Efficient Ammonia Production
Jim Gosnell
13 October 2005
Hydrogen Conference
Argonne National Laboratory
Topics to be Covered
Overview of KBR Activities
Ammonia Supply & Demand
History of Ammonia Manufacture
Ammonia Plant Market Trends
Current Manufacturing Technology
Ammonia from Renewable Energy
Summary
Organization
Halliburton Company
Energy Services Group
Engineering & Construction
(Energy Services)
Overview
Organization (Contd)
Energy & Chemicals
Division
Process Technology
Development
Licensing
Engineering
Procurement
Construction
Operations
Maintenance
Government &
Infrastructure Division
CFO
Legal
Largest
government
logistics & services
contractor with
premier worldwide
civil infrastructure
capabilities
Administration
KBR Energy & Chemicals Operations
Edmonton
Baku
Aberdeen
Greenford
Calgary
Leatherhead
Algiers
Yokohama
Houston
Singapore
Monterrey
Indonesia
Muscat
Cairo
Doha
Perth
Rio de Janeiro
Johannesburg
= Operating/Execution Centers
= Joint Venture Alliances
Jakarta
KBR E&C Business Lines
Gas Monetization
Oil & Gas
Petrochemicals
Refining
Syngas
Overview of Syngas Markets
Methanol
Hydrogen
GTL
Urea
Ammonia
Other
Fertilizers
Topics to be Covered
Overview of KBR Activities
Ammonia Supply & Demand
History of Ammonia Manufacture
Ammonia Plant Market Trends
Current Manufacturing Technology
Ammonia from Renewable Energy
Summary
Demand for Basic Chemicals-2004
Millions MT/Year
Sulfuric acid
Ammonia
Urea
Ethylene
Chlorine
Soda
Methanol
167
142
121
105
50
43
35
Sources: Purvin & Gurtz, SFA Pacific, Fertecon.
Ammonia Uses
Fertilizers
82%
Other Uses
18%
explosives
fibers
resins
animal feed
World Arable Land
Source: SRI
1,600
M illions of hectares
1,400
1,200
Rest of World
Southwest Asia
Socialist Asia
FSU
Europe
North America
1,000
800
600
400
200
0
1980
1990
2000
World Population
8,000
Average Annual Growth Rate = 1.35%
7,000
Millions
6,000
5,000
4,000
3,000
2,000
1,000
0
1980
Industrialized
1990
2000
EE & FSU
China
Source: EIA
2010
India
2020
Rest of World
World Ammonia Capacity
(Source Fertecon)
195
MILLIONS of MT/YEAR
185
175
Average annual growth:
2000-2010 = 1.6%/year
165
2005-2010 = 2.2%/year
155
For 2005-2010 this equates to
5 to 6 new plants/year @ 2000 mt/d
145
135
125
2000
2001
2002
2003
2004
2005
YEAR
2006
2007
2008
2009
2010
World Ammonia Capacity & Demand
(Source-Fertecon)
195
MILLIONS of MT/YEAR
185
Installed Capacity
175
Capacity
165
155
Demand
145
Demand
135
125
2000
2001
2002
2003
2004
2005
YEAR
2006
2007
2008
2009
2010
Implications of Capacity/Demand Curves
Required plant availabilities to satisfy anticipated
demand are in the range of 80 to 85%
Industry is capable of plant availabilities in the
range of 91-92%
This means ~40,000 mt/day of capacity is idle.
Much of this idle capacity is in:
United States
Eastern Europe
Outlook is for continued rationalization of high
cost producers & shift to low gas-cost regions
Ammonia Plant Capacity by Region
13%
14%
12%
46%
3%
5%
7%
ASIA
China
India
Indonesia
All other
27%
8%
4%
7%
Trends in World Ammonia Exports
(Percent of World Production)
14.0%
PERCENT EXPORTED
13.5%
13.0%
12.5%
75% of new capacity in next few years
is aimed at the export market.
