Bioethanol steam reforming for production of hydrogen

Valeria Castao Arboleda1 Valentina Naranjo Castao2

1

Ingeniera Quimica, Universidad Nacional de Colombia, Manizales, Colombia.

Corresponding author. Tel: +57 3116706379
E-mail address: vacastanoar@unal.edu.co
2

Ingeniera Quimica, Universidad Nacional de Colombia, Manizales, Colombia.

Corresponding author. Tel: +57 3106671567
E-mail address: nvnaranjoca@unal.edu.co

ABSTRACT
Hydrogen production from bioethanol can get it from a renewable resource, non-toxic, without a net
contribution of CO2 to the atmosphere and which can be obtained from sugar cane, one of the most
widespread crops in Colombia and Latin America. Hydrogen is considered the fuel of the future, among
other reasons for being great bearer of energy per unit mass. His character of clean and renewable fuel
gives it a particular appeal for the demands of a market that looks more closely at oil depletion.
Technical, economic and environmental analysis of the above process is shown.

Key words: Hydrogen, cleaner production, bioethanol reforming of hydrocarbons.

Introduction
Hydrogen has become a topic of great interest
to many global and national companies, due to
their wide applications and their ecological
aspects. Therefore it has been done extensive
research in many countries in terms of
development of new methods for their
preparation, and use of increasingly affordable
technologies.
Hydrogen is produced predominantly from fossil
fuels; roughly 96% of hydrogen is produced by
steam reforming natural gas. Perhaps 4% of
hydrogen is produced by electrolysis of water.
However
from
emerging
research
is
accomplished predict that in the future

production of hydrogen will be provided by the

gasification of biomass and enzyme [1]
processes. It is therefore necessary to devote
some attention to biological methods, especially
its effectiveness.
From the above, it is clear that the selection of
resources and methods of hydrogen production
must be carefully evaluated, because besides
the point of view of the environment also the
economic point of view is important, not so
much by the availability of resources but by the
effectiveness of the process. [2]
The main advantage that has hydrogen is the
most abundant element on earth, is both water
and fossil fuels, is present in the universe, and

its combustion does not produce harmful

emissions of carbon dioxide as oil . The main
problem is that rarely is in free state, which is
key to develop ways to effectively exploit it. [3]
Market analysis
-

Hydrogen production companies in the

world: For reference, the 13 trillion SCF
(Standard Cubic Feet) produced in 2008
by the major production companies (Air
Liquide, Praxair, Linde, Air Products,
Shell, Chevron, BP, ConocoPhillips,
ExxonMobil ) nearly half was destined to
produce
ammonia
for
fertilizer
production, while the rest was used
almost entirely in petroleum refining
(hydrocracking) to break the chains of
hydrocarbons into lighter fractions and
get used liquid fuels in transport. The
largest producer in the world is the
United States followed by South Korea
and Spain.
Hydrogen production companies in
Europe: In Europe, 6% hydrogen used
corresponds to that sold in the market,
cylinders for different industrial use.
The remainder is produced internally by
companies that have their own needs.
The remaining 94% of production is
generated by large gas producers
vector, which include Air Liquide, Linde
and Air Products that represent 95% of
the European market. [4]
Colombia: The cost of hydrogen
production in Colombia is very sensitive
to prices of electricity and natural gas
and production volumes. Colombia is
expected to have the required
production capacity to demand from
2018 [5]. The main use is proposed to
give this product by our country is for
the fuel cell engine, replacing traditional

fuels such as gasoline and diesel, by one

that provides the environment a cleaner
combustion with fewer CO2 (emissions
vary depending on the route of
hydrogen production). Hydroforce
company, with its principal share of
production Oxyhydrogen (HHO) or
Hydroxy Gas that is generated from
water electrolysis. By conducting
electric current through the steel plates
Generator cell (which is installed in the
vehicle) in which water is submerged
with a minimum amount of electrolyte,
the resulting molecule HHO (Hydroxy
Gas), it is delivered to the combustion
engine. [6] It also raises him to use
hydrogen as an energy supplier in hydro
plants, which have smaller, low
environmental impact, prone to
distributed generation. It also opens the
possibility for the country to export
energy as H2. It is important, therefore,
further studies to complete the
necessary elements to establish the
feasibility of the project. [7]
Raw Materials
Natural gas: the partial oxidation of methane to
produce hydrogen gas has a major impact on oil
chemical and allied industries. Methane, a
source of potential energy is available in natural
gas. And after the partial oxidation is converted
into synthesis gas, production of hydrogen from
gas has been studied as compared to other
reforming reactions this reaction is slightly
exothermic, and can use the gas formed to feed
the production methanol, carbon dioxide is

