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B.Eng (Hons) Chemical Engineering
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9. References ................................................................................................................................ 12
1. Hydrogen Production
Hydrogen can be produced through multiple pathways
First would be through the electrolysis of water which can be done using a multitude of
electrical sources. The first source would be fossil fuels. However, the cost incurred would be
high as this would require a constant source fuel to run the generators which may reduce profit.
The environmental impacts as well as the longevity of the process should also be considered
as fossil fuel sources will eventually run out. [1]
Second would be the production of hydrogen through the conversion of biomass which can be
further separated into 2 categories: thermal gasification and pyrolysis. Typical gasification
method requires high temperature to heat up the biomass and disengage to combustible gas. To
increase the energy value, air; steam or oxygen can be used as an agent for gasification. This
process is operated at a temperature of 300⁰C, pressure from 103.41 to 206.82 kPa and it also
favors wet biomass. The optimal condition was determined at 500⁰C, atmospheric pressure and
steam to biomass ratio of 10:1 for the thermos-chemical gasification process. 65% volume of
hydrogen will be produced with the presence of nickel catalyst. Pyrolysis is a process whereby
biomass is being convert into liquid oils, solid charcoals and gaseous compounds at a high
operating temperature of 650 to 800K and an operating pressure of 0.1 to 0.5 MPa under an
anaerobic condition. Fast pyrolysis is considered to be the most suitable condition for hydrogen
production instead of slow pyrolysis as the products are mainly charcoal. Fast pyrolysis
requires high and rapid heating process of the biomass feedstock in the absence of air. The
vapor product is then condensed to a dark brown mobile bio-liquid. [2]
Lastly, the production of hydrogen through catalytic steam reforming. The process is an
endothermic process where the system is operated at a very high temperature, where the
temperature of the gas leaving the catalyst is commonly in an overabundance of 650⁰C.
Hydrogen gas will be produce through catalytic steam reforming a hydrocarbon feedstock such
as methanol. Steam and/or carbon dioxide is the reforming gases that reacts with the feedstock
in the presence of a catalyst such as nickel, cobalt with aid of refractory oxidic material like
alumina, zirconia or calcium aluminate cement. Conventional feedstock like methane are used
to produce hydrogen and carbon monoxide. [3]
1
2. Input/ Output Diagram
By taking into considerations all the reactions that occur during the pre-reforming of
hydrocarbons, tubular reforming and medium temperature shift, the input-output diagram
shown below has been constructed. The reactants are methane, ethane and steam, while the
products are carbon dioxide, hydrogen gas and carbon monoxide.
𝐶2 𝐻6 30 17.50[5] -1.15
𝐻2 2 0.556[7] 1.00
𝐶𝑂 28 0.6[9] 2.15
The price in terms of USD/kg of each component is calculated to determine the feasibility of
the reaction in terms of profit. Hydrogen (H2) is the product. The value of hydrogen product
over raw materials is calculated to be -$18.26 which infers that the reaction is not profitable.
This is due to the high cost of ethane (C2H6) at US$17.50/kg. However, the reaction is still
selected to be further designed due to the steady decrease in the cost of ethane every year,
which will turn the reaction to be profitable and feasible.
2
3. Functions Diagram
3
4. Operations Diagram
Reaction Information
Temperature between 210°C to Decisions
330°C; Pressure at 25bar Temperature at 270°C
Exothermic reaction A cooler after the reactor
Copper catalyst
Separator
Separation Information
Temperature at 25°C; Pressure at Decisions
25bar Pressure swing adsorption
Product stream contains carbon Recycle carbon dioxide, carbon
dioxide, carbon monoxide, hydrogen monoxide and methane to the feed
and methane
Purity of hydrogen gas > 90%
4
5. Process Flow Diagram
Table 4: Respective Unit Operations and Decisions made on each Process Stage
Separator, S-100 to remove Sulfur [10]
Unit Operations Decisions
Separator S-100 is used to remove A compressor before the reactor
sulfur from the feed mixture
(25bar)
containing methane and carbon
Temperature at 500°C
dioxide.
A heater after the reactor
5
Reduce capital cost
Medium Temperature Shift MT-Shift [12]
Unit Operations Decisions
Isothermal shift conversion High oxygen storage capacity
High temperature CO shift Great mobility of surface
conversion at about 210°C to 330°C. oxygen/hydroxyl groups.
To approximately around is 2.5% Optimized hydrogen yield
CO on dry basis at the outlet of the production
reactor. Temperature at 270°C
Copper catalyst
Separator S-101
Unit Operations
Pressure swing adsorption Decisions
Carbon dioxide, carbon Increases production yield
monoxide and methane are being Obtain a purity of more than 90%
recycled to the feed hydrogen gas
6
Table 6: Pre-Reformer Feed and Product Flowrates
7
Energy Balance
The assumptions made during the calculation of the energy balance for all the units are:
1. Molar flowrate into the system = Molar flowrate out of the system.
2. 𝑄 = 𝑚𝐶𝑝∆𝑇 applies for every unit of the system.