12.0%
11.5%
11.0%
2000
2001
2002
2003
2004
2005
YEAR
2006
2007
2008
2009
2010
Net World Ammonia Trade in MM MT/Year
(Plus=export, minus=import)
+4.9
-2.9
-5.4
-1.5
-0.1
+1.1
+3.9
Total trade in 2004 = 17.9 mt
(Fertecon)
Net trade in 2004 = 9.9 mt (Estimate)
Historical US Gulf Coast NH3 Prices
(Fertecon, current dollars)
500
450
US$/tonne fob, Quarterly range
New capacity in Trinidad &
Qatar, increased production
in Algeria
Oil price shock due to
Yom Kippur War/OPEC embargoes
400
350
300
250
1 mill t increase in US imports
in 1994/ increase in Ukrainian
gas costs
Fertrin plants o/s
in Trinidad 1981/2
Extreme volatility in
US gas prices
PCS closes
Trinidad capacity
due to lack of gas
price agreement
fall in European fertilizer
demand / new units in
Belgium and Turkey
displacing imports
200
Oil prices fall
150
100
Bahrain plant o/s 1985
50
0
new Saudi plant o/s
1987
FSU gas prices in $ terms
India cuts NH3 imports collapse w ith Rouble devaluation
70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 0 1 2 3 4
Predicted US Gulf Coast NH3 Prices
(Fertecon, current dollars)
Current $/tonne
300
250
Price cfr Tampa/USG
200
150
100
Supply Cost fob USG plant
50
0
1995
Forecasts assume base case US gas prices
2000
2005
2010
Topics to be Covered
Overview of KBR Activities
Ammonia Supply & Demand
History of Ammonia Manufacture
Ammonia Plant Market Trends
Current Manufacturing Technology
Ammonia from Renewable Energy
Summary
History of Ammonia Manufacture
Ammonia is synthesized from hydrogen
and nitrogen
3H2 + N2
2NH3
Nitrogen source is always air
Hydrogen source has varied over the years
Discovery of Hydrogen
Described by Robert Boyle in 1671
Fe + H2SO4
FeSO4 + H2
Recognized as an element in 1766 by Henry
Cavendish
Named by Antoine Lavoisier in 1783 after he
discovered its ability to generate water
2H2 + O2
2 H2 O
History of Hydrogen Production
First commercial production in early 19th
century making town gas from coal
Coal + H2 O
H2 + CO + CH4
In early 20th century, coke and coal were
gasified with either air or oxygen to produce H2
+ CO mixtures for chemical synthesis
First steam-methane reformer on-line in 1931
CH4 + H2 O
3H2 + CO
Hydrogen Sources for Making Ammonia
Process
Reaction
Approximate
Relative
Energy
Consumption
Water electrolysis
2H2O 2H2 + O2
300%
Coal gasification
C + 2H2O 2H2 + CO2
170%
Heavy fuel oil
CH + 2H2O 2 H2 + CO2
135%
Naphtha reforming
CH2 + 2H2O 3H2 + CO2
104%
Nat. gas reforming
CH4 + 2H2O 4H2 + CO2
100%
History of Ammonia Manufacture
Ammonia consists of hydrogen & nitrogen
First equilibrium test by Haber
Haber patent
Catalyst program by Haber & BASF
Equipment program begun by Bosch at BASF
First commercial plant - 30 mt/d at BASF
World capacity reaches 2000 mt/d
World capacity reaches 450,000 mt/d
YEAR
1784
1904
1908
1908 - 1922
1910
1914
1927
2005
19
20
19
30
19
40
19
50
19
60
19
70
19
80
19
90
20
00
20
10
20
20
20
30
20
40
20
50
Population (Billions)
10
9
8
7
6
5
4
3
2
1
0
300
250
200
``
Year
150
100
50
Million Tons/Year of N2
World Population & NH3 Production Trends
Topics to be Covered
Overview of KBR Activities
Ammonia Supply & Demand
History of Ammonia Manufacture
Ammonia Plant Market Trends
Current Manufacturing Technology
Ammonia from Renewable Energy
Summary
Market Situation Old Plants
Older plants often struggle to remain competitive
Old technology which is less efficient
Located in high gas cost area
Smaller capacities
Energy efficiency revamps have already taken
place
Many operators debottleneck existing capacity to
improve economy of scale
New Plant Trends in Energy Consumption
11
Gcal/mt - LHV
10
9
8
7
6
5
THEORETICAL MINIMUM
1940
1950 1960
1970
1980
1990
2000
Ammonia Plant New Capacity by Region
14
Projects shift to ME and LA where gas is available at
lower cost and to APAC (higher consumption growth)
Thousand MTPD
12
10
Source: KBR
LA
ME
IN - AF
APAC
Europe
NA
8
6
4
2
0
85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04
Year of Award
Average Capacity Built by Decade
KBR Licensed Plants
M etric Tons/Day
2000
1500
1000
500
0
1950s
1960s
1970s
1980s
1990s
2000s
History of Maximum Size NH3 Plants
5000
2X?
