Process Design B

B49CG

Group 18
“Hydrogen Production from Ethanol Steam Reforming”

Marcus Clarke - Safety & Materials of construction

Ross Kohler – Environmental impact, Executive Summary, Mass &
Energy Balances
Dominic Newport – Costing & Location
Aisosa Osunde – Sustainability & Market
Alastair Robinson – Process, Cradle-to-Grave, PFD

Remit:
The aim of this project is to assess the feasibility of producing 300,000 tonnes
of hydrogen gas per year, using steam reforming of ethanol.

1
1. Executive Summary
In recent years, the need for cleaner and more sustainable methods of production have
become very important. As a result of this, companies have begun to research ways of
reproducing their products but from more sustainable raw materials. This project analyses
the feasibility of producing hydrogen via ethanol steam reforming. This report delves into
the process, economic, potential market, safety and environmental feasibility. It also looks
at the long term sustainability of this process in terms of raw materials, cost, future market
potential and environmental sustainability.

For the process, this project will be entirely feasible while it is very energy intensive initially;
the overall process is thermodynamically feasible. The process requires a lot of natural gas
combustion in order to maintain the required temperature of the reaction. This could be a
potential problem in the long term, but it is expected that another form of adequate heat
generation will be developed by in the near future.

This project found the market for hydrogen also very feasible with two potential marketing
sectors in the prime location Texas. The hydrogen gas produced can be passed through
pipes to industrial markets that produce ammonia or refine oil. It can also be cryogenically
stored as liquid and sold off as a fuel used in energy industry for hydrogen fuel cells in cars
and other forms of transport. This is an emerging market and trends indicate a large
potential growth as stated in the marketing section.

There was no real safety concerns found while investigating this project. There is a
possibility, as in any plant of minor injuries occurring from burns on hot pipes, slips, trips
and falls. There is a possibility of a hydrogen explosion due to the large amounts of
hydrogen produced, but there are reasonable steps which can be taken to ensure that this
does not happen. The plant will also be situated in an isolate d area in Texas ensuring that a
major incident does not lead to significant damage to the surrounding area.

In terms of economics, the process will continue to be profitable for the first ten years of
operation. The cumulative profit will be approximately $2.8 billion in this period of
operation.
The environment, the project can be determined as almost carbon neutral from cradle to
grave, due to the large amounts of CO2 which the sugar cane photosynthesises. There will
also be no significant impact the surroundings in terms of air pollution as most of the CO 2
can possibly be captured using a carbon capture scheme. Though at this time is maybe not a
sound investment

In terms of sustainability, this project is feasible in both the present market and future
markets. The feedstock which is used to produce the ethanol (sugar cane) can be readily
grown, giving the plant a sustainable source of ethanol. In terms of product, there is a
current market for ammonia production and a future market for hydrogen fuel cell cars.

It can be concluded from the report that this project is feasible in all areas and would be
able to significantly contribute to the production of cleaner hydrogen fuel. The only concern
with this project would be the eventual cost of upgrading to use the carbon capture and
storage initiative to reduce emissions

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Table of Contents
1. EXECUTIVE SUMMARY.............................................................................................................. 2
2. PROCESS .................................................................................................................................. 4
2.1 PROCESS DESCRIPTION ....................................................................................................................... 4
2.2. PFD ............................................................................................................................................... 7
2.3. MASS & ENERGY BALANCES ............................................................................................................... 8
2.4 PRODUCTION RATES .......................................................................................................................... 8
2.5. MATERIALS OF CONSTRUCTION........................................................................................................... 9
3. MARKET ................................................................................................................................. 10
3.1 INDUSTRIAL MARKETS ...................................................................................................................... 10
3.2 EMERGING MARKETS ....................................................................................................................... 10
3.3 COMPETITION ................................................................................................................................. 11
3.4. SWOT ANALYSIS............................................................................................................................ 12
3.5. LOCATION ..................................................................................................................................... 13
4. COSTING ................................................................................................................................ 14
4.1 CAPITAL COSTS ............................................................................................................................... 14
4.2 REACTANT COSTS ............................................................................................................................ 14
4.3 SELLING PRICES ............................................................................................................................... 15
5. SAFETY ................................................................................................................................... 18
5.1INHERENTLY SAFE DESIGN .................................................................................................................. 18
5.2PROCESS SAFETY ANALYSIS ................................................................................................................ 18
5.3 SAFETY DEVICES .............................................................................................................................. 19
5.5 SAFETY MATRIX .............................................................................................................................. 21
6. ENVIRONMENTAL IMPACT...................................................................................................... 22
6.1 SIGNIFICANT CO2 PRODUCTION ......................................................................................................... 22
6.2 ADHERING TO REGULATIONS ............................................................................................................. 22
6.3 TECHNIQUES FOR DEALING WITH THE LARGE AMOUNT OF CO2 PRODUCED ................................................ 22
6.4 CURRENT ENERGY EFFICIENCY TECHNIQUES .......................................................................................... 23
6.5 CARBON MONOXIDE EMISSIONS ........................................................................................................ 23
7. SUSTAINABILITY ..................................................................................................................... 24
7.1 ENVIRONMENTAL SUSTAINABILITY ...................................................................................................... 24
7.2 SOCIAL SUSTAINABILITY .................................................................................................................... 24
7.3 ECONOMIC SUSTAINABILITY .............................................................................................................. 25
7.4 RENEWABLE FEED STOCK .................................................................................................................. 25
7.5 PRODUCT SUSTAINABILITY ................................................................................................................ 26
7.7 CRADLE-TO-GRAVE DIAGRAM ............................................................................................................ 27
8. CONCLUSION.......................................................................................................................... 28
10. APPENDIX ............................................................................................................................ 29
10.1 SAMPLE CALCULATION ................................................................................................................... 29
11. REFERENCES ......................................................................................................................... 33

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2. Process
2.1 Process Description
Steam Reformer (SR-HX)
The process begins at the steam reformer, which is a large direct-contact heat exchanger.
The purpose of this reactor is to superheat the ethanol/steam mix (SR102) to the operating
temperature. This is carried out using a mix of compressed air (SR1) and natural gas to feed
the open fire, which the process line travels through. Natural gas has a high energy to mass
ratio, thus releases a large amount of energy upon ignition, the air acts as a medium for
combustion. The flue gas (SR2) will be let out via a chimney. The natural gas/air mixture and
the ethanol/steam mixture do not mix.

The feed consists of ethanol and steam, both of which are pre-heated (HX-1, HX-2, and HX-
3) to maintain an efficient energy recovery. The ethanol to steam mix is set at 1:8 (SR102).
The materials are moved (SR100 & SR101) via pumps in the liquid state through to the first
heat exchanger (HX-1). The heat exchangers will form large energy stripping cascades
though they themselves may not be enough to fully remove all the heat from the
downstream product line.
Upon reformation the ethanol rapidly decomposes into methane, producing small amounts
of hydrogen. The reaction is carried out at 650oC

C2H5OH (g) → CH4 (g) + CO (g) + 3H2 (g)

The methane will then further react with the steam forming more hydrogen along with
carbon monoxide gas (reverse methanation).