3. Compressor is adiabatic (Q=0) with 100% efficiency.
8
7. Steam Reforming Process UniSim Model and Calculations
Boundary Layer
9
Sample calculations for both material balance, energy balance and stream data are shown in appendix.
Table 11: Material and energy balance from UniSim
Material Balance
Assumptions: Therefore, for molecular balance,
1. Density of components remain constant In - Out = Accumulation + Generation
2. Steady state production As system is in steady state, Accumulation = 0, In – Out = -Generation
As there are no liquid components exiting the 3 reactors, the overall (𝑀𝑖𝑥 𝑓𝑒𝑒𝑑 + 𝑆𝑡𝑒𝑎𝑚) − ( 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝐺𝑎𝑠 + 𝐹𝑙𝑢𝑒 𝑔𝑎𝑠) = −𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛
molar flow balance around boundary can be written as; 𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 1.76 × 104 𝑘𝑔𝑚𝑜𝑙𝑒/ℎ
The generation of the reaction in all 3 reactors can be calculated.
Pre-reformer Reformer MT-SHIFT reactor Total
Material balance (kgmole/hr)
6020 11600 0 17600
Energy Balance
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑒𝑑 = 𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡 + 𝑄 + 𝑊 , 𝐴𝑡 𝑆𝑡𝑒𝑎𝑑𝑦 𝑠𝑡𝑎𝑡𝑒, 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑒𝑑 = 0
0 = 𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡 + 𝑄 + 𝑊 for an ideal system
Ein Eout Qin Qout Win
Energy Balance(kJ/hr) 10 10 9 9
-1.974 x 10 -2.239 x 10 3.937 x 10 6.748 x 10 1.655 x 108
Rate of energy accumulated in system (kJ/hr) 2.9 x 106
Energy balance done on UNISIM values does not tally with an ideal system where for a steady state system, the rate of energy accumulated in the
system is = 0. A possible explanation for the discrepancy could arise from the rounding up of values in UNISIM and during calculation. Comparatively,
the calculated rate of energy accumulation is significantly lower by a factor of 3-4.
10
8. GAANT Chart
Table 12: Activities for designing, building and commissioning a plant
11
9. References
[2] Kalinci, Y., Hepbasli, A. and Dincer, I. (2009). Biomass-based hydrogen production: A
review and analysis. International Journal of Hydrogen Energy, 34(21), pp.8799-8817.
[3] Ni, M., Leung, D., Leung, M. and Sumathy, K. (2006). An overview of hydrogen
production from biomass. Fuel Processing Technology, 87(5), pp.461-472.
[4] Energy.gov. (2014). How To Calculate The True Cost of Steam. [online] Available at:
https://www.energy.gov/sites/prod/files/2014/05/f15/tech_brief_true_cost.pdf [Accessed 9
Jan. 2018].
[5] Icis.com. (2016). Fears of US ethane price spike overblown - analyst. [online] Available
at: https://www.icis.com/resources/news/2016/09/06/10031804/fears-of-us-ethane-price-
spike-overblown-analyst/ [Accessed 9 Jan. 2018].
[6] Eia.gov. (2017). United States Natural Gas Industrial Price (Dollars per Thousand Cubic
Feet). [online] Available at: https://www.eia.gov/dnav/ng/hist/n3035us3m.htm [Accessed 9
Jan. 2018].
[7] Heshydrogen.com. (2016). Hydrogen Fuel Cost vs Gasoline. [online] Available at:
http://heshydrogen.com/hydrogen-fuel-cost-vs-gasoline/ [Accessed 9 Jan. 2018].
[8] Synapse-energy.com. (2015). 2015 Carbon Dioxide Price Forecast. [online] Available at:
http://www.synapse-
energy.com/sites/default/files/2015%20Carbon%20Dioxide%20Price%20Report.pdf
[Accessed 9 Jan. 2018].
[9] Kraemer, S. and Kraemer, S. (2012). Zero Carbon Cement Production with Solar Thermal.
[online] CleanTechnica. Available at: https://cleantechnica.com/2012/04/10/zero-carbon-
cement-production-with-solar-thermal/ [Accessed 11 Jan. 2018].
12
[10] Rostrup-Nielsen J, Rostrup-Nielsen T. Large-scale Hydrogen Production [Internet].
Topsoe.com. 2007 [cited 11 January 2018]. Available from:
https://www.topsoe.com/sites/default/files/topsoe_large_scale_hydrogen_produc.pdf
[12] Alijani, A. and Irankhah, A. (2013). Medium-Temperature Shift Catalysts for Hydrogen
Purification in a Single-Stage Reactor. Chemical Engineering & Technology, 36(2), pp.209-
219.
