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GAS TO LIQUIDS PLANT DESIGN

Prepared For Dr. J.D. PALMER Professor Chemical Engineering Department Louisiana Tech University

By Bajracharya Prabuddha Enaohwo Enakeme Obe Akeem Cmen 432 Students

May 5nd, 2011

EXECUTIVE SUMMARY
This report discusses the details of how we designed a Fischer-Tropsch Reaction unit (FTR) to convert syngas (CO and H2) to hydrocarbons. The purpose of the design is to produce liquid fuels and reduce our overdependence on importation of oil from foreign countries.

In achieving our goal of effectively designing a Fischer-Tropsch Reaction unit to produce liquid fuel, design objectives were adhered to strictly. The design was made to ensure that it does not pose any environmental, health or safety hazards by ensuring that appropriate control valves were placed in needed areas. Rigorous research was also done on the material of construction of the equipment to ensure that no reaction between the components and the material of construction occur. This may lead to an unwanted product that could greatly affect the purity and specification of our final product.

Also, rigorous economic analysis was done to ensure that the design is feasible. In the economic analysis, the designed capital investment, expense costs of the air separation unit, syngas unit, FTR unit, and hydroisomerization unit were reflected. After an economic analysis on the design process, a net present value of 4.96 billion dollars was achieved under the process conditions defined in the report.

INTRODUCTION
Synthetic fuels production is one of the promising alternatives to petroleum fuels. Synthetic fuels can be produced by converting natural gas to liquid petroleum products. One of these gases to liquid processes is Fischer-Tropsch synthesis. Fischer-Tropsch is one of the oldest and mature processes to produce alternative fuel source. This process converts carbon monoxide and hydrogen gas in combination called synthetic gas into liquid hydrocarbon fuels like diesel and jet fuel.

The objective of this project is to provide preliminary design package for a grass roots Fischer-Tropsch reactor unit with reactor effluent separation facilities. We are to design a safe, environmentally clean, thermally integrated FTR unit operating cost utilization. The project should also reflect that the optimal cost/benefit balance is achieved.

Some of the design specifications are: Effective heat integration Environmental, health or safety hazards properly mitigated No continuous flaring/venting of hydrocarbons

The economic constraints for the plant are: 15 year project life, depreciation is SL over 15 years. Tax is 33% 3% projected yearly inflation Total capital investment estimated by multiplying equipment cost by 4.8 Operating expenses above and beyond utilities is estimated using 3% of the total capital investment FTR unit will have 1 month turnaround to coincide with catalyst replacement

SUMMARY
The effective and efficient production of liquid fuel from syngas involves three processes. These processes are conducted in the syngas unit (SU), Fischer-Tropsch Reaction (FTR) unit, and the hydro-isomerization (HI) unit. In the syngas unit (SU), methane gas, steam, carbon dioxide, and oxygen are reacted in the syngas unit to produce carbon monoxide and hydrogen gas. The syngas unit was designed to convert 500 MSCF/D (Actual conditions: 500 PSIG, 100F) of clean methane to syngas. In the syngas unit, three reactions occur. The first reaction is a steam reforming reaction between methane gas and water to produce syngas; the second reaction is a partial oxidation reaction between methane gas and oxygen to produce carbon monoxide, and water. It should be noted that the heat required to drive the endothermic auto thermal reforming reaction is supplied in-situ by partial oxidation of methane.

In the Fischer-Tropsch reaction unit, the carbon monoxide and hydrogen gas from the syngas unit are fed into two tubular fixed reactors arranged in series. In these reactors, different hydrocarbons were formed at specific temperatures and pressures. The products from the FTR unit are sent to distillation columns to separate products based on differences on their boiling points.

In the hydro-isomerization unit, the distillate and heavier fractions (material with greater than 350 F boiling point) are fed to a catalytic hydro-isomerization reactor, where paraffins are isomerized and wax is converted to lighter products. A catalyst was used to reduce the activation energy of the reaction. It should be noted that this catalyst is sensitive to water and carbon monoxide; therefore the liquid feed to the hydro-isomerization reactor was free from water above the solubility limit and the makeup gas has a carbon monoxide content no greater than 0.1 mol%.

In order to check the viability of the design, an economic analysis is done to obtain a net present value that would justify the investment to this process.

DISCUSSION
SELECTION OF THERMODYNAMIC MODEL To ensure a good process simulation, an accurate thermodynamic model must be chosen. Choosing an accurate thermodynamic model will depend on the components of the incoming feed stream and the products.
In order to simulate portions of the GTRL plant, we have to have an appropriate thermodynamic model. Choosing a thermodynamic model will depend on the data available and the most cumbersome compounds. We consulted a decision tree to narrow down the choice of thermodynamic models and we came up with SRK, and PR or their variants. We were able to find data for different binary system and we used that data to compare with the data given by chemcad model. To identify the best fit model that simulated the data we used sum of least square method and found out that MSRK produced the best fit. The following diagrams show the graphical fitting for one of our component system

n-Butane/n-Heptane TP-xy Experimental


200 180 160 Temperature C 140 120 100 80 60 0 0.2 0.4 0.6 n-Butane Mole Fraction 0.8 1 Exp Liquid Exp vapor

In order to find the best thermodynamic model, the TP-XY for n-butane and n-heptane were plotted for SRK, PR, PSRK, and MSRK. They were plotted alongside the experimental data and a regression analysis was done on the data to determine what model was the best fit. The plots are shown below:

SRK/TP-xy Experimental
200 180 160 Temperature C 140 120 100 80 60 0 0.2 0.4 0.6 n-Butane Mole Fraction 0.8 1 Exp Liquid Exp vapor SRK liquid SRK vapor

Peng Robinson/TP-xy Experimental


200 180 160 Temperature C 140 120 100 80 60 0 0.2 0.4 0.6 0.8 1 n-Butane Mole Fraction Exp Liquid Exp vapor PR Liquid PRvapor

PSRK/TP-xy Experimental
200 180 Temperature C 160 140 120 100 80 60 0 0.2 0.4 0.6 n-Butane Mole Fraction 0.8 1 Exp Liquid Exp vapor PSRK liquid PSRK vapor

The graphs all seem similar and we can decide to just go with one of them, but to achieve even more accuracy in our simulation, a regression analysis is done on the data for the vapor phase:

R2 value vs. Thermodynamic Models


1 0.95 R2 Value 0.9 0.85 0.8 0.75 0.7 SRK PR PSRK MSRK Thermodynamic Models
Hexane Vs Heptane
Methane vs. Decane Methane vs. Butane Butane vs Heptane

Based on the analysis, we found out that some were better than others for different binary systems but for a global thermodynamic model we found out that MSRK was the right choice. So MSRK was chosen as our thermodynamic model.

MATERIAL OF CONSTRUCTION
When choosing the material of construction for any process, the corrosive effects of the components in the process must be factored in, because it make the difference between having to replace equipment in the future and not having to do that at all. The material of construction for the different equipments will depend on the contents of the feed and exit streams. In order to choose the material of construction for our process, the NACE corrosion database was consulted. We were able to find corrosion data for each major component: Column1 # 1 2 3 4 5 6 Column1 # 1 2 3 4 5 6 Column1 # 1 2 3 4 5 6 Column1 # 1 2 3 4 5 6 CH4 exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy Steam exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy H2 exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy CO exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy Column2 Conc % 100 100 100 100 100 100 Column2 Conc % 100 100 100 100 100 100 Column2 Conc % 100 100 100 100 100 100 Column2 Conc % 100 100 100 100 100 100 Column3 temp (F) 25-225 25-475 25-225 25-475 25-475 25-225 Column3 temp (F) 212-475 212-475 212-475 212-475 212-475 212-475 Column3 temp (F) 25-475 25-500 25-500 25-500 25-500 275-500 Column3 temp (F) 25-500 25-500 25-500 25-500 25-500 275-500 Column4 Corrosion rate(mpy) <2 <2 <2 <2 <2 <2 Column4 Corrosion rate(mpy) <2 <2 <20 <2 <2 <2 Column4 Corrosion rate(mpy) <2 <2 <2 <2 <2 <2 Column4 Corrosion rate(mpy) <2 <2 <2 <2 <2 <2 8

Column1 # 1 2 3 4 5 6

C2H6 exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy

Column2 Conc % 100 100 100 100 100 100

Column3 temp (F) 25-500 25-500 25-255 25-500 25-500 25-500

Column4 Corrosion rate(mpy) <2 <2 <2 <2 <2 <2

The corrosion data for C3 is similar to that of C4, so it is not shown.

