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Commercialization of Nitrogen- Rich Natural Reservoirs Albert Bradley Curtis S. Monique Wess Miguel Bagajewicz.

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Presentation on theme: "Commercialization of Nitrogen- Rich Natural Reservoirs Albert Bradley Curtis S. Monique Wess Miguel Bagajewicz."— Presentation transcript:

1 Commercialization of Nitrogen- Rich Natural Reservoirs Albert Bradley Curtis S. Monique Wess Miguel Bagajewicz

2 Overview BackgroundGoalsSuperstructure of Process Process Descriptions Mathematical ModelResults Conclusions 2

3 Background

4 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

5 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

6 Background Most popular contaminants – Carbon Dioxide > 2% – Nitrogen > 4% – Hydrogen Sulfide > 4ppm – Water Minor contaminants include – Helium – Argon – Hydrogen – oxygen 6

7 This Work Objective Perform an economic analysis on the feasibility of production and commercialization of LQNG 7

8 Superstructure of Processes

9 9 Low Quality Natural Gas Reservoir BoilerSteam Turbine Central Utility Plant Usage Sold in Market Low Quality Natural Gas Steam Electricity Power Generation Process Flow Steam Electricity LQNG *All intermediates can be used in other processes or sold in market

10 Low Quality Natural Gas Reservoir BoilerSteam Turbine Central Utility Plant Usage Sold in MarketSteam ReformingWater Gas ShiftHaber-BoschBosch-Meiser Methanol Synthesis Methanol Oxidation CarbonylationDehydrationFischer-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 Synthesis Gas Hydrogen Methanol AmmoniaUrea Formaldehyde Acetic Acid Dimethly Ether Diesel and Naphtha Nitrogen Plant Oxygen

11 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 Synthesis Gas Electricity Synthesis Gas Ammonia Methanol Urea Formaldehyde Acetic Acid 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

12 Costs 12

13 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 A o 13

14 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

15 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

16 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 Synthesis Gas Electricity Synthesis Gas Ammonia Methanol Urea Formaldehyde Acetic Acid 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

17 Synthesis Gas Conversion ProductGeneralProductionFormulaUses Methanol Simplest alcohol, light, volatile steam-methane reforming 2H 2 +CO →CH 3 OHantifreeze, solvent, fuel, intermediate in the production of other products Acetic Acid weak carboxylic acidmethanol carbonylation CO + CH 3 OH → CH 3 COOH vinyl acetate monomer and acetic anhydride Formaldehyde simplest aldehydeoxidation and dehydrogenation of methanol CH 3 OH → H 2 CO + H 2 polymers and a wide variety of specialty chemicals Dimethly Ether Gaseous ethermethanol dehydration2CH 3 OH → CH 3 OCH 3 + H 2 O aerosol spray propellant or a refrigerant 17

18 Synthesis Gas Conversion ProductGeneralProductionFormulaUses Ammonia colorless alkaline gas with penetrating odor Haber-Bosch process 3H 2 + N 2 → 2NH 3 nitrogen source in fertilizer and the manufacture of urea Urea solid produced as prills or granules Bosch- Meiser2NH 3 + CO 2 → NH 2 CONH 2 + H 2 O fertilizers, plastics, and protein supplement in animal feed Hydrogen Colorless, odorless gas Steam reforming / Water gas shift reaction CH 4 +H 2 O → 3H 2 + COprocessing of fossil fuels and to produce ammonia or methanol Synthetic Fuel liquid hydrocarbonsFischer-Tropsch process 3H2 + CO → CH 4 +H 2 Odiesel and naptha 18

19 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 TechnologyTypical Emission Levels SCONO x TM 2-5 ppm XONON flameless combustion3-5 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 combustor9-25 ppm Water or steam injection25-40 ppm

