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BASIC DESIGN OF PRIMARY REFORMING OF METHANE Final Report

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BASIC DESIGN OF PRIMARY REFORMING OF METHANE
Final Report Submitted
By
Ayush Adhikari Roll No.: 01
Atlantic Bhandari Roll No.: 07
Prakash Bhattarai Roll No.: 08
Saroj Raj Kafle Roll No.: 12
Shyam Lamichhane Roll No.: 15

DEPARTMENT OF CHEMICAL SCIENCE AND ENGINEERING

SCHOOL OF ENGINEERING
KATHMANDU UNIVERSITY

January 2019
Contents

List of Figures ........................................................................................... i

List of Tables ............................................................................................ii
Abstract .................................................................................................. iii
1 Introduction ........................................................................................ 1
1.1 Primary Reformer .......................................................................................2
2 Design Basis ........................................................................................ 3
3 Process Description ............................................................................ 5
4 Process Flow Diagram ....................................................................... 6
5 Piping and Instrumentation Diagram ............................................. 7
5.1 Piping and Insulation Specification ...........................................................8
6 List of Equipment and Instrumentation.......................................... 9
6.1 List of Equipment ........................................................................................9
6.2 List of Instrumentation ...............................................................................9
7 Equipment Specification Sheet ....................................................... 11
8 Conclusion ........................................................................................ 13
Appendix I: Symbol List ....................................................................... 14
Appendix II Reformer Calculations .................................................... 15
Appendix III Other Calculations ......................................................... 17
9 References ......................................................................................... 19
List of Figures

Fig 1.1Urea Production Process Flow Diagram ..................................................... 1

Fig 3.1 Primary Reformer ...................................................................................... 5
Fig 4.1 Process Flow Diagram (PFD) of Primary Reformer ................................... 6
Fig 5.1 P&ID of Primary Reformer ........................................................................ 7

i
List of Tables

Table 5.1 Piping and Insulation Specification ........................................................ 8

Table 5.2 Insulation Properties............................................................................... 8
Table 6.1 List of Equipment................................................................................... 9
Table 6.2 List of Instrumentation (Part 1/2) ........................................................... 9
Table 6.3List of Instrumentation (Part 2/2) .......................................................... 10
Table 7.1 Equipment Specification Sheet ............................................................. 11

ii
Abstract

Urea is manufactured from a two-step process, ammonia synthesis followed by conversion of

ammonia and carbon dioxide to urea. Ammonia synthesis is done by production of synthesis gas
and then oxidation of carbohydrates in natural gas. The Primary Reformer is a tubular reformer,
which produces synthesis gas from the natural gas by catalytically reacting it with steam. For the
design of the Primary Reformer, various design parameters like Capacity, Feed and Product
Specification, Utility Requirement, Safety and Environmental Regulations, Design Codes and
Climatic Data were considered. Within the Reformer, two reactions occur, namely: Steam
Reforming Reaction, in which hydrocarbons react with steam to form Synthesis gas (CO + H2);
and Water-gas Shift Reaction, in which carbon monoxide reacts with water to give Water gas
(CO2 + H2). After the calculations of the parameters, the Process Flow Diagram(PFD) was
constructed along with the Piping and Instrumentation Diagram (P&ID). The various equipment
and instrument used, were specified. Basic design parameters of the equipment were also
calculated. A Primary Reformer of carbon steel of the dimensions 120ft * 12ft * 50ft was
designed with an arrangement of 340 Inconel tubes packed with Nickel catalyst, to produce
9252.422kg-mol/hr product from 7220.116kg-mol/hr feed.

iii
1 Introduction
Urea is the most widely used fertilizer in Nepal, and so the Nepalese Ministry of Supplies
decided to build a urea factory in Bardaghat, Nawalparasi. The proposed plant is expected
to cost Rs. 72 billion and its annual capacity is estimated to be 700,000 tons. Urea is
normally synthesized from ammonia and carbon dioxide. The ammonia that is used to
make urea is produced by combining hydrogen from natural gas with nitrogen from the
air.[1]
It is known that it is possible to produce urea from natural gas in a two-step method. In a
first step, nitrogen is bound as ammonia, and at the same time carbon dioxide is produced
from the natural gas, while in a second method step the ammonia and the carbon dioxide
are converted to urea. Normally, in the first method step, that is the ammonia synthesis, a
synthesis gas is produced from natural gas, and an oxygen-containing gas, e.g. air, in a
steam reformer, and then in a further method step (“secondary reformer”) the oxidation of
the carbohydrates contained in the natural gas is largely concluded. [2]