Column1 # 1 2 3 4 5 6 Column1 # 1 2 3 4 5 6 Column1 # 1 2 3 4 5 6 7

C4H10 exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy Naphtha (C5-C10) exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy C12H26 exposure medium CS SS 12Cr Al alloy SS 304. SS 316. (Ni-30Mo) alloy tantalum

Column2 Conc % 100 100 100 100 100 100 Column2 Conc % 100 100 100 100 100 100 Column2 Conc % 100 100 100 100 100 100 100

Column3 temp (F) 25-225 25-225 25-255 25-255 25-255 25-225 Column3 temp (F) 25-225 25-225 175-225 25-225 25-225 175-225 Column3 temp (F) 25-225 25-225 25-225 25-225 25-225 25-225 25-225

Column4 Corrosion rate(mpy) <2 <2 <2 <2 <2 <2 Column4 Corrosion rate(mpy) <2 <2 <2 <2 <2 <2 Column4 Corrosion rate(mpy) <20 <20 <20 <20 <20 <2 <2 9

The table below shows a suitable material for the syngas unit reactor, but not the corrosion rate.

Column1 # 1

CO2/N2/O2/H20 exposure medium (chlorendic unsaturated polyester, glass fiber reinforced)

Column2 Conc % 100

Column3 temp (F) 120

Column4 Corrosion rate(mpy)

Based on the data collected in the tables above, a combination of materials has to be used for the process. For example, we can use carbon steel for the naphtha reboiler, we also have to use a Nickel alloy for the equipment that will be separating the diesel from naphtha. These are just examples of how the equipment will be chosen; safety handbooks will also be consulted to see if the contents of the entry stream have any adverse reactions with our chosen material.

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EQUIPMENT TYPE AND SIZING In this FT synthesis processes utilized different equipment like heat exchangers, distillation columns. The brief description of general equipment sizing and detailed description of specialized equipment sizing is shown below.

1. Heat Exchangers: There are multiple heat exchangers integrated in our design .All of the heat exchangers were sized using the following equation Where Q is the duty, U is the overall heat transfer coefficient, A is the heat transfer area and Tlm is the log mean temperature difference. The overall heat transfer coefficient for the condenser is 850 W/m2C, and for the reboiler is 1140 W/m2C.

2. Distillation columns: Three distillation columns are used to meet the purity specifications of the products. The tower height can be calculated with the help of number of trays and tray spacing .The number of trays can be changed as the tower is optimized. Therefore, the tower height (H) is given by,

Volume of the tower is given by

3. Reflux tank: The reflux tank was sized according to hold uptime and volumetric flow rate. The holdup time for the reflux tanks was 10 min. Reflux Tanks can be sized using the following relation:

Where V is the volume of the drum, M is the mass flow rate; t is the holdup time and density.

is the liquid

Diameter of the drum for totally condensed liquid is given by4 the following relation which considers diameter to be 4 times the height. [ ]

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4. Pumps: Centrifugal pumps were used because they are cost efficient and can be easily controlled using controlled valves. Each of the pump was sized according the formula below; ( ) ( ( ) ( ))

5. Tray efficiency Based on 41 sets of performance data for different sets of trays Drickamer and Bradford correlated the overall stage efficiency. The data was collected for mainly hydrocarbons mixtures and few water and miscible organics4. The correlation produces the following empherical equation ( ) Where is the viscosity of liquid in centipoise, Eo is the overall efficiency in percent.

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SPECIALIZED EQUIPMENT DESIGN Syngas Reactor Syngas reactor was one of the major equipment for our design .It is the reactor where methane feed with addition of carbon dioxide, oxygen and steam is converted into carbon monoxide and hydrogen. For the syngas reactor different reactions were given in the problem statement and are as follows:

Here the first reaction is the partial oxidation reaction. This was modeled offline and the two reactions that follow are equilibrium reaction these reactions were modeled in chemcad in an equilibrium reactor. The partial oxidation reaction is exothermic and two equilibrium reactions are exothermic. The reactors were aligned in series in such a way that the exothermic partial oxidation would provide the heat needed for the endothermic equilibrium reaction. The reactor had to be optimized in such a way that the steam to methane ratio would be 0.5 mol/mol so as to prevent coking and hydrogen to carbon monoxide molar ratio out of the syngas reactor was to be optimal at 2:1 molar ratio. The following optimization was done to achieve this.

H2/CO ratio
2.25 H2/CO molar ratio 1000F preheat 500F

2.2
2.15 2.1 2.05 2 1.95 0 1000 2000 3000 Molar Flow rate CO2 (kmol/h) 4000 5000

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From the optimization we found out that the preheat temperature did not make any difference. The best ratio was achieved at 2.01:1 molar ratio of hydrogen to carbon monoxide. The molar flow rates of components are given in the table. Best ratio at 3300 and 3400 T. (F) 500 750 1000 CO (kmol/hr) 8664 8664 8664 H2(kmol/hr) 17410 17410 17410

The above diagram shows the PFD of the syngas section. Methane, steam and carbon dioxide are sent in as feed. These components are then sent to a preheater which heats the feed to 600 F .The preheated feed is then mixed with oxygen, compressed and sent to the syngas reactor. The product that comes out of the syngas reactor is mostly carbon monoxide and hydrogen. The stream also contains some water and unreacted carbon dioxide and oxygen. The stream coming out of the syngas reactor is then cooled by a train of heat exchangers and sent to a phase separator. In the phase separator water is separated out as liquid and sent to waste treatment whereas the gas is sent to FTR section of the plant.

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FISHER TROPSCH REACTOR DESIGN The FTR reactor was the most important piece of equipment in the project. Therefore a proper design of this equipment was necessary. It was also one of the most difficult parts of the design. FTR reactor is the reactor where conversion of syngas to different hydrocarbon chains takes place. The product selectivity of different hydrocarbon chains was based on different equation as given below:

Conversion of syngas ( Product Selectivity )

The selectivity of C5+ was based on Anderson Shulz Flory probability distribution ( * ) +

The calculations for the FTR reactor had to be done by simultaneous solving of material, hydraulic and heat balance around the reactor. The following equations were used in solving the reactor. The material balance was given by the general mole balance around a packed bed reactor.

Where the rate equation was given by Langmuir Hinshelwood form ( )

The rate equation here was heavily based on the partial pressures of the components and the temperature. The hydraulic balance around the reactor was achieved using the Ergun equation relating catalyst weight to the pressure drop.

The heat balance around the reactor was achieved using: ( ( ) )

The overall heat transfer coefficient was given in the problem statement as:

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Where G is the inlet mass velocity and D is the tube diameter. The equations above were solved simultaneously using math lab and we found out that the optimum conversion was 30% and the pressure drop was 38.0 psi. The temperature profile down the reactor seemed to increase at the end of the reactor and was calculated to be 650 K.

