Senior Design Phase Two

Process Selection
Zachary Sayler, Azra Omerovic, Ken Davidson, Alex Kon, Stephanie Hare

A - Process Selection
Process selection for the completion of Phase 2 is based on a back-of-the-envelope calculation, determining which process has the highest possible profitability (100 % conversion) strictly based on the cost of raw materials, and the price of the product leaving the process. The first of the two processes put forward in the first phase was a simplified Fischer-Tropsch Module, with two main product streams: a fuel oil stream and a blend of other products which would theoretically be sold for a very low price to another production facility. The second process discussed in Phase 1 was a standard methanol production facility, taking methane, and catalytically synthesizing it into methanol. In the following sections, the methanol production facility is proved more profitable than the Fisher-Tropsch process.

A.1 - Cost of Raw Materials

For both processes, natural gas at a price of $4.5/MMBTU is the primary starting material. Natural gas has an energy value of around 23,000 BTU/lb [1], or 0.023 MMBTU/lb. At this price, that calculates out to 10.3 cents/lb. Assuming that our plant will purchase $100M/year of natural gas, this means that we will be processing 971 lb/year. Water, air, and other raw materials are used in the processing of methane into Syngas, the feed material for both reactors. Because each process will use the same amount of these materials per amount of natural gas put in, these raw material costs have been omitted in the rough calculation of profit margin, which should not affect the relative profitability of the two processes.

A.2 - Fischer-Tropsch
The proposed Fischer-Tropsch process produces many products, which need to be priced out separately. For this calculation, the products are divided into two main streams: a fuel oil, which is a blend of C12 to C15 hydrocarbons (diesel fuel), and a crude blend of other heavy hydrocarbons. Additionally, for the sake of this calculation, 100% conversion of the natural gas entering is assumed on all reactions. Due to the blend of products typically produced by the Fischer-Tropsch process, an idealized upper bound estimate of 50 % wt. will be used for the material leaving the Fischer-Tropsch reactor that is of appropriate carbon number in the fuel oil or naphtha stream [2]. This stream will be assumed to contain C12 to C15 (diesel fuel). The rest

of the process product will have the general properties and processing potential of sweet heavy crude (low sulfur, heavy hydrocarbon) [2]. This is justified based on the principle that they have similar compositions, and would be processed in the same way; therefore, they would have the same potential price if sold to a refining customer [3]. This stream will be approximated as containing, on average, C18. See Figure 1 for a simplification of the Fischer-Tropsch process.
Diesel Fuel (C12 C15) Synthesis Gas Fischer-Tropcsh Process Heavier Compounds (> C15)

Figure 1. Simplified Fischer-Tropsch Process.

The price reported for vehicle grade Diesel Fuel is $3.611/gallon in the U.S. [4]. The specific gravity of diesel is reported at 0.9 [1], giving Diesel a density of 8.006 lb/gallon. Therefore, Diesel costs roughly 45 cents/lb. However, given that only 50% [2] of the mass of methane is assumed to produce this product, the overall margin of this process will be lower. The remainder stream in our proposed FT process is being estimated as having the price of Crude Oil. Crude Oil is reported to have a price of 24 cents/gallon [4]. It has a variable specific gravity but is assumed to be .88 for domestic crude [5]. Therefore, the heavy hydrocarbon stream costs an estimated 3.2 cents/lb.

A.3 - Methanol
Methanol, hydrogen, and other byproducts are produced by this process. However, only methanol is considered as a source of income in this rough profitability analysis. Byproducts, such as dimethyl ether, are formed in a side reaction from methanol, but to a negligible extent for this primary analysis [6]. Methanol is reported to have a price of $2.53/gallon [7] and a specific gravity of 0.791 [5], giving it a density of 6.59 lb/gallon. Therefore, methanol costs 38.9 cents/lb. A rough calculation of the profitability of each process, given certain idealized conditions stated previously, is shown in Table 1 below. It should be stressed that the values presented are only meant to provide a theoretical upper bound on the profitability of the two processes for comparison. It is estimated that, pound for pound, the methanol process has the potential to be more than six times more profitable than the Fischer-Tropsch process. Therefore, we will

proceed onward through this phase in presenting a Process Flow Diagram and process conditions which will be required in our proposed methanol plant.

