Commercialization of Nitrogen- Rich Natural Reservoirs Albert Bradley Curtis S. Monique Wess Miguel...
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Transcript of Commercialization of Nitrogen- Rich Natural Reservoirs Albert Bradley Curtis S. Monique Wess Miguel...
Commercialization of Nitrogen-Rich Natural Reservoirs
Albert Bradley CurtisS. Monique Wess
Miguel Bagajewicz
OverviewBackground
Goals
Superstructure of Process
Process Descriptions
Mathematical Model
Results
Conclusions
2
Background
Background
• Natural gas is one of the most vital sources of energy in U.S.
• It is made up of primarily of methane and significant quantities of heavier hydrocarbons
• Several contaminants are common (CO2, N2, H2S)
• Advantages over other fuel types: Lower capital cost, higher efficiency, lower air pollutant emissions
4
Background
• Low quality natural gas (LQNG) has one or more impurities that prevent it from being put into a pipeline without going through a pretreatment process
• Approximately 30% of known reserves contain LQNG– Lower heating value– Corrodes pipe lines– Lower Wobbe index – interchangeability of fuel types
5
Background
• Most popular contaminants– Carbon Dioxide > 2%– Nitrogen > 4%– Hydrogen Sulfide > 4ppm– Water
• Minor contaminants include– Helium– Argon– Hydrogen– oxygen
57%33%
10%
Top Contaminants of LQNG Reserves
Nitrogen Content Carbon Diox-ide ContentOther Con-tamininants
6
This Work Objective
Perform an economic analysis on the feasibility of production and commercialization of LQNG
7
Superstructure of Processes
9
Low Quality Natural Gas Reservoir
Boiler
Steam Turbine
Central Utility Plant Usage
Sold in Market
Low Quality Natural Gas
Steam
Electricity
Electricity
Power Generation Process Flow
----- Steam----- Electricity LQNG
*All intermediates can be used in other processes or sold in market
Low Quality Natural Gas Reservoir
Boiler
Steam Turbine
Central Utility Plant Usage
Sold in Market
Steam Reforming
Water Gas Shift
Haber-Bosch
Bosch-Meiser
Methanol Synthesis
Methanol Oxidation
Carbonylation
Dehydration
Fischer-Tropsch
Power Generation and Synthesis Gas Process Flow
----- Steam----- Electricity----- Hydrogen Ammonia Nitrogen Product Streams
*All intermediates can be used in other processes or sold in market
Low Quality Natural Gas
Low Quality Natural Gas
Steam
Electricity
Electricity
Synthesis Gas
Synthesis Gas
Synthesis Gas
Hydrogen
Methanol
Ammonia Urea
Formaldehyde
Acetic Acid
Dimethly Ether
Diesel and Naphtha
Nitrogen Plant
Oxygen
Molecular Gate Pressure Swing Adsorption
Bosch-Meiser
Bosch-Meiser
Methanol Oxidation
Boiler
Central Utility Plant Usage
Steam Reforming
Diesel and Naphtha
Low Quality Natural Gas
Low Quality Natural Gas
Low Quality Natural Gas
Methanol
Steam
Pipeline Quality Natural Gas
Synthesis Gas
Hydrogen
Ammonia
Ammonia
Synthesis Gas
Synthesis Gas
Electricity
Electricity
Synthesis Gas
Synthesis Gas
Synthesis Gas
Ammonia
Methanol
Urea
Urea
Urea
Formaldehyde
Formaldehyde
Acetic Acid
Acetic Acid
Dimethly Ether
Dimethly Ether
Diesel and Naphtha
Methane/Nitrogen Stream mixture
Power Generation and Synthesis Gas Process Flow
----- Steam----- Electricity----- Hydrogen Ammonia Nitrogen ----- Nitrogen rich
stream Product streams*All intermediates can be used in other processes or sold in market
Nitrogen Plant
Oxygen
CostsProcess Method of
SeparationApplication Total Capital Cost
($/Mscfd)*Operating Cost ($/Mscf)*
Cryogenic Distillation
Distillation at cryogenic
temperaturesHigh flow
rates $1184 $ 1.30
Pressure Swing
AdsorptionAdsorption of
methane
Small to Medium flow
rates$1320 $1.65
Lean Oil Absorption
Absorption of methane in chilled
hydrocarbon oilHigh Nitrogen
Content N/A $3.35
MembranesMethane moves
faster though barrier
Low flow rates $277 $.30
Molecular Gate PSA
Adsorption of nitrogen in solvent
High Nitrogen Content $226 $.16
12
PSA
• Engelhard Corporation’s Molecular Gate PSA– Traps nitrogen while letting methane flow through
at high pressure– Capable of reducing nitrogen content from 30% to
4%.– Adsorbent material is titanium silicate (CTS-1)
designed with a pore size of 3.7 Ao
13
Molecular Gate Adsorber
• Operates at pressure levels between 100 – 800 psia• Uses a series of 3-9 fixed bed adsorber vessels• Methane rich steam that is recycled to increase the
methane recovery• Spent vessel is depressurized to produce a nitrogen
rich low pressure fuel stream.