CH4 + H20 (v) ↔ CO (g) + 3H2 (g)

Thus the overall reaction in the vessel ends up as:

C2H5OH (v) +H2O (v) → 2CO (g) + 4H2 (g)

Water Gas Shift Reactor (WGSR)

The feed is passed to the WGSR along SR4; the main intention of this process is to convert
any carbon-monoxide and water present in the stream into hydrogen and carbon dioxide.
This works with a metal catalyst nickel supported by an Al2O3 base which favours a high
yield of clean hydrogen gas with no carbon monoxide emissions, with temperatures as low
as 250oC. Furthermore, this catalyst favours the steam reformation of methane which
should prevent high degrees of methanation.

CO (g) + H2O (v) ↔ H2 (g) + CO2 (g)

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Selective Oxidation Reactor
The feed (SR6) reacts in the selective oxidation with as many as three reactions occurring
simultaneously which involves the combustion of feed products. This leads to the formation
of steam, carbon dioxide and hydrogen.
The reaction is carried out at about 199oC:

CO (g) + 0.5O2 (g) → CO2 (g) (Desired)

H2 (g) + 0.5O2 (g) → H2O (v) (Undesired)

H2 (g) + CO2 (g) → CO (g) + H2O (v) (Undesired)

This reactor is for the purpose of completely combusting carbon monoxide to form the non-
toxic, inert carbon dioxide. This is achieved by adding air to the reactor and making sure
there is at least a 1:1.5 mixture of oxygen to carbon monoxide in the reacting vessel. This
particular mixture favours the combustion of carbon monoxide over those where desired
product is lost (Avelar et al., 2011, pp. 22–24).

Pressure Swing Adsorber (PSA)

(The PSA must be carried out at 50oC with pressure ranges from 40-50 Bara)
Temperatures above 50oC may remove the PSA ability to adsorb unwanted products.

The PSA deals with the removal of unwanted gases from the product stream to allow for an
almost pure hydrogen stream. The PSA uses the tendency of larger molecules to adsorb into
activated carbon under high pressure to separate from the desired hydrogen.
The product streams and waste purge streams are titled SR9 and W-100 respectively. The
gases that are not hydrogen adsorb into surfaces of the activated carbon in the reactor and
are thus removed from the product stream. There are PSA made specifically for the
selectivity that hydrogen is shown in the activated carbon process. Indeed it is not unheard
of to find some PSAs with zeolite adsorbers. For this particular process, however, hydrogen
is far too similar in size on a molecular level to the undesired products that zeolites cannot
be used due to low selectivity.
When the PSA becomes saturated with undesired gases, the chamber is simply
depressurised and the gases detach and are pushed out of the chamber by a pressure drop.
After a purge cycle, the chamber is then simply pressurised again to the desired pressure as
the chamber is then regenerated.
The PSA section is designed with four reaction chambers allowing a regeneration process to
take place. When one reactor is being depressurised and regenerated, another can be in
operation and thus maintain a constant product stream of hydrogen.
This should yield a clean highly pure product line of 99.9999% hydrogen (Linde-Engineering,
2014).

5
Catalyst
Catalysts will make the process more efficient by lowering the reaction temperatures and
increasing the yield per feed of hydrogen. This will make the entire process far cheaper to
run. It is also highly important for the process of ESR to have a catalyst capable of limiting
the formation of coke in the reactors. Ethanol can be dehydrated inside the reactors leading
to coke deposits forming and causing high fowling in the reaction chambers. This can occur
when using nickel or certain transition metals in pure form. Choosing a catalyst with neutral
or basic supports will limit the chances of coke formation occurring.
The selected catalyst was nickel based over a support of aluminium oxide. This choice of
catalyst and support seem to be a popular choice in the hydrogen through steam reforming
industries and therefore is a tried and tested method. As further catalysts may be
developed the choice of catalyst may be subject to change (Llera et al., 2012).

Storage
The storage of hydrogen is a technical feat within itself. It is absolutely paramount for
hydrogen to be stored properly. Due to the unique chemical properties of hydrogen, cryo-
compressed storage is to be considered.
Cryo-compressed hydrogen is an invested idea by several automotive industries most
notably BMW. Cryo-storage is a process that involves cooling the hydrogen down to 20K this
causes the hydrogen to liquidise and hence can be stored. The main difference between
cryogenic and cryo-compressed is that the compressed in the latter refers to the hydrogen
being stored in a pressure capable vessel. Cryo-compressed can handle hydrogen pressures
of up to 36 bara with the tanks sized around 450,000 litres (U.S. Department of Energy Hydrogen
Program, 2006).

The main cooling is a very energy intensive process however it has shown to be a very
promising move forward as it can meet specified targets for the automotive industries and
further industries using hydrogen as an energy source.

The only major problem that can be faced when applying this type of deep cooling to the
hydrogen product is the boil-off cause by the ambient conditions. This is accelerated by the
fact that there will be a large temperature gradient between the hydrogen and the outside
temperature. Coupled with the fact that operations are to be carried out in south Texas
where summer temperatures can be very hot.
The tanks will be designed in a similar way found in the hydrogen car manufacturing
industry. This is where the tanks are designed to withstand inner pressures of up to 36 bar.
They tend to be vacuum insulated and thus this reduces any heat transfer with the outside
would.

Both the PSA and hydrogen storage vessel can be sourced from contractors such as Linde-
Engineering. They specialise in hydrogen purification and storage and would be an ideal
choice for this project (Linde-Engineering, 2015).

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2.2. PFD

Figure 1 - Process Flow Diagram

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2.3. Mass & Energy Balances

Table 1 - Mass balance over the system with all values in tonnes/hour

M.W SR1 SR2 SR3 SR4 SR5 SR6 A-1 SR7 SR8 SR9 W100 SR100 SR101 SR102 SR103 SR104 SR105
H2 2 0 0 27 27 37 37 0 37 37 37 0 0 0 0 0 0 0
CO2 44 0 58 0 0 223 223 0 298 298 0 298 0 0 0 0 0 0
Ethanol 46 0 0 0 0 0 0 0 0 0 0 0 156 0 156 156 156 156
CO 28 0 0 189 189 47 47 0 0 0 0 0 0 0 0 0 0 0
H20 18 0 47 426 426 335 335 0 335 335 0 335 61 426 487 487 487 487
N2 28 278 278 0 0 0 0 89 89 89 0 89 0 0 0 0 0 0
O2 32 84 0 0 0 0 0 27 0 0 0 0 0 0 0 0 0 0
Methane 16 21 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
*it should be noted that all values are rounded to the nearest integer and that complete combustion was assumed for methane in SR1. It
should further be noted that the products from the SOR (SR7) are assumed to be completely due to the desired reaction. In reality, there is a
selectively associated with this reactor which would be carried out on a rigorous plant design.