Fig 1.1Urea Production Process Flow Diagram [4]

The reforming of the hydrocarbon feed takes place in two stages – first, in a direct fired primary
reformer and later in an auto-thermal catalytic secondary reformer. [3] In this report, we will be
dealing with the design of Primary Steam Reformer where, the Natural gas is converted to synthesis
gas.

1
1.1 Primary Reformer [4]
In the primary reformer, synthesis gas is produced by the reaction of natural gas with steam.
Primary reformers are basically fired heater, in which the reforming reaction occurs.
Primary reformers are of different types based on their burner position:
i. Bottom Fired
ii. Top Fired
iii. Terrace Wall
iv. Side Fired

In our design of primary reformer, we have used bottom fired primary reformer with the
tubes lined at the walls of the reformer.

2
2 Design Basis
The primary reformer design has been based on the following data:
 Capacity: 2000 kg-mole/hr (Inlet)
 Feed and Product Specification: The feed and product specifications were
calculated based on the data provided, using Appendix II.

Operating Conditions Feed[5] Product

Temperature, oC 370 800
Pressure, bar 40.0 38.0

Total molar flow rate, kg-mol/h 7220.116 9252.422

Molar Flow rates, kg-mol/h

H2 55.215 3563.178

N2 106.964 106.964

CH4 1637.113 676.1736

C3H8 18.408 0

CO2 81.358 577.6676

H2O 5321.058 3808.594

CO 0 519.8448

 Utilities Requirement:[5]

The following utilities have been utilized:

Fuel: Natural Gas a 25oC and 1 atm
Air Provided: 15% Excess
Steam: 650 psig
Electricity: 480V

 Regulations for Safety and Environment

 As per the Environment Protection Act, 1997[6]:
For Gaseous Effluents:
Maximum Allowable CO concentration = 9.4 ppm
Maximum Allowable SO2 concentration = 75 ppb

3
 Maximum Allowable NO2 concentration = 100 ppb
Maximum Allowable Particulate Matter = 36.4 micron

For Liquid Effluents:[7]

Waste water generation standards = 5 m3/ton of urea produced
Particulate Matter = 2kg/ton of product, 50mg/Nm3
Stack height limit for dispersal ofSO2, min: 9m for steam generation of less than 2
ton/hr

For Noise:
Noise levels: Maximum 75db at day, 70db at night
 Occupational Health and Safety Guidelines
 National Occupational Safety and Health Policy

 Design Code: ASME BPVC Section I - Rules for Construction of Power Boilers

 Climate Data[8]:
For the location of Bardaghat, the nearest climatic data was found for Bhairahawa for
the years 2012/13.
 Approx. Maximum Temperature: 43.8oC
 Approx. Minimum Temperature: 3.5oC
 Maximum Rainfall: 233.6 mm
 Average Rainfall: 22.4 mm

4
3 Process Description [9]
First the hydrocarbon mixture and steam are mixed in the reformer. The conversion of
hydrocarbons to a mixture of CO, CO2 and H2 takes place by two reactions:
1. Steam Reforming
At high temperature (700 – 1100 °C) and high pressure in the presence of a metal
based catalyst (nickel), steam reacts with methane to yield carbon monoxide and
hydrogen. This reaction is strongly endothermic.
CH4 +H2O↔ CO + 3H2

2. Water gas Shift Reaction

Additional hydrogen can be obtained by reacting the CO with water via the water gas
shift reaction which is mildly endothermic.
CO + H2O ↔ CO2 + H2

Here the Rate of shift is fast compared to reforming and Methane conversion favored by:
– High pressure
– high temperature
– high steam to carbon ratio

