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https://www.slideshare.net/Arrayes/report-on-hydrogen-production-research-in-mexico-a-review 45 38.29 %

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Review.pdf 15 14.32 %

https://www.researchgate.net/publication/3091_A_comparative_overview_of_hydrogen_production_processes 11 4.08 %

https://en.wikipedia.org//Microbialelectrolysis_cell 9 18.09 %

https://www.scribd.com/document/368820385-0-S1364032116305366-main 4 11.86 %

Analysed text

1. ABSTRACT
The present report is aimed to present a review of research activities in the field of hydrogen production. Main research activities are reflected in journal
publications and conference proceedings within the last several years. These resulted in the following topics and contributions: Hydrogen production (HP)
from biological processes and wastes 40.4%, followed by HP through conventional and non- conventional fuels (CO2 capture and Catalysis) 22.4%, HP by
photocatalysis and photoelectroncatalysis 14.1%, HP systems and controls 12.2%, theoretical and thermodynamic studies for HP 7.7%, and HP by electrolysis
3.2%. A wide variety of potential applications can be followed by these contributions, while the spread of this report can be a key for future national or
international collaborations that may strengthen this important area to take advantage of the upcoming opportunities in the country and worldwide. Hydrogen
Production Techniques: A review

2. INTRODUCTION
At present, there are different methods for producing hydrogen, and these are characterized by their primary source. Among the primary sources are fossil fuels
like natural gas and coal as well as renewable sources such as biomass, solar, wind, hydro and nuclear. Additionally, in production technologies there is also
many alternatives, such as chemical, biological, electrolytic, photolytic, and thermo-chemical processes. The choice of the primary energy source and the
technology to produce hydrogen are strongly linked to parameters such as fuel costs as well as environmental and social impacts. Fig. 1 shows the most
employed current technologies to produce hydrogen.

Fig. 1Most employed current technologies to produce hydrogen [1].

In general, electrical and thermal energy can be produced from fossil fuels, nuclear, or recovered energy and renewable energies such as solar, wind, hydro,
thermal and biomass. Photonic energy originates from solar irradiation, while biochemical energy is recovered from organic matter. Carbon and biomass (with
solar energy as a source) can be gasified to produce syngas (a mixture of H2 and CO) followed by gas processing and separation to obtain pure hydrogen.
Reforming options include catalytic steam methane reforming (SMR), partial oxidation (PO) and other variants under development (i.e. CO2 capture). In SMR,
methane reacts with steam at 700'C 950'C to produce syngas, CO is then converted into CO2 , producing additional H2 by the water gas shift reaction (WGS). In
the POx process, methane reacts initially with pure O2 to generate syngas. Hydrogen can be produced using nuclear energy as a source of primary energy,
through thermal splitting of the water Hydrogen Production Techniques: A review

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molecule, electrolysis and thermochemical processes, the three alternatives are free of carbon emissions. The electricity produced in the offpeak or no-demand
time, or at the time of huge river flows in the spring can be stored in the form of hydrogen, and later, when the peak energy is needed, the hydrogen converted to
electricity. One of the advantages of the proposed system is that the resource for production of hydrogen (the water) is available directly at the site.
3.CRITERIA FOR EVALUATING HYDROGEN PRODUCTION
There are various perspectives when we evaluate hydrogen production [1-4]. 1. Environmental perspective Energy conversion - how much energy is required to
make and store vs output. Carbon dioxide emission - common criteria - as it is a greenhouse. Fossil fuel consumption how much is used in order to produce
hydrogen. 2. Economic perspective If we want to incur the hydrogen production technology in the industry, the cost comes into the picture. There are various
costs such as Capital cost, physical cost, storage cost, operating cost, etc. 3. Social perspective Land required Safe area for surroundings and people. 4.
Technological perspective

4. HYDROGEN PRODUCTION TECHNIQUES: A REVIEW

Research related to hydrogen technologies is today very active and specifically, one of the major contributions is generated in the field of hydrogen production.
In this field major contributions come from the following areas: hydrogen production from biological processes, modified hydrogen production and catalysis
(CO2 capture), photocatalysis and photoelectrocatalysis, systems and controls, theoretical and thermodynamic studies and electrolysis, as shown in Fig. 2.
Hydrogen production based on biological processes, hydrocarbon processing, photocatalysis, electrolysis, theoretical studies and systems and control.

Hydrogen Production Techniques: A review

Fig. 2Major research areas in H2 production.

Within the biological processes for hydrogen production the Research activities in focused on five main fields: 1. Bioreactors their operation and specific
applications. 2. Micro-algae as source for photosynthetic hydrogen. 3. Bacteria and microorganisms. 4. Fermentation of organic matter.
5. Microbial electrolysis cells (MEC). With respect to the hydrocarbon processing field, conventional processes (