20 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

21 Mathematical Model

22 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

23 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

24 Mathematical Model Why use a mathematical model instead of using Microsoft Excel? Combinations: – 176,640,000 24

25 Mathematical Model 25 Bring in clear copy and highlight equation for explanation

26 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

27 Results

28 Low Quality Natural Gas Reservoir Molecular Gate Pressure Swing Adsorption Steam Reforming Water Gas ShiftHaber-BoschBosch-MeiserHaber-BoschBosch-Meiser Methanol Synthesis Methanol Oxidation CarbonylationDehydrationFischer-TropschBoilerSteam Turbine Central Utility Plant Usage Sold in Market Steam Reforming Water Gas ShiftHaber-BoschBosch-Meiser Methanol Synthesis Methanol Oxidation CarbonylationDehydrationFischer-Tropsch Diesel and Naphtha Low Quality Natural Gas Low Quality Natural Gas Low Quality Natural Gas Methan ol Steam Pipeline Quality Natural Gas Synthesis Gas Hydrog en Ammonia Synthesis Gas Electricit y Synthesis Gas Ammonia Methan ol Urea Formaldehyde Acetic Acid Dimethly Ether Diesel and Naphth a Methane/Nitrogen Stream mixture Nitrogen Plant Oxygen Below 5 MMscf/day < 30% N 2 Low Quality Natural Gas Reservoir Molecular Gate Pressure Swing Adsorption Sold as pipeline quality gas At 3 MM SCF/D 15% N 2 NPV = $20,425,000 Investment = $475,000

29 Low Quality Natural Gas Reservoir Molecular Gate Pressure Swing Adsorption Steam Reforming Water Gas ShiftHaber-BoschBosch-MeiserHaber-BoschBosch-Meiser Methanol Synthesis Methanol Oxidation CarbonylationDehydrationFischer-TropschBoilerSteam Turbine Central Utility Plant Usage Sold in Market Steam Reforming Water Gas ShiftHaber-BoschBosch-Meiser Methanol Synthesis Methanol Oxidation CarbonylationDehydrationFischer-Tropsch Diesel and Naphtha Low Quality Natural Gas Low Quality Natural Gas Low Quality Natural Gas Methan ol Steam Pipeline Quality Natural Gas Synthesis Gas Hydrog en Ammonia Synthesis Gas Electricit y Synthesis Gas Ammonia Methan ol Urea Formaldehyde Acetic Acid Dimethly Ether Diesel and Naphth a Methane/Nitrogen Stream mixture Nitrogen Plant Oxygen Above 5 MMscf/day 15% - 30% Low Quality Natural Gas Low Quality Natural Gas Steam HydrogenAmmonia Synthesis Gas Electricity Urea Oxygen Ammonia Nitrogen At 10 MM SCF/D 25% N 2 NPV = $138,600,000 Investment = $9,250,000

30 Low Quality Natural Gas Reservoir Molecular Gate Pressure Swing Adsorption Steam Reforming Water Gas ShiftHaber-BoschBosch-MeiserHaber-BoschBosch-Meiser Methanol Synthesis Methanol Oxidation CarbonylationDehydrationFischer-TropschBoilerSteam Turbine Central Utility Plant Usage Sold in Market Steam Reforming Water Gas ShiftHaber-BoschBosch-Meiser Methanol Synthesis Methanol Oxidation CarbonylationDehydrationFischer-Tropsch Diesel and Naphtha Low Quality Natural Gas Low Quality Natural Gas Low Quality Natural Gas Methan ol Steam Pipeline Quality Natural Gas Synthesis Gas Hydrog en Ammonia Synthesis Gas Electricity Synthesis Gas Ammonia Methan ol Urea Formaldehyde Acetic Acid Dimethly Ether Diesel and Naphth a Methane/Nitrogen Stream mixture Nitrogen Plant Oxygen Above 5 MMscf/day 4% - 15% At 10 MM SCF/D 10% N 2 NPV = $169,350,000 Investment = $6,200,000 Low Quality Natural Gas Reservoir BoilerSteam Turbine Central Utility Plant Usage Steam ReformingWater Gas ShiftHaber-BoschBosch-MeiserNitrogen plant Oxygen Urea Steam Electricity Syn GasHydrogenAmmonia Nitrogen

31 Results Summary 31 Option #Reserve Size% N 2 ContentInitial InvestmentNPV 1 Less than 5 MMSCF/D Less than 30% $475,000$ 20,425,000 2 Greater than 5 MMSCF/D Between 15 – 30 % $9,250,000$ 138,600,000 3 Greater than 5 MMSCF/D Less than 15% $6,200,000$169,350,000

32 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

33 Urea The demand, however, is fairly constant and seems like a good business decision: 33

34 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

35 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

36 Acknowledgements Dr. Miguel Bagajewicz Quang Nguyen Liu Shi Roman Voronov 36

37 References g.asp#water g.asp#water 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 37


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