Fig 3.1 Primary Reformer[4]

5
4 Process Flow Diagram

Fig 4.1 Process Flow Diagram (PFD) of Primary Reformer

6
5 Piping and Instrumentation Diagram

Fig 5.1 P&ID of Primary Reformer

7
5.1 Piping and Insulation Specification [10][11]

a. Pipe used for steam, natural gas and Syn Gas

 Steel name - X2 Cr Ni Mo 18 14 3
 Type - TP316LUG
 Tubacex Code – C26
 Main application - Urea, Ammonia

b. Pipe used for fuel

 Steel name: SS 304

Table 5.1 Piping and Insulation Specification

Required Nominal Inside Outside Insulation

Insulation
Stream Diameter Diameter Schedule Diameter Diameter Thickness
Type
(in.) (in.) (in.) (in.) (in.)

Cellular
Steam 7.841 8 40 7.981 8.625 3.15
glass
Natural Cellular
6.787 8 40 7.981 8.625 3.15
Gas glass
Mineral
Syn
25.512 30 80 29 30 Wool 10.98”
Gas
(Rock)
Fuel 33.94 36 40 35.25 36 - -

Table 5.2 Insulation Properties

Materials Maximum Temperature Thermal conductivity

Cellular gas 430 ⁰C 0.0039 W/m.K

Mineral Wool(rock) 850⁰C 0.0855 W/m.K

8
6 List of Equipment and Instrumentation
6.1 List of Equipment
Table 6.1 List of Equipment[12]
EQUIPMENT LIST
SPEC OPERATION DESIGN
ITEM EQUIPMENT INSUL. DRIVING
NO. QTY AND PART MATERIAL TEMP PRESS REMARKS
NO. NAME TEMP(oC) PRESS(Bar) mm SYSTEM
SIZE (oC) (Bar)
H- FIRED Carbon
1 1 - SHELL 65 1 75 1.1 - -
224 HEATER Steel
H- FIRED INCONEL
2 340 - TUBES 1000 38 1100 42 - -
224 HEATER 601

6.2 List of Instrumentation

Table 6.2 List of Instrumentation (Part 1/2)
OPERATING CONDITIONS
SERVIC FLUID MO VIS
TAG NO. PRESS(Bar) TEMP(OC) FLOW RATE (kgmol/hr) SP. ∆P
E (STATE) L C
NOR MAX. NOR. MAX NOR. MAX. MIN. GR (bar)
(1) WT. Cp
1 TI-214 H-224 STEAM (S) 45.5 50 260 300 5321.06 5400 5200

2 TI-218 H-224 NG (G) 40 45 370 400 1915.2 2000 1900

3 TC-222 H-224 FUEL (G) - - - - - - -

SYN
4 TT-223 H-224 38 42 800 880 9252.422 9500 9000
GAS(SG)
5 PI-213 H-224 STEAM (S) 45.5 50 260 300 5321.06 5400 5200

6 PI-219 H-224 NG (G) 40 45 370 400 1915.2 2000 1900

7 PI-210 H-224 FUEL (G) 10.13 11.14 25 50 15721.86 16000 15500

8 FT-216 H-224 NG (G) 40 45 370 400 1915.2 2000 1900

9 FT-211 H-224 STEAM (S) 45.5 50 260 300 5321.06 5400 5200

10 FT-220 H-224 FUEL (G) 10.13 11.14 25 50 15721.86 16000 15500

11 FY-215 H-224 - - - - - - - -
FIC-
12 H-224 STEAM (S) - - - - - - -
212
FIC-
13 H-224 NG (G) - - - - - - -
217
FIC-
14 H-224 FUEL (G) - - - - - - -
221
15 CV-101 H-224 STEAM (S) 45.5 50 260 300 5321.06 5400 5200

