity down to 10% after 3 month (expected 3 years)
• source of problem: 200-300 ppmv heavy hydrocarbons
• solution: short cycle HRU with Sorbead® H before membrane unit
(2 trains; each 4 vessels)
• result: total removal of aromatics and C9+
• membrane operation: now better than expected, no deterioration in first year
• total cost: US$12MM (extremely short pay back time)
HRU case study: Grissik (II)
Company: Gulf Resources Indonesia
Location: South Sumatra
Start-up: May 2000
Application: Hydrocarbon Removal / Membrane Protection
Design Flow rate: 460 MM SCFD (230 MM SCFD per train)
Estimated lifetime: 4 Years
Total cost: $12MM
competitive analysis (I)
• Majority of competitive beaded silica gel originates in PRC; QC poor/limited.
• Low class heritage; manufactured in same plants used to produce kitty litter;
first used in the packaging industry
• Manufacturer near zero knowledge of end use markets.
• Limited commercial experience in dynamic markets.
• Protection layer:
Obtain water stability by heat treatment; results in very poor adsorption
properties.
Sorbead® H vs competition: surface area
TP-H competition (best) Tendency Tendency
Adsorption w ith moist air, regeneration w ith moist air at 300°C
800
600
BET- surface area / m²/g
400
200
0
Start 10 Cycles 20 Cycles 60 Cycles 80 Cycles 100 Cycles 120 Cycles
Sorbead® H vs competition: pore volume
TP-H competion (best) Tendency tedency
Adsorption with moist air, regeneration with moist air at 300°C
0,60
0,50
Pore volume / ml/g
0,40
0,30
0,20
0,10
0,00
Start 10 Cycles 20 Cycles 60 Cycles 80 Cycles 100 120
Cycles Cycles
references
• Sorbead® units: market share > 90% • track record of competitive failures
(not comprehensive):
Country No of units Total installed – OxyPermian, Sundown, Tx
Total mtons
Netherlands 10 1,887 (membrane protection)
Great Britain 4 582
USA 57 2,138 – Amoco, Whiting (LPG)
Middle East 8 919
Italy 8 56 – Duke Energy, Peggo, Canada
Canada 79 1,162
Germany 4 112 (HRU)
North Africa 10 25
Egypt 1 96 – BP Amoco, Wapiti South B,
Bangladesh 11 246
Thailand 1 100
Canada (HRU)
Argentina 6 139
CIS 1 495 – Centrica, N. Morecambe (HRU)
Indonesia 1 140
Total 201 8,098
SordecoTM: motivation
• external:
– ever more requests for performance guarantees
– ever more detailed studies requested
– more agressive design requested
• internal
– recognition that certain features of then-used models resulted in
faulty designs
SordecoTM alliance
Shell Global Solutions
•operation experience
•most experience
•design capabilities
•best adsorbent
•testing facilities
SORDECOTM
investment: > US$1 MM
SordecoTM package: added value
• advantages of a Sordeco license
– high reliability
– performance guarantees (dew point, pressure drop)
– full support in design phase (optimisation) / best design tools
– review of final design
– mobile adsorption unit available for on-spot investigations
• Sordeco does not imply or request
– use of any other Shell (or Engelhard) technologies or standards
– clocking man-hours for changes
SordecoTM: the workings
• ideal process
1. inital contact/new project
2. EC determines feasibilty and submits cost estimate for SordecoTM,
HRU-unit (FOB basis, indicative ±30%)
3. if still interested customer signs „Secrecy and restricted use
agreement“
4. design basics and active support from EC (fee)
5. closing of license agreement (license fee) incl. performance guarantee
if project is to be realised (continuing support, review of design)
6. trouble free start-up and operation
SordecoTM case study – basics/specs
• No. of units: 4
• Flow rate: min. 187,500 Nm3/h
max. 625,000 Nm3/h
• Temp. min. 45°C
norm. 50°C
max. 55°C
• Pressure min. 70 bara
max. 86 bara
• Gas composition: as given
• dewpoint: as specified
SordecoTM case study – first results
• spec. dewpoint can be reached with SordecoTM unit at all temperatures
• water content in effluent < 0.2mol% (reduced corrosion!)
• design temperature influences overall costs heavily
120
110
TIC
vessel dimensions [%]
100 Di h
% 40°C 94 79
90 45°C 94 93
50°C 100 100
80
55°C 102 110
70
40°C 45°C 50°C 55°C