2.4 Production Rates

As shown in the mass balance, the system produces 37 tonnes per hour of hydrogen. When scaled up, this equates to the 300,000 tonnes
required to be produced annually. In this, there is 4 weeks of downtime which have been taken into account. This downtime is for required
maintenance and safety checks.

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2.5. Materials of Construction
The choice of the materials of construction depends on the conditions that the materials
will undergo and the composition of the fluids inside of the pipes.
The materials that are near the cryogenic storage of hydrogen will be suitably chosen so not
to undergo hydrogen embrittlement which is explained in further detail later in the report.
Carbon steel was chosen as the main material because it is cheap, very versatile and easily
fabricated. It will be able to easily withstand the pressures and temperatures that this
process has.
Low-Alloy steel was used when carbon steel was unsuitable. The presence of hydrogen and
high temperatures in the fluids in this process means that the carbon steel pipes must have
undergone decarburization otherwise they would not be suitable. This stops the chance of
hydrogen attack which in turn can cause hydrogen embrittlement. Using alloys of steel with
molybdenum (Mo) and/or chromium (Cr) reduces the chance of this happening. Mo
provides strength when high temperatures are used while Cr improves the hardness,
abrasion resistance, corrosion resistance, and resistance to oxidation. The graph below was
used to decide the levels of Mo and Cr that were acceptable under the temperatures and
pressures of specific pipes.
Table 2 shows the materials that were selected for this design.

Figure 2- Operating limits for steels in hydrogen service (‘Materials of

construction’, 1997).

Table 2 – Selected Materials (‘Materials of construction’, 1997).

Pipe number Material of construction

SR1, SR6, A-1, SR7, SR8, SR9, W100, SR100, Carbon Steel
SR101, SR102, SR103 and SR104 UNS Number: G10200
SR2, SR3 and SR105 0.6 Cr - 0.5 Mo Steel
UNS Number: K41545
SR4 and SR5 0.5 Mo Steel

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3. Market
The global hydrogen generation market has been estimated to reach $138.2 billion by 2019
with a compound annual growth rate of about 5.9% (marketsnmarkets2015) showing a
significant yearly increase in demand and the major market sectors that will influence this
growth are the energy and oil refining industry (marketsnmarkets2015). The energy sector
utilises hydrogen as a fuel from renewable sources which favours ethanol steam reforming
as the purchased ethanol is produced from a renewable agricultural source called bio-mass.
In oil refining hydrogen is used in the desulphurisation of petroleum products making them
more efficient. In order to satisfy the increasing hydrogen demand an efficient and
sustainable supply is required.
The broad range of hydrogen uses enables it to have a number of potential markets and the
prime location as Texas offers a suitable industrial environment with a growth rate across all
its industrial sectors from 0.088-0.309 % (Ali Anari Jan 2015) between 2013 and 2014. This
opens market opportunities for the remit of 300,000 tonnes per year in niche, emerging
markets and larger industrial sectors.

Potential hydrogen markets may include the following:

3.1 Industrial Markets

On a global scale the chemical industry consumes between 80-90% (Levin and Chahine,
2010) of the hydrogen produced. Hydrogen can be used to manufacture ammonia which
serves as one of the main components for artificial fertilizer production. This is vital for
modern agriculture to sustain the increasing world’s population. Oil refining and steel
production are other industrial uses of hydrogen particularly oil refining which also needs a
high hydrogen demand in order to improve the hydrogen to carbon ratio of fuels. Texas is
one of the largest oil producers in the United States and this would also help boost the
viability of this supply of hydrogen to this sector.
The industrial hydrogen market can be divided into two main parts called the captive and
merchant market (Lipman, 2011). In the captive market the hydrogen is produced and
utilised onsite while in the merchant market the hydrogen produced is to be delivered to
other locations for other purposes. However research has shown that both type markets are
available for this project with onsite cryogenic storage the hydrogen produced can be sold
off to oil refineries in Texas. The merchant market can also be satisfied by transporting the
hydrogen gas through the pipe connections to buyers such as ammonia production plants.

3.2 Emerging Markets

Hydrogen has been widely produced and used for numerous applications for decades
however the hydrogen fuel cell market is now growing in niche applications for stationary
power i.e. electricity production (U.S. Department Of Energy 2014). It can also be used in
portable devices as batteries.

The current awareness on negative environmental impacts have now put focus on hydrogen
fuel cells as a secondary energy carrier thus making it alternative fuel source in the
transport sector. Fuel cell shipments in the United states saw an increase by more than 60%
between 2011 to 2012(Energy.Gov) and in 2013 the world wide fuel cell industry sales
reached $1.3billion marking the first time this sector surpassed $1billion dollars from sales

10
(U.S. Department Of Energy 2014).It is estimated that commercialization of fuel cells will
take place by 2017(Energy.Gov) with support from companies like Hyundai which began
leasing fuel cell transport vehicles in 2014(U.S. Department Of Energy 2014).
From these past trends and future predictions, it can be seen that this market has a lot of
growth potential however an additional energy intensive liquefaction cycle would be
needed for the steam reforming. This can then as be stored as liquid hydrogen in a
cryogenic storage tank adding additional costs which could possibly affect the economic
sustainability in the long run.

There is also the advantage of the fuel being almost entirely self-sufficient in the US and
therefore the country can avoid the turbulent politics of oil in today’s volatile world.

3.3 Competition
Hydrogen production by steam reforming of ethanol is a renewable and sustainable process
that offers the added advantage of a catalytic conversion to increase the efficiency of the
hydrogen production rate. Processes such as gasification of coal and steam reforming of
methane are already well established in the hydrogen market and thus serves as rivals to
the newly emergent ethanol. Air Products and Linde-Engineering are two very large
producers of hydrogen located in Texas that use steam reforming of methane. They are able
to exploit the economies and handle the additional costs that come with the process. CO2
capturing and the desulphurization of the hydrogen are two additional costs that their
economies of scale can cover.
Steam reforming of methane is one the most common form of hydrogen production
methods because of the ease of acquiring the large amounts of natural gas at a cheap rate
of $0.24/kg compared to ethanol at $0.51/kg (Texas Natural Gas prices). Natural gas may be
cheaper however the burning hydrocarbon produces large amounts of CO2 and is
environmentally unfriendly. The ethanol may be more expensive but the bio-mass it is
fermented from is produced from agricultural means giving it a cleaner and more
sustainable outlook. This gives steam reforming of ethanol a more competitive edge within
a modern market.
Other rival processes could include the hydrogen production via methanol production in the
by-product hydrogen market where it is recovered as a tail gas in the separators and then
sold off to refineries or as a chemical feed stock in ammonia and hydrogen peroxide
production (Levin and Chahine, 2010).