16 CV-102 H-224 NG (G) 40 45 370 400 1915.2 2000 1900

17 CV-103 H-224 FUEL (G) 10.13 11.143 25 50 15721.86 16000 15500

18 GV-105 H-224 STEAM (S) 40 45 260 300 5321.06 5400 5200 5

STEAM
19 SV-104 H-224 40 45 - - - - -
AND NG
NOR- NORMAL FLOW RATE
MAX-MAXIMUM DESIGN FLOW RATE
MIN- MINIMUM DESIGN FLOW RATE
(1) FLUID STATE (2) LOCATION (3) SIGNAL
L: LIQUID L: LOCAL E: ELECTRIC
G: GAS OR VAPOR AO: ANALOG OUTPUT
S: STEAM

9
Table 6.3List of Instrumentation (Part 2/2)[13]
REFE
LINE RENC
TAG NO. SPECIFICATIONS P&ID
NO. ES
(4)
RFQ
LO RANGE CONN. MATERIAL CONT.
NO./ SIG.
INSTRUMENT C. OF SET SIZE BODY/ELEM ACTIO
MAKE (3)
(2) POINT (INCH) ENT N
R
Nickel-
Temperature Indicator 12-16 0-450 PID-
1 TI-214 L - Chromium/Nic -
(Thermocouple) mV (oC) 0010
kel-Alumel
Nickel-
Temperature Indicator 12-16 0-450 PID-
2 TI-218 L - Chromium/Nic -
(Thermocouple) mV (oC) 0010
kel-Alumel
Nickel- Tempe-
TC- Temperature Controller 12-16 0-850 PID-
3 L - Chromium/Nic rature
222 (Eurotherm T.S.) mV (oC) 0010
kel-Alumel Control
Nickel-
TT- Temperature Transmitter 4-10 0- PID-
4 L - Chromium/Nic -
223 (Thermocouple) mA 850(0C) 0010
kel-Alumel
Pressure Indicator 4- 0-50 Copper-Nickel PID-
5 PI-213 L - -
(Strain Gauge) 20mA (bar) Alloy 0010
Pressure Indicator 4-10 0-50 Copper-Nickel PID-
6 PI-219 L - -
(Strain Gauge) mA (bar) Alloy 0010
Pressure Indicator 4-10 0-50 Copper-Nickel PID-
7 PI-210 L - -
(Strain Gauge) mA (bar) Alloy 0010
Flow Transmitter 0-100 PID-
8 FT-216 L 1-5 v - SUS-316 -
(Differential pressure) (Ft/s) 0010
Flow Transmitter 0-200 PID-
9 FT-211 L 1-5 v - SUS-316 -
(Differential Pressure) (Ft/s) 0010
Flow Transmitter 0-100 PID-
10 FT-220 L 1-5 v - SUS-316 -
(Differential Pressure) (Ft/s) 0010
3:1
FY- 4- PID-
11 Flow Transducer L (steam: - - -
215 20mA 0010
carbon)
FIC- 4-10 0-200 Flow PID-
12 Flow Indicator Controller L - -
212 mA (Ft/s) control 0010
FIC- 4-10 0-100 Flow PID-
13 Flow Indicator Controller L - -
217 mA (Ft/s) control 0010
FIC- 4-10 0-100 Flow PID-
14 Flow Indicator Controller L - -
221 mA (Ft/s) control 0010
ASTM A182
CV- Control valve PID-
15 L - 8 F316
101 (Globe valve) 0010
SS
ASTM A182
CV- Control valve PID-
16 L - 8 F316
102 (Globe valve) 0010
SS
CV- Control valve ASTM A182 PID-
17 L - 8
103 (Globe valve) F316 SS 0010
GV- ASTM A182 PID-
18 Glove valve L - 8
105 F316 SS 0010
SV- ASTM A182 PID-
19 Safety Relief Valve L - 8
104 F316 SS 0010
NOR- NORMAL FLOW RATE
MAX-MAXIMUM DESIGN FLOW RATE
MIN- MINIMUM DESIGN FLOW RATE
(1) FLUID STATE (2) LOCATION (3) SIGNAL
L: LIQUID L: LOCAL E: ELECTRIC
G: GAS OR VAPOR AO: ANALOG OUTPUT
S: STEAM

