Kamal Mustafa Dawood Zafar Osama Hasan Oun Hasan Syed

Supervisor: Dr. Arshad Hussain Department of Chemical Engineeirng SCME, NUST H-12

OBJECTIVE
To design a Chemical Production Plant that produces NH3 and CO2 for urea fertilizer using Coal Syn gas rather than conventional Natural Gas feedstock.

MOTIVATION
Gas curtailment to fertilizer plants Rising fertilizer demand Hiking fertilizer prices Unexploited coal deposits

PROCESS FLOW DIAGRAM

(PFD)

PROCESS DESCRIPTION
SECTION
Air Separation

UNIT
Operation

KEY FOCUS
To separate air into N2 and O2 to ensure supply into UCG well and Ammonia Reactor Convert CO to CO2 and maximum hydrogen production To reduce concentration of CO2 up to 0.05 vol% on dry basis. To get synthesis gas free from CO2 and CO up to less than 5 ppm To separate methane from hydrogen

METHOD
Pressure Swing Adsorption

ASSISTANCE
Carbon Molecular Sieves

AUXILIARIES
Compressors, De Oxo Reactor, Chilled Water Air Cooler Cooling Water, HP Waste heat boiler, BFW Pre Heater LP Steam, LP BHW Pre-Heater, Cooling Water Heat Exchangers, Cooler, Separator Compressors, Chilled Water BFW Pre-Heater, Chillers, Heat Exchangers, Compressors

Shift Conversion

Process

Catalytic Shift Conversion

Iron Oxide Catalyst, Copper Oxide Catalyst, Steam aMDEA absorbent, Piperazine Activator Packing Rings PKR Catalyst (Nickel Based) Carbon Molecular Sieves

CO2 Removal

Process

Absorption

Methanation

Process

Catalytic Bed Reactor Pressure Swing Adsorption

Methane Separation

Operation

Ammonia Synthesis

Process

To produce ammonia from nitrogen and hydrogen

Habers Process

Iron Oxide Catalyst

MATERIAL BALANCE
Streams Components CO CO2 CH4 H2 Air PSA inlet Mole% kmol/hr De-oxo reactor inlet Mole% 1.56 kmol/hr 8.41 HTSC inlet Mole% 17.05 23.86 4.54 34.09 20.46 100.00 kmol/hr 71.53 100.14 19.06 143.06 LTSC inlet Mole% 1.70 39.21 4.54 49.43 kmol/hr 7.15 164.52 19.06 207.44 CO2 Absorber Inlet Mole% 0.18 42.25 4.71 52.86 kmol/hr 0.72 170.95 19.06 213.88 Methanator Inlet Mole% 0.3055 0.2190 8.14 91.33 kmol/hr 0.7153 0.5129 19.06 213.88

O2
H2O N2 NH3 (NH2)2CO Total Streams Components CO CO2 CH4 H2 O2 H2O N2 NH3 (NH2)2CO Total

21.00
79.00 100.00

140.11
527.06 667.17

0.78
97.66 100.00

4.20
527.06 539.67

85.84 419.63

5.11 100.00

21.46 419.63

0.0033 100.00

0.0135 404.62

0.0058 100.00

0.0135 234.18

Methane PSA inlet Mole% 0.0003 0.0002 8.82 91.18 0.0007 100.00 kmol/hr 0.0007 0.0005 20.29 209.69 0.0016 229.97

NH3 reactor inlet Mole% 10.42 63.79 23.39 2.40 100.00 kmol/hr 144.91 886.93 325.22 33.31 1390.36

Urea reactor inlet Mole% 33.33 66.67 100.00 kmol/hr 68.75 137.50 206.25

Urea reactor outlet Mole% 100.0000 100.00 kmol/hr 69.4444 69.44

Recycle Mole% 13.00 61.00 23.00 3.00 100.0 0 kmol/hr 144.30 677.24 255.32 33.31 1110.33

Purge Mole% 13.00 61.00 23.00 3.00 100.00 kmol/hr 0.61 2.86 1.08 0.14 4.69

ENERGY BALANCE
Tin
Reactant Trxn Hremoved Reaction

Hsupplied

Tout
Product

ENERGY BALANCE
CO CO2 CH4 H2 H2O (g)
T in deg C 25 25 25 25 25 T in deg C 200 200 200 200 200 a b c d

36.11 28.95 34.31 28.84 33.46

4.23E-02 4.11E-03 5.47E-02 7.65E-05 6.88E-03

-2.9E-05 3.55E-06 3.66E-06 3.29E-06 7.60E-06

7.46E-09 -2.2E-09 -1.1E-08 -8.7E-10 -3.6E-09

n kg mole/hr 7.153 164.52 19.06 207.44 21.46

H J/gmol 1.21E+02 5.16E+03 7.09E+03 5.06E+03 6.01E+03 2.34E+04

Enthalpy of Syn Gas (kW) Heating Potential (kW)

1760.179 n.H*1000 J/hr 8.63E+05 8.48E+08 1.35E+08 1.05E+09 1.29E+08 2162121716 600.589365 1159.59012