11
3.4. SWOT Analysis

STRENGTHS WEAKNESSES

 Fermentation of bio-mass feed is more  Costs associated with ethanol

sustainable than burning hydrocarbons purchases and cryogenic storage
 High hydrogen yield from catalytic  Prime location Texas is a bit far from
conversion ethanol production plant.
 Available markets in highly industrial
area Texas
 Large growth potential of hydrogen in
emerging markets e.g. fuel cell
production, electricity production.

OPPORTUNITIES THREATS

 Demand for cleaner and more  Rival process steam reforming of

sustainable energy sources methane
 Penetration into energy and  Competition from established
automobile market with hydrogen hydrogen suppliers in Texas e.g. Linde
reputation as a clean fuel. engineering, Air products.

Figure 3 - SWOT Analysis

The SWOT analysis highlights the strengths and weaknesses of remit as well as opportunities
open to take advantages of and the possible threats it may face. The various marketing
sectors open to hydrogen have been highlighted as one of the main strengths that will
support the remit because it opens up sales opportunities that will support the economic
sustainability. However the most important strength stems from the fact that the ethanol
feed stock is renewable and can be sourced from biomass which is derived by agricultural
means. This has the potential to boost social sustainability creating jobs to local farmers as
well reducing their dependence on government subsidies in the United States. The main
weaknesses are the large running costs from the ethanol purchase and transportation of the
purchased ethanol as ethanol is quite expensive and will be sourced from mid-western
states such as Missouri which is quite far from Texas, despite this the economics shows
profitable years for the future so the weaknesses can be tackled. The market is very
competitive with steam reforming methane being a very common method of hydrogen
production due to the cheap costs of natural gas but future opportunities show a demand in
the energy sector for more renewable sources of energy thus steam reforming of ethanol
will be competitive in the long run.

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3.5. Location
The location that has been selected for our process is Texas, USA. There are several reasons
for this placement. The main reason for this is that out of the entire production of hydrogen
in the world, the US make between 9 and 10 million metric tonnes. Texas is also a highly
industrialised area, and therefore is an ideal location for selling the hydrogen once it is
produced. There are other companies can use the hydrogen that we produce in their
processes.

It also the case that the highly industrialised areas are good material sourcing grounds. The
reason for this is there are many railroads that link the big cities in Texas with the upper
portions of the USA. This would allow us to maintain a good supply line of feedstock as
transportation by train is far more efficient than convoys of trucks.

The large amounts of arable land where we can source the ethanol feedstock make the
Midwestern Southern States a firm choice to site the plant. As Missouri is an area of largely
agricultural communities, they can benefit from industrial development of this type. There
will be a growing hydrogen industry that will guarantee full purchase of crops and give extra
financial security.

It is also a prime location to give another company in the area the CO2, so that it can be
used for a process such as carbon capture to reduce the amount of waste products that
would be released from the process. The construction of one of the largest carbon capture
facility has just started being built in the local area of our intended situation. Out of 22 sites
specialising in Carbon Capture and Storage, 16 are situated in the US, and from that 16, 4
are in Texas. We will therefore send the waste carbon dioxide from our process to one of
these sites so that it can be used. (The climate brief Accurate Reporting of Climate Science, no date), (Eco
Global Fuels, 2012), (Joseck, 2012), (PETROLEUM & OTHER LIQUIDS, 2014)

While considering location, it must also be taken into consideration that there are large
amounts of hydrogen and ethanol on site. It is therefore advised, for safety purposes that
the plant is situated as far from large settlements of people or wildlife.

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4. Costing
4.1 Capital Costs
The capital investment for this process is primarily the machinery used to produce the
hydrogen. It is assumed that the price of each piece of the machinery is a middle or
averaged value, of the stated range for each respective component. Almost all of the
machinery prices have been taken directly from the same place (Alibaba, 1999-2015). Rough
estimations were made about the sizes of each piece of machinery, and more rigorous
calculations would have had to have been made to ensure the correct sizes were being
used.
It was decided that the pipe length should be between 150-200m. 200m was then chosen to
ensure there was enough piping for the entire process. An extra mile of piping was then
added to this for the piping used to send hydrogen gas to other companies for use in
processes such as ammonia production (Lipman, 2011). The storage tank for the ethanol
has been purchased at a quantity that allows us to store around a weeks’ worth of ethanol
on site. This allows being able to have continuous use of it in the process, without the
requirement for constant feed deliveries.
A cryogenic tank has also been purchased for the storing of the hydrogen that would be
used as fuel. The methane supplied is natural gas from the grid and will just be sent down
pipes as normal. All prices are shown in Table 3 in the appendix.

4.2 Reactant Costs

With respect to the reactants purchased for the process to occur, the overall change in the
prices of these cannot be predicted accurately. Therefore in this situation it has been
decided that there is a cumulative interest increase over the 10 years. The natural gas has
been found to be 0.24$/kg for year 1(Texas Natural Gas Prices, no date), and the ethanol
has been found to be 0.51$/kg for year 1. The ethanol will be purchased from Missouri and
sent down via the train links and then stored in the storage tanks on site. The cost of
delivery of the ethanol has been assumed to be incorporated in the price, due to the vast
amounts being purchased throughout the year. The full list for results can be found in Table
4.
The catalyst is bought in metric tonnes. Due to the catalyst being expected to last a
reasonable amount of time; and only hundreds of grams worth of the catalyst will be used
at one time, the metric tonne is expected to last for quite a while. As stated above, the
projected costs of the reactants are set at a slow increase over the 10 years; this will not
necessarily be the case. This however does mean that the catalyst can and has been
incorporated in the costs each year.
After extensive research, no values were found for the cost of carbon capture, which is the
desired way to cleanly remove the CO2 produced. Therefore, this has meant that this cost
has had to be omitted from the calculations even though there would be a cost involved.
The costing of the workers has not been included in the overall process for the calculations
due to the negligible impact that they would have made to the overall outcome of the profit
for each year.

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4.3 Selling Prices
The sales prices of the hydrogen have been taken from a graph in a journal article and then
been used to gauge what the price change may be, as estimated by said article (Song and
Ozkan, 2010). The difference between the years has been reduced incrementally. This may
not be the case in real life, as a commodity such as hydrogen will not fall linearly each year
like suggested. The reason for the chosen decline in the price of the hydrogen is that, as a
fuel it will eventually become more readily available, as more companies will be producing
it. Therefore the market will become more competitive and this will drive the prices down
to allow the consumers to purchase of it at a similar rate to current fuels such as petrol or
diesel.
Due to the amount of hydrogen we are producing being only a fraction of the total amount
consumed in a year by the US (Lipman, 2011); we are assuming that all of the hydrogen that
we produce is going to be purchased. This is also our only point of income throughout the
process and therefore the core part of our success. When looking at the overall economic
viability, the worst-case scenario will be values used. This is because the cost of the
hydrogen per kg seems the most realistic, as it has been decided that the hydrogen
produced is not solely intended for the use in fuel cells. Another reason for this is that the
selling values in the journal article were solely for the sales of hydrogen as a fuel.
In this scenario, this is not the case. It is intended for the hydrogen to be sold not only for
fuel cells, but also for other industrial processes such as ammonia production and for use in
oil refineries. This type of hydrogen is normally sold at a lower rate and therefore the
highest selling price used would not be appropriate. By choosing the worst scenario and the
lowest initial and final selling prices over the 10 years, the sale of the hydrogen in both
markets has been taken into consideration.