10
7 Equipment Specification Sheet
Table 7.1 Equipment Specification Sheet
PURCHASER / OWNER : ITEM NO. :
SERVICE : LOCATION :
1 UNIT: PRIMARY REFORMER *NUMBER REQUIRED:
2 MANUFACTURER: REFERENCE:
3 TYPE OF HEATER:TUBULAR REFORMER
4 TOTAL HEATER ABSORBED DUTY, MW. :
5 PROCESS DESIGN CONDITIONS
6 CALCULATED DESIGN
7 PROCESS DUTY MM BTU/HR. 357.1692 392.88
1000.4664 1100.51
` C
8 FIRING DUTY, MM BTU/HR
9 WALL HEAT LOSS, MM BTU/HR 20.0093 22.01 VB
10 PCT FIRING DUTY LOST THRU 2.0000 0.022
WALL, %
11 ADIABATIC FLAME TEMP. FROM 1863.2488 2049.57
LHV, OC
12 RADIATING GAS TEMPERATURE, 1224.5765 1347.03
A
OC

13 AVERAGE TUBESKIN 1000.0000 1100

TEMPERATURE, OC
14 MAX TUBE SKIN TEMPERATURE, 1000.0000 1100 D
O
C
LMTD, OC 433.8425 477.22
15
16 WALL TEMPERATURE, OC 65.5556 72.11
17 AMBIENT TEMPERATURE, OC 24.8500 27.335
18 GAS TO TUBE U*A, BTU/HR-OF4 1.415E-05 1.55E-05
19 TUBE TO PROCESS U*A, BTU/HR- 4.574E+05 5.03E+05
O
F Top View
20 GAS TO WALL U*A, BTU/HR-OF4 3.798E-07 4.17E-07
21 WALL TO ATM U*A, BTU/HR-OF 2.731E+05 3.004E+05

22 BRIDGE WALL TEMPERATURE, OC 1060.4929 1166.54

23 COMBUSTION SIDE CALORIFIC 2.886E+04 3.17E+04

VALUE(LHV), BTU/LB-MOL
24 HEAT TRANSFER IN 2.8E+07 3.08E+07
RADIATION SECTION, Watt
25 TOTAL HEAT CONTENT IN 1.45E+08 1.6E+08
CONVECTION SECTION, Watt
26 STACK GAS OUTLET 373.15
TEMPERATURE, K
27 HEAT LOAD, Watt 1.04E+08
28 INLET CONDITIONS :
29 TEMPERATURE, OC 370 (NG) ; 250 (Steam)
30 PRESSURE, BAR 40
31 MOLAR FLOW RATE, 1915.2
KGMOL/HR
32 VAPOR FLOW, KGMOL/HR 5321.058
A
33 OUTLET CONDITIONS :
34 TEMPERATURE, OC 800
35 PRESSURE, BAR 38
36 MOLAR FLOW, KGMOL/HR 9252.422 B
37 COMBUSTION DESIGN CONDITIONS
38 EXCESS AIR, % 15
39 RADIANTION LOSS, PERCENT OF HEAT RELEASE 2 C
40 RADIANT 1060.4929
o
SECTION, C
FLUE GAS TEMPERATURE
41 LEAVING: CONVECTION 100 D
SECTION, oC
42 FLUE GAS QUANTITY, KGMOL/HR 15721.8616
43 FUEL CHARACTERISTICS
44 GAS TYPE:
45 COMPONENT FLOW RATE(KGMOL/HR)
46 METHANE 1315.42
47 OXYGEN 3025.46
48 NITROGEN 11381
49 PRESSURE(PSIA) 146.95
50 TEMPERATURE(C) 25
Front View
51 ENTHALPY( BTU/LB-MOL) 1651.31

