Chapter-2: H2 Production by SMR and Purification

M. Mozahar Hossain
January 27, 2025

Hydrogen production and storage

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H2 Production and Storage
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H2 Production – SMR Major steps
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H2 Production – SMR Process Description
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 Hydrogen Production and Use (in Fuel cells)
CHE-CX

When used in a PEMFC, the product gas from the water – gas shift must be further
processed to reduce CO to < 10 ppm.
H2 Production – SMR Mass/Energy/Economy
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 H2 Production – Steam Methane Reforming
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Table of contents
Steam Reforming of Natural Gas

Process Descriptions

Unit Operations

Chemistry

Thermodynamics – equilibrium, gibbs free energy, equilibrium

constant, conversion, coposition, mole balance, energy balance,
effects of T & P, etc

Catalytic Convrsion - conversion, coposition, mole balance, energy

balance,

Reaction Kinetics, catalytic effects, rate, rate law, etc

Reactor design

Modeling and Simulation, Process Analysis, Optimization etc

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Typical natural gas composition in Saudi Arabia

Non-hydrocarbon gases
“wet’= which condense on compression at T ambient
Associated gas is invariably ‘wet’ than ‘dry’ natural gas
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H2 Production – SMR Process
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H2 Production – SMR Process Description
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H2 Production – SMR Process Description
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H2 Production – SMR Process Description
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 H2 Production – SMR Major Units Operation
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Major units
Hydrotreating/Cracking/pre-
reformer

Desulfurization unit (DSU).

Methane Steam Reformer (SMR)

Primary Reformer

Secondary Reformer

Low-Temperature Water gas Shift

Reactor (LT-WGS)

High-Temperature Water gas Shift

Reactor (LT-WGS)

Hydrogen purification units

H2 Production – SMR Process Conditions
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 H2 Production – Desulfurization Process
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Owing to the high sensitivity of
.
the reforming and WGS catalysts
to sulfur poisoning, a high degree
of feedstock desulfurization is
required - Sulfur levels less than 2
ppm are required.

It is accomplished in the
desulfurization unit (DSU).

Sulfur–organic compounds (e.g.,

thiols) are first converted into This is followed by H2S scrubbing by a
H2S by catalytic hydrogenation ZnO bed (at 340–390°C) according to
reaction (Co–Mo catalyst, 290– the following reaction:
370°C).

A small split stream of the H2 In some cases, traces of halides (Cl, Br, F, I)
product is used as a are also present in the NG & these are
hydrogenating agent in this step. removed by an Al2O3 guard bed.
 HDS (hydrodesulfurization) –
Unit operation and Chemistry CHE-300
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This is followed by H2S scrubbing by a ZnO bed (at

340–390°C) according to the following reaction:

Co–Mo catalyst
290–370°C In some cases, traces of halides (Cl, Br, F, I) are also
present in the NG & these are removed by an Al2O3
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Major units - Desulfurization unit (DSU)
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After the DSU, NG is fed to a catalytic
reforming Unit 2 where it reacts with
steam to produce synthesis gas.

Pre-reformer is designed to remove

higher (C2+) hydrocarbons – > 10
vol%.

Pre-reforming process converts C2+

hydrocarbons in the feed to CH4, COx,
and H2 in an adiabatic reactor at
300–525°C using Ni/Al2O3 catalyst.

Reactions -
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Methane Steam Reformer (SMR)
Objective of the steam reforming process
is to produce syngas.

A catalytic process using Nickel based

catalyst.

Steam is the source of oxygen in the

primary reformer and also it provides
hydrogen.

Steam also suppress coke formation.

The main variables of SMR are;

Temperature, (500 – 900 °C)

Pressure (4-30 atm, typically 20

atm), and

Steam/hydrocarbon ratio (2.5 to 3)

 H2 Production – SMR reactions
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Reactions and Thermodynamics –

 H2 Production – SMR Process Description
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Although the stoichiometry for Equation
2.1 suggests that only 1 mol of H 2 O is
required for 1 mol of CH 4 , the reaction in
practice is being performed using high
steam - to - carbon (S/C) ratio, typically in
the range 2.5 – 3 in order to reduce the
risk of carbon deposition on the catalyst
surface.

Steam and natural gas in the ratio of

2.5:6.0 are reacted (CH4 + H2O ↔ CO +
3H 2 ) at a high temperature (750 – 900 °
C) and pressure (4 – 30 atm) over a nickel
catalyst.