As seen in the figure above the conversion profile down the reactor increased until it reached a plateau. Different boiler feed water temperatures were used to achieve optimum conversion. The optimum conversion achieved was 30% at boiler feed water temperature of 450 K and catalyst weight of 45000 lbm. Above BFW temperature of 450 K the conversion did increase but was unstable and led to a runaway reaction.

The figure above shows the temperature profile down the length of the reactor related by catalyst weight. The conversion profile showed us that the temperature increased as the catalyst weight/length down the reactor increased and around 50000 lbm of catalyst there was a runaway reaction. Therefore use of 45000 lbm of catalyst which was below the runaway conditions was used and optimized. The following summarizes the different values that we got for the FTR reactor.
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Conversion (X) = 30% Pressure Drop (P) = 38.9 psi GHSV = 100/hr 11 reactors in parallel in 1st train 8 reactors in parallel in 2nd train 1.4 in diameter tubes 1 in tube spacing 3857 tubes per reactor.

The figure above is the PFD of the FTR section. Syngas containing carbon monoxide, hydrogen and carbon dioxide enters the FTR section from Syngas section. The stream is first sent to an absorber where carbon dioxide is absorbed off using MEA. From the absorber we have almost pure carbon monoxide and hydrogen coming out. This pure syngas is first sent to a heat exchanger where it is heated and then to a compressor. From the compressor the syngas is then sent to the FTR reactor where conversions into different hydrocarbons take place. The hydrocarbons out of the reactor are then sent to a heat exchanger and separation section for further processing.

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PRODUCT SELECTIVITY After calculating the reactor conversion, we were able to calculate the product selectivity for the different alkanes. Methane is dependent on temperature over the range of 390-450oF, the equation is below: ( [ T is the reactor operating temperature in degree K. After calculating the selectivity of methane, we could calculate the selectivity of the C2-C4 alkanes. They are linked to that of methane by the following equations: ( ) ( ) )]

The selectivity for C5+ can be calculated using the Anderson Shultz-Flory equation: ( Mn is the relative mol fraction of carbon n. is the chain growth parameter, which is slightly temperature dependent and can be calculated using the following formula: )

Using these equations, the relative mole fraction of the hydrocarbons in the feed was calculated, and the actual molar flow rates are gotten by multiplying the relative mole fractions by the converted molar flow rate of CO into the system.

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ABSORBER SIZING

Number of Equilibrium Stages Absorption is a process in which a gas mixture is contacted with a liquid (the absorbent or solvent) to selectively dissolves one or more components by mass transfer from the liquid. In our project two absorption columns were used in different stages of our design. In the first stage of our design, an absorption column was used to remove CH4 from the incoming gas stream. In the second stage of our design, an absorption column was used to remove CO, H2, and CH4. 1st Absorption column From Seaders Separation process principles,

Where, A is the absorption factor; N is the number of equilibrium trays The absorption factor is given as,

Where, L is the volumetric flow rate of solute-free absorbent; V is volumetric flow rate of solute-free gas; K is the vapor-liquid equilibrium ratio. The incoming gas stream has the following composition. Components CO2 CH4 H2 O H2 O2 N2 CO Total(V) Molar flow rate (kmol/h) 5.98 0.26 0.20 53.71 5.27 0.18 26.07 91.7

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The K values of the different components were obtained at a pressure of 1.88 atm and a temperature of 25C. Components CO2 CO H2 N2 O2 CH4 K-values 0.83 0.023 0.019 0.015 0.032 4.45

Components CO2 CO H2 N2 O2 CH4

A-values 1.80 64.54 78.66 100.54 47.17 0.34

The fraction of each component that is absorbed at different number of stages is presented in a table below.

Components CO2 CO H2 N2 O2 CH4

1 0.64 0.98 0.99 0.99 0.98 0.25

2 0.83 1.00 1.00 1.00 1.00 0.31

3 0.92 1.00 1.00 1.00 1.00 0.33

4 0.96 1.00 1.00 1.00 1.00 0.33

The number of equilibrium stages needed in the first absorption column is 4

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2nd Absorption Column T = 95 F P = 342.43 psia

Components H2 CO H2 O CH4 C2H5 C3H7 N-Butane N-Pentane N-Hexane N-Heptane N-Octane N-Nonane N-Decane N-Undecane N-Dodecane N-Tridecane N-Tetradecane N-Pentadecane N-Hexadecane N-Heptadecane N-Octadene N-Nonadecane N-Eicosane Total

kmol/h 6.124 11.5 0.1011 0.4399 0.0176 0.0176 0.0176 0.7639 0.71032 0.66049 0.61416 0.57107 0.531 0.4938 0.45911 0.4269 0.397 0.3691 0.3432 0.31913 0.2967 0.2759 0.2566 25.7062

K 27.77 15.38

A 0.05402 0.09753

6.65 1.64 0.584 0.195 0.0713 0.02 0.008 0.0001 0.00001 0.000001 0.0000001 0.0000001 0.0001 1E-10 1E-11 1E-12 1E-13 1E-14 1E-15 1E-16

0.22556 0.91463 2.56849 7.69231 21.0379 75 187.5 15000 150000 1500000 1.5E+07 1.5E+07 15000 1.5E+10 1.5E+11 1.5E+12 1.5E+13 1.5E+14 1.5E+15 1.5E+16

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The fraction of each component that is absorbed at different number of stages is presented in a table below

Components H2 CO CH4 C2H5 C3H7 N-Butane N-Pentane N-Hexane N-Heptane N-Octane N-Nonane N-Decane N-Undecane N-Dodecane N-Tridecane N-Tetradecane N-Pentadecane N-Hexadecane N-Heptadecane N-Octadene N-Nonadecane N-Eicosane

1 0.05 0.09 0.18 0.48 0.72 0.88 0.95 0.99 0.99 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

2 0.05 0.10 0.22 0.64 0.90 0.99 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

3 0.05 0.10 0.22 0.72 0.96 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

4 0.05 0.10 0.23 0.76 0.99 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

5 0.05 0.10 0.23 0.79 0.99 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

6 0.05 0.10 0.23 0.82 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

7 0.05 0.10 0.23 0.83 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

8 0.05 0.10 0.23 0.85 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00

The number of equilibrium stages needed in the first absorption column is 8.

Overall Efficiency Using the correlation by OConnell (Seader), the overall efficiency is given as; ( Where,
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))

Ki = K-value of species being absorbed ML =molecular weight of the liquid, lb./lbmol L = viscosity of the liquid, cP L = density of the liquid, lb/ft3 1st Absorption column Component CO H2 2nd Absorption column Component CO H2 Overall Stage Efficiency, % 6.83 7.49 Overall Stage Efficiency, % 50.06 50.85

Tower Diameter 1st Absorption Column The flood velocity, Uf is given as; ( Where, C = capacity parameter of Souders and Brown. L = density of the absorbing liquid = 1000 kg/m3 V = density of the gas stream = 10.5 kg/m3 )

Where, FST = surface tension factor = (/20)0.5 =1.87 FF = foaming factor FHA = 1.0 for Ah/Aa >/0.10 and 5(Ah/Aa) + 0.5 for 0.06 < Ah/Aa <0.1 = liquid surface tension = 70 dyne/cm For no foaming systems, FF = 1.0; for many absorbers, FF may be 0.75 or even less (Seader).