Co-eff H f (25 deg C) H rxn (25 deg C) T in deg C 25 25 25 25 H Reactants H Products

kJ/gmol -41.164 T out deg C 200 200 200 200

CO 1 -110.52 kJ/gmol a

Efficiency b

H2O 1 -241.826 90% c

CO2 1 -393.51 H rxn (25 deg C) d m g mol 1 1 1 1

H2 1 0 -37.0476

CO H2O CO2 H2

36.11 33.46 28.95 28.84

H (CO) + H (H2O) H (CO2) + H (H2)

4.23E-02 6.88E-03 4.11E-03 7.65E-05

-2.9E-05 7.60E-06 3.55E-06 3.29E-06

1.31E+01 1.02E+01 kJ/mol -4.0E+01

7.46E-09 -3.6E-09 -2.2E-09 -8.7E-10

CpdT J/gmol.K 7.08E+03 6.01E+03 5.16E+03 5.06E+03

m.Cp.dT kJ/K 7.07877044 6.00975088 5.1557207 5.05690913

H rxn (200 deg C)

H p - H r + H rxn(25 deg C)

kJ/hr -1.1E+06

kW -317.314

ENERGY BALANCE
H HTSC LTSC
in

Sup/Rem

Rxn

Prd. Rem

out

(kW)

(kW)

(kW)

(kW)

(kW)

-313.29 1760.18

161.52 -1159.59

1911.95 317.314

1760.18 917.904

LTSC - Absorber
Absorber-Methanator Methanator

917.904
131.414 538.604

-775.89
464.89 55.9

10.6
57.7

131.414
538.604 594.504

PSA
Compressor Compressor - Convertor Convertor

594.504
7.534 238.374 327.104

-581.125
228.02 88.73 675.722 3940.57

5.845

7.534
235.554 327.104 4943.396

4202.328

-897.723

6225.734

74.145

9456.194 9456.194

H out = Hin + H rxn - H pr + H sup/rem

SHELL AND TUBE HEAT EXCHANGERS

SPECIFICATION SHEET
Heat Duty Mass of Oil LMTD Number of Tubes Tube Side Flow Area Tube Side HT Co-Efficient Shell side Flow Area Tube Wall Temperature Q m LMTD Nt at hio
as

229520 KJ/hr 4477.15 kg/hr 39.11 C 313 tubes 0.05995 m2 920.94 kJ/hr.m2. C

0.01871 m2
168.43C 1026.6 kJ/hr.m2. C 485.45 kJ/hr.m2.K 469.16 kJ/hr.m2.K 124.884 m2 0.00071 7.6 psi 0.1203 psi

tw Ho Uc UD A Rd Ps PT

Shell Side

Santotherm

Shell Side HT Coefficient Clean Overall Coefficient,

280OC
Tube Side 300OC

10OC
Syn-Gas 80OC

Design Overall Coefficient, Total Heat Transfer Area

Dirt Factor
Shell Side Pressure Drop Tube Side Pressure Drop

SYN GAS COMPRESSOR

SPECIFICATION SHEET
Average Molecular Weight MWavg 20.98 kg kmol

Compressibility Factor
Heat Capacity Ratio Inlet Volume

Z
k V

0.999
1.343 0.3564 m3 kg 2494 m3 hr 11,500 rp 398.24 kJ kg 154.625 oC 14

Volumetric Flowrate
Nominal Speed Overall Head

Q
Nnominal H T2

ELLIOT / MOLLIER METHOD TEMPERATURE 80OC PRESSURE 4 bar 30 bar 155OC

Outlet Temperature Number of Stages Actual Speed Approximate Power Required

N G

1250 rpm 992.863 kW

HIGH TEMPERATURE SHIFT CONVERSION

Iron based catalyst Porosity = 0.3

SPECIFICATION SHEET
Weight of the catalyst Volume of Catalyst Bed Volume of Reactor Diameter of Reactor Height of Reactor W Vc VR D H 714.778 kg 0.18 m3 0.24 m3 0.467 m 1.4 m

Conversion 90 %
Catalyst Weight (Plug Flow Fixed Bed Reactor Equation)
F W= CO rCO 0.9 0 dX

Rate of Reaction
Ea PCO PH 1 2 2 rco =ko e RT Pco n PH O m PCO p PH q 1 2 2 2 Keq PCO PH O 2

Catalyst Area
Height of Catalyst Bed Volumetric Flow-rate Space Time Wall Thickness Density of Gas Mixture Viscosity of Gas Mixture Pressure Drop Across Catalyst Bed

Ac
Hc Vo

0.17 m2
1.06 m 0.184 m3/s 1.287 s 0.012 m

Reaction Rate constant

ko =725

mol mnpq s gcat kPa

Equilibrium Constant
Keq =exp 45577.8 4.33 =16.27 T

11.21 kg/m3 0.0212 cP 3.3 atm

LOW TEMPERATURE SHIFT CONVERSION

Copper based catalyst
Weight of the catalyst W 483.53 kg

Porosity = 0.3 Conversion = 90%

Catalyst Weight (Tubular Fixed Bed Reactor Equation)
FCO 0.9 W= r 0 dX CO

Volume of Catalyst Bed

Volume of Reactor Diameter of Reactor Height of Reactor Catalyst Area Height of Catalyst Bed
PCO PH 2 2 Keq

