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Final Year Design Project 2017

Wax from Methane via Fe-LTFT

1. The Fischer-Tropsch Synthesis

Fischer-Tropsch Synthesis (FTS) – Some basics Conversion of synthesis gas (CO + H2) to organic molecules ● Polymerization reaction where the monomer is made in-situ ● Mostly paraffins and olefins ● Some oxygenates (aldehydes.. acids) ● Some branching (mostly methyl branches) The relative amount of olefins/oxygenates depends on the catalyst and operating conditions ● Co-LTFT makes significantly less olefins and oxygenates than Fe-LTFT While cyclic molecules are formed (mostly in Fe-HTFT). ● High α – long chains ● Low α – short chains Maintaining momentum 3 .α. alcohols. ketones. these form via secondary reactions The products produced follow an Anderson-Shultz-Flory distribution with a fixed probability of a chain growing by one carbon number at every step .

but happen in parallel. Maintaining momentum 4 .Fischer-Tropsch Synthesis (FTS) – Some basics Additional reactions that are not formally part of the FT synthesis. include: ● Water-gas shift (WGS) 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2 ● Methanol formation 𝐶𝑂 + 2𝐻2 ↔ 𝐶𝐻3 𝑂𝐻 Formic acid can also form as an intermediate of the WGS reaction 𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻𝐶𝑂𝑂𝐻 ↔ 𝐶𝑂2 + 𝐻2 These reactions are considered non-FT as they are direct reactions with CO and do not go via the FT monomer.

like for many polymerisation reactions. follow a Schultz-Flory distribution Maintaining momentum 5 . adapted from literature There are four basic steps: ● Monomer formation ● Chain Initiation ● Chain Growth ● Chain Termination The products.The Reaction Mechanism Many reaction mechanisms have been proposed for the FTS The mechanisms differ depending on the active metal. the promoters that are added to the catalyst and many other factors The mechanism given below is a very simplified one.

Monomer formation H2 H H CO CO CO H HCO HC O CH H CH2 CH4 … O H OH OH H H2O Maintaining momentum 6 .

Monomer formation H2 H H CO CO CO H HCO HC O Monomer CH H CH2 CH4 … O H OH OH H H2O Maintaining momentum 7 .

Chain growth CH3 CH2 CH2 CH2 CH CH2 CH3 CH3 CH H H CH3 OR Maintaining momentum 8 .

Chain growth CH3 CH2 CH2 CH2 CH CH2 Initiation CH3 CH3 CH H H CH3 OR Maintaining momentum 9 .

Chain growth CH3 CH2 CH2 CH2 CH CH2 Termination CH3 CH3 CH H H CH3 OR Termination Maintaining momentum 10 .

The chain can desorb after monomer insertion  Terminates as olefin Two hydrogenations in a row  Terminates as paraffin Maintaining momentum 11 .Chain growth CH3 CH3 CH3 CH2 CH2 R3 CH CH2 CH CH CH2 CH etc.

Anderson-Schulz-Flory (ASF) Distribution Assume a fixed growth probability – α ● Fixed here means invariant with regards to carbon number ● There are models where α is chain length dependent. but they generally add complication without additional accuracy The growth probability is the ratio of the growth reaction rate to the sum of the growth and all termination rates 𝑟𝑔 𝛼= 𝑟𝑔 + 𝑟𝑡 Maintaining momentum 12 .

.Anderson-Schulz-Flory (ASF) Distribution 1-a C1* C1 product a 1-a C2* C2 product a 1-a C3* C3 product a . . * 1-a Cn Cn product a 1-a Cn+1* Cn+1 product Maintaining momentum 13 13 .

β) for the heavier distribution (α2). two growth probabilities are used – α1 and α2 with a weight β for the lighter distribution (α1) and (1.Anderson-Schulz-Flory (ASF) Distribution Carbon selectivity (Sn) is the fraction of the total FT product carbon atoms that form chains of length n 𝑃𝑛 = 𝛼 𝑛−1 1 − 𝛼 𝑛𝑃𝑛 Sn = ∞ = n𝛼 𝑛−1 1 − 𝛼 2 σ1 𝑛𝑃𝑛 2 𝑆𝑛 1−𝛼 ∴ log = log 𝛼 𝑛 + log 𝑛 𝛼 For non-ideal cases. Maintaining momentum 14 .

0E-02 Alpha : 0.5E-02 4.5E-02 1.5E-02 Alpha : 0.90 1.Anderson-Schulz-Flory (ASF) Distribution 4.0E+00 0 10 20 30 40 50 60 70 80 90 100 Carbon Number Maintaining momentum 15 .92 Alpha : 0.94 2.0E-02 3.0E-02 Carbon Selectivity (Sn) 2.0E-03 0.0E-02 5.5E-02 3.