15
 Cumulative Cash Return Profile
6,000

5,000
Cumulative Cash Return (Millions of $)

4,000

3,000

2,000
Best Scenario

1,000 Middle

Worst Scenario
0
0 1 2 3 4 5 6 7 8 9 10

-1,000 Time (Years)

Figure 4 - Cumulative Cash Return Profile

Figure 4 shows the cumulative cash return profile for our process. It was decided that our
projection would be made for three different scenarios over 10 years. The difference
between each scenario is specifically the selling price of the hydrogen. The profile shows
that in the economic/costing side, the remit stated for this project is viable. This statement
is true for all three scenarios, the reason being all three have a profitable result. Each year
has been evaluated as 48 weeks of continuous running, with 4 weeks of downtime and
maintenance.
The ROI for all three of the scenarios are positive. The worst-case scenario value has a ROI
of 53%. This is another indication that the remit is economically viable.

16
 Cash Return Profile
1,800
Best Scenario
1,600
Middle
1,400

1,200 Worst
Scenario
Cash Return (Millions of $/yr)

1,000

800

600

400

200

0
0 2 4 6 8 10
-200

-400

-600

-800
Time (Years)
Figure 5 - Cash Return Profile

Figure 5 above shows that the profit over the years steadily declines. The reason for this is
due to the reduction in sales prices of the hydrogen over the 10 year period, the
maintenance price of the machinery slowly increasing over the 10 years and the overall
compound interest used on the reactants for the process. This projection is conservative
with respect to the reactants as it is more than likely that the cost of both ethanol and
methane over the 10 years will not increase by that much. Therefore the profit shown in the
figure above is less than what is to be expected.
(no date b). Available at: http://www.alibaba.com/trade/search?fsb=y (Accessed: 5 March 2015).

17
5. Safety
5.1 Inherently safe design
The plant will be designed and manufactured so that it is inherently safe. Inherently safe
design means that the plant will be able to withstand mistakes and accidents and not have
the safety, output, or efficiency seriously affected. (Process Safety, 1997). The plant is also
relatively simple, providing few opportunities for error or equipment failure. The equipment
that is used in the plant will all have a large tolerance for poor installation, poor
maintenance and conditions that are not expected under normal circumstances.

Inspection and Maintenance

Inspections of the equipment should be performed on a regular basis, depending on
experience with the equipment and the experience of the worker. During the four week
down time, the equipment will be serviced and cleaned to remove any build-up of coke and
other fouling. Regular maintenance of the equipment is essential so that the continuous
process is not disrupted by malfunctions. The downtime is used for essential maintenance
that may not have been possible or would have been a hindrance to normal service if
performed during the process. Due to the presence of heavy metal there is a small
possibility of heavy metal poisoning, precautions such as masks and overalls will be taken
when in close proximity to the build-up.

Training
Training will be given to all workers on the safe and proper use of the equipment that they
work with, they will be shown what to do in case of an emergency or accident with their
equipment and the procedure that needs to be followed if people are injured or killed. Fire
and emergency drills will be performed regularly as is the industry standard.

5.2 Process Safety Analysis

Documentation and Procedure

 All the incidents, major and minor will be documented in an incident book.
 A document will be made easily available where employees can write down any
health and safety concerns that they have and feel should be addressed.
 Safety handbooks that explain and give the reasons behind all the procedures will be
also be made readily available.
 At least one worker will have been to an accredited First Aid course and trained in
using the defibrillator.
 Risk assessments must be completed for each possible hazard and regularly
reviewed, to ensure that they are not endangering themselves, their fellow workers
or the surrounding area. Permit to work systems and the Standard Operating
Procedures should also be reviewed regularly.

18
Local Community
Access to information will be made easy for local residents and businesses regarding
hazardous substances, such as hydrogen, to which those persons may be exposed during
emergency situations or as a result of proximity to the manufacture or use of those
substances. This information will also be given to the emergency services and other local
emergency planning committees and organisations responsible for dealing with chemical
hazards during an emergency. The plant will also work with these organisations to decide on
emergency procedures and protocols that will be employed if an incident were to occur
where they are needed. (Public Employer Community Right-To-Know Act, 1993) and the
(Manufacturing Facility Community Right-To-Know Act, 1993)

PPE
Wearing appropriate Personal Protective Equipment is the most important step someone
can take as an individual to protect themselves against non-lethal accidents. Gloves must be
worn to protect anyone around the hot or cold pipes or vessels. The PPE must be
appropriate for the risks and the conditions where it is used and take into account the
ergonomic requirements and the state of health of the person wearing it. It must also fit the
wearer correctly and prevent or control the risk involved. (OSHA - Hazardous Materials,
Hydrogen, 2015) (Cryogenic Liquids - How Do I Work Safely with: OSH Answers, 2008).

Location
The plant will be located away from residential areas, although very unlikely is an explosion
were to happen the damage to residential or commercial property in surrounding area
would be minimal. (‘Process Safety’, 1997).

5.3 Safety Devices

Pressure Relief System
This process has very high pressures. Therefore this plant will have pressure relief valves
after each piece of equipment (PSA, SR-HX…); this is to ensure that if the pressure builds up,
it can be released in a safe and controlled manner. The pressure can cause an explosion
called a ‘boiling liquid expanding vapour explosion’. Unusual or accidental conditions may
cause a very rapid pressure rise. The pressure relief valve should be able to handle this
increased pressure. (‘Process Safety’, 1997).

Ventilation
The workplace must be sufficiently ventilated. The stream SR2 is extremely hot and must be
released into the atmosphere at a sufficient height as not to affect the building or workers
below. Carbon monoxide is produced in this plant, although the vast majority of it is
removed in the selective oxidation reactor, there is a small possibility of leaks occurring
from SR3 through to the SOR. Therefore because of its toxicity, CO meters will be placed
along the route that it travels. This is to minimise the risk of CO poisoning, which can be
deadly. Ventilation is essential when storing cryogenically, it is needed to separate the
exhaust fumes from the cryogenic liquids. The ventilation system will be explosion proof,

19
due to the nature of hydrogen. The containers will be kept in a cool, moisture free and well
ventilated environment. Asphyxiation when using cryogenic storage is a serious danger; the
super cold liquids expand to heavy gases and displace the oxygen at the bottom of the
room. (Cryogenic Liquids - Hazards: OSH Answers, 2007). Even if, as is the case with
hydrogen, it is non-toxic it displaces the air. If asphyxiation occurs then death or brain
damage is a not improbable outcome. (Cryogenic Liquids - How Do I Work Safely with: OSH
Answers, 2008).