The endothermic SMR reactor effluent gas

containing 70% – 72% H2 , 6% – 8% CH 4 ,
8% – 10% CO, and 10% – 14% CO2 (dry
basis) is cooled to 300 – 400 ° C (steam
produced) and subjected to the exothermic
WGS reaction (CO + H 2 O ↔ CO 2 + H 2 ),
cooled again, and purified in a
H2 Production – SMR Major catalysts
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H2 Production – SMR Major catalysts suppliers
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 H2 Production – SMR Process Description
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The reaction is highly endothermic
& favored by low pressures (since 4
mol of gas are produced from 2 mol). .

𝐶𝐻4 + 𝐻2 𝑂 ↔ 𝐶𝑂 + 3𝐻2

However, in most industrial

application areas, H2 is required at
the pressure of at least 2.0 MPa,

Therefore, the SMR are operated at

elevated pressures (2.0–2.6 MPa). However, in practice: an excess of
steam (commonly, H2O:CH4 = 2.5 -
High pressures allow for a more 3 is used - to prevent carbon (coke)
compact reactor design, thus deposition on the catalyst surface.
increasing the reactor throughput
and reducing the cost of materials. 𝐶𝐻4 + 𝐻2 𝑂 ↔ 𝐶𝑂 + 3𝐻2

Stoichiometrycally - , the molar ratio

of steam to CH is H2O:CH4 = 1:1
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Two reactions responsible for carbon
deposition on the SMR catalyst are
.
(1) CH4 decomposition to H2 & C
𝐶𝐻4 ↔ 𝐶 + 2𝐻2

(2) CO disproportionation
𝐶𝑂 + 𝐶𝑂 ↔ 𝐶 + 2𝐶𝑂2
An addition of the supplemental
steam shifts the reforming reaction
equilibrium away from “C” formation.
To supply heat for the endothermic SMR
reaction, the catalyst is loaded into a
bundle of reactor tubes (~ 15 m long & 12
cm ID) made out of heat-resistant Ni alloy.

The tubes are placed inside a rectangular

furnace with multiple burners mounted
along the inside walls of the box.
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The typical inlet temp. are 450–
650°C, with the product gas leaving
the reformer at 700–950°C.

In a tubular reformer furnace, about

50% of the heat produced by
combustion in the burners is
transferred through the reformer
tube walls & utilized by the process.

The other half of the fired duty is

Therefore, a great deal of effort is
recovered for preheat duties and
spent to optimize the heat flux to the
steam production.
catalyst, the tube thickness, the
Owing to the high endothermicity of catalyst load, etc. to ensure a good
the SMR reaction, the process may reactor performance.
suffer from heat transfer limitations.
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The gaseous mixture containing H2,
CO, and steam (and usually about
4% of unconverted methane) leaves
the reformer at about 800–900°C. .

It is cooled rapidly to about 350°C

(thereby generating steam) and is
fed to WGS reactors, where CO
reacts with steam over a catalyst bed
producing H2 and CO2:

WGS is moderately exothermic.

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Figure below depicts the
equilibrium concentrations of CO
and CO2 in the CO–H2O–H2–CO2
mixture as a function of temperature .
at different H2O/CO ratios.

The increase in the catalyst

temperature, while favorably
increasing the rate of reaction, tends
to shift the thermodynamic
equilibrium to the left.

In practice, a compromise is made

between a high rate and unfavorable
equilibrium and a lower rate and
more favorable equilibrium.
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To achieve high CO conversion, two
reactors are commonly used in
series: HT- and LT-WGS reactors,
respectively. .

The HT-WGS reactor operates at the

inlet temperatures of 340–360°C
and uses an iron–chromium-based
catalyst (90–95% magnetite iron
oxide, stabilized with 5–10% of
chromia, Cr2O3). The combination of HT- and LT-
WGS reactors allows converting
A typical LT-WGS catalyst consists of
92% of the CO in the reformate gas
CuO: 15–30%, ZnO: 30–60%, and
into H2 & lowering the CO content
Al2O3: balance, and it promotes a
in the gas to about 0.1 vol%.
favorable reaction rate between 200
and 300°C.
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The H2 is separated from CO2 and
purified at the final stage of the
process.
.
Older variations of the SMR process
used solvents to remove the acid gas
(CO2) from the gaseous stream after
WGS reactors.