2E+01 Carbon Number Maintaining momentum 16 .0E+00 0 10 20 30 40 50 60 70 80 90 100 -2.0E+00 log(Sn/n) Alpha : 0.0E+00 -4.Anderson-Schulz-Flory (ASF) Distribution “Schulz-Flory plot” for an ideal distribution gives a straight line with slope of log(α) 0.0E+00 -1.0E+00 Alpha : 0.90 -8.0E+01 -1.94 -6.92 Alpha : 0.

Anderson-Schulz-Flory (ASF) Distribution HTFT LTFT Maintaining momentum 17 .

2. Your Catalyst .

2𝑃𝐻2 𝑂 + 6.5 𝑃 2 𝐶𝑂 𝑟𝐹𝑇 = 𝐴𝐹𝑇 2 1 + 0.Your Catalyst You are being supplied with a novel catalyst developed by your company’s R&D department The FT reaction rate was found to fit the model proposed by Botes (Botes.2 𝑃𝐶𝑂 1 1 𝐴𝐹𝑇 = 28.5 2 1 1 𝐴𝑊𝐺𝑆 = 8. 𝑠 𝑇 508 Maintaining momentum 19 .5 𝑃𝐻0. 𝑠 𝑇 508 1 𝑃𝐶𝑂 𝑃𝐻2 𝑂 − 𝑃𝐻2 𝑃𝐶𝑂2 𝐾𝑊𝐺𝑆 𝑟𝑊𝐺𝑆 = 𝐴𝑊𝐺𝑆 𝑃𝐻2 𝑂 1 + 1.5 exp −12000 − 𝜇𝑚𝑜𝑙𝐶𝑂 /𝑔.5 exp −15500 − 𝜇𝑚𝑜𝑙𝐶𝑂 /𝑔. 2008): 𝑃𝐻0.

5 2 𝐺≝ = 𝐺0 0.Your Catalyst The catalyst represents a major breakthrough for Fe-based LTFT. measured at H2:CO = 1.185𝑛 𝑃 𝑛 The catalyst was found to produce a product slate according to an ideal ASF distribution with an alpha value of 0.5 and at a temperature of 245°C It was also found that the growth probability varies with reactant partial pressures according to 𝛼 𝑃𝐻0. 2008) 𝑂 = 7.2𝑒 −0.5 1−𝛼 𝑃𝐶𝑂 Maintaining momentum 20 . as it produces no oxygenated products – only paraffins and olefins The ratio of paraffin to olefin at any given carbon number is given according to a model by Botes (Botes.945.

00% 0.00% 0 20 40 60 80 100 Carbon Number Paraffin Olefin Total Maintaining momentum 21 .Your Catalyst 2.50% 1.50% 0.00% Carbon Selectivity 1.50% 2.

3. Synthesis gas generation Haldor-Topsøe Autothermal Reforming .

Auto-Thermal Reforming (ATR) Ref: Haldor Topsoe Brochures Maintaining momentum 23 .

Autothermal Reforming Reactions Internal Combustion Zone Cold Tip Swirl Burner CH4 + 3/2O2 → CO + 2H2O (CTS) Endothermic Reforming Reaction CH4 + H2O ↔ CO + 3H2 Water Gas Shift Reaction Nickel type reforming CO + H2O ↔ CO2 + H2 catalysts Boudouard Reaction (Soot formation) .Limit is 650°C 2CO ↔ CO2 + C (soot) Maintaining momentum 24 .

Pictures of Synthesis Gas Unit 3-D drawing of ATR with Waste Heat Boiler & Fluid Dynamic modelling of an ATR burner HTAS Heat Exchanger Reforming unit Steam Superheater Ref: Haldor Topsoe Brochures Fired Heaters Maintaining momentum 25 .

4. The Design Brief .

This hydrogen may be used to hydrogenate the FT products. ● Existing reactors are available to you. but should you decide to use them.The Design Brief You are tasked with designing a plant to produce wax from methane. It is the only source of hydrogen available. using the supplied catalyst ● The required production rate will be supplied As per your company’s preference. the reactor will be an isothermal. multi-tubular. fixed-bed reactor. Maintaining momentum 27 . should you wish. The H2:CO of the synthesis gas may be adjusted by extracting hydrogen via a membrane system. you will need to compress the hydrogen to 55bara and you will need to supply the compressor The wax products must be fractionated (and optionally hydrogenated) into ten possible products that your company will sell at prices that will be given to you. operating at 245°C The synthesis gas will be produced from natural gas using auto-thermal reforming (ATR) ● A detailed design is not required as this is a package unit supplied by HTAS.

The Design Brief The primary objective of the project is to maximise the profits (IRR) for your company by: ● Selecting an optimal product slate ● Operating the plant at optimal conditions to produce this slate ● Minimizing CAPEX and OPEX ● Maximising the efficiency of the unit Maintaining momentum 28 .

Questions? Maintaining momentum 29 .