Vc
VR D H Ac Hc Vo

0.11 m3
0.15 m3 0.4 m 1.2 m 0.126 m2 0.9 m 0.1538 m3/s 0,975 s 0.01 m

Rate of Reaction
Ea rco =ko e RT PCO PH O 2

Volumetric Flow-rate Space Time

Reaction Rate Constant

ko =2.96105 mol hr gcatatm2

Wall Thickness Density of Gas Mixture Viscosity of Gas Mixture Pressure Drop Across Catalyst Bed P

13.42 kg/m3 0.0212 cP 4 atm

Equilibrium Constant
Keq =exp 45577.8 4.33 =197.79 T

ABSORBER
Loading Point = 0.5 kmol CO2/kmol MDEA
Absorption Factor Theoretical Number of Trays Ae N 1.723 9

Superficial Velocity
Column Efficiency Actual Number of Trays Height of Column Bottom Flooding Velocity Top Flooding Velocity Total Diameter of the Column Height to Diameter Ratio Flow Arrangement Entrainment Actual Efficiency Total No. of Holes of Sieves Minimum Vapor Velocity

VG
EmV Nac H Vf Uaf D H/D Cross Flow Ea

0.268 ft/s
75% 12 6.33 m 0.333 m/s 0.0625 m/s 1.67 m 3.80 Single Pass 0.0015 74.9% 810 8.46 m/s

Total Plate Pressure Drop

Down comer Liquid Backup Residence Time

Ht
hb Tr

211.45 mm liq.
0.365 m liq. 6.2 s

METHANATOR
Nickel based catalyst
Weight of the catalyst Volume of Catalyst Bed Volume of Reactor Diameter of Reactor W Vc VR D H Ac Hc Vo 402.76 kg 0.124 m3 0.164 m3 0.41 m 1.234 m 0.132 m2 0.732 m 0.13 m3/s 1.26 s 0.01 m P 1.44 kg/m3 0.0201cP 0.32atm

Porosity = 0.3 Overall Conversion = 99%

Catalyst Weight (Tubular Fixed Bed Reactor Equation)
FCH 0.999 4 W= r 0 dX CH4

Height of Reactor Catalyst Area Height of Catalyst Bed Volumetric Flowrate

Rate of Reaction
Ea rco =ko e RT PCO 0.7 PH 0.3 2

Space Time Wall Thickness Density of Gas Mixture Viscosity of Gas Mixture

Reaction Rate Constant

lbmol ko =50105 hrlbcat atm

Pressure Drop Across Catalyst Bed

AMMONIA REACTOR
Iron Oxide (Fe2O3) catalyst Single Pass Conversion 25 % Porosity = 0.3
Reaction Rate Weight of the catalyst Volume of Catalyst Bed Volume of Bed 1 Volume of Bed 2 Volume of Bed 3 Volume of Reactor ra W Vc 1 2 3 VR D 2.109103 kgmol/m3hr 293.7 kg 0.11 m3 0.02 m3 0.033 m3 0.061 m3 0.164 m3 0.3 m

Catalyst Volume (Fixed Bed RxnEquation)

2 0.25 dX Vcat = 0 rA FH

Diameter of Reactor

Height of Reactor
Catalyst Area Height of Catalyst Bed Volumetric Flow-rate

H
Ac Hc Vo P

2.86 m
0.07 m2 1.63 m 0.08 m3/s 2.53 s 41.8 kg/m3 0.029 cP 20.2 atm

Rate of Reaction = . .
. . . .

Space Time Density of Gas Mixture Viscosity of Gas Mixture Total Pressure Drop

INSTRUMENTATION AND PROCESS CONTROL

MANIPULATED VARIABLES
Feed stream flow rate Temperature of the reactor jacket Fluid level inside the reactor

DISTURBANCES
Temperature of the reactor Pressure of the reactor Composition of streams

CONTROL LOOPS USED

Feed backward control loop Feed forward control loop

HAZOP Study
LTSC INLET TEMPERATURE
Deviation Possible Cause Effect Corrective Action High Low flow rate of Cooling Medium Catalyst damage Increase cooling media flow rate

COST ESTIMATION
Fixed Capital Cost Working Capital $ 7,398,087.404 $ 369,904.37

Total Project Cost

Total Variable Cost Total Fixed Cost Direct Production Cost

$ 7,767,991.77
$ 4,584,218.32 $ 4,734,775.94 $ 9,318,994.26

Annual Production Cost

Production Cost Total Production Cost

$ 11,182,793.11
$ 0.0314/kg $ 3140/day

CONCLUSIONS
Process is feasible and is a solution to current Natural Gas Crisis Pinch Point Analysis Heat Integration. Surplus CO2 production for other facilities.

Methane produced can be used as fuel.