Solvents commercially used for CO2

removal in the gas separation unit
The remaining residual CO2 & CO
include monoethanolamine (MEA),
are removed in the methanation
water, ammonia solutions,
(type a, old) reactor where they
potassium carbonate solutions, and
are converted to CH4 in the
methanol.
presence of H2 (320°C, catalyst: Ni
This operation allows the reduction or Ru on oxide support).
of CO2 concentration in the process
gas to about 100 ppm.
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Modern SMR plants (type b)
incorporate a PSA unit for purifying
H2 from CO2, CO, & CH4 impurities.
.
The PSA unit consists of multiple
(parallel) adsorption beds, most
commonly filled with molecular
sieves of suitable pore size

PSA operates at about 20 atm.

The PSA off-gas is composed of

(mol%) CO2–55, H2–27, CH4–14,
CO–3, N2–0.4, and some water vapor
and is burned as a fuel in the
primary reformer furnace.

Generally, SMR plants with PSA need

only a HT-WGS stage, which may
somewhat simplify the process.
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The H2 plant efficiency is defined as
the total energy produced by the H2
plant divided by the total energy
consumed by the plant, as follows: .

where η is the energy efficiency, EH2 the energy in

H2 product, Esteam, 4.8 MPa the 4.8 Mpa steam
energy (exported), ENG the NG energy, and Esteam, 2.6 If 2.6 MPa steam is considered as an energy input
MPa the 2.6 MPa steam (required). (i.e., it is not produced internally).

The estimated that for the hydrogen plant with the Scholz (another group)- estimated the energy
capacity of 1.5 × 106 Nm3/day, the energy efficiency efficiency of SMR plant at 81.2%.
was 89% (on high heating value [HHV] basis).

If the steam were not included in the equation (e.g.,

4.8 MPa steam could not be used by another
source), the energy efficiency would decrease to
79.2%. The hydrogen plant efficiency drops to
69.1% if
H2 Production – SMR reactions
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 H2 Production – Steam Methane Reforming
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Table of contents
Steam Reforming of Natural Gas

Process Descriptions

Unit Operations

Chemistry

Thermodynamics – equilibrium, gibbs free energy, equilibrium

constant, conversion, coposition, mole balance, energy balance,
effects of T & P, etc

Catalytic Convrsion - conversion, coposition, mole balance, energy

balance,

Reaction Kinetics, catalytic effects, rate, rate law, etc

Reactor design

Modeling and Simulation

H2 Production – SMR Mass/Energy/Economy
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 H2 Production – SMR Major steps
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Typical natural gas composition in Saudi Arabia

Non-hydrocarbon gases
“wet’= which condense on compression at T ambient
Associated gas is invariably ‘wet’ than ‘dry’ natural gas
H2 Production – SMR reactions
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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 H2 Production – SMR equilibrium
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The increase in pressure result in reduced

efficiency, necessitating higher temperatures
to achieve equivalent conversion values
attainable at lower pressures.
 H2 Production – SMR reaction equilibrium
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Effects of Pressure, Steam and Temperature – on

methane conversion

The methane conversion increases with higher

S/C ratios (S/C varies from 1 to 5) and decreases
with increasing pressures (1 – 20 bar pressures
were studied).

A complete conversion of methane could be

achieved around 700 ° C at 1 bar pressure and the
S/C ratio of above 2.5, while a temperature of
above 900 ° C would be required to achieve the
complete methane conversion at 20 bar pressure.

[Importance of Thermodynamics and Kinetics]

 H2 Production – SMR Effects of Pressure, Steam and Temperature –
on methane conversion
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1.0
𝐂𝐇4 + 𝐇2 𝐎 ↔ 𝐂𝐎 + 3𝐇2 0.9
𝐂𝐎 + 𝐇2 𝐎 ↔ 𝐂𝐎2 + 𝐇2 0.8
0.7
ቀPCO )× PH2 3 ቀyCO )× yH2 3

Composition
2
K1 = = 𝑃 0.6
PCH4 )×(PH2O yCH4 )×(yH2O 0.5 H2 (1 bar)
PCO2 ) × (PH2 yCO2 ) × (yH2 0.4 CH4 (1 bar)
K2 = = 0.3 H2 ( 30 bar)
PCO ) × (PH2O yCO ) × (yH2O 0.2
CH4 ( 30 bar)