Reaction Processes Material natural gas (C4) diesel (C13) crude (C18) Total Process 2: Methanol methanol 32.04 60.54 1940 $ 0.389 MW (lb/lbmol) 16.04 basis (lb) 971 In (lbmol) 60.54 Out (lbmol) Out (lb) Price/lb $ 0.103

Economics Expense $ 100 Revenue Profit

Process 1: Fischer-Tropsch 170.33 282.55 2.54 1.53 432 432 $ 0.451 $ 0.032 $ 195 $ 14 $ 209 $ 109

$ 754

$ 654

Table 1: Comparative margins of selected processes (Price Product Cost RM) *All values are given in millions of dollars, lb, or lbmol.

B - Methanol Production PFD

C-101 Feed Gas Compressor V-102 & V-103 Flash Train R-101 Sulfur Hydrogenation Reactor C-104 Recycle Compressor E-101 Fired Steam Methane Pre-Heater (furnace) E-105 Recycle Heater R-102 Steam Reformer V-105 Flash E-102 Synthesis Gas Cooler E-106 Heat Exchanger V-101 Process Gas Separator (Flash) C-102/C-103 Compression Train E-103 Interstage Cooler E-112 Tower Reboiler R-103 Methanol Reactor V-106 Methanol Reflux Drum
C-104 17 E-105 R-103 6 7 E-102 V-101 R-102 4 10 8 9 C-102 E-103 C-103 11 V-102 14 V-103 16 15

E-104 Methanol Product Cooler P-102A/B Methanol Reflux Pump

V-104 Crude Methanol Surge Tank

T-101 Methanol Distillation Column

E-111 Tower Condenser

Steam

E-101

Excess Water

12 E-104

13

Feed Gas

2 C-101

18

19

R-101 20

22 V-104 E-111 24 21
FIC

25

Methanol

V-106

LIC

V 105

P-102 A/B 23 E-106 T-101 26

Byproducts to Fuel

27 E-112

Water

C - Process Description
Included in the Process Description is a narrative describing the overall process and an equipment table detailing the specifics of the process equipment. The narrative outlines how streams flow and interact in the process plant. The equipment table supplements the narrative with more specific information about the expected operating conditions and efficiencies of the process equipment.

C.1 - Process Flow Narrative

The overall conversion of methane to methanol can be broken into three distinct process steps. First, methane is processed into synthesis gas, also known as syngas, a mixture of carbon monoxide and hydrogen, by a process known as steam reforming. Next, the synthesis gas is compressed and reacted to produce methanol and water. Finally, to isolate the end product, methanol and water are separated by a distillation column. In the following paragraphs, each process step is analyzed in detail. Before steam reforming, the natural gas being pulled out of the ground must go through treatment before it can be used as a safe and environmentally sound feed material. This treatment is largely required due to the presence of sulfur compounds, which, if released in the flue gas, can cause large amounts of H2S and SO2 to enter the atmosphere. Catalysts used later in the process are also very sensitive to potential poisoning by elemental sulfur, therefore warranting desulfurization treatment for both environmental and productivity reasons. Natural gas typically enters the process as a wet gas with roughly 50 ppm wt. of sulfur compounds. The desulfurization unit reduces this concentration down to negligible levels [8]. Natural gas enters the plant contaminated with organic sulfur compounds. A recycled hydrogen stream is then mixed with the dry gas stream to treat the sulfur. The combined stream is then compressed to a pressure of 30 barg in preparation for the hydrogenation reactor (R-101). In this reactor, organic sulfur compounds are hydrogenated, releasing their sulfur as H2S. Hydrogen sulfide is then adsorbed onto a zinc oxide bed and removed as a solid waste stream. The hydrogenation reactor also converts lower hydrocarbons into methane. The treated methane stream is then sent to the reforming section [9].

Steam is mixed with the pre-treated methane gas and hydrogen leaving the ZnO bed at a ratio of 3-5:1:1 (expected steam to methane to hydrogen ratio) and sent through a tubular packed bed reactor packed with a Ni- Al2O Catalyst. The steam methane reformer (R-102) is governed by a series of reactions, which are dominated by the overall reaction of H2O + CH4 CO +3H2. Because the dominating and desired reaction is a highly endothermic, it is pushed to the products side by adding large amounts of heat using a reformer furnace [10]. The product of the reactor is synthesis gas (CO and H2), which is the key raw material for the methanol conversion reactor (R103). The syngas is compressed to roughly 70 barg and converted to methanol by a packed bed reactor holding pellets of copper catalyst. Due to low single pass conversion of syngas to methanol, syngas is easily separated from reactor products (water and methanol), recompressed and recycled back to the reactor. The methanol water mixture produced by the methanol conversion reactor is then sent through a separation process where first volatiles (mostly hydrogen) are topped off of the mixture in a flash drum, and methanol and water are separated using distillation (T-101).

