Pilot Scale Plant: Production of

Hydrogen via Steam Reforming of

Methane.
– Membrane Reactor-

GROUP 3
AHMAD ALIYAN ALIF BIN ISMAIL (24121)
FARIDA HAMIMI BINTI RUSLAN (21379)
MOHAMAD HAFEZ BIN MAZLAN (18557)
MUHAMMAD IKRAM FIRMAN (16001278)
MUHAMMAD RAHMAT SYAFIQ BIN ZAINAL ABIDIN (24120)
VELISIA CHANDRA GUNAWAN (24084)
Catalysts
Catalysts Advantages Disadvantages

Ni/PSS <84% conversion

(membrane reactor)

Fe-Cr Oxide Up to 83% conversion At 400°C favor CO

production

Ni/SBA-15 Commercially used (low 53-55% conversion

cost)
OPERATING CONDITION

Operating Condition Value

Temperature 500˚C
Pressure 9 bar
Membrane Pd/PSS
Thickness of Membrane 6μm
Permeability 0.0101779 m3atm/hr
Feed CH4
H2 recovery 90%
Sweep gas N2
MEMBRANE SELECTION

Membrane Type Advantages Disadvantages

Pd based - Commercialization still limited
membrane - Low hydrogen permeability
- Low mechanical resitance
- High costs
Pd-alloys - Less brittle - Contamination/ deactivation of palladium
- Improve hydrogen by carbon compound at T > 450˚C
solubility - Irreversible poisoning by Sulphur
- High cost of Pd
Pd/PSS (Dense - High H2 perm-selectivity
Pd-layer - High permeability and
deposited into permselectivity
porous support) - Good mechanical
resistance
Optimum Condition
Reaction Operating Conditions Disadvantages/Advantages

ΔH°298K = +164.9kJ/mol Used in steam reformers

(800-850°C) High energy consumption
Requires expensive high alloy
ΔH°298K= -41 kJ/mol steel

ΔH°298K= 206 kJ/mol higher CH4-conversion by H2-

(500-600°C) removal
Reducing CO(poisonous to
catalyst)
Increasing the potential
formation of carbon deposits
on the catalysts.
These temperatures can be dramatically decreased when using
membrane reactors as hydrogen recovery through Pd based
membranes drives the reactions toward the products [43]
 Volume & Space Time Calculation
𝐹𝐴0 FD
𝑊
Calculate Volume 𝑉=
𝜌
FD = 2536.79 Find rnet [1]

2 3 4
Volume =

Find Space Time

Mass Balance
𝑥
𝐹𝐴0 𝑑𝑥
1 5 𝐹𝐴0 = 𝐶𝐴0 𝑉0
𝑊𝑃𝐵𝑅 = න
0 𝑟𝑛𝑒𝑡 STEPS τ = V/ Ѵ0

[1] (Silva D.Y, Moraes de Abreu C.A, 2016)

6
 𝑘𝑔
𝑞𝑝 = 2283.11
ℎ MEMBRANE OVERALL LENGTH 280
𝑦𝑝 = MEMBRANE OVERALL SURFACE AREA 498.5745
Low-pressure MEMBRANE LENGTH 1.5
𝑃ι = 1 bar
side NO OF STAGES 5
STAGE LENGTH 0.3
High-pressure 𝑃𝐻 = 9 bar MEMBRANE LENGTH PER STAGE 56
side
𝑘𝑔 𝑘𝑔 NO OF HOLLOW MEMBRANE PER STAGE 186.6667
𝑞𝑓 = 3170.98 𝑞0 = 887.87
ℎ ℎ MEMBRANE OVERALL DIAMETER 0.187
𝑥𝑓 = 0.73 𝑥0 = 0.286
𝑞𝑝 qf xf qo xo qp yp θ ph pl t p'A D L A
θ= 3170.986 0.73 887.8761 0.285714 2283.11 0.795932 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 200 0.628319
𝑞𝑓
3170.986 0.73 887.8761 0.285714 2283.11 0.822753 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 210 0.659734
3170.986 0.73 887.8761 0.285714 2283.11 0.848755 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 220 0.69115
θ𝑞𝑓 𝑦𝑝 3170.986 0.73 887.8761 0.285714 2283.11 0.873973 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 230 0.722566
𝐴𝑚 =
𝑃′𝐴 3170.986 0.73 887.8761 0.285714 2283.11 0.898443 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 240 0.753982
( 𝑡 )(𝑃ℎ 𝑥0 − 𝑃ι 𝑦𝑝 ) 3170.986 0.73 887.8761 0.285714 2283.11 0.922198 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 250 0.785398
3170.986 0.73 887.8761 0.285714 2283.11 0.945268 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 260 0.816814
𝑃ℎ 𝑥0 3170.986 0.73 887.8761 0.285714 2283.11 0.967683 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 270 0.84823
𝑦𝑝 = 3170.986 0.73 887.8761 0.285714 2283.11 0.98947 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 280 0.879646
θ𝑞𝑓
൘ 𝑃′𝐴 + 𝑃ι 3170.986 0.73 887.8761 0.285714 2283.11 1.010655 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 290 0.911062
𝐴𝑚 ( 𝑡 ) 3170.986 0.73 887.8761 0.285714 2283.11 1.031263 0.72 8.716707 0.986923 0.000006 1.02E-02 1.00E-03 300 0.942478
 STAGES STAGE 1 STAGE 2 STAGE 3 STAGE 4 STAGE 5
MEMBRANE LENGTH 0.3 0.6 0.9 1.2 1.5
MEMBRANE OVERALL LENGTH 56 112 168 224 280
PERMEATE MOLE FRACTION 0.288342 0.517547 0.704117 0.858934 0.98947
How Membrane Works
𝐶𝐻4 + 2𝐻2 𝑂 𝐶𝑂2 + 4𝐻2
Ni/α-𝐴𝑙2 𝑂3 𝐶𝑂2