4000
3000
MT/D
2000
1000
2X
2X
0
1960 1965
1970 1975
1980 1985 1990 1995
Year
2000
2005
Indicative Capital Cost
(Assumes 0.7 exponent)
Relative $/MT
100%
90%
80%
70%
60%
1
1.5
2.5
Capacity Factor
3.5
Trends in Maximum Capacity
All licensors are now claiming that they can
design single-train plants for >3000 mt/day
KBR has a 2200 mt/day plant under
construction in Australia
KBR is willing to offer and guarantee a
single-train 4000 mt/day plant
KBR internal studies have shown that a
single train capacity of 5000 mt/day is
possible
Market Implications Capacity Trend
There will be fewer projects
Large amounts of ammonia (& urea) will
suddenly come on the market
Projects will require more capital, leading to
increased industry partnering to share risks
These mega-capacity projects will be in low
gas cost areas
Market Implications (Continued)
These mega-capacity plants will be located at
coastal sites
There will be some logistics issues moving
large volumes of product
Plants that are older, smaller, and in locations
with high feed costs will continue to shut down
Topics to be Covered
Overview of KBR Activities
Ammonia Supply & Demand
History of Ammonia Manufacture
Ammonia Plant Market Trends
Current Manufacturing Technology
Ammonia from Renewable Energy
Summary
Sections in an Ammonia Plant
Process Air
Carbon
Dioxide
Natural
Feed
Gas
Treatment
Feed
Syngas
Production
Syngas
Purification
Synthesis
Loop
Ammonia
Condensate
Steam
Steam & Water
System
Make-up
Water
Chemistry of Syngas Production
Process
Chemical Reaction
Favorable
Conditions
Primary Reforming
heat + CH4 + H2O 3H2 + CO
High temp &
High stm/carbon
Secondary
Reforming
O2 + 2H2 2H2O + heat
heat + CH4 + H2O 3H2 + CO
High temp &
High stm/carbon
High temp shift
CO + H2O CO2 + H2 + heat
Low temperature
High steam/CO
Low temp shift
CO + H2O CO2 + H2 + heat
Low temperature
High steam/CO
Engineering of Syngas Production
Process
Equipment
Features
Primary Reforming
Catalyst-packed tubes in a
furnace
Nickel catalyst
Secondary Reforming
Refractory-lined pressure
vessel
Nickel catalyst
High temp shift
Low temp shift
Pressure vessel
Iron-chrome
catalyst
Pressure vessel
Copper-zinc
catalyst
Primary Reforming
Fuel
Air to Secondary Reformer
To Feed
Treatment
Feed
Air
Reformer
Outlet
700
oC
BFW
Steam
ID Fan
Mixed Feed
Superheated Steam
Secondary Reforming
Excess Air
Primary
Reformer
Effluent
700 oC
100-125 bar
Steam
870 oC
BFW
To High
Temperature
Shift Reactor
Primary & Secondary Reformers
Primary Reformer with Gas Turbine
Shift Conversion
Syngas 370 C
from
Boiler
200 C
Low
Temperature
Shift Reactor
High
Temperature
Shift Reactor
430 C
240 C
Shifted
Syngas
to CO2
Removal
Separator
35 C
BFW Heating &
Steam Generation
Water
Cooler
Process
Cond.