generated during the processes making this

procedure is unfriendly to the environment
because the CO
2 is the main cause of
the greenhouse effect.
Wheat hydrolyzate of wheat flour may be used
to replace the commercial glucose for hydrogen
production by fermentation and thereby reduce
the production cost for large scale hydrogen.
Due to the high content of starch,
carbohydrates can be used for producing
hydrogen by anaerobic bio-fermentation. The
first step in the production of bio-hydrogen is
acid or enzymatic hydrolysis of starch / cellulose
producing highly concentrated sugar solution.
Anaerobic fermentation of concentrated sugar
solution is given using a mixed culture bacteria
and sludge, thus allowing the production of
hydrogen
Bioethanol: The use of ethanol as a source of H
2 can not only reduce emissions and
dependence on fossil fuels, but also increase the
efficiency of the use of energy. The bioethanol
can be supplied by the existing fuel alcohol
plants in the country, right from the area of
Valle del Cauca, or can be implemented
throughout the distillation fermentation system
within the production plant bio hydrogen.
Date palm (Phoenix dactylifera L.) is one of the
most important fruit growing in the Arab world
and neighboring countries and represents a
good cash crop for many farmers. The date palm
starts to bear fruit at an average age of 5 years,
and continues production with an average yield
of 400-600 kg / tree / year for up to 60 years.
The date palm is considered a symbol of life in
the desert, because it tolerates high
temperatures, drought and more than many
other plant species of fruit crops salinity. It is
one of the oldest trees which man has obtained
benefit, and has been cultivated since ancient

times. It is the only indigenous wild desert plant

definitely domesticated in their native hostile
environments seems to be the date palm. The
goal is to produce hydrogen from rotten fruit of
the palm through three fermentations where
different for each microorganism used in
Colombia this palm is grown in Soata Boyaca
and in moderate proportions.
Vinasse: The possibility that waste can be used
to
produce
energy
can
stimulate
implementation of treatment plant wastewater
in factories ethanol / sugar. biodigestion of
vinasse for biogas production is an alternative
means of disposal.
For this case you are used bioethanol, later
specifying the reason
Location and Impact
Considering we chose feedstock bioethanol, had
certain considerations to choose the purchase
of this raw material, one of which was that
some admissions distributors put a stop to the
sale, in some cases this cap reached the 200,000
metric tons per year .
As our country a major producer of sugarcane
and considering that for about 8 years, 5 sugar
mills
(Incauca,
Providencia,
Manuelita,
Mayagez and Risaralda), invested more than $
150 million in the construction of distilleries for
the production of bioethanol from sugar cane,
which is enough to meet domestic demand,
decided to buy the ethanol in our country and
thus support the Colombian industry, and
prioritize buy distilleries located in the coffee
because our production Hydrogen will be
located in this area.
We note that cities such as Armenia and Pereira
are 14.4% and 13.5% respectively in third and
sixth place in the cities with the highest

unemployment in the country, considering that

the production of bioethanol may be a strategy
to mitigate these unemployment rates, to not
only reduce dependence on non-renewable
energy sources but also generate formal
employment in the area.
A very important factor besides the social in
terms of employment, was the environmental
as ethanol from sugar cane as Colombian
literature reports reduces by 74% the emissions
of greenhouse gases that cause this when
compared with the corn ethanol produced in
the United States and produced from sugar cane
in Brazil, another advantage of the Colombian
bioethanol is that sugar cane is more efficient
than other crops in storage of energy from solar
radiation. Sugarcane stores this energy in the
form of biomass, releasing 40 tons of oxygen
into the atmosphere and setting 60 tons of
carbon dioxide. Thus, the production of
bioethanol based on sugar cane has a better
environmental performance than alcohol made
from other raw materials.