0.1
Methane conversion increases with
0.0
temperature. 500 700 900 1100 1300 1500 1700
Temperature (K)
The methane conversion increases with 100

Methane % Conversion
higher S/C ratios (S/C varies from 1 to 5) and 80
decreases with increasing pressures (1 – 20
60
bar pressures were studied).
40
A complete conversion of methane could be 20
achieved around 700 ° C at 1 bar pressure and 0
the S/C ratio of above 2.5, while a 200 400 600 800 1000 1200
temperature of above 900 ° C would be Temperature (℃)
required to achieve the complete methane For Steam/Methane Ratio = 1
conversion at 20 bar pressure. For Steam/Methane Ratio = 2.5
For Steam/Methane Ratio = 5
 H2 Production – SMR equilibrium
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The hydrogen and carbon monoxide 0.7

contents of the equilibrium gas

0.6
increase with temperature, which is
explained by the fact that the CO (1 bar) CO2 ( 1 bar) H2O (1 bar)
0.5 CO ( 30 bar) CO2 ( 30 bar) H2O ( 30 bar)
reforming reactions are endothermic.

Composition
0.4
The carbon dioxide content goes
through a maximum. This can be 0.3
explained as follows:
0.2
carbon dioxide is formed in
exothermic reactions only, while it is a 0.1
reactant in the endothermic reactions.
0.0
Hence, at low temperature carbon 500 1000 1500 2000
dioxide is formed, while with Temperature (K)
increasing temperature the
endothermic reactions in which
carbon dioxide is converted become
more important.
[Importance of Thermodynamics and
Kinetics]
H2 Production – SMR equilibrium
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 H2 Production – SMR reaction equilibrium
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Effects of Pressure, Steam and
Temperature – on methane conversion

The methane conversion increases

with higher S/C ratios (S/C varies from
1 to 5) and decreases with increasing
pressures (1 – 20 bar pressures were
studied).

A complete conversion of methane

could be achieved around 700 ° C at 1
bar pressure and the S/C ratio of above
2.5, while a temperature of above 900 °
C would be required to achieve the
complete methane conversion at 20
bar pressure.

[Importance of Thermodynamics and

Kinetics]
 H2 Production – SMR reaction equilibrium
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Effects of Pressure, Steam and Temperature – on
methane conversion

The methane conversion increases with higher

S/C ratios (S/C varies from 1 to 5) and decreases
with increasing pressures (1 – 20 bar pressures
were studied).

A complete conversion of methane could be

achieved around 700 ° C at 1 bar pressure and the
S/C ratio of above 2.5, while a temperature of
above 900 ° C would be required to achieve the
complete methane conversion at 20 bar pressure.

[Importance of Thermodynamics and Kinetics]

H2 Production – SMR equilibrium
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H2 Production – SMR equilibrium
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H2 Production – SMR equilibrium
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H2 Production – SMR equilibrium
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H2 Production – SMR equilibrium
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H2 Production – SMR equilibrium
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H2 Production – Example on Mole balance with multiple
reactions CHE-300
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H2 Production – Example on Mole balance with multiple
reactions CHE-300
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H2 Production – Example on Mole balance with multiple
reactions CHE-300
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 H2 Production – SMR Mass/Mole and Energy Balance
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100 kmol/h of a stream containing 20 mol% CO, 20 mol% H2O, and 60 mol% H2 is combined
with additional steam and fed to a water–gas shift reactor to produce more hydrogen
according to the reaction:

CO+H2O = CO2 +H2

The equilibrium constant of the water–gas shift reaction is 200, and the mole fraction of
hydrogen at the outlet is 0.75. Write and balance the chemical equation. How much
additional steam is fed to the water–gas shift reactor? (Answer: 5.1 kmol/h)
H2 Production – SMR Mass/Mole and Energy Balance
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Housam Binous and

Ahmed Bellagi
"Steam Reforming of
Propane"
[Link]
[Link]/SteamRe
formingOfPropane/
Wolfram
Demonstrations
Project
Published: September
21 2016

[Link]
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Problem 2
A reactor is designed to take in a feed of 200 mol/min of methane and 50% excess steam, and
convert them to CO and H2 with a 65% conversion rate.

Determine the mole flow rates methane, hydrogen and CO in the reactor product stream.
Calculate the Energy Efficiency based on LHV

(For your verification - Answer: methane flow rate at the outlet is 70 mol/min)

CH4 + H2O ↔ CO+ 3H2

(ΔHSR = 206 kJ/mol).