C.2 - Process Equipment Table

PFD Equipment Table Item Feed Gas Compressor Equipment ID C-101 Purpose Compress Natural Gas and Hydrogen Stream for Sulfur Treatment Reactor Hydrogenate organic sulfur compounds to H2S and remove the sulfur via adsorbent ZnO pellets. Also convert higher hydrocarbons down to methane. Operating Conditions 20C < T < 100 C 20 barg < P < 30 barg Efficiency = 0.65 Key Information (description, efficiency, conversion, materials etc.) Working duty for this compressor will be determined in ASPEN Simulation. Materials: thick walled carbon steel. Assumptions & Justifications Efficiency for this Compressor assumed to be .70 justified by compressor heuristics [11, p. 380] Inlet pressure specification [9]. Assume enough sulfur is removed from the gas stream in this reactor that it is a negligible concentration in the feed stream to the reforming section. This is justified by [8] which states that there is a 99% potential removal of sulfur in these processes. Enough such that the only issue caused by this is poisoning of catalyst over the long term. Another piece of literature to justify this is [9] Design Specifications Provided by [12] justified by [11]

Sulfur Hydrogenation Reactor

R-101

320C < T < 370 C 28 barg < P < 32 barg

Raw gas is treated by heating with hydrogen to convert all sulfur compounds to H2S. Sulfur is removed as a solid waste product. Removing efficiency is assumed to be near 100% hydrogensteammethanereforming.pdf] Materials: thick walled carbon steel.

Fired Steam Methane PreHeater (furnace)

E-101

Heat Treated Methane and Steam for Reformer

50 < T < 950 C 10 barg < P < 40 barg Efficiency = 0.7

Working duty for this boiler will be calculated from an ASPEN model in our phase 3 Simulation. Materials: thick walled carbon steel.

Steam Reformer

R-102

Convert methane, steam, and hydrogen into synthesis gas (CO & H2)

850C < T < 950 C 10 barg < P < 40 barg

Synthesis Gas Cooler

E-102

Process Gas Separator (Flash) Compression Train

V-101

C-102 ,E103, & C103 R-103

Cool down Syngas stream leaving Reformer to condense unreacted steam (if any) Remove Condensed H2O from Reformer Product Stream. Pressurize Synthesis Gas

50 C <T < 950 C 10 barg < P < 40 barg

Net reaction occurring is CH4 + 2H2O < Cat > CO2 +4H2. Reaction is highly endothermic and requires heat (high temperatures to push high conversion). 100-1000 Tubes are Packed with Ni/Al2O3 Catalyst. Kinetics based on equilibrium conditions for specific catalyst residence times provided by literature [13] At these steam: methane: H2 ratio of 5:1:1, CH4 single pass conversion = 25 - 40% for Wt./Flow of 2000-10000 kgcat s/kmol. S CO2 goes up with reduction in temperature. This reactor will be modeled as a PBR. Materials: thick walled carbon steel. Shell and tube heat exchanger, thick walled carbon steel. Heat exchanger to be modeled in ASPEN for actual duty

Literature sources [12] and [13].

Table 6.2, Table 11.11 in [11]

50 C <T < 100C 20 barg < P < 40 barg

20 barg< P <70 barg 50 C < T < 250 C

Methanol Reactor

Convert synthesis gas to MeOH

70 barg, 250 C

Thick walled Carbon Steel Construction, Separation Efficiency and equipment temperature requirements to be determined in ASPEN for effective water separation. Two stage compressor with interstage cooling (~ 80 % efficiency), Thick-walled Carbon-steel (# of units to be determined by analysis in ASPEN). PBR (Copper catalyst), Thick-walled carbonsteel reactor rated for pressure. Kinetics provided by [14] Net conversion reaction is CO2 + 3 H2 < (Cu)> CH3OH + H2O. Conversion/wt. of catalyst to be determined via MATLAB ODE solving. Kinetic law to be used to develop this in ASPEN provided by [6] & [14]. Materials: thick walled carbon steel.