Financing
BANCOLDEX:
Is
Colombia's
business
development bank. Designs and delivers new
tools, financial and non-financial, to boost
competitiveness, productivity, growth and
development of micro, small, medium and large
Colombian companies, whether domestic or
export market.
Kinetics and reactions
The process for production of hydrogen occurs
in several stages: [9]
Steam reforming of ethanol
Depending on the type of catalyst, the reactions
and the mechanism that takes place in the
steam reforming of ethanol is different. the
catalyst of choice for this reaction is Ni / Al2O3, Laborde et al are based on experimental
results and the following proposed reaction
scheme for high values of W / F ratio and waterethanol, where ethanol is the conversion of 100
% for any temperature, the only gaseous
products, even at 300 C, are CH4, CO2, CO and
H2, not appreciating the formation of
acetaldehyde and ethylene.
Steam reforming
reactions:

involves

the

C2H5OH CO + CH4 + H2
CO + H2O CO2 + H2
C2H5OH + H2O CO2 + CH4 + 2H2
CH4 + H2O CO + 3H2
CO Conversion

following

CO + H2O CO2 + H2

k E 1 (898.15K)

1.13E-07

Ea E 1

122.9 kJ/mol

For this reaction it is apparently CO

chemisorbed on iron oxide and both the H2O
and CO2, are strongly adsorbed. CO2 has an
inhibitory effect on the rate of reaction forward
and H2 appears to be adsorbed. Furthermore, in
the above reaction, there are no other
significant reactions.

k E 2 (898.15K)

3.06E-07

Ea E 2

195.5 kJ/mol

k R 1 (898.15K)

2.48E-03

Ea R 1

174.0 kJ/mol

k R 2 (898.15K)

9.12E-04

Ea R 2

166.3 kJ/mol

CO formation for this exothermic reaction is

thermodynamically
favored
at
low
temperatures, but the reaction rate is low at
these conditions. For high conversions and low
reactor volume (high reaction rate) this reaction
is carried out in two stages, the first and second
high temperature low. The catalyst commonly
used for the first stage contains CO conversion
mainly iron oxide and chromium oxide; for the
second stage catalyst used usually contains a
mixture of copper oxide and zinc oxide
supported on alumina.
Selective oxidation (SOX)
The thermodynamically irreversible general
reactions that describe the selective oxidation
are:
CO + O2 CO2
H2 + O2 H2O

() = (898.15)

1
1
)(
))

898.15

((

[8]

METHODOLOGY
The raw material for this process is ethanol
produced from sugarcane industry in Colombia
The basic production scheme includes a
feedstock pretreatment with heat, a reaction
zone consisting of four reactors, and finally a
separation zone, which because of the difficulty
would be more optimal inclusion membrane
separation
This process requires a good exchange of heat,
all the reactions involved to minimize the
concentration of carbon monoxide in the
output.
Therefore they are included in the process six
exchange units. An excellent alternative would
be to implement energy integration, in order to
give a lot more out of energy as heat coming out
of the reactors.

Catalysts which have proven to be selective for

the SOX and high reaction rates are the
commercial Pt / -Al2O3 (Ref. 31) and Ru / Al2O3.
Kinetic parameters for the process are:
E1: C 2 H 5 OH CO + CH 4 + H 2
E2: C 2 H 5 OH + H 2 O CO 2 + CH 4 + 2H 2
R1: CH 4 + 2H 2 OCO 2 + 4H 2
R2: CO 2 + H 2 CO + H 2 O

Figure 1. Process diagram of hydrogen production

for reforming steam ethanol.

Pretreatment
The ethanol-water solution is pumped through
the regenerative pump to greater than
atmospheric (2 atm) to ensure the flow pressure
throughout the system.
The water-ethanol mixture is preheated and
partially vaporized in heat exchanger 1 and a
superheated steam is generated to 526 C to be
reformed.
Reaction zone
The preheated feed enters the reactor, and heat
for the endothermic reaction is supplied by
burning natural gas (methane), using an excess
of oxygen fed as air. The products of this
reaction out at 700 C. Then cooling occurs up
to 300 C to enter the second reactor, where
out is to bring high-Shift reaction. This reaction
is exothermic and the products leave at a higher
temperature (500 C). Subsequently cooling
heat exchange to 110 C for a second stage
adiabatic low temperature shift conversion
takes place Low, there is the CO content
decreases further. This stream is cooled to 50
C and the excess water is condensed and
removed in a flash.
To carry out the selective oxidation of CO (SOX)
and decrease its concentration, the wet gas is
heated to 168.6 C by an exchanger, and is
mixed with air at 30 C, obtaining a reactor
outlet temperature of 200 C.