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[Link]
H2 Production – SMR Mass/Mole and Energy Balance
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H2 Production – SMR Mass/Mole and Energy Balance
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H2 Production – SMR Mole Balance in the Furnace
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H2 Production – SMR Mole Balance in the Furnace
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H2 Production – SMR Mole Balance in the Furnace
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H2 Production – Example on mole Balance in the Furnace
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H2 Production – Example on Mole balance with multiple reactions
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H2 Production – Example on mole Balance in the Furnace
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H2 Production – Example on mole Balance in the Furnace
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H2 Production – SMR equilibrium
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H2 Production – Example on Absorber/separation
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H2 Production – Example on Absorber/separation
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H2 Production – Example on Absorber/separation
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H2 Production – Example on WGS reactor and
Absorber/separation mole balance CHE-300
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H2 Production – Example on WGS reactor and
Absorber/separation mole balance CHE-300
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H2 Production – Example on WGS reactor and
Absorber/separation mole balance CHE-300
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H2 Production – Example on reactions and seperation
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H2 Production – SMR reactions
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H2 Production – SMR reactions
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 The CO2 Balance in the Hydrogen Plant
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In a modern SMR H2 plant fed by NG, up to approx. 60% of

the total CO2 produced is contained in the shifted gas (& then
in the PSA tail gas),
The remaining 40% is the product of the combustion of the
additional fuel gas required by the steam reformer.
At last, all the CO2 ends up in the flue gas of the SR heater.

Figure 1 – Simplified H2 block flow diagram

 The CO2 Balance in the Hydrogen Plant
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Typical CO2 flow rates and partial pressures for a 100,000
m3/h (STP) H2 plant are reported in the following Table 1.
It is clear from this example that one ton of H2 produced will
also produce about 9 tons of CO2.
Table 1 – Typical H2 plant CO2 balance

m3/h L/h mol/h kg/hr ton CO2/ton H2

H2 m3/h 100000 100000000 4464286 8928.6
CO2 (kmol/h) 1850000 81400 9.1168
Vm (L/mol) 22.4

100,000 m3/h (STP)

Figure 1 – Simplified H2 block flow diagram

 The CO2 Capture in the Hydrogen Plant
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The CO2 could be captured from any of these three streams
(Fig. 2), with removal efficiency of about 90% (from PSA
tails gas and from SR flue gas) and up to more than 99%
(from raw H2 at higher pressure).

Figure 2 – CO2 removal locations

 The CO2 Capture in the Hydrogen Plant
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The total CO2 potentially removed from the three locations,

calculated with the formula,
 The CO2 Removal Technologies from Syngas
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CO2 removal from syngas is performed at relatively high total

pressure (25-30 barg) & CO2 partial pressure (3-4 bar abs).
 The CO2 Removal Technologies from Syngas
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There are several technologies available,

Amines (MEA, MDEA, aMDEA);
Hot potassium carbonate;
Physical solvents (PEGE, Methanol);
Membranes.
Most of them being used in ammonia plants CO2 removal
section, or in the “old fashion” H2 plant - before the
availability of the PSA technology for H2 purification.
 The CO2 Removal Technologies from Syngas
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The first three categories use

liquid solvents in an absorption -
regeneration sequence.
The “chemical” solvents in this
application are generally less
expensive than the “physical”
ones and allow an almost
complete removal of the CO2;
depending on plant layout, the CO2 stream is
made available at high purity (say >98.5%
vol) and at a pressure of 0.5-1.5 barg.

Membranes performances in
terms of removal efficiency and
purity are expected to be lower.
 The CO2 Removal Technologies from Syngas
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When a traditional plant is retrofitted with the addition of
such removal unit, the SMR burners have to be checked for
the new tail gas composition
which, being poorer in CO2, has a higher tendency to NOx
formation, with the consequence that low-NOx burners
Space for a future installation of a de-NOx catalytic system in
the convection section of the heater, could be considered at
the design stage.
As a consequence of the retrofit the PSA will have some
capacity margin due to the reduced inlet flow rate after CO2
removal.
Licensors active in these technologies include: BASF,
Giammarco-Vetrocoke, Linde, Lurgi, UOP, etc.
 The CO2 Removal Technologies from Flue gas
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CO2 in the SMR flue gas has a very low partial pressure (~0.2
bar abs) and the flue gas actual volumetric flow is 20 times or
more the raw syngas volumetric flow (m3/h).