Chemistry of Syngas Purification
Process
Description
CO2
Removal
Physical Dissolution
or Chemical Reaction
Methanation
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O
Drying
Physical Adsorption to
remove water & CO2
Cryogenic
Purification
Separation of argon,
residual CH4 and excess
N2 from syngas
Favorable
Conditions
Low temp &
High pressure
280 - 350C
2 - 4 C
-180 C
Engineering of Syngas Purification
Process
CO2
Removal
Equipment
Features
Absorb/regen
Contact syngas with
columns with solution solution over packing
circulation pumps
Methanation Pressure vessel
Nickel catalyst
Drying
Two pressure vessels Cyclic operation of mol
sieve desiccant
each with a filter
Cryogenic
Purification
Plate fin exchanger,
expander, column
Aluminum, generator
brake, trays, set H/N =
3.0
Syngas Purification
CO2
Regenerator
CO2
Dryers
CO2 Methanator
Absorber
Pure, Dry
Syngas to
Compressor
CW
Raw
Syngas
from
Shift
Process
Condensate
to Stripper
Cryogenic
Purifier Waste Gas
to Fuel
NH3
Synloop
Purge
KBR Cryogenic Purifier
Waste
Gas to
Fuel
Syngas to
2 C Compresso
2C
-182 C
Syngas
from
Dryers
H2
N2
CH4
A
4C
Vol%
62-68
30-35
2-3
~0.6
H2/N2 = 3
Inert <0.3%
CO2 Removal System
1500 t/d plant in China
KBR Cryogenic Purifier
1850 t/d plant in Holland
Chemistry of Ammonia Synloops
Process
Description
Favorable
Conditions
Synthesis
3H2 + N2 2NH3 + heat
Low T & high P
Heat
Recovery
Generate 100 bar+ steam
High T
Product
Recovery
Condense via refrigeration
Low T & High P
Engineering of Ammonia Synthesis
Process
Equipment
Features
Synthesis
Catalyst filled pressure
vessel
P = 90 175 bar
T = 400 - 500 C
Heat
Recovery
Shell & tube heat
exchanger
Proprietary
design
Product
Recovery
Compression
refrigeration system
Ammonia as the
refrigerant
Ammonia Synthesis Loop
Synloop Purge
Syngas
from
Purifier
2C
31.6 bar-a
93 bar-a
Steam
& BFW
Let Down
Drum
HP BFW
-18 C
Ammonia
Reactor
Unitized
Chiller
CW
Refrigeration System
Condenser
Refrigeration
Compressor
Ammonia
Accumulator
NH3
from
Letdown
Drum
HP Case
LP Case
-33 C
0 bar-g
Unitized Chiller
Warm NH3
Cold
NH3
Single-case Synthesis Gas Compressor
Ammonia Converter
KAAP Catalyst
Topics to be Covered
Overview of KBR Activities
Ammonia Supply & Demand
History of Ammonia Manufacture
Ammonia Plant Market Trends
Current Manufacturing Technology
Ammonia from Renewable Energy
Summary
Ammonia from Water Electrolysis
Conceptual Process Scheme
O2 & A
Air
Circulation
& Refrigeration
Compressors
Air
Sep
Unit
N2
Ammonia Ammonia
Synthesis
Loop
Air Compressor
Water
Elect.
Cells
100 bar-g
H2
O2
Material Balance
(tons/ton of ammonia assumes no losses)
IN
Air
1.09
Water
1.59
OUT
Ammonia
1.00
Oxygen
Argon
1.67
0.01
TOTAL
2.68
2.68
Electric Power Input to Process
kWh/MT of NH3
Compressors
390
Pump
Electrolytic cells
TOTAL
8
7000 9000 (1)
~7400 9400
(1) Based on 3.5 4.5 kWh/Nm3 of H2
Approx. Energy Consumption of Process
GCal/MT of NH3
Electricity @ 860 kcal/kWh
Heat recovery from loop
TOTAL
(1) Based on 3.5 4.5 kWh/Nm3 of H2
6.4 8.1(1)
-0.6
5.8 7.5
Approx. Energy Consumption (Contd)
Gcal/Metric Ton NH3
860 kcal/kWh
2150 kcal/kWh(2)
Electricity (1)
6.4
16.0
Heat recovery
-0.6
-0.6
TOTAL
5.8
15.4
(1) Based on 3.5 kWh/Nm3 of H2
(2) Conversion of primary energy to electricity at 40% efficiency.