you can get a product of hydrogen at a purity of

90%.
Environmental analysis
Environmental analysis will be done with the
help of a supplement called WAR, of Aspen plus.
V7.2. Traditionally chemical process designs the
WAR screen shot below were optimized using
purely economic measures such as rate of
return. The Waste Reduction Algorithm (WAR)
was developed by EPA scientists so that
environmental impacts of designs could easily
be evaluated.
Economics analysis
Economic analysis will be done with the help of
a supplement called Aspen process economics
analyzer, of Aspen plus V7.2
Aspen process economics analyzer develops and
provides knowledge-based process evaluation
technology, software, and services.
Aspen PEA executes Compare alternative
technologies and designs.
Generate capital cost (CAPEX) estimates,
operating cost (OPEX) estimates, and
investment cash flow curves to evaluate the
lifecycle economic impact of process decisions
during conceptual design with Aspen Process
Economic Analyzer
RESULTS AND DISCUSSION

Separation zone.

Simulation of Aspen Plus

After leaving the fourth reactor stream is sent to

a unit heat exchanger and then removing the
remaining water, and steam is sent to a
separator which is considered ideal, as the most
effective method to accomplish this would be
separation by membrane technologies, finally

The simulation was conducted on ASPEN PLUS

in order to analyze products and production
quantities of hydrogen.

The production of hydrogen simulated in Aspen

is 0,3509768 kg/hr, with a purity of 90%.

Environmental analysis
WAR analysis software, in which different
sources of energy are compared to the same
process, was performed. Coal, Oil and Gas, and
cleaner production is obtained by using gas.
This is because fewer PEI deliveries by
acidification, a lesser extent contributes to the
production of greenhouse gases.
When reviewing the overall impact of the
process it is obtained that the impact is
negative, meaning that the process is mitigated.

CONCLUSIONS
Hydrogen production is a very viable process
that arises from the need to find alternative
energy sources. Being one of the major goals of
our future engineers, to perform to perfection
these processes. Although it still has many
uncertainties especially in this storage. Since
this is one of the drawbacks to the time of
obtaining hydrogen since it must have adequate
facilities for this, since they are necessary quite
high pressures in order to compress the
product.
Observing our project must take into account
that at the time of producing hydrogen occurs
as a by-product the methane and CO2, which is
a fairly contaminant by-product for the
environment, hence there is a need to
implement techniques of recycling or
exploitation of this. In order to not be thrown
into the environment and contaminate it.
References
[1] Production of hydrogen from renewable
resources and its effectiveness. Olga Bicakova,

Economics analysis
Data obtained from the simulation software
Aspen Plus
Total Project Capital
Cost
Total Raw Materials
Cost
Total Products Sales
Total Operating
Labor and
Maintenance Cost

Cost
Cost/period
Cost/period
Cost/period

Total Utilities Cost

Cost/period

Total Operating Cost

Cost/period

3,475,957.6
2 USD
9,962.40
USD
0 USD
442,980.00
USD
38,859.29
USD
889,155.03
USD

Pavel Straka. Institute of Rock Structure and

Mechanics of the AS CR.
[2] Fermentative hydrogen production using
wheat flour hydrolysate by mixed culture. Wei
Han, Xiaonan Wang, Lan Ye, Jingang Huang,
Junhong Tang, Yongfeng Li, Nanqi Ren. College
of Materials and Environmental Engineering,
Hangzhou Dianzi University. 2015.
[3]
http://www.acofipapers.org/index.php/acofipaper
s/2013/paper/viewFile/580/90

[4]
http://web.ing.puc.cl/~power/alumno14/hidrog/te
cnologias.htm
[5] Proyeccin al ao 2025 para el uso del
hidrgeno en el sector transporte del Valle de
Aburr. Juan Guillermo Meja Arango, Carlos
Alberto Acevedo Alvarez. Facultad de
ingenieras, Instituto Tecnolgico Metropolitano,
Medelln, Colombia. Agosto de 2013.
[6] http://www.hydroforce.com.co/
[7] Estudio sobre produccin de H2 con
hidroelectricidad para una economa de
hidrgeno en Colombia. Hernn CarvajalOsorio, Jhon H. Babativa , Julio A. Alonso.
Universidad La Gran Colombia, Bogot, D.C.,
Colombia. 2010.
[8] Bio-ethanol steam reforming on Ni based
catalyst. I. Llera, V. Mas , ML Bergamini , M.
Laborde. Chemical Engineering Science. 2011.
[9] Diseo de una planta piloto para la
produccin de hidrogeno
a partir de bioetanol para pilas de combustible
Alan Farith Caballero Malaver. universidad
industrial de Santander. 2004