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)(

) (

From Fig 6.24(Seader), with a tray spacing of 24inches, CF = 0.33ft/s Because FLV < 0.1, Ad/A = 0.1 and FHA = 1.0. Thus, ( )( ( )( )( ) )

2nd Absorption Column ( )( ) ( ) ( )

From Fig 6.24(Seader), with a tray spacing of 24inches, CF = 0.23ft/s Because FLV < 0.1, Ad/A = 0.1 and FHA = 1.0. Thus ( )( ( )( )( ) )

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PROCESS FLOW DIAGRAM

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The figure above is the overall process flow diagram of the whole process. The FTR products from the reactor are first sent to a stripping section where leftover methane, hydrogen and oxygen are stripped of the hydrocarbon stream. The hydrocarbons are then sent to a settler where due to their density differences the water can be separated off of the hydrocarbons. The hydrocarbons are then sent to a flash drum where tail gas is separated and sent to the preheater as fuel. The bottom stream from the flash is then sent to another flash drum where 50% LPG is recovered as gas and sold. The bottom stream of the 2nd flash is sent to a series of distillation column where products are separated as ethane, LPG, and Naphtha. The bottom stream of the last distillation column is then sent to hydro- isomerization unit where hydrogen is introduced and the heavier hydrocarbons are broken into LPG, naphtha and diesel.

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UNIT CONTROL AND INSTRUMENTATION


For Unit control and instrumentation a relief valve was sized for the Fischer Tropsch reactor for vapor service. Shown Below is the calculations and equations used for relief valve sizing. In sizing reliefs in vapor service, the downstream pressure must be checked to ensure that it is less than the choked pressure (Daniel, 2008). ( Where Qm is the discharge mass flow Co is the discharge coefficient A is the area of the discharge P is the absolute upstream pressure is the heat capacity ratio for the gas gc is the gravitational constant M is the molecular weight of the gas Rg is the ideal gas constant T is the absolute temperature of the discharge The area of the relief vent given a specified mass flow rate Qm is; ( The required relief vent area for an ideal gas is; ( ( ( ) ( ) (( ( ) ( ) ( ) ) ) ( ( ) )

The pressure, P is the maximum absolute relieving pressure. It is given for the fixed-unit case by,

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From ASME Boiler and Pressure Vessel Code, the following guidelines are recommended for vapor reliefs.

Pmax = 1.1Ps for unfired pressure vessels, Pmax = 1.2 Ps for vessels exposed to fire, Pmax = 1.33 Ps for piping

Using the input streams to the FT R, the area of the relief valve can be calculated. From Chemcad simulation Qm = 1169.75 lbm/h T = 392 F = P = 362.59 psia Cp/Cv = = 1.3683 M = 27.54 lbm/lb-mol ( ( ( ) ( )

( Using the fire scenario for calculation

Co = 0.975

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For our unit control we focused on the control of the FTR reactor as it is the most dangerous piece of equipment in all of the plant. We came up with the following process control.

In the figure above there are many ways safety controls can be triggered. First of all the flow of boiler feed water is controlled by temperatures from different parts of the reactor specifically the hot spots. From the calculations we found out that the hotspots existed around the middle and at the end of the reactor. Next control is the liquid level of the utility fluid. This is to ensure that there is no decrease in the liquid level and hotspot formation. The differential pressure sensors also work in conjunction with the temperature sensor at the exit stream of the boiler feed water. The information from these sensors are sent to an indicator alarm/DIC which then decides to close or open the incoming feed valve if there is any spike in temperature or pressure difference. The closing of feed valve triggers the opening of a PSV in the feed stream so as to direct the feed to an emergency flare. The flow of gas in the emergency flare then triggers the nitrogen purge into the system. This flow of nitrogen then triggers the valve in the exit process stream to clos and PSV activates to direct the contaminated process stream to a bypass vessel. This is done so as to avoid any contamination downstream.

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SAFETY AND ENVIRONMENTAL SUMMARY


HAZARD ANALYSIS The following table shows the potential hazards related to some chemicals in the process. The table is based on SAXs dangerous properties of industrial materials.
Material Health Hazards
A simple asphyxiant High concentrations can cause nausea and unconsciousness due to lack of oxygen Toxic by inhalation can cause systemic changes like nausea, changes in blood pressure etc. Prolonged exposure can cause heart disorders, nerve damage, reproductive effects, brain damage etc. Blurred vision reported when in contact with eye Inhalation in large concentrations can cause rapid circulatory insufficiency and death. An asphyxiant Contact with solid carbon dioxide snow can cause burns A simple asphyxiant Exposure to higher concentration may lead to oxygen deficiency and may cause dizziness, drowsiness, nausea, loss of consciousness and death. Breathing high concentrations (< 75) can cause hyperoxia. Liquid form can severely burn tissue due to extreme cold. Liquid form may cause frostbite An asphyxiant. Moderate concentrations may cause headache, drowsiness and dizziness. Lack of oxygen due to high concentrations of fuel gas may cause death. Inhalation of butane may produce anesthetic effects and feeling of euphoria.

Fire/Explosion Hazard
Very dangerous fire and explosion hazard when exposed to heat or flame. Explosive in form of vapor when exposed to heat or flame. Very dangerous fire and explosion hazard when exposed to heat or flame. Violent or explosive on contact with certain materials like iron oxide, chlorine dioxide, bromine trifluoride and liquid oxygen. Minimal fire hazard (only reacts with certain materials like magnesium, zirconium, titanium etc and explodes). Highly flammable and explosive when exposed to heat, flame or oxidizers. Flammable or explosive when mixed with air, oxygen and chlorine Noncombustible itself but essential to combustion

Corrosion/Reactivity Hazard
Reacts violently with powerful oxidizers (e.g.: chlorine trifluoride, chlorine, fluorine) Incompatible with halogens and interhalogens. Can react with oxidizing materials, halogens, metal oxides, metals and lithium

Methane

Carbon monoxide

Carbon dioxide

Incompatible with acryladehyde, metal acetylides, sodium peroxide.

Hydrogen

Can react vigorously with oxidizing metals. Forms explosive mixtures with bromine, chlorine, chlorine dioxide, liquid nitrogen etc. Can react with all flammable materials. If proper conditions met can react with secondary alcohols, aluminum alloys, alkali metals. The C2-C3 is normally stable. Avoid oxidizing agents, chlorine dioxide, and chlorine.

Oxygen

C2-C4

Highly flammable gas.(C2-C3) Forms explosive mixtures with air and oxidizing agents. Gas may leak, spread and create and explosive region. Flammable when combine with air (C4) .

30

Material Health Hazards


May cause lung damage if swallowed. Minor skin irritant can cause redness or inflammation Inhalation may cause irritation to respiratory system Mildly irritating to eyes Contact with liquid or vapor may cause mild irritation Causes skin irritation with prolonged contact Aspiration may result in chemical pneumonia. Can cause gastrointestinal disturbances, nausea and vomiting. Can also effect the brain and severe cases can cause death.

Fire/Explosion Hazard
Highly Flammable Vapors can ignite rapidly when exposed to ignition source. Moderate fire hazard. Vapors can ignite rapidly when exposed to ignition source. Runoff to sewers may cause fire or explosion hazard

Corrosion/Reactivity Hazard
Stable under normal conditions of use. Avoid heat, flames and sparks and strong oxidizing agents Mostly stable Incompatible with strong oxidizers Can form hazardous decomposition products.

Naphtha Products

Diesel Products

31

The following table shows the safety and first aid measures related to the above mentioned hazards.
Material Methane First Aid Measures Remove to fresh air if inhaled. If not breathing administer artificial respiration and oxygen. Carbon monoxide C2-C4 Fire/Explosion Safety Environmental Safety Follow proper procedures for waste disposal following federal, state and local environmental control. Return in shipping container properly labeled to your supplier. Do not dispose to sewers or water sources Follow proper procedures for disposal following federal, state and local environmental control.