11
52 TUBE DESIGN :
53 DESIGN BASIS: TUBE INCONEL 601[14]
SPECIFICATION
54 DESIGN PRESSURE, BAR 44 (Ministry of Environment, NOTE: TUBES MUST BE REMOVABLE FOR CATALYST
Government of India, 1986) LOADING
O
55 DESIGN FLUID TEMPERATURE, C 407
DESIGN TUBE METAL 1100 Type
56
TEMPERATURE, OC
57 TUBE ARRANGEMENT : A Raschig Ring Nickel
58 TUBE ORIENTATION VERTICAL Catalysts Packing
59 SERVICE TEMPERATURE OF 1100 B Insulating Firebricks
TUBE,0C
60 TUBE OUTSIDE DIAMETER, mm 127 C Carbon Steel Vessel
61 MELTING POINT OF TUBE,0C 1370 Shell
62 TUBE WALL THICKNESS, mm 3.4056
D Burner
63 NUMBER OF TUBES 340
64 OVERALL TUBE LENGTH, m 13
65 TUBE PITCH, mm 191
66 TUBE SUPPROT 25Cr-20Ni
67 AVERAGE TUBESKIN 1100
TEMPERATURE, OC
68 CATALYST: Remarks:
69 CATALYST MATERIAL NICKEL[15]
70 BULK DENSITY, KG/m3 849.74
71 VOLUME OF CATALYST, m3 52.52
72 MASS OF CATALYST, KG 44620.8
73 STACK:
74 TYPE NATURAL
75 AMBIENT TEMPERATURE, K 298.15
76 FLUE GAS TEMPERATURE, K 1333.64
77 ATMOSPHERIC PRESSURE, millibar 1013.24
78 STACK MATERIAL(ASTM AND 316 SS
SPECIFICATION)
79 DRAFT, mm H2O 12.7
80 STACK HEIGHT, m 14
81 REFORMER SPECIFICATION
82 VESSEL SHELL: Carbon Steel SA516-70 [12]
83 REFRACTORY:TYPE INSULATING
FIREBRICKS (C-26) [16]
84 REFRACTORY(ASTM C182-88
SPECIFICATION)
85 THERMAL CONDUCTIVITY, 0.35
W/m.K
86 SOFTENING TEMPERATURE, OC 1200
87 MELTING TEMPERATURE, OC 1650-1700
88 THICKNESS OF FIREBRICKS, mm 63.5

12
8 Conclusion

The inlet temperature and pressure of the feeds were taken at 370oC and 40 bar while the outlet
conditions are at 800oC and 38 bar. The total molar flow rate of inlet being 7220.116 kg-mol/hr,
the outlet total molar flow rate, calculated on the basis of mass balance, was 9252.422 kg-mol/hr.
Also, the calculated heat load was 1.04E+08 watt with 15% excess air.
Raschig Ring Nickel catalysts were used with removable tubes for catalyst loading. The bulk
density and volume of catalyst were taken as 849.74 kg/m3 and 52.52m3 respectively, and mass
of catalyst was calculated to be 44620.8 Kg.
The tubes inside the fire heater being specified as Inconel 601 material was designed with
pressure at 44 bar. Fluid and tube metal temperature were designed as 4070C and 11000C
respectively. Tube arrangement was done vertically with tubes of outside diameter of 127mm
and wall thickness 3.4056mm. Calculated number of tubes was 340 and length was assumed to
be 13m with tube pitch 191mm. The dimension of fired heater was estimated as 120ft * 12ft *
50ft.
Natural type stack of material stainless steel was designed at 1013.24 millibar whose ambient
and flue gas temperatures were 298.15 k and 1333.64 k respectively with height 14m and draft
12.7 mm H2O.
Reformer was specified by vessel shell of carbon steel SA516-70, with the walls lined by
insulating firebricks of thickness 63.5mm with specification of C182-88 whose thermal
conductivity is 0.35 W/m.k and melting temperature is around 17000C.