14
Synthesis Gas Production
• Syngas consists primarily of carbon monoxide, carbon dioxide, and hydrogen
• Synthesis gas can be generated by steam reforming of methane.
• We considered steam reforming with and without nitrogen removal to investigate the impact of additional processing and reactor size
• Used as fuel source or intermediate for production of other chemicals
15
Molecular Gate Pressure Swing Adsorption
Bosch-Meiser
Bosch-Meiser
Methanol Oxidation
Boiler
Central Utility Plant Usage
Steam Reforming
Diesel and Naphtha
Low Quality Natural Gas
Low Quality Natural Gas
Low Quality Natural Gas
Methanol
Steam
Pipeline Quality Natural Gas
Synthesis Gas
Hydrogen
Ammonia
Ammonia
Synthesis Gas
Synthesis Gas
Electricity
Electricity
Synthesis Gas
Synthesis Gas
Synthesis Gas
Ammonia
Methanol
Urea
Urea
Urea
Formaldehyde
Formaldehyde
Acetic Acid
Acetic Acid
Dimethly Ether
Dimethly Ether
Diesel and Naphtha
Methane/Nitrogen Stream mixture
Power Generation and Synthesis Gas Process Flow
----- Steam----- Electricity----- Hydrogen Ammonia Nitrogen ----- Nitrogen rich
stream Product streams*All intermediates can be used in other processes or sold in market
Nitrogen Plant
Oxygen
Synthesis Gas Conversion
Product General Production Formula Uses
Methanol Simplest alcohol, light, volatile
steam-methane reforming
2H2 +CO →CH3OH antifreeze, solvent, fuel, intermediate in the production of other products
Acetic Acid weak carboxylic acid methanol carbonylation
CO + CH3OH → CH3COOH
vinyl acetate monomer and aceticanhydride
Formaldehyde simplest aldehyde oxidation and dehydrogenation ofmethanol
CH3OH → H2CO + H2 polymers and a widevariety of specialty chemicals
Dimethly Ether Gaseous ether methanol dehydration 2CH3OH → CH3OCH3 + H2O
aerosol spray propellant ora refrigerant
17
Synthesis Gas ConversionProduct General Production Formula Uses
Ammonia colorless alkaline gas with penetrating odor
Haber-Boschprocess
3H2 + N2 → 2NH3 nitrogen source in fertilizer and the manufacture of urea
Urea solid produced as prills or granules
Bosch- Meiser 2NH3 + CO2 → NH2CONH2 + H2O
fertilizers, plastics, and protein supplement in animal feed
Hydrogen Colorless, odorless gas
Steam reforming / Water gas shift reaction
CH4 +H2O → 3H2 + CO processing of fossil fuelsand to produce ammonia or methanol
Synthetic Fuel liquid hydrocarbons Fischer-Tropsch process
3H2 + CO → CH4 +H2O diesel and naptha
18
Utility Integration
• Use a fire-tubed boiler to create steam, which is used in Steam Methane Reforming.
• This produces NOx emissions, which are regulated from the EPA.