These two factors & presence of O2, SOx, NOx, dust, makes the
CO2 removal from this stream complicated & expensive.
Nevertheless its quantity is very high & its capture is an
environmental & economical challenge. Main technologies -
Amines (MEA, MDEA); Chilled ammonia
Membranes.
 The CO2 Removal Technologies from Flue gas
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The basic principles of CO2 removal from flue gas are the
same as from raw H2, but the experience is so far limited.
The environmental concern related to the GHG emissions is
determining a growing interest for this application in many
industries, for example in the power sector.
In practical terms a CO2 removal of 85 - 90% is an acceptable
target, and the CO2 is also in this case obtained at high purity
and low pressure.
No pre-investment is needed in case of retrofit of a traditional
plant, however additional ducting and ID fan addition shall be
considered when the unit is added to the SMR plant.
Licensors active in these technologies are: Axens, Fluor, GTC,
MHI, MTR etc.
 The CO2 Capture – Case Study
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We will examine an example of the economic impact of a

CO2 removal unit (from raw hydrogen and from flue gas)
when added to a SMR hydrogen plant.
The technologies considered are in both cases amine based,
using in-house simulations and available technical
documentation.
Different technical solutions may of course lead to different
results, especially considering the different level of maturity
of the technologies involved.
 The CO2 Capture – Case Study
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The selected hydrogen production is 150,000 Nm3/h (134.3 MMSCFD)

from natural gas.

The CO2 removal efficiency from raw H2 and from flue gas is considered
100% (rounded off) and 90% respectively.

The pure CO2 stream is then compressed to 150 barg for sequestration,
EOR or other utilisation (out of the scope of the study).

The economics of the alternatives are evaluated through the “abatement

cost” concept.
“Abatement cost (AC)” is defined as the incremental cost of a low-emission
technology compared to the reference case, measured as € per ton CO2
abated emission (ICCA, 2009).
The CO2 Capture – Case Study CHE-300
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The CO2 Capture – Case Study CHE-300
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The CO2 Capture – Case Study CHE-300
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Simulation, Sensitivity Analysis and Optimization of H2
Production by SMR Using Aspen Plus
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Fig 1. Aspen Plus model of SMR reactor without mixer

Fig 1. Aspen Plus model of SMR reactor with mixer

Simulation, Sensitivity Analysis and Optimization of H2
Production by SMR Using Aspen Plus
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Thermodynamic equilibrium analysis of

steam methane reforming based on a
conjugate solution of material balance
and law action mass equations with the
detailed energy balance
[Link]
Simulation, Sensitivity Analysis and Optimization of H2
Production by SMR Using Aspen Plus
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Simulation, Sensitivity Analysis and Optimization of H2
Production by SMR Using Aspen Plus
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Simulation, Sensitivity Analysis and Optimization of H2
Production by SMR Using Aspen Plus
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Simulation, Sensitivity Analysis and Optimization of H2
Production by SMR Using Aspen Plus
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 H2 Production – SMR Mass/Energy Balance
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Major units
Desulfurization unit (DSU).

Hydrotreating unit

Methane Steam Reformer (SMR)

Low-Temperature Water gas Shift

Reactor (LT-WGS)

High-Temperature Water gas Shift

Reactor (LT-WGS)

Hydrogen purification units

 H2 Production – Steam Methane Reforming
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Table of contents
Steam Reforming of Natural Gas

Process Descriptions

Unit Operations

Chemistry

Thermodynamics – equilibrium, gibbs free energy, equilibrium

constant, conversion, coposition, mole balance, energy balance,
effects of T & P, etc

Catalytic Convrsion - conversion, coposition, mole balance, energy

balance,

Reaction Kinetics, catalytic effects, rate, rate law, etc

Reactor design

Modeling and Simulation, Process Analysis, Optimization etc

H2 Production – SMR Mass/Energy Balance
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 H2 Production – SMR Process Description
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The H2 plant efficiency is defined as the total energy produced by the H2 plant
divided by the total energy consumed by the plant, as follows:

where η is the energy efficiency, EH2 the energy in H2 product, Esteam, 4.8 MPa the 4.8
Mpa steam energy (exported), ENG the NG energy, and Esteam, 2.6 MPa the 2.6 MPa
steam (required).