13
Appendix I: Symbol List

Symbol Symbol used for Symbol Symbol used for

H2 Hydrogen FT Flow Transmitter
N2 Nitrogen FIC Flow Indicator Controller
CH4 Methane PI Pressure Indicator
C3 H8 Propane TI Temperature Indicator
CO2 Carbon Dioxide FY Flow Transducer
H20 Steam TC Temperature Controller
C0 Carbon monoxide TT Temperature Transmitter
𝐾𝑟𝑒𝑓𝑜𝑟𝑚 Reforming reaction Rate CV Control Valve
𝐾𝑠ℎ𝑖𝑓𝑡 Shift reaction rate GV Globe Valve
𝑃𝑖 Partial Pressure H Fired Heater
𝑦𝑖 Mole Fraction SV Safety Valve
𝑃𝑡𝑜𝑡 Total Pressure NG Natural Gas
V Volumetric Flow Rate STE Steam
P Pressure SYNG Synthesis Gas
N No of Moles MW Mineral Wool (Rock)
R Gas Constant 𝑃𝑑 Draft
T Temperature 𝐿𝑠 Stack height
𝜌 Bulk Density of Catalyst 𝐹𝑗𝑜 Inlet molar flow rate
𝐶𝑝𝑖 Heat Capacity V1 Reactor Volume
𝑄𝑟𝑎𝑑 Heat Transfer in Radiation 𝐻𝑓𝑗 𝑜 Heat of formation
𝑄𝑐𝑜𝑛𝑣 Heat Content in Convection 𝑣 Velocity of Fluid
𝑇𝑎 Ambient Temperature Z Length of tube
𝑇𝑔𝑎 Flue gas Temperature d Diameter of tube
𝑇𝑔 flue gas Temperature R Universal Gas Constant,
0.0821 [Link]/mol.K
𝑇𝑤 Wall Temperature 𝜎 Stephen-Boltzmann
constant,
5.67*10-8 W/m2.K4

𝑇𝑏 Bridge Wall Temperature α Absorption efficiency

factor
𝑇𝑑 Dew point Temperature F Radiation exchange factor

14
Appendix II Reformer Calculations
1. Material Balance in the Reformer[17]
Steam to carbon ratio 3:1
H20 (Steam) = (3*1773.686) =5321.058
Inlet (Ii) Outlet (Oi) 𝑦𝑖
Element (E)
55.215 6787.717-4x-y 𝑂1
H2 z
106.964 106.964 𝑂2
N2 z
1637.112 x 𝑂3
CH4 z
81.358 1773.686-x-y 𝑂4
CO2 z
18.405 0 𝑂5
C3 H8 z
5321.058 1936.402+2x+y 𝑂6
H20 z
0 y 𝑂7
C0 z
I z 1
Total

1. CH4 + H2O↔ C0 + 3H2

2. C0 + H2O ↔ CO2 + H2

Total C
1637.112+(3*18.405)+81.35 = x + y + CO2out
CO2out = 1773.686 - x - y

O balance
(2*81.358)+5321.058 = y +(2* CO2out) + (H20out)
H20out = 1936.402+ (2*x) + y

H2 balance
55.215 +(2*1637.113)+(4*18.405)+5321.058 = (H2 )out +(2*x)+ H20
(H2 )out = 6787.717- (4*x) – y
3
𝑃 ∗𝑃 26830
𝐾𝑟𝑒𝑓𝑜𝑟𝑚 = 𝑃 𝐶𝑜 ∗ 𝑃H2 = exp (30.114 − ( ))
CH4 H20 𝑡
1
𝑃CO2 ∗𝑃H2 4400
𝐾𝑠ℎ𝑖𝑓𝑡 = = exp (( ) − 4.036)
𝑃Co ∗ 𝑃H20 𝑡

𝑃𝑖 = 𝑦𝑖 *𝑃𝑡𝑜𝑡

15
2. Polymath results

POLYMATH Report No Title

Nonlinear Equations 26-Jan-2019

Calculated values of NLE variables

Variable Value f(x) Initial Guess
1x 676.1736 -6.289E-10 0.5 X
2y 519.8448 2.259E-11 0.5

Variable Value
1 kref 166.1407
2 kshi 1.066177
3 P 38.
4 t 1073.15
5 ych4 0.0730807
6 yco 0.0561847
7 yco2 0.0624342
8 yh2 0.3949428
9 yh2o 0.4116321
10 z 9252.422

Nonlinear equations
1 f(x) = ((yco*P*((yh2*P)^3))/(ych4*P*yh2o*P))-kref = 0
2 f(y) = ((yco2*P*yh2*P)/(yco*P*yh2o*P))-kshi = 0
Explicit equations
1 z = 10604.769-(2*x)
2 yco = y/z
3 yh2 = (6878.717-(4*x)-y)/z
4 ych4 = x/z
5 yh2o = (1936.402+(2*x)+y)/z
6 yco2 = (1773.686-x-y)/z
7 t = 800+273.15
8 kref = exp(30.114-(26830/t))
9 kshi = exp((4400/t)-4.036)
10 P = 38