19
Control Technology Typical Emission Levels
SCONOxTM 2-5 ppm
XONON flameless combustion 3-5 ppm
Selective catalytic reduction (SCR) 5-9 ppm
Selective non-catalytic reduction (SNCR) 9-25 ppm
Non-selective catalytic reduction (NSCR) 9-25 ppm
Dry low NOx combustor 9-25 ppm
Water or steam injection 25-40 ppm
Utility Integration
• Using a turbine to convert steam to electricity, which is used inside the plant to fuel other processes and can be sold to outside markets.
• Combustion Turbine Operation– Ambient air is drawn in and compressed– Fuel is introduced, ignited, and burned– Hot exhaust gas is recovered in the form of shaft
horsepower
20
Mathematical Model
Mathematical Model
• Mathematical model was coded and run using the Generic Algebraic Modeling System (GAMS) as interface
• Based on Mixed Integer Linear Programming (MILP) (Cplex is the solver used)
• The objective function maximized is the Net Present Value (NPV) of the project
22
Mathematical Model
• Specifications– 23 processes were considered– 20 years of production was assumed– Reaction stoichometry, raw materials, demand,
operating costs, and product flow were included in the model
– Began with a total available investment of $100,000,000
23
Mathematical Model
• Why use a mathematical model instead of using Microsoft Excel?
• Combinations:– 176,640,000
24
Mathematical Model
25
Bring in clear copy and highlight equation for explanation
Mathematical Model
• An Example:FCI(i,t) .. FC(i,t) =e= (Y(i,t)*alpha(i) + beta(i)*initialcapacity(i,t));
– i = Process– t = year– Y = binary expansion variable– alpha = Additional capital cost per mole – beta = Initial capital cost per mole– initialcapacity = variable
26
Results
Steam R efo rm in g
W ater G as Sh ift
H ab er-B o sch
H ab er-B o sch
C arb o n ylati o n
D eh yd rati o n
Fisch er-Tro p sch
Steam Tu rb in e
So ld in M arket
Steam R efo rm in g
W ater G as Sh ift
H ab er-B o sch
B o sch -M eiser
M eth an o l Syn th esis
C arb o n ylati o n
D eh yd rati o n
Fisch er-Tro p sch
Diesel and Naphtha
Low Quality Natural Gas
Low Quality Natural Gas
Low Quality Natural Gas
Methanol
Steam
Pipeline Quality Natural Gas
Synthesis Gas
Hydrogen
Ammonia
Ammonia
Synthesis Gas
Synthesis Gas
Electricity
Electricity
Synthesis Gas
Synthesis Gas
Synthesis Gas
Ammonia
Methanol
Urea
Urea
Urea
Formaldehyde
Formaldehyde
Acetic Acid
Acetic Acid
Dimethly Ether
Dimethly Ether
Diesel and Naphtha
Methane/Nitrogen Stream mixture
Nitrogen PlantOxygen
Below 5 MMscf/day < 30% N2
Low Quality Natural Gas Reservoir
Molecular Gate Pressure Swing Adsorption
Sold as pipeline quality gas
At 3 MM SCF/D 15% N2
NPV = $20,425,000Investment = $475,000
Steam R efo rm in g
W ater G as Sh ift
H ab er-B o sch
H ab er-B o sch
C arb o n ylati o n
D eh yd rati o n
Fisch er-Tro p sch
Steam Tu rb in e
So ld in M arket
Steam R efo rm in g
W ater G as Sh ift
H ab er-B o sch
B o sch -M eiser
M eth an o l Syn th esis
C arb o n ylati o n
D eh yd rati o n
Fisch er-Tro p sch
Diesel and Naphtha
Low Quality Natural Gas
Low Quality Natural Gas
Low Quality Natural Gas
Methanol
Steam
Pipeline Quality Natural Gas
Synthesis Gas
Hydrogen
Ammonia
Ammonia
Synthesis Gas
Synthesis Gas
Electricity
Electricity
Synthesis Gas
Synthesis Gas
Synthesis Gas
Ammonia
Methanol
Urea
Urea
Urea
Formaldehyde
Formaldehyde
Acetic Acid