𝐻2
 Reaction Separation System

Porous Stainless steel

Palladium Membrane
Catalyst Bed
Fig 1: Cross Sectional Area of the
membrane reactor
• Effects of Pressure on the performance of the membrane
• Pressure generally increases the conversion and rate of reaction
• A range of optimum pressure have to be used to avoid the rupturing of the
membrane
• A study have shown after other variables have been fixed and pressure is
varied from between 2 bar to 10 bar ,as the operating pressure or the pressure
of the feed was increased, the H2 mole fraction in the retentate decreases
implying H2 removal (Rui Ma et al. , 2016)
• FBMR is an alternative to the current steam reforming
technologies .
• Current technologies faces a number of constraints the
main being the requirement of high exit temperatures
due to the Thermodynamics.
• The system is constructed using two concentric tubes
where the external layer is made of stainless steel while
the inner layer is made up of Palladium based
membrane.
• Palladium membrane was selected because hydrogen gas
can permeate it. Near 100% permeation can be achieved.
• The catalyst is placed in the annular space between the
tubes.
• Steam, Methane gas and N2 is added to the area where
the catalyst is placed which is the annular space between
the two tubes.
• Its job is to combine chemical reaction and hydrogen
separation in only one system reducing capital costs.
 Strategy to Maximize Selectivity and Yield
• Le Chatelier’s Principle is the key to formulating strategies to increase yield and selectivity.
• In order to decrease the carbon deposit on the surface of Ni catalyst due to unwanted side
reactions such as conversion of CO to CO2, a high H2O/CH4 ratio has been usually adopted.
• The position of equilibrium will move so that the concentration of H2O decreases again - by
reacting it with CH4 and turning it into CO2 and H2. The position of equilibrium moves to the right.
• Increasing the partial pressure of Steam and methane, the rate of reaction of the desired reaction
increases, hence the reaction shifts to the right. The selectivity of the desired reaction to the
undesired also increase. This can also be seen from the Langmuir-Hinshelwood Equation below

Jie Hu, De Hua, Yinwei Li, Hui Wang, Xin Zhang, “Influences of Reaction Conditions on Steam Reforming of Methane Over Ni/ZrO2 Catalyst”, American Chemical Society, Division of
Fuel Chemistry Society,Vol 48 pp.739,2011.
 Strategy to minimize the undesired reactions
& maximize yield and selectivity.
In particular, the use of a Pd-based MR allows for the continuous removal of H2, owing to the complete selectivity of the Pd
membrane towards hydrogen permeation, shifting the reactions toward further product formation and, consequently, yielding an
increase in conversion [1,2].

Pore Size
• The degree of selectivity of a membrane depends on the membrane pore size. The pore size must be specific for 𝐻2 /𝐶𝑂2 and need
to be maintained.
Sweep Gas
• Lin et al. [4], applied both a higher reaction pressure and sweep gas with respect to Shu et al. [5], which induced a higher hydrogen
driving force and greater shift effect resulting in improved MR performance.
Membrane Thickness
• Thinner membrane, higher hydrogen permeation flux, more pronounced shift effect, increase conversion. Gallucci et al. [6] and
Jørgensen et al. [7] performed SMR experiments at 400 °C using a fully-dense Pd-Ag, unsupported membrane, with thicknesses of
50 µm and 100 µm, obtaining 52% and 25% methane conversion, respectively.
Membrane Fouling
• Membrane fouling is a critical problem which refers to the blockage of membrane pores during filtration by the combination of
sieving and adsorption of particulates and compounds onto the membrane surface or within the membrane pores. It reduces the
permeate flux, and requires periodic cleanings. Membrane fouling reduction by using different techniques such as pre-treatment
of the feed water, membrane modification, improving the operational conditions and cleaning [8].