Carbon dioxide

Hydrogen Oxygen

Wear a full face positive pressure self-contained breathing apparatus. Use water spray to stop escaping gas and stop the flow of gas. Remove to fresh air if inhaled To fight fire use foam. Dry chemical and water to blanket If not breathing administer fire. artificial respiration and oxygen. Control containing vessels with If eye in contact with liquid water jets to reduce pressure and immediately flush eyes with plenty explosion of water. Remove to fresh air if inhaled N/A (noncombustible) If not breathing administer artificial respiration and oxygen Flush with plenty of water if exposed to skin or eye Remove to fresh air if inhaled Use dry chemical powders to control small fires. Provide adequate oxygen if Use water spray, fog or foam to exposed to high concentrations control large fire. Remove to fresh air if inhaled in Exclude itself from fire area of high concentrations fire Provide assisted respiration if unconscious. If skin or eye exposed to liquid Immediately spray the fire with immediately warm the frostbite water from maximum distance. area with warm water. Remove ignition source if In inhaled immediately remove to without risk. fresh air. Evacuate all personnel from Provide adequate oxygen if danger area. exposed to high concentrations May use Dry chemical If digested do not induce vomiting extinguisher or water for and contact a physician butane fires

Follow proper procedures for waste disposal following federal, state and local environmental control. Return in shipping container properly labeled to your supplier. Do not dispose to sewers or water sources Follow proper procedures for disposal following federal, state and local environmental control. Return in shipping container properly labeled to your supplier. Follow proper procedures for disposal following federal, state and local environmental control. Follow proper procedures for waste disposal following federal, state and local environmental control. Return in shipping container properly labeled to your supplier. Do not dispose to sewers or water sources

32

Material

First Aid Measures Remove the affected person to fresh air. If not breathing apply artificial respiration. Flush the contaminated skin with large amounts of water and use soap. Flush eye with plenty of water if contaminated. Immediately flush with clean water if exposed to eyes. In inhaled immediately remove to fresh air. Provide adequate oxygen if exposed to high concentrations If digested do not induce vomiting and contact a physician immediately. Remove contaminated clothing and wash the contaminated area with soap and water

Fire/Explosion Safety Isolate from heat source and naked flames. Use foam, water spray or CO2 dry chemical powder for controlling fires

Environmental Safety Recover and recycle if possible. Contain spill with sand, earth or absorbent material. Follow proper procedures for waste disposal following federal, state and local environmental control.

Naphtha Products

Diesel products

Use any extinguisher suitable for small class B fires, dry chemical, water spray, firefighting foam etc. Use water spray, fog or firefighting foam to fight large fires

Follow proper procedures for waste disposal following federal, state and local environmental control. Return in shipping container properly labeled to your supplier. Do not dispose to sewers or water sources

33

Hazard Analysis for Unsafe Operation (HAZOP)


Equipment Process Parameter Guide Deviation Words More Less Level More Less Reactor Temperature More Less Control valve for one of the incoming streams malfunctions Pump Failure Pump malfunction No Power Too much or too less flow in utility stream. Downstream compressor malfunctions, side reactions occurring Tubes in reactor corrodes Wear and tear in control valve. Lack of communication between operators Failure of reboiler utility flow or failure of the condenser Too much flow rate into the tower Causes Consequences Explosions due to over pressurization, Process downtime No control over feed flow to the reactor. Possible runaway reaction Explosion of reactor Runaway reaction Disintegration of products Reduced conversion, Explosion hazard Contamination of product Actions A pressure gauge should be installed between the spring relief valve and rupture disk Install flow indicator in the pipes leaving and entering the pump Install cascade of temperature and flow controllers in the reactor Install back up compressor, Install flow control valves and pressure controllers.

Clogged relief valve

Temperature of the reactor fluctuates Pressure inside the reactor deviates

Pressure

More Less

Level Distillation Column Temperature

More Less

Level indicator malfunctions or insufficient logging of feed data

Adding too much feed to the process and causing over pressurization in the tower or adding too little and damaging the reboiler. Temperature in column reaches unsafe levels. Separation not achieved Flooding the tower, Separation not achieved

More Less More Less More Less

Pressure Heat Exchangers

Temperature of the tower deviates from the set point Overpressure in distillation column Supply too little or too much cooling/heating fluid

All indicators should be maintained and updated regularly and proper protocol should be followed when logging feed data Install control valves on both utility streams of condenser and reboiler Install control valves for the flow in and out of the unit op. Install backup controllers

Flow

Wear and tear of control valves

Excess water is sent to the S/L separator 34

Equipment

Process Parameter Level

Pumps

Guide Deviation Words Liquid level rises More rapidly or decreases Less rapidly

Causes

Consequences Reduces the amount of feed produced. Too much flow or too less flow to unit op. Overflowing of tank and or over pressure. Cooling not achieved.

Actions Making sure all interlocks are appropriately timed

Interlocks malfunctioning

Reflux Drums

Level

More Less

Tank Level

Too high or too flow rate to or from the reflux drums

Level Absorbers

More Less

Output flow rate

Temperature

More Less

High liquid/gas flow temperature Low liquid/ gas flow temperature High or low flow rate into the system

Wear and tear of control valve, or inappropriate dilution of corrosive compounds Temperature of the tower too high or too low Flow rate not controlled Flow control valves malfunction Flow rate not controlled Flow control valves malfunction Level controller malfunctions

Rapid corrosion of MOC, loss in HCl revenue

Low absorption. More/less utility flow rate.

Relief valve should be installed, and an appropriate means of diverting excess fluid should be implemented Care should be taken in calculating the required amount of water for dilution, and the appropriate MOC should be used Install temperature control indicator, set low and high alarms Install appropriate flow control valves upstream and downstream

Flow

More Less

Settler Level More Less

High or low flow rate into the system

Settling velocity is not met. Phase separation not achieved and product is contaminated Separation not achieved. Product may be contaminated by heavies or lights

Install appropriate level controllers in the settler.

35

ENVIRONMENTAL IMPACT An environmental impact analysis was done on the waste water streams and the compounds in our process. By utilizing the environmental impact tool on Chemcad we were able to evaluate each compound and its impact on the environment. The tables showing the impacts are below:

Raw Component Factors


Component Name Carbon Dioxide Methane Water Hydrogen Oxygen Nitrogen Carbon Monoxide Ethane Propane n-Butane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane n-Decane n-Undecane n-Dodecane n-Tridecane n-Tetradecane n-Pentadecane n-Hexadecane n-Heptadecane n-Octadecane n-Nonadecane n-Eicosane Ozone Depletion 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Global Warming 1 11 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Smog Formation 0 0.007 0 0 0 0 0 0.082 0.42 0.41 0.408 0.421 0.529 0.493 0.469 0.464 0.436 0.412 0 0 0 0 0 0 0 0 Acid Rain 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Component Name

Raw Component Factors Human Toxicity

Eco Toxicity
36

OSHA PEL Carbon Dioxide Methane Water Hydrogen Oxygen Nitrogen Carbon Monoxide Ethane Propane n-Butane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane n-Decane n-Undecane n-Dodecane n-Tridecane n-Tetradecane n-Pentadecane n-Hexadecane n-Heptadecane n-Octadecane n-Nonadecane n-Eicosane 9000 0 0 0 0 0 55 0 1800 1900 2950 1800 2000 2350 1050 0 0 0 0 0 0 0 0 0 0 0

LD 50 0 0 0 0 0 0 0 0 0 1226.95 1523.13 28710 2115.28 2411.46 2707.64 3003.61 3300.01 3595.76 3892.16 4145.69 4484.31 4780.49 5076.67 5372.64 5668.82 5965