Table 6.4 and Table 11.10, Table 6.2 in [10], see Justification for Compressor Train [6] [14], Table 6.2 in [11]

Methanol Product Cooler Flash Train

E-104 V-102 & V103

Cool Reactor Outlet Contents Separate unused reactants (CO2, CO, and H2) to recycle to reactor Compress recycle synthesis gas

40 barg < P < 70 barg 50 C < T < 250 C 40 barg, 50 C

Shell tube cooling water heat exchanger. Materials: thick walled carbon steel. Simple flash drum, high recovery, Carbonsteel. To be modeled in ASPEN for actual temperature & duty required for adequate removal of CO, CO2 and H2 Single compressor unit. Duty expected from ASPEN. Likely ~80 % efficient based on compression ratio. Materials: thick walled carbon steel. Working duty for this boiler will be calculated from an ASPEN model in our phase 3 Simulation. Materials: thick walled carbon steel. Store crude methanol from conversion module. Materials: carbon steel. Simple flash drum, high recovery, Carbonsteel. To be modeled in ASPEN for actual duty and operating temperatures required for effective separation. Materials: carbon steel. Shell tube steam heat exchanger, carbonsteel. To be modeled in ASPEN for actual duty Expected 10-14 stage tower with reboiler and condenser, targeting a 98 wt% purity of methanol [15]. Materials: carbon steel.

Table 6.2, Table 11.11 in [11] Expect high recoveries (large difference in boiling points)

Recycle Compressor

C-104

40 barg < P < 70 barg 50 C < T < 250 C

Table 6.4 and Table 11.10, Table 6.2 in [11]

Recycle Heater

E-105

Reheat recycle synthesis gas

10 barg < P < 70 barg 50 C< T < 250 C

[10]

Crude Methanol Surge Tank Flash

V-104

V-105

Store Crude Methanol for Surge Purposes Separate hydrogen from Conversion Product Stream Heat MeOH and Water for distillation Separate MeOH and Water

1 < P < 10 barg 25C < T <100C 0 < P < 10 barg, 25 C

[10]

Vessel separates last of H2, CO, CO2 from stream, Pressure drop across drum. Outlet temp between the BP of Methanol and Water at atmospheric conditions See Expected Number of Stages (further analysis when inlet, outlet specs. are defined) Rigorous Aspen Simulation will be required to properly size the column

Heat Exchanger

E-106

0 barg < P < 10 barg 25 C < T < 100 C 0 barg, 65 C < T < 100 C

Methanol Distillation Column

T-101, E111, E-112, V-106 & P102 A/B

D - Phase Three Plans

In order to evaluate a rigorous mass and energy balance, the process as shown in the PFD (see page 2) will be modeled in the simulation software Aspen. There are many sources of kinetics data for our process, further research will need to be conducted to determine the most fitting correlation for our production facility. In phase three a rate law will be determined using literature data on conversion and operating conditions. We will conduct additional research if needed to satisfy any missing parameters. The property package that will be used in order to depict the vapor-liquid equilibrium behavior of the components in the process will be Wils-2. This package characterizes component behavior in terms of the Wilson equation, which takes into account gas and liquid non-idealities due to polarity and is robust at higher pressures. Based on the PFD and process equipment table (see page 5), a calculation of the fixed capital investment (FCI), cost of manufacturing (COM), and profitability will be completed using CAPCOST. CAPCOST is a capital cost estimation software which utilizes the same relationships presented in Analysis, Synthesis, and Design of Chemical Processes [17]. .

E - Appendix
E.1 - Phase One BFD
Presented below is the BFD for methanol production from natural gas. It is identical to the BFD presented in phase one.
Steam

Natural Gas

Feed Compression & Pretreatment

Catalytic Partial Oxidation

Heat Recovery & Steam Generation

Syngas Compression

Air Separation Unit Air Oxygen

Methanol Reactor

Recycle Stream

Methanol Methanol Distillation

Raw Methanol Separation

Pure Gas

Water

Figure 2. Phase 1 BFD for methanol production from natural gas.

E.2 - Sample Calculations

Outlined in this section are sample calculations for items requiring the use of equations and assumptions, which would clutter the document if directly inserted.

E.2.1 - Justification for Compressor Train

This section justifies why we expect at least a two stage compressor will be required to compress the outgoing synthesis gas from the steam reformer to pressure specifications required by the methanol reactor. A multistage compression system is expected because synthesis gas coming out of the steam reformer flash drum (V-101) is expected to be at a much lower pressure than what is required by the methanol reactor (R-103) for considerable conversion. Assumptions made in the calculation are: 1) the gas mixture is diatomic (synthesis gas with small amounts of CO2), 2) adiabatic reversible compression (first order estimate), 3) worst case scenario (10 barg to 70 barg) compression requirement, 4) the compression ratio cannot be greater than 3 [11, p. 159] and 5) the gases behave ideally (first order estimate). Two key equations are the reversible adiabatic compression equation [11, p. 380], ( ) where ( , ) and ( , ) are the inlet, outlet temperature and pressure of the stream entering is (k 1)/k where k is the ratio of the heat

and exiting the compressor respectively, and

capacity at constant pressure to the heat capacity at constant temperature and ideal gas law.