Storage of Materials
Due to the Flixborough disaster which occurred on 1 st June 1974, that killed 28 people and
injured 36 at the plant and many more in the surrounding area, it was concluded that
“limitations of inventory should be taken as specific design objectives in major hazard
installations.”(‘Process Safety’, 1997). It should be noted, however, that reduction of
inventory may require more frequent and smaller shipments and improved management.
The Flixborough investigation made it clear that the large inventory of flammable material
in the process plant contributed to the scale of the disaster. Therefore this plant will limit
the storage of flammable materials, namely hydrogen and ethanol and we will pump the
natural gas directly from the grid. Cryogenic storage is where a substance is stored at a
temperature below -150°C; because of this extreme temperature it poses very specific
dangers to the workplace. All workers who work with the low temperature liquefied
hydrogen will be given adequate training on the risks of asphyxiation, fire hazards, cold
burns, frostbite and hypothermia. (Cryogenic Liquids - How Do I Work Safely with: OSH
Answers, 2008). Special attention will be drawn to the insidious nature of the risks due to
the rapidity of the effects, coupled with the fact that an operator may be completely
unaware that a hazardous condition has developed due colourless nature of hydrogen.
When exposed to extreme cold for a prolonged period there may be serious damage done
to a person if they are not suitably protected. Frostbite may occur, to ensure that this does
not happen suitable protection must be worn, such as gloves and long aprons, although
even these may be redundant after a time. (Cryogenic Safety, 2009)

Hazardous Materials
The workers shall ensure that the hazardous substances (ethanol, hydrogen etc.) used are
labelled sufficiently to inform its user of the dangers involved in using, storing, or handling
the substance, of actions to be taken or avoided, and to give instructions as necessary for
proper first aid treatment. The company shall develop labelling instructions consistent with
and in conformity with federal requirements. (Manufacturing Facility Community Right-To-
Know Act, 1993) and (Public Employer Community Right-To-Know Act, 1993).

Safety Matrix
The measures taken will reduce the consequences and the probability of the possible
incidents that may occur during this process. It will reduce the consequence of frostbite
which will move along from 12 to 6 along to the left. Another example is the possibility of an
explosion occurring which will move 5 down to 4.

The process is safe and none of the possible incidents that may occur should stop the
continuation of the research into the feasibility of this process.

20
 5.5 Safety Matrix
5 10 15 20 25
Minor injury due to hand held
tools

4 8 12 16 20
Slip due to water or ethanol Minor burn due to hot pipe,
leak. hot vessel or steam leak
Minor burn after measures
Probability of event

taken.
3 6 9 12
Major burn after measures Major burn due to hot pipe, 15
taken hot vessel or steam leak.

2 4 6 8 10
Smoke inhalation. Carbon Monoxide poisoning. Hydrogen explosion.
Ethanol draining into the local Heavy metal poisoning. Ignition of ethanol or natural
water supply Frostbite. gas
Natural gas leak. Hydrogen leak. Process Vessel explosion due
to high pressure.
1 2 3 4 5
Smoke inhalation after Carbon Monoxide poisoning, Asphyxiation from cryogenic
measures taken. heavy metal poisoning, hydrogen leak.
frostbite and hydrogen leak Vessel explosion after
after measures taken measures taken
Consequence
Figure 6 - Safety Matrix

21
6. Environmental Impact
Global Warming is becoming an ever more prevalent issue and with carbon dioxide as the
main gas contributing significantly to this issue (El-Sharkawy, 2014, pp. 161–178). A close
analysis needs to be carried out to ensure that these emissions meet all known regulations.
Carbon dioxide is expected to account for more than 55% of all greenhouse gases in the 21st
century.

6.1 Significant CO2 production

A close analysis of the mass balance will show that this plant emits approximately 6.75kg of
CO2 per kg of hydrogen that is produced within the process itself. On top of this, there is
also a significant amount of CO2 emitted from the combustion of Methane to heat the
steam reformer. By coupling these two values together, this plant will emit approximately
9.55kg of CO2 per kg of Hydrogen. There is a significant amount of CO2 produced in this
process however, there are far less other pollutants released into the atmosphere. For
example, the reactor is brought up to temperature by the combustion of methane,
producing CO2. The alternative to this process would be to use coal combustion which
results in methane being produced (EPA, 2014, pp. 1441 – 1442) and this is significantly
worse for the environment than CO2 (Zhang et al., 2014, pp. 11–21). It is therefore
environmentally pragmatic to produce a significant amount of CO2 over a very similar
amount of more polluting greenhouse gases. It is possible to show that this process, from
cradle to grave, can be classed as almost carbon neutral. (Avelar et al., 2011).

It should also be taken into consideration that the hydrogen, which is being produced, will
potentially be able to power fuel cell vehicle’s (FCV). These vehicles will either have very low
emissions or no emissions of greenhouse gases (García et al., 2013, pp. 4791–4804). The
amount of CO2 produced in this plant should therefore be weighed up against the amount
of CO2 that would be produced by an equivalent number of petrol-powered cars. It is then
possible to show that this is actually an environmentally sustainable project.

6.2 Adhering to regulations

We need to adhere to the Clean Air Act (CAA) as it is federal regulation in America. Only CO2
is regulated but CH4 and NOx are not the reason there is not sufficient data on legislation
regarding these emissions.

There is also a recommendation to reduce the amount of CO2 produced per million dollars
of GDP. This amount was set at 559 tonnes of CO2 per million dollars of GDP (Projected
Greenhouse Gas emissions, 2006) Responsibility has to be taken to ensure that this target is
met.

6.3 Techniques for dealing with the large amount of CO2 produced
There are several options for dealing with the vast amounts of CO2 produced in this process.
Carbon dioxide exits the system through stream W-100. The simplest option for dealing with
the carbon dioxide would be to simply vent this to the atmosphere. While this is the
simplest option, it is also the most environmentally damaging. Approximately 1.2tonnes per
hour would be a significant amount of carbon dioxide to vent. Venting this amount of CO2 to

22
the atmosphere would be very bad for the surrounding areas. It is for this reason that more
environmentally pragmatic options should be investigated.

One possible option of dealing with this is using a carbon capture system. A recent study
found that in a pilot plant, as much as 99.13% of the carbon dioxide from a dirty flue gas
could be absorbed using an amine absorber (Khan, Halder and Saha, 2015, pp. 15–23). The
monoethanolamine (MEA) is also almost totally recoverable. With the right loading, this
would reduce the amount of carbon dioxide that the process emits to well within acceptable
levels. In fact, it would reduce the carbon dioxide emissions to virtually nothing. It is
possible to “strip” the carbon dioxide from the absorber, cool it, and store it as either a
liquid or a solid; to be sold on or stored underground.

Another possible method of reducing the amount of carbon dioxide is to use algae
microorganisms (Pires et al., 2012). These microorganisms are very good at absorbing the
carbon dioxide.