[13] Adiabatic heat compressor. (2018). Camesainc.com. Retrieved 2 January 2018, from
http://www.camesainc.com/Resource_/TechnicalReference/2366/Camesa-TechBulletin-
024.pdf
[14] B.A, Y., & J.F, E. (2018). Thermophysical Properties of Fluid II. Methane, Ethane,
Propane, Isobutane and normal Butane. Nist.gov. Retrieved 2 January 2018, from
https://www.nist.gov/sites/default/files/documents/srd/jpcrd331.pdf
[15] Specific Heat and Individual Gas Constant of Gases. (2018). Engineeringtoolbox.com.
Retrieved 1 January 2018, from https://www.engineeringtoolbox.com/specific-heat-capacity-
gases-d_159.html
[16] Chibane L, Djellouli B. Methane Steam Reforming Reaction Behaviour in a Packed Bed
Membrane Reactor [Internet]. 2011 [cited 11 January 2018]. Available from:
http://www.ijcea.org/papers/93-A561.pdf
[17] Chemical Composition of Natural Gas - Union Gas [Internet]. Uniongas.com. 2018
[cited 11 January 2018]. Available from: https://www.uniongas.com/about-us/about-natural-
gas/Chemical-Composition-of-Natural-Gas
[18] Abbas S, Dupont V, Mahmud T. Kinetics study and modelling of steam methane
reforming process over a NiO/Al 2 O 3 catalyst in an adiabatic packed bed reactor [Internet].
Science Direct. 2018 [cited 11 January 2018]. Available from:
https://www.sciencedirect.com/science/article/pii/S0360319916333821
13
10.Appendix
10.1 Sample Calculations for Material Balance
Using the first reaction in the pre-reformer as a sample calculation:
C2H6 + 2H2O 2CO + 5H2
Table 10: Molar flowrate of each component
Components C2H6 H2O CO H2 Total
Feed Molar Flowrate (kmol/hr) 997.4 1994.7 0 0 2992.1
Product Molar Flowrate (kmol/hr) 59.8 119.7 803.6 2009 2992.1
The table below represents the molar flowrate into Heater 1 with the respectively components.
The molar composition and Cp, specific heat capacity of the components is obtained from
various literatures. The mole ratio and the Cp of each component is multiplied to produce the
total Cp of the feed inlet entering Heater 1. The temperature in and out of Heater 1 is 298K and
773K.
Table 12: Heater 1 inlet molar flowrate and specific heat capacity
Inlet Molar
Molar Cp with
Components Flowrate Mole ratio Cp
composition mole ratio
(kmol/hr)
C2H6 0.061 997.3536697 0.007176471 52.5 0.376764706
CH4 0.939 15352.70649 0.110470588 35.52 3.923915294
H20 7.5 122625.4512 0.882352941 35.46 31.28823529
Total 8.5 138975.5113 1 123.48 35.58891529
𝑄 = 𝑚𝐶𝑝∆𝑇
𝑘𝑚𝑜𝑙 𝑘𝐽
𝑄 = (138975.51 ) ∗ (35.59 ) ∗ (773𝑘 − 298𝐾)
ℎ𝑟 𝑘𝑚𝑜𝑙. 𝐾
𝐺𝐽
𝑄 ≈ 2349.34
ℎ𝑟
14
10.3 Sample calculations for compressor
Assumptions:
1. Adiabatic compressor
2. 100% efficiency
To find the temperature of compressor outlet, an Equation of state[13] is used where
𝑃2 𝑘−1
𝑇2 = 𝑇1 ( ) 𝑘
𝑃1
𝐶𝑝
𝑘𝑛𝑎𝑡𝑢𝑟𝑎𝑙 𝑔𝑎𝑠 = = 1.27 [15]
𝐶𝑣
2500 1.27−1
𝑇2 = 298( ) 1.27 = 589.11𝐾
101.325
M=16350kmol/hr M=16350kmol/hr
T1 = 298K T2 = 589.11K
15
UNISIM Stream data
16
Sample calculations for UNISIM material balance
Material Balance
Assumptions: Therefore, for molecular balance,
1. Density of components remain constant In - Out = Accumulation + Generation
2. Steady state production As system is in steady state, Accumulation = 0, In – Out = -Generation
As there are no liquid components exiting the 3 reactors, the overall (𝑀𝑖𝑥 𝑓𝑒𝑒𝑑 + 𝑆𝑡𝑒𝑎𝑚) − ( 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝐺𝑎𝑠 + 𝐹𝑙𝑢𝑒 𝑔𝑎𝑠) = −𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛
molar flow balance around boundary can be written as; (1.109 × 104 + 8.319 × 104 ) − (3.4375 × 104 + 7.751 × 104 )
The generation of the reaction in all 3 reactors can be calculated. 9.428 × 104 − 11.188 × 104 = −𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛
17
𝑂𝑣𝑒𝑟𝑎𝑙𝑙 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 1.76 × 104 𝑘𝑔𝑚𝑜𝑙𝑒/ℎ
18