16
Appendix III Other Calculations
1. Pipe diameter calculation[18]
Rules of Thumb:
- Velocity for gases: 100 ft/s (dry), 60 ft/s (wet)
- Velocity for steam: 100 ft/s (< 8 bar), 150 ft/s (> 8bar)

From Ideal Gas Equation,

n∗R∗T
V= 𝑃

𝑣 = velocity of fluid
𝑉
Area (a) = 𝑣
4∗𝑎
Diameter (d) = √ 𝜋

2. Calculation of heat load[15]

Heat load = ∑𝑛𝑗=1 𝐹𝑗𝑜 (𝐻𝑓𝑗 𝑜 +𝐻𝑗 - 𝐻𝑗 𝑜 ) - ∑𝑛𝑗=1 𝐹𝑗𝑜 (𝐻𝑓𝑗 𝑜 +𝐻𝑗 - 𝐻𝑗 𝑜 )o

𝑇
𝐻𝑗 - 𝐻𝑗 𝑜 = ∫𝑇 𝑜 𝐶𝑝𝑖 ∆𝑇
𝑓
𝑜 𝑇
𝐻𝑗 - 𝐻𝑗 = ∫𝑇 𝑖 𝐶𝑝𝑖 ∆𝑇
𝑓

• 𝐶𝑝𝑖 =( A+ BT + C𝑇 2 + 𝐷𝑇 −2 )*R
ℎ𝑒𝑎𝑡 𝑙𝑜𝑎𝑑(𝑄)
• Number of tube(n) = ℎ𝑒𝑎𝑡 𝑓𝑙𝑢𝑥 ∗3.142∗𝐷∗𝑍 ; heat flux = 20,000 Btu/ hr.ft2
• Reactor volume(𝑉1) = 𝑛*𝜋 *𝐷2 *Z/4

17
 Component A [19] B [19] C [19] D [19] Hfjo [19]

H2 3.249 4.22E-04 0.00E+00 8.30E+03 0

N2 3.28 5.93E-04 0.00E+00 4.00E+03 0

O2 3.639 5.06E-04 0 -2.27E+04 0

CH4 1.702 9.08E-03 -2.16E-06 0.00E+00 -74520

C3H8 1.213 2.88E-02 -8.82E-06 0.00E+00 -104680

CO2 5.457 1.05E-03 0.00E+00 -1.16E+05 -393509

CO 3.376 5.57E-04 0.00E+00 -3.10E+03 -110525

H2 O 3.47 1.45E-03 0.00E+00 1.21E+04 -241818

3. Calculating catalyst required

Mass of catalyst Required = 𝑉1 * 𝜌

𝜌 = 849.74 kg/m3

4. Reformer Calculation [20]

• 𝑄𝑟𝑎𝑑 = 𝜎* α * A* F * (𝑇𝑔 4 -𝑇𝑤 4 )
• α = 0.4
• F = 0.65
• 𝐴 = n * tube pitch * exposed length
• Tube pitch = 1.5d
𝑇 𝑇
• 𝑄𝑐𝑜𝑛𝑣 = ∫𝑇 𝑏 𝐶𝑝𝑖 ∆𝑇 - ∫𝑇 𝑑 𝐶𝑝𝑖 ∆𝑇
𝑟𝑒𝑓 𝑟𝑒𝑓

5. Stack Design [21]

1 1
𝑃𝑑 = 0.35*𝐿𝑠 *P*(𝑇 – 𝑇 )
𝑎 𝑔𝑎

Pd = 12.7 mm H2O; p = 1013.25 mbar

18
9 References

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[Link]
[Link]
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[4] C.M., K. (2017). Primary Reformer Design: Production of Ammonia from Naptha.
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[15] Steam Reforming, Case Study 111.

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 [16] Christy Refractories. (2004, June). Insulating Firebrick. St. Louis, USA: Christy
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