Approx. Variable Operating Cost
$/MT of NH3
Electricity @ $0.035/kWh
$259 (1)
Water @ $5/1000 gallons
By-product O2 @ $25/t
Heat recovery @ $40/Gcal
2
-42
-24
TOTAL
(1) Based on 3.5 kWh/Nm3 of H2
$195
NH3 as Auto Fuel Supply & Demand
Daily WORLD ammonia capacity
Is about 450,000 tons
Corresponds to about 8 x 106 million Btu
Daily US demand for gasoline
Is about 9 x 106 barrels(1)
Corresponds to about 47 x 106 million Btu
(1) US DOE, EIA
Ammonia as Auto Fuel
Fuel Price Comparison
NH3 @ $400/mt = $23/mm Btu
Gasoline @ $3/gal = $24/mm Btu
Ammonia Storage Issues
Boiling point @ 14.7 psia is minus 28 F
Storage requires either
Refrigeration at atmospheric pressure
Pressurization to ~ 20 atmospheres
Implications for NH3 as Auto Fuel
US gasoline demand is about six times the worlds
installed ammonia capacity
Ammonia via electrolysis with power @ $0.035/kWh may
be competitive at todays ammonia prices
To satisfy 10% of US gasoline market with NH3 via
electrolysis requires ~ 80,000 to 100,000 MW, depending
on assumed efficiency of electrolytic cells
Installed US electric power plant capacity (2000) is about:
605,000 MW for utility owned
210,000 MW for non-utility owned
There will be some ammonia storage issues
Topics to be Covered
Overview of KBR Activities
Ammonia Supply & Demand
History of Ammonia Manufacture
Ammonia Plant Market Trends
Current Manufacturing Technology
Ammonia from Renewable Energy
Summary
1970s a decade
of rapid capacity
expansion
40%
35%
30%
25%
20%
15%
10%
5%
0%
Gcal/mt - LHV
Percent of Plants by D ecade
Ammonia Technology Summary
1950s
1960s
1970s
1980s
1990s
THEORETICAL MINIMUM
2000s
1980s a decade
of reduced energy
consumption
Ammonia Market Summary
14
Thousand MTPD
12
10
LA
ME
IN - AF
APAC
Europe
NA
8
6
4
2
1990s a decade
of moving
projects to low
gas cost areas
85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04
Year of Award
Metric Tons/Day
2000
2000s a decade
of increased
plant capacities
1500
1000
500
0
1950s
1960s
1970s
1980s
1990s
2000s
Ammonia Market Summary (Contd)
195
MILLIONS of MT/YEAR
185
175
165
155
145
135
125
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
YEAR
A lot of capacity will come on line in next four years
This will drive ammonia prices down towards their historic average
of about $150/mt
Which will cause further capacity rationalization in high gas cost
areas
Ammonia via Electrolysis
Technically feasible but current technology(1) limits:
Cells at 100 bar to ~3600 kg/year of hydrogen
Cells at 1 bar to ~380,000 kg/year of hydrogen
Capital cost issues
Capital cost of scheme has not been estimated
Do electrolytic cells have economy of scale?
Operating cost issues
Requires very cheap power to be competitive
Reliability of cells may be an issue
(1) NREL Report, Sept 2004
Ammonia as Auto Fuel - Issues
To meet 10% of US gasoline demand from NH3 via
electrolysis will consume about:
80,000-100,000 MW of electric power @ 3.5 kWh/Nm3 of H2
Ammonia equivalent to 60% of world capacity
Ammonia is classified as a toxic chemical
Ammonia Handling
Distribution
Storage
Transfer to vehicle tank
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