LC 50 24 38.7995 0 0 0 0 15 95.7331 74.2984 11.6925 6.45919 2.5 1.96554 1.96735 0.477075 0.22227 0.167683 0.330536 0.593462 0.334588 0.194356 0 0 0 0 0

LD 50 0 0 0 0 0 0 0 0 0 1226.95 1523.13 28710 2115.28 2411.46 2707.64 3003.61 3300.01 3595.76 3892.16 4145.69 4484.31 4780.49 5076.67 5372.64 5668.82 5965

37

Below, the environmental impacts of one of our waste water streams are shown: Component Name Water Stream Analysis Flow rate Ozone Global Smog Acid Rain (kg/hr) Depletion Warming Formation (impact/hr) (impact/hr) (impact/hr) (impact/hr) 0.01 0 4.76E-06 0 0 0 5.41E-07 2.23E-06 187.54 0 0 0 0.02 0 0 0 Water Stream Analysis OSHA PEL LD50 (impact/hr) (impact/hr) 4.85E-07 0 0 8.66E-05 0 0.00 0 0

Carbon Dioxide Methane Water Carbon Monoxide

0 0 0 0

Component Name

Flow rate (kg/hr) 0.01 0 187.54 0.02

LC50 (impact/hr) 0.00135 8.66E-06 0 2.36E-03

LD50 (impact/hr) 0 0 0 0

Carbon Dioxide Methane Water Carbon Monoxide

SAFETY CONSIDERATIONS
It is not enough to be able to design a plant that would be able to produce the desired products correctly; the safety of the processes should also be put into consideration. In ensuring a safe process conditions, control valves would be placed on all equipment to control pressure, temperature, and flow rate when needed. Additional process modifications will also be carried out on important equipment. These modifications are shown below; Reactor Drums Provide dip legs in all drums to prevent the free fall of solvent resulting in the generation and accumulation of static charge
38

Install a high-temperature alarm to alert the operator in the event of cooling function loss Install a high-temperature shut-down system .This system would automatically shut down the process in the event of a high reactor temperature Install a check valve in the cooling line to prevent reverse flow Study the cooling water source to consider possible contamination and interruption of supply Install a cooling water flow meter and low-flow alarm ( which will provide an immediate indication of cooling loss) Isolate Reactor with explosion walls

All Equipment Ground all equipment Check the room periodically with colorimetric tubes to determine if any leaked vapors are present Increasing the ventilation with blowers Isolating process lines that contain hazardous streams Regular leak detection would be carried out

It is important to quantitatively carry out a risk analysis. The Chemical Process Quantitative Risk Analysis (CQPRA) is a methodology designed to provide management with a tool to help evaluate process safety in the chemical process industry. The steps1 involved are shown below;

In the event of leak from a vessel, the discharge rate can be quantified for liquid and gaseous flow. From a general discharge rate model

Where P= pressure (kPa) = density ( kg/m3) g = acceleration due to gravity (m/s2) gc = gravitational constant (N/kg-m/s2)
39

z = vertical height (m) v = fluid velocity (m/s) f = frictional loss term Ws = shaft work (J/s) = mass flow rate ( g/s) ef = frictional loss term

Kf = excess head loss due to the pipe (dimensionless)

f = fanning friction factor L = flow path length D = flow path diameter Using the 2k-Method to Estimate Kf ( Where, IDmin = internal diameter in mm For pipe entrances and exits )

For a normal entrance k1 = 160 k = 0.50 Border type entrance k1 = 0 = 1.0 For high Reynolds number NRe > 10000 Kf = k
40

For low Reynolds number NRe < 50 ; Kf = k1/NRe The fanning, f factor is calculated from the equation below; ( ( ) )

{ Where, = pipe roughness For large Reynolds number

For liquid discharge from a pipe assuming the flow is frictionless and that there is no shaft work would result in a Bernoulli equation. ( ) ( ) ( )

The discharge of pure liquids through a sharp edged orifice Where, m = liquid discharge rate (kg/s) A = area of hole (m2) CD = discharge coefficient = density of fluid ( g/m3) gc = gravitational constant (N/kg-m/s2) P1 = pressure upstream of the hole (N/m2) P2 = pressure of downstream of the hole (N/m2) Tank Drainage Time Assumptions used in the equation above are; Constant area Constant discharge coefficient Where,
41

( )

t = time to drain tank from volume V2 to Volume V1 (s) V = liquid volume in the tank above the tank (m3) h = height of the liquid above the leakage (m) Mass discharge rate of liquid from a hole in a tank Where, Pg = gauge pressure at the top of the tank (N/m2) hL = height of liquid above the hole (m) It should be noted that the mass discharge rate decreases with time as the liquid level drops. Therefore, the maximum discharge rate happens when the leak first occurs. Mass discharge rate of gas from a hole in a tank Assumptions Ideal gas No heat transfer No external shaft work Where, k = heat capacity ratio Rg = ideal gas constant T1 = initial upstream temperature of the gas The mass discharge rate at choked flow is given as;
( )

{( )

( )

For ideal gas flow for both sonic and non-sonic conditions is represented by the Darcy formula and is given as; ( )

42

Y = gas expansion factor (unitless) Tempered Reaction ( Where, Q = heat generation by reaction m = mass within reactor vessel (kg) Cv = heat capacity at constant volume (J/kg-C) T= absolute temperature of the reacting material (C) t = time (s) hfg = enthalpy difference below liquid and vapor (J/kg-C) V = reactor vessel (m3) vfg = specific volume difference between liquid and vapor Heat release rate during overpressure {( Where, s = set conditions m = turnaround conditions ) } )

For the quantitative analysis of the safety we considered a situation where there is a leak in oxygen power plant and calculated the effects of the gas leak

Safety Calculation Assuming that there is a leakage of gas in the Air separation unit, the discharge rate of the can be calculated to determine if the leakage can be temporarily fixed or a shutdown of the system is needed. The oxygen flow conditions are provided below; P = 500 psig =34.77 bar T = 75F Heat capacity = 1.37 ( )

43

Assume the diameter of the hole that is causing the leakage is 10mm ( )

( Assume CD = 0.85

Initial flow rate of gas = 651040.8 kg/h

Mass flowrate Vs Diameter


discharge mass flowrate(kg/s) 60 50 40 30 20 10 0 0 0.02 0.04 0.06 0.08 0.1 Diameter(m)

44

As we can see from the figure the quantity of mass discharge can be quantifies. According to our calculations we found out that at around 0.018 m diameter 1% of the mass is lost .This mass lost can be significantly high taking in account the total amount of mass flow rate through the system.

45

HEAT AND MATERIAL BALANCE


Mass balance was done according to kg/hr basis taking in consideration the molecular weight of each component in the entire system. The following table summarizes the overall mass balance of the system.