Table 2. Compressor Train Calculation.

Table 2 summarizes the calculation and justifies why a compressor train with inter-stage cooling is required.

E.2.2 - Expected Number of Stages

In this section, the expected number of stages for the methanol water distillation column is justified. The target specification for methanol purity in the distillate stream is 98 wt% (roughly 96 mol%). Using methanol-water equilibrium data, the minimum number of stages is 5 using McCabe-Thiele analysis and assuming the bottoms methanol concentration to be 5 mol% (Figure 3). Next using tower heuristics found in Turton, the optimum number of stages is roughly twice the minimum number of stages (10) [11, p. 383]. Because a number of assumptions (constant molal overflow, 100 % stage efficiency etc.) and a heuristic were used in the calculation, the number of stages is expected to be between 10 and 14 (assuming 70 % tray efficiency). The exact number of stages will be determined using the process flow simulator ASPEN Plus.

Figure 3. First order McCabe-Thiele analysis [16].

G - References [1] The Engineering Toolbox, "Fuel Gases - Heating Values," [Online]. Available: www.engineeringtoolbox.com/heating-values-fuel-gases-d_823.html. [Accessed 23 2 2013]. [2] D. Leckel, "Upgrading of Fischer-Tropsch Products to Produce Diesel," Sasol Technology Research and Development, Munkerupgaard, 2010. [3] G. N. Choi, S. J. Kramer and S. S. Tam, "Design and economics of a Fishcer-Tropsch plant for converting natural gas to liquid transportation fuels," Fuel and Energy, pp. 667-671, 1997. [4] U.S. Energy Information Administration, "Gasoline and Diesel Fuel Update," 15 Feb 2013. [Online]. Available: www.eai.gov/petroleum/gasdiesel. [Accessed 16 2 2013]. [5] The Engineering Toolbox, "Specific Gravity - Liquids," [Online]. Available: www.engineeringtoolbox.com/specific-gravity-liquids-d_336.html. [Accessed 2013 23 2]. [6] B. K. a. K. W. Bos, "The Kinetics of the Methanol Synthesis on a Copper Catalyst: An Experimental Study," Chemical Engineering Science - Pergamon Press, Great Britain, 1988. [7] ICIS, "Indicative Chemical Prices," 2013. [Online]. Available: www.icis.com/chemicals/channel-info-chemicals-a-z/. [Accessed 23 2 2013]. [8] N. Russamee, "Simulation and Design of Ammonia Process from Natural Gas Reforming," Kasetsart University, Kasetart, 2009. [9] M. &. Doctor, "Hydrogen from Steam-Methane Reforming with CO2 Capture," Argonne National Laboratory, Argonne, IL, 2003. [10] Methanex, "Making Methanol," [Online]. Available: www.methanex.com/education/methanol/english/main.html. [Accessed 21 2 2013]. [11] Turton, Analysis, Synthesis, and Design of Chemical Processes 4th Ed., Ann Arbor, MI: Prentice Hall, 2012. [12] J. Kimia, Artist, P3. [Art]. University of Mayala. [13] H. e. al., "The Kinetics of Methane Steam Reforming over NI/Al2O catalyst," Chemical Engineering Journal, Salford, Manchester, UK, 2000. [14] D. Rahman, "Kinetic Modeling of Methanol Sysntehsis From Carbon Monoxide, Carbon Dioxide, and Hydrogen over A Cu/ZnO/Cr2O3 Catalyst," San Jose State University, San Jose, CA, 2012. [15] M. Funk, "Methanol Fuel Quality Specification Study," Xcellsis, Poway, CA, 2002.

[16] J. Gmehling and U. Onken, "Vapor-Liquid Equilibrium Data Collection," Frankfurt, Germany, 1977. [17] H. E. Curry-Hyde and R. Howe, Natural gas conversion II: proceedings of the Third Natural Gas Conversion Symposium, Sydney, July 4-9, 1993, Amsterdam: Elselvier, 1994.