Acetic Acid
Dimethly Ether
Dimethly Ether
Diesel and Naphtha
Methane/Nitrogen Stream mixture
Nitrogen PlantOxygen
Above 5 MMscf/day 15% - 30%
Low Quality Natural Gas Reservoir
Molecular Gate Pressure Swing Adsorption
Steam Reforming
Water Gas Shift
Haber-Bosch
Bosch-Meiser
Boiler
Steam Turbine
Central Utility Plant Usage
Nitrogen Plant
Low Quality Natural Gas
Low Quality Natural Gas
Steam
Hydrogen AmmoniaSynthesis Gas
Electricity
Urea
Oxygen
Ammonia Nitrogen
At 10 MM SCF/D 25% N2
NPV = $138,600,000Investment = $9,250,000
Steam R efo rm in g
W ater G as Sh ift
H ab er-B o sch
H ab er-B o sch
C arb o n ylati o n
D eh yd rati o n
Fisch er-Tro p sch
Steam Tu rb in e
So ld in M arket
Steam R efo rm in g
W ater G as Sh ift
H ab er-B o sch
B o sch -M eiser
M eth an o l Syn th esis
C arb o n ylati o n
D eh yd rati o n
Fisch er-Tro p sch
Diesel and Naphtha
Low Quality Natural Gas
Low Quality Natural Gas
Low Quality Natural Gas
Methanol
Steam
Pipeline Quality Natural Gas
Synthesis Gas
Hydrogen
Ammonia
Ammonia
Synthesis Gas
Synthesis Gas
Electricity
Electricity
Synthesis Gas
Synthesis Gas
Synthesis Gas
Ammonia
Methanol
Urea
Urea
Urea
Formaldehyde
Formaldehyde
Acetic Acid
Acetic Acid
Dimethly Ether
Dimethly Ether
Diesel and Naphtha
Methane/Nitrogen Stream mixture
Nitrogen PlantOxygen
Above 5 MMscf/day 4% - 15%
At 10 MM SCF/D 10% N2
NPV = $169,350,000Investment = $6,200,000
Low Quality Natural Gas Reservoir
Boiler
Steam Turbine
Central Utility Plant Usage
Steam Reforming
Water Gas Shift
Haber-Bosch
Bosch-Meiser
Nitrogen plant
Oxygen
Urea
Steam
Steam
Electricity
Syn Gas Hydrogen Ammonia
Ammonia Nitrogen
Results Summary
31
Option # Reserve Size % N2 Content Initial Investment NPV
1 Less than5 MMSCF/D
Less than30% $475,000 $ 20,425,000
2 Greater than5 MMSCF/D
Between15 – 30 % $9,250,000 $ 138,600,000
3Greater than5 MMSCF/D Less than
15% $6,200,000 $169,350,000
Urea
• Major markets:– ≈90% of urea goes into fertilizers– ≈10% in other commodity markets such as
cigarettes, toothpaste, pretzels ect…• Price is quite volatile and is largely dependent
on the price of nitrogen and natural gas.• Since nitrogen is included in utility integration,
nitrogen price is no longer a variable.
32
Urea
• The demand, however, is fairly constant and seems like a good business decision:
33
Future Prices
• The current Urea Price: $390/ton
• If future prices decrease more than 20%, compared to other products, another option should be considered.
• The next highest process rout was the combination of formaldehyde and acetic acid.
34
Conclusions
• Molecular gate pressure swing adsorption is the most cost effective way of separating oxygen.
• After compiling the superstructure of processes in the mathematical model, the model gave three separate results dependent on the reserve size and nitrogen concentration.
35
Acknowledgements
• Dr. Miguel Bagajewicz• Quang Nguyen• Liu Shi• Roman Voronov
36
References
• http://www.naturalgas.org/naturalgas/processing_ng.asp#water
• http://www.lowimpactliving.com/pages/your-impacts/electricity1
• “Green is Seen in Fertilizers” - A New Approach to Municipal Solid Waste Management - Carrie Farberow and Kevin Bailey
• Upgrading low BTU gas of high nitrogen content to power or pipeline - Javier Lavaja, Bryce Lawson, Andres J. Lucas
• http://www.moleculargate.com/37