Feed CO2 Water Oxygen Nitrogen CO Hydrogen Methane sum

Kg/hr 44.01 237.17 393.59 3.446 0 0 422.41 1100.6

Syngas R CO2 Water Oxygen Nitrogen CO Hydrogen Methane sum

Kg/hr 44.01 208.7 1.814 3.446 730.1 108.3 4.224 1101

HE CO2 Water Oxygen Nitrogen CO Hydrogen Methane sum

Kg/hr 44.01 21.16 1.814 3.446 730 108.3 4.224 913

Absorber 1 CO2 Water Oxygen Nitrogen CO Hydrogen Methane sum

Kg/hr 0.02 10.6 0 0 730 108 4.22 853

CO2 out CO2 Water Oxygen Nitrogen sum

Kg/hr 43.995 10.582 1.8136 3.4457 59.836

Out HE Water FTR CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum Kg/hr 0 10.582 0 0 430.76 63.63 37.46 0.388 0.569 0.75 40.44 44.91 48.56 51.47 53.74 55.43 56.63 57.38 57.75 57.78 57.53 57.02 56.31 55.41 54.36 53.19 1402.1 Absorber 2 CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum Kg/hr 0 10.58 0 0 430.8 63.63 37.46 0.388 0.569 0.75 40.44 44.91 48.56 51.47 53.74 55.43 56.63 57.38 57.75 57.78 57.53 57.02 56.31 55.41 54.36 53.19 1402 Top Out CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum

Kg/hr 187.5 kg/hr 0 0 0 430.8 63.63 37.46 0 0.016 0.023 0.031 1.65 1.84 1.99 2.11 2.2 2.27 2.32 2.35 2.36 2.36 2.35 2.33 2.3 2.27 2.22 2.22 567.1 Settler CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum kg/hr 0 10.6 0 0 0 0 0 0.37 0.55 0.72 38.8 43.1 46.6 49.4 51.5 53.2 54.3 55 55.4 55.4 55.2 54.7 54 53.1 52.1 51 835 Sett Out CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum AsTo kg/hr 0 10.58 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10.58

46

Colmn 1 CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum

kg/hr 0 0 0 0 0 0 0 0.37 0.55 0.72 38.78 43.08 46.57 49.37 51.54 53.17 54.31 55.03 55.39 55.42 55.17 54.69 54 53.14 52.14 51.01 824.45

Dist 1 C2 C3 C4 C5 C6 sum Colm 2 CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum

kg/hr 0.356 0 0 0 0 0.356 kg/hr 0 0 0 0 0 0 0 0.017 0.546 0.719 38.78 43.07 46.57 49.37 51.54 53.17 54.31 55.03 55.39 55.42 55.17 54.69 54 53.14 52.14 51.01 824.1

Dist 2 CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 sum Colm 3 CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum

kg/hr 0 0 0 0 0 0 0 0.017 0.546 0.413 0.001 0.977 kg/hr 0 0 0 0 0 0 0 0 0 0.307 38.78 43.07 46.57 49.36 51.54 53.17 54.31 55.03 55.38 55.41 55.17 54.69 54 53.14 52.13 51.02 625

Dist 3 CO2 Water Oxygen Nitrogen CO Hydrogen C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 sum Botms 3 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 sum

kg/hr 0 0 0 0 0 0 0 0 0 0.31 38.8 43.1 46.6 49.4 51.5 52.8 2.33 0.01 285 kg/hr 0.36 52 55 55.4 55.4 55.2 54.7 54 53.1 52.1 51 538

To HI

Tot out Tot in

Kg/hr 1203.9 1100.62

47

ENERGY BALANCE

The energy balance around the reactor was achieved by considering the enthalpy of all the incoming streams and outgoing streams. The following table summarized the energy balance. Overall Energy Balance Feed streams Product Total Heating Total Cooling Power Added Power Generated Total 2.05E+06 -1.00E+07 5.54E+05 -4.87E+04 -1.43E+07 -1.38E+07 MJ/h (Input) -6.12E+06 -1.38E+07 MJ/h (Output)

From the table we calculated the % closure.

48

CONCLUSION
OPTIMIZATIONS AND RESULTS The optimizations were done using the parametric optimization process. In the parametric optimization process important decision variables were varied in order to obtain the most positive net present value in dollars. The following variables were varied in order to achieve optimum conditions.

Feed preheat optimization The feed preheat temperature entering the syngas reactor was optimized in this optimization. This was done until an optimum value was achieved.

NPV vs. Feed Preheat Temp

-$3.64 350 -$3.66 NPV (Billions of Dollars) -$3.68 -$3.70 -$3.72 -$3.74 -$3.76 -$3.78 -$3.80 -$3.82 Preheat Temp. (F) 450 550 650 750 850 950 1050

600 F (-3.65 Billion)

From the optimization we found out that the optimum feeds preheat temperature was 600F at net present value of -3.65 billion dollars.

49

Initial breakdown of NPV The following pie chart shows the initial breakdown of COMd.

Initial Breakdown of COMd


Col FCI 0% 11% Cwt 0%

Cut 21% Crm 68%

COM CWT CUT CRM COL FCI Revenue NPV

4.29E+09 4.18E+06 9.10E+08 2.90E+09 2.80E+06 4.70E+08 4.72E+09 -4.77E+09

From the initial breakdown of COMd we found out that the most expensive contributing factor was cost of raw materials. As we had no control over the price of the raw material, we decided to optimize the consumption of it. We also decide to optimize the FTR unit.

Syngas Unit Optimization To ensure the optimum usage of raw material the syngas unit was optimized using different pressure temperature and oxygen rate. This was done until optimum conditions were achieved.
50

NPV vs. SU (T/P/O2 rate)


4.00 3.00 NPV (Billions of $) 2.00 1.00 1600 1700 1800 1900 2000

0.00 1500 -1.00 -2.00 -3.00 -4.00 -5.00

Pressure 300 psig 2:1 molar ratio 400 psig 500 psig

Syngas Temp (F)


P (psig) 300 500 T (F) 1600 1950 CO (kmol/h) 15314 20058 H2(kmol/h) 31806 41076 O2( kmol/h) 27000 20000

From the optimization we found out that the optimum condition was achieved at the pressure of 500 psig, optimum temperature of 1950 F and oxygen flow rate of 20000 kmol/hr. The net present value obtained was optimum at 2.63 billion dollars.

FTR unit optimization The FTR unit reactor entering the FTR reactor was optimized in this optimization. This was done until optimum conditions were achieved.

FT Reactor Temperature
5 4 NPV ($ Billions) 25 atm 30 atm 20 atm

3
2 1 0 -1 -2 -3 Reactor Temp (C) 200 250 300 350 400

51

From the FTR unit optimization we found out that the optimum entering temperature into the FTR reactor was 251.7 C. This bumped out net present value to 4.2 billion dollars.

Final breakdown of NPV The following pie chart shows the final breakdown of COMd.

Col 0%

Break down of COMd after SU/FT unit optimization


FCI 16%

Cwt 0%

Crm 49%

Cut 35%

COM CWT CUT CRM COL FCI Revenue NPV

5.95E+09 7.64E+06 2.06E+09 2.36E+09 2.80E+06 9.79E+08 7.52E+09 4.95E+09

From syngas and FTR unit optimization as we can see the cost of raw material decreased but cost of utilities increase. Nevertheless the NPV value also went up.

52

Effect if reactor trains in series

Effect of reactor trains in series

X= 60 %
4 NPV (Billions of $) 3 2 1 0 1 2 # of Reactors

X= 30

The above graph shows the effect of reactor trains. We increased the reactor train from just one to two in series this made out conversion increase up to 60% and the optimum NPV obtained was 3.9 Billion dollars

Taking credit for utilities

Taking credit for utilities


5 4.8 4.6 4.4 4.2 4 3.8 Credit for utilities NPV(Billions of $)

No credit forutilities

We also added the credit for different utility streams and tail gas streams according to their heating values. This drastically increased our NPV from 4.2 billion dollars to 4.96 billion dollars

53

Number of Trays/Feed Tray location optimization The numbers of trays/feed tray locations were varied in the three distillation columns in order to achieve the most positive net present value. This was done until an optimum was achieved.

T-101 Optimization
$3,866.80 $3,866.40 NPV ($X106) 15 $3,866.00 $3,865.60 $3,865.20 $3,864.80 $3,864.40 4 6 8 10 Feed Tray Location 12 16 17 18 20 14

For T-101 a net present value of $3866.33X106 was obtained at 15 trays and feed tray location of 7.