6.4 Current energy efficiency techniques

As explained in the process description, there are three heat exchangers to pre-heat the
ethanol-water feed stream. This stream is being pre-heated by a stream, consisting mainly
of hydrogen. Hydrogen has a much higher heat capacity than water. This means that the
ethanol-water feed stream can effectively be heated up to almost the 650°C of the steam
reformer. This technique is adapted from a similar system investigated in an academic
journal. (Avelar et al., 2011)

6.5 Carbon Monoxide emissions

There are also carbon monoxide emissions in this system. In the selective oxidation reactor,
there is an unfavourable reaction which produces carbon monoxide. It is possible to use
reaction conditions which favour the desirable reaction. This is explained in the “Process
Description” section of this report. Due to the SOR being very reaction specific, these
emissions should not pose a problem, but care must be taken to ensure that they fall below
recommended emissions.

23
7. Sustainability
On a global scale there is now a rise in demand for energy and the International Energy
Agency has predicted an energy consumption rise by about 50% between now and
2030(Palma et al 2012). Petroleum has served as a major source of energy for long enough
with the current decrease in petroleum prices which has majorly affected the oil and gas
sector, the dwindling petroleum oil wells and the continuous threat of environmental
impacts on climate and health of people, it is clear that an alternative energy source is
needed.
In order to reduce the dependence on petroleum there is now a search for more renewable
sources of energy such as hydrogen which can be sustainably produced using Ethanol Steam
reforming.

Generally the sustainability of the project can be divided into three main topics which affect
it directly environmental, social and economic Sustainability.

7.1 Environmental Sustainability

In 2012 the Environmental Protection Agency (EPA) stated the greenhouse emissions in the
transportation sector accounted for 28% of the United States greenhouse emissions due to
the use of petrol, making it the 2nd largest contributor after electricity. These past trends
have created the necessity for cleaner and more sustainable fuels with lower emissions such
as hydrogen which only produces water as a by-product.
The main environmental concern during the steam reforming of ethanol is the large amount
of CO2 produced alongside hydrogen on reaction of carbon monoxide and steam at the
water gas shift reactor; it is also one of the products of the desired reactions at the selective
oxidation reactor on combustion of carbon monoxide.
In order to eliminate the CO2 a carbon capture system could be put in place and there are
four possible carbon capture sites in the chosen location Texas which creates a flexible
approach. The CO2 produced from the process will be transported through a pipe to the
carbon capture site where it will be separated from other gases cooled and then stored
underground. This will help reduce the CO2 produced to below 5000ppm which is the
acceptable permissible exposure limit in any working environment according to the OSHA
(OSHA Gov 2015) this will help reduce the risk of health problems to workers.
On initial start-up however a carbon capture initiative is too expensive as a capital cost and
may have to be assessed for viability after several years of operation.
Other environmental risks involved with ethanol steam reforming are the possible
production of carbon monoxide which is initially produced in the steam reformer at SR3
(189tonnes/hr) and reduced significantly by the water gas shift reactor at SR5
(47tonnes/hr), however it is not a desired reaction in the selective oxidation reactor and is
thus assumed not to be produced anymore at SR7 and should not pose a problem. The main
environmental concerns can be tackled making this process environmentally sustainable.

7.2 Social Sustainability

According to the bureau of labour statistics unemployment rates in Texas has been falling
since July 2014 to December 2014 from 5% to 4.6% (BLS Gov 2014) thus an additional

24
hydrogen production site will further reduce the unemployment rate providing jobs to all
qualified engineers and managerial staff, regardless culture gender or age group in order to
maintain social sustainability.
Process engineers would be one of the most highly sought disciplines responsible for
running the plant on a day to day basis while safety engineers will be needed ensure all risk
assessments are followed thoroughly and safety precautions are obeyed at high risk areas.
Some of these areas include the pressure swing absorbers which operate at high pressures
at about (40-50Bara) and the steam reformer with temperatures at 650°C. Summer
placements will be opened up to University students with the relevant degrees in order to
maintain the inflow of qualified engineers. Bonuses and holidays will be made available to
staff that show good work ethic and have been working for a number of years thus
providing a suitable and ethical working conditions for the staff. By having an inflow of
quality staff with a suitable and ethical working environment, staff will be kept satisfied and
thus can be retained for as long as possible. This will thus create and maintain social
sustainability ensuring a continuous decline in unemployment rates in Texas.

7.3 Economic Sustainability

The fact that hydrogen has broad ranges and can thus be used in various marketing sectors
is one of the strengths of the remit that will support the economic sustainability due to the
large potential of high sales. Bio-mass is grown in large quantities in places like Missouri in
the mid-western regions of the United States. This makes the proximity to the chosen
location, Texas, quite distant leading to potentially large transportation costs that may not
be economically stable in the long run. However an onsite storage for the ethanol may be
put in place meaning large orders could be made once a month that would be sufficient to
satisfy the remit. The transport costs of the ethanol were assumed to be included in the
selling price at $0.51/kg (Texas Natural Gas prices).
The most feasible markets are the sale of hydrogen gas for ammonia production and the use
of the cryogenically stored hydrogen liquid for fuel cells and the economics section has
shown the worst case scenario of profitability to be $2.8 Billion operating between these
two markets.
The largest costs associated with this are the cryogenic storage and the ethanol purchases
which initially would hinder the economic sustainability but due to the vast amount of
hydrogen being produced at 300,000 tonnes/year and research which has shown that the
energy industry will start utilizing fuels from more renewable sources
(marketsnmarkets2015). It can be concluded the remit is economically sustainable.

Other sustainable features of the process include:

7.4 Renewable Feed Stock

A renewable feed stock provides the added advantage of a prolonged product life span
because it would provide an inexhaustible source of feed. Bio-mass ethanol is the main
feedstock of the steam reforming process and is domestically produced in the Midwest
region of the United States where large areas of land are allocated to grow crops such as
corn and sugarcane. These crops are then subjected to hydrolysis and fermentation in order
to convert complex polysaccharides to sugars to ethanol and CO2, the ethanol is then
separated from other bi-products such as CO2 and finally dehydrated to remove any water.

25
7.5 Product Sustainability
The diversity of the uses of hydrogen ranges across different industries from the production
of hydrogenated vegetable oils in the food industry to producing ammonia in the process
industry. In recent times hydrogen has attracted a lot of attention around the world as one
of the fuels of the future particularly in the transportation industry where it is being used as
fuel cells because it is a renewable, clean fuel with low waste emissions and produces water
as a by-product.

In fuel cells hydrogen is combined with oxygen to produce electricity which is able to power
cars, forklifts and hybrid trains; thus with no burning of fuels involved this makes hydrogen
powered internal combustion engines, efficient and increases its overall performance. The
other markets for hydrogen fuel cell technology include stationary power and portable
power where it can be used for backup power in large generators and portable phone
chargers.

The growing trend in reducing carbon footprints and reducing emissions has now
highlighted a greater need to increase the hydrogen economy. Market research for
hydrogen fuel cells showed worldwide fuel cell sales at 35000 units in 2013, 26% more than
the previous year with revenue reaching $1.3 Billion for the first time (U.S. Department Of
Energy 2014) along with major car brands like Hyundai and Toyota increasing their fleet of
hydrogen powered cars last year. It is thus evident that the production of hydrogen has a
sustainable future ahead.