The estimated that for the hydrogen plant with the capacity of 1.5 × 106 Nm3/day,
the energy efficiency was 89% (on high heating value [HHV] basis).

If the steam were not included in the equation (e.g., 4.8 MPa steam could not be used
by another source), the energy efficiency would decrease to 79.2%. The hydrogen
plant efficiency drops to 69.1% if

If 2.6 MPa steam is considered as an energy input (i.e., it is not produced internally).

Scholz (another group)- estimated the energy efficiency of SMR plant at 81.2%.
 H2 Production – Reactor Design
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H2 Production – Reactor Design

 H2 Production – SMR Mass/Energy Balance
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Major units
Desulfurization unit (DSU).

Hydrotreating unit

Methane Steam Reformer (SMR)

Low-Temperature Water gas Shift

Reactor (LT-WGS)

High-Temperature Water gas Shift

Reactor (LT-WGS)

Hydrogen purification units

H2 Production – SMR Mass/Energy Balance
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H2 Production – SMR Mass/Energy Balance
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H2 Production – Reactor Design
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H2 Production – Reactor Design
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 Steps in heterogeneous catalytic reactions
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Catalyst
Reactant (A) Product (B)

Product (B)
Boundary layer
Bulk fluid phase

Active sites
Product (B)

Reactant (A) Solid catalyst

Reactant (A)121
 Steps in heterogeneous catalytic reactions
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Catalyst
Reactant (A) Product (B)

Bulk fluid phase

Summary of the steps
Product B 7) Bulk diffusion of B
1. Bulk diffusion of reactant A
2. Pore diffusion of reactant A
1) Bulk diffusion of A
3. Adsorption of reactant A
6) Pore diffusion of B
2) Pore diffusion of A 4. Surface reaction to form
Reactant (A)
product B
5. Desorption of product B
3) Adsorption of A 5) Desorption of B
6. Pore diffusion of product B
4) Surface reaction to form B 7. Bulk diffusion of product B

Active site
A section of a porous catalyst 122
 4. Design of Isothermal Packed-Bed Reactor
Substituting (3) into (2) gives:

(4a)

(4b)

Remarks:
▪ While catalyst deactivation is unavoidable, as we have seen in Chapter VI, there are
many applications in which it is very slow (say, 2-3 years), so that catalyst activity is
essentially constant

▪ Accordingly, PBR design calculations should take into account variation of pressure
along the reactor, as described by the Ergun equation. The design problem then
becomes more complicated and in most situations we need to combine Equation
(4a) or (4b) with the Ergun equation and solve a set of differential equations
numerically
123
 H2 Production – Reactor Design
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The SMR reaction results in the production of H2 and CO2 and is a strongly
endothermic reaction and favored at high temperatures.

Heat transfer is critical to ensure fast kinetics as the reaction moves forward.

To enhance SMR reaction, the following approaches can be employed:

Integration of SMR reaction and products (H2 or CO2 ) separation steps to shift
the equilibrium and enhance the reaction rate in the forward direction.

This also lowers the reforming temperature to achieve the same conversion
level.

Novel reactor design with improved mass and heat transfer.

Efficient heat transfer facilitates reaction kinetics and decreases energy

consumption. As such, reactor size and cost can be significantly reduced.

Alternative heating sources to increase system efficiency. This may lead to

additional benefit of reducing CO2 emissions.
 4. Design of Isothermal Packed-Bed Reactor
In considering the subject of isothermal, catalytic, reactor design, we
are usually interested in answering questions such as:
a) Given data on reaction kinetics, catalyst particle, and product
specifications, how much catalyst is required, and what is the required
reactor volume?
b) Given data on reaction kinetics, catalyst particle, and a fixed amount
of catalyst, what is the expected conversion of the limiting reactant
and what is the product distribution?
c) In trying to answer (a) and (b), how significant are inter-phase and
intra-phase mass transfer effects in the reaction system under
consideration?

In this section we shall focus attention on questions (a) and (b), by

developing and applying the performance equation for an isothermal,
steady-state, PBR.

125
 4. Design of Isothermal Packed-Bed Reactor
❑In the case of solid catalytic reactions, the amount of catalyst is what
is important for product formation
❑Therefore it is more suitable to define the bulk rate of the catalytic
reaction on the basis of catalyst mass (W) as follows :

❑The bulk rate of the reaction per mass of catalyst can be related to
reaction rate per volume of reactor, (-rA), using the bulk bed density,
ρB [mass of catalyst/volume of reactor]. Therefore,

126
 4. Design of Isothermal Packed-Bed Reactor
▪ We need to distinguish between the density of the particle, ρp, and
bulk density of the bed ρB. The two densities are related as follows:

where εB is bed porosity or bed void fraction, which is defined as the

volume of voids per volume of the reactor. Thus the fraction of solids
in the reactor, i.e., volume of catalyst per volume of reactor, is (1- εB)

127
 4. Design of Isothermal Packed-Bed Reactor
Assumptions:
❑Plug flow of the fluid phase; i.e. the velocity profile is flat across the
bed.
❑Even distribution of flow over the bed cross-section ( no radial
velocity profiles)
❑The heterogeneous nature of the system may cause appreciable
concentration differences between the bulk fluid and internal and/or
external surface of the catalyst particles. These differences are
accounted for using the effectiveness factor concept
❑Pressure drop across the catalyst bed is negligible
❑Catalyst deactivation is insignificant

128
 4. Design of Isothermal Packed-Bed
Reactor (cont.)

We can write a steady-state mole balance for component A, over the differential
element ΔW, as follows:
in – out + generation – consumption = accumulation

(1)

where FA is the molar flow rate of component A, and is the effectiveness factor

129
 4. Design of Isothermal Packed-Bed Reactor
Taking the limit of ΔW → 0 re-arrang; we obtain the differential form of the
performance equation:
(2)

we can integrate Equation (2) to obtain the integral form of the performance
equation:

We can also express the performance equations in terms of conversion of reactant A:

knowing that:
FA =FA0 - FA0 XA.
Or:

dFA dX A
= 0 − FAo (3)
dW dW
130
 4. Design of Isothermal Packed-Bed Reactor
Substituting (3) into (2) gives:

(4a)

(4b)

Remarks:
▪ While catalyst deactivation is unavoidable, as we have seen in Chapter VI, there are
many applications in which it is very slow (say, 2-3 years), so that catalyst activity is
essentially constant

▪ Accordingly, PBR design calculations should take into account variation of pressure
along the reactor, as described by the Ergun equation. The design problem then
becomes more complicated and in most situations we need to combine Equation
(4a) or (4b) with the Ergun equation and solve a set of differential equations
numerically
131
H2 Production – Reactor Design
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A plant for producing 500 tons/day of H2 gas

using refinery off gas
H2 Production – Reactor Design
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A plant for producing 500 tons/day of H2 gas

using refinery off gas
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H2 Production – Reactor Design
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H2 Production – Reactor Design
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Production of 1.5 ton H2/hr
SMR is endothermic rxn – Heat of reaction 225 kJ/mol
No of reactor tubes supposed “n” we calculated
(height 15 m, 12 cm internal tube diameter)

Does it satisfy heat transfer?

Consider the above catalytic reaction. Using the rate equation found for
this reaction determine the amount of catalyst needed in a packed bed
reactor(assume plug flow) for 35% conversion of A to R for a feed of
2000 mol/hr of pure A at 3.2 atm and 117°C.
Example - 1

Consider the above catalytic reaction. Using the rate equation found for
this reaction determine the amount of catalyst needed in a packed bed
reactor(assume plug flow) for 35% conversion of A to R for a feed of
2000 mol/hr of pure A at 3.2 atm and 117°C.
Example - 2
 4. Design of Isothermal Packed-Bed Reactor
Example-1:

143
 4. Design of Isothermal Packed-Bed
Reactor (cont.)

We can write a steady-state mole balance for component A, over the differential
element ΔW, as follows:
in – out + generation – consumption = accumulation

(1)

where FA is the molar flow rate of component A, and is the effectiveness factor

144
 4. Design of Isothermal Packed-Bed Reactor
Taking the limit of ΔW → 0 re-arrang; we obtain the differential form of the
performance equation:
(2)

145
 4. Design of Isothermal Packed-Bed Reactor
Example-1:

149
 4. Design of Isothermal Packed-Bed Reactor
Example-1:

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 4. Design of Isothermal Packed-Bed Reactor
Example-1:

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 4. Design of Isothermal Packed-Bed Reactor
Example-1:
H2 Production – SMR equilibrium
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H2 Production – SMR Kinetics/rate
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