T-102 Optimization
$3,891.60 $3,891.55 $3,891.50 $3,891.45 $3,891.40 $3,891.35 $3,891.30 $3,891.25 $3,891.20 $3,891.15 4 6 8 10 Feed Tray Location 12 14

NPV ($X106)

16 17 18

For T-102 a net present value of $3891.566X106 was obtained at 16 trays and feed tray location of 10.

54

T-103 Optimization
$3,891.58 $3,891.57 NPV ($X106) $3,891.57 $3,891.56 $3,891.56 $3,891.55 $3,891.55 $3,891.54 $3,891.54 4 9 14 Feed Tray Location 19 19 20 21 22 23

For T-101 a net present value of $3891.573X106 was obtained at 22 trays and feed tray location of 10.

Tie Spec optimization After concluding on the working conditions for the separation process, we changed the recovery rate of the various organics from each column. To achieve this tie spec for the reboiler of the distillation columns were optimized by also varying the tie spec for the condenser. T-101:Tie Spec Optimization

3892 NPV ($X106) 3891.6 3891.2 3890.8 3890.4 3890 0.85 0.9 0.95 1 Tie spec for reboiler 1( MCB-TCB) 1.05 Tie spec Reboiler 0.9 0.99 0.999

A maximum NPV value of $3891.554X106 was obtained at reboiler tie spec 0.99 mole fraction of and condenser tie spec of 0.9999 mole fraction.

55

T-102:Tie Spec Optimization


3891.6 3891.2 3890.8 3890.4 0.85 0.9 0.95 1 1.05 Tie spec for reboiler 1( MCB-TCB)

NPV ($)

Tie spec Reboiler 0.999

A maximum NPV value of $3891.554X106 was obtained at reboiler tie spec 0.999 mole fraction of and condenser tie spec of 0.99 mole fraction.

T-103:Tie Spec Optimization


3891 3890.5 3890 3889.5 3889 3888.5 3888 3887.5 3887 0 0.5 1 1.5 2 Tie spec for reboiler 1( MCB-TCB)

Tie spec Reboiler 0.9 0.99 0.999

A maximum NPV value of $3890.722X106 was obtained at reboiler tie spec 0.9 mole fraction of and condenser tie spec of 0.3 reflux ratio.

NPV ($)

56

ENERGY EFFICIENCY We calculated the mass of carbon in the feed stream and exiting LPG, Naphtha, and Diesel streams by doing a species balance on the carbon and estimating the closure with the following formula:

Hydrocarbon Feed CH4 LPG C3 C4 Naphtha C5 C6 C7 C8 C9 C10 Diesel C11 C12 C13 C14 C15 C16 C17 C18 C19 C20

Carbon Mass 2.99E+05 6.90E+03 9.17E+03 6.05E+03 6.97E+03 7.28E+03 2.43E+03 1.27E+03 6.85E+02 2.06E+04 2.20E+04 2.29E+04 2.38E+04 2.45E+04 2.51E+04 2.56E+04 2.61E+04 2.65E+04 2.68E+04

Mass of carbon in out energy efficiency

kg 2.99E+05 2.85E+05 95.23

The energy efficiency of our system is approximately 95%; we have assumed that the rest of the carbon is used up as fuel in the power generation unit or the unaccounted recycle stream..

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RESULTS We calculated the capital and operating cost of a GTL plant that utilizes a low temperature FT reactor. After performing all the optimizations we found out that these are the best conditions for our GTL plant. The following table summarizes the best case conditions: Economics Summary
Best case NPV FCI Top 5 equipment (name/cost) 1 2 3 4 5 COM ($/yr.) Top 5 utilities (name/dollars) 1 FTR 290,000,000 FTR E-109 E-105 T-102 T-103 33,207,000 2,800,000 1,560,000 900,000 832,000 5,903,400,000 $ 4,960,000,000 5,200,000,000 Cost of Raw materials ($/yr.) Methane Oxygen Carbon Dioxide Steam Catalyst MEA Waste treatment ($/yr.) Revenue Total ($/yr.) LPG Naphtha Diesel 2,360,000,000 339,000,000 543,000,000 9,300,000 7,900,000 40,260,000 879,000,000 6,220,000 7,520,000,000 526,000,000 1,410,000,000 5,589,000,000

2 3 4 5

Oxygen Plant 217,000,000 E-101 E-109 E-105 183,000,000 61,000,000 60,300,000

Credit For Utilities ($/yr) 1 2 3 4 Fuel gas lps mps

18,287,000 1,370,000 4,800,000 11,800,000

Steam Condensate 407,000 MSRK

Operating Labor ($/yr)

1,240,000

Thermodynamics

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After performing all the optimizations and calculation our final NPV value obtained was $ 4.96 Billion. The pie chart below shows different utility breakdown; which is followed by equipment specifics of final design.
C-102 0% C-SU1 P- 0%

Utility Breakdown
O2 plant 19% E-101 16% E-102 E-103 E-104 0% 7% 3% E-105 5% E-107 2%

10 P-102 A/B 3 0% A/ B C-101 P-101 A/B 0 0% 0% H-101 1% R-102 15%

E-106 1% R-101 26% E-109 5% E-108 0%

The most contributing utility in our final design were the two reactors followed by oxygen plant and syngas cooling heat exchanger train.
NPV Feed Ratio (Hydrogen/Carbon monoxide) Reactor 1 Volume Pressure Temperature Reactor 2 Volume Tower 101 Number of Trays Feed tray location Tower 102 Number of Trays Feed tray location Tower 103 Number of Trays Feed tray location Tie spec for T-101 Distillate Comp mole fraction Bottoms Comp mole fraction Tie spec for T-102 Distillate Comp mole fraction Bottoms Comp mole fraction Tie spec for T-103 Distillate Reflux Ratio Bottoms Comp mole fraction 0.3 0.9 0.99 0.999 0.9999 0.99 22 10 16 10 15 7 533 m3 533 m3 25 atm 500 of $4.96E+9 2:1

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RECOMMENDATIONS
We used a distillation column to separate the tail gas (ethane) from the rest of the FT products. This method proved cumbersome, because we either had to operate the column at pressures above 300 psia, or use a refrigerant at -50C. Both alternatives were expensive; we would recommend that a different means of removing the ethane be researched. Another alternative to our process will be to operate the FT reactor at temperatures that favor the product that is in demand. For instance, the FT reactor produces more diesel at temperatures between 200 and 250C and more of the lighter alkanes at higher temperatures. Also we have evidence that suggests the separation of LPG from Naphtha, and Diesel can be done in a fractional distillation column. The product selling price in the problem statement is not current. The increase of price of the product to current values will positively impact the NPV. However as the fuel prices increase there will inevitably increase in utility and raw materials but from the following graph we see that 25% increase in selling price will increase the NPV by 79%.This will definitely impact NPV positively even with the increase in utility and raw materials.

25% increase in Product Selling Price


30.00 20.00 10.00 0.00 0.3 Naphtha $100/bbl Diesel $118/bbl

NPV (Billions of $)

0.4
Selling Price ($/lb)

Also investigating production of oxygen with the plant is another option to consider. As oxygen was the most expensive utility production of oxygen will drastically reduce raw materials cost. Also there are different methods of syngas production which are more efficient. From our research we found out one of them is auto thermal reforming .This can also impact NPV. Another option is investigating catalyst life. From a quantitative analysis we found out that doubling the catalyst life increase the NPV by 6%.The graph below shows the relation.
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5.50 NPV(Billions of $)

Effect of Doubling Catalyst Life


6% increase in NPV (317

5.00

4.50 4 Catalyst Life 8

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10.Fixed-Bed Catalytic Reactors. Nob Hill Publishing, LLC. 11.Beiermann, Dipl.-Ing. Dagmar. From Fischer Tropsch Rawproducts to Fischer Tropsch
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