26
7.7 Cradle-to-Grave diagram

Figure 7 - Cradle-to-Grave

27
8. Conclusion
The findings of this project have seen that the overall remit given for the project is indeed
viable.

The process involves using the renewable feedstock ethanol to make the environmentally
clean hydrogen. The plant can indeed be designed to deal with a production rate of 300,000
tonnes a year of hydrogen gas.

The project has further found that there is certainly a highly values market for hydrogen.
This is particularly the case in the US, where the hydrogen fuel cell market was fit to grow
quite considerably in the next few years.

It was further found that the selling point of the ethanol made it attractive due to the offset
of CO2 production by the large scale agriculture. It could further be argued that the prospect
of a completely self-sufficient source of fuel was a particularly attractive one in today’s oil
and energy politics.

The cost benefit analysis of the project displayed that even in the worst case scenario (low
hydrogen prices) the project resulted in $2.8 billion in profit after ten year of operation.
Therefore, the project is quite viable in an economic sense and furthermore recovers the
initial investment cost required to start the facility up.

The project discussed safety and showed quite well that there were no major safety
implications associated with the process. Inherently, any real safety concerns could be dealt
with effectively with prudent application of both PPE and safe practices.

Environmentally, the project was seen to not be very damaging. The only real concern was
the CO2 given off by the reactants and the fuel consumption. Any damage by the CO2 gas
was seen to have highly reduced effect on the environment due to the increased crop
growth. Furthermore, hydrogen has a high energy value for every small amount of CO2
produced which further reduces the first impression environmental impact.

Lastly, the production of hydrogen from ethanol was overall seen to be very sustainable as
an industrial practice. As discussed the environmental impact was seen to be reduced. The
social aspects show that the site will create jobs and security for local residents.
Economically, a market has been identified and it is believed to be quite sustainable for the
upcoming future. Hydrogen being a highly sought reactant implies that there will be a
continuous demand for the product.

Therefore, it can be stated that the remit: “The aim of this project is to assess the feasibility
of producing 300,000 tonnes of hydrogen gas per year, using steam reforming of ethanol” is
not only viable but also a sound investment to make on the future of energy.

28
10. Appendix
10.1 Sample Calculation
A rough energy balance was carried out on the steam reformer reactor as it is believed this
is where a large amount of energy will go and hence a large cost will be associated with this.
For the purposes of these, simplified, calculations, it is assumed that the stream containing
the water/ethanol mix has the properties of water.
In terms of start-up, the amount of methane required to heat up one hour of flow is
calculated as follows:

Energy required to heat from 25C to 100C:

𝑄 = 𝑚𝑐𝑝 ∆𝑇
642545𝑘𝑔 4.18𝑘𝐽
= ∗ ∗ 75𝐾
ℎ𝑟 𝑘𝑔𝐾
201438000𝑘𝐽
=
ℎ𝑟
Energy required vaporising stream:
𝑄 = 𝑚ℎ𝑓𝑔
642545𝑘𝑔 2675𝑘𝑗
= ∗
ℎ𝑟 𝑘𝑔
8
10 𝑘𝑗
= 1.72 ∗
ℎ𝑟
Energy required to heat from 100C to 650C:

𝑄 = 𝑚𝑐𝑝 ∆𝑇
642545𝑘𝑔 1.9𝑘𝑔
= ∗ ∗ 550𝐾
ℎ𝑟 𝑘𝑔𝐾
108 𝑘𝑗
= 6.71 ∗
ℎ𝑟
Total energy needed:
𝑄𝑡𝑜𝑡𝑎𝑙 = ∑ 𝑄𝑖
𝑘𝑗
= 2.592 ∗ 109
ℎ𝑟
Assuming 100% of the enthalpy of combustion of methane is transferred to the
ethanol/water stream, then:

𝐸𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑒 𝑛𝑒𝑒𝑑𝑒𝑑 =
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 𝑛𝑒𝑒𝑑𝑒𝑑
𝑘𝑗
2.592 ∗ 109
= ℎ𝑟
𝑘𝑗
890.4
𝑚𝑜𝑙
𝑚𝑜𝑙
= 2.91 ∗ 106
ℎ𝑟

29
Converting to mass:
𝑘𝑚𝑜𝑙 𝑘𝑔
𝑀𝑎𝑠𝑠 𝑛𝑒𝑒𝑑𝑒𝑑 = 2.91 ∗ 103 ∗ 16
ℎ𝑟 𝑘𝑚𝑜𝑙
3
𝑘𝑔 𝑡𝑜𝑛𝑛𝑒𝑠
= 46.57 ∗ 10 = 46.57
ℎ𝑟 ℎ𝑟
Then, the energy needed to maintain the reaction at constant temperature of 650C:
Enthalpy of reaction = 347kJ/mol.

The energy used by the reaction:

𝑄𝑟 = ∆𝐻𝑟 ∗ 𝑛
𝑘𝑗 𝑚𝑜𝑙
= 347 ∗ 3.57 ∗ 107
𝑚𝑜𝑙 ℎ𝑟
𝑘𝑗
= 1.173 ∗ 107
ℎ𝑟
Moles of methane needed to re-supply this energy:

𝑄𝑟
𝑀𝑜𝑙𝑒𝑠 =
∆𝐻𝑟
𝑘𝑗
1.173 ∗ 107
𝑀𝑜𝑙𝑒𝑠 = ℎ𝑟
𝑘𝑗
890.4
𝑚𝑜𝑙
𝑚𝑜𝑙
𝑀𝑜𝑙𝑒𝑠 = 1.32 ∗ 106
ℎ𝑟
𝑡𝑜𝑛𝑛𝑒𝑠
= 21.09
ℎ𝑟

30
Table 3 - Capital Investment

Table 4 - Reactant costs for year 1

Table 5 - Selling price of hydrogen over the 10 years

31
Table 6 - Project profile for worst scenario

32
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2015).
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Avelar, A., Augusto, B., Lima, L. and Ourique, J. (2011)

‘PROCESS DESIGN OF ETHANOL REFORMING FOR HYDROGEN PRODUCTION’, PROCESS
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Cryogenic Liquids - Hazards: OSH Answers (2007).

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Canadian Centre for Occupational Health and Safety.
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March 2015).

Cryogenic Safety (2009) NIST - National Center for neutron Research.

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El-Sharkawy, M. (2014) ‘Global warming: causes and impacts on agroecosystems

productivity and food security with emphasis on cassava comparative advantage in the
tropics/subtropics’,Photosynthetica. Springer, 52(2), pp. 161–178. doi: 10.1007/s11099-014-
0028-7.

Energy Dept. Reports: U.S. Fuel Cell Market Production and Deployment Continues Strong
Growth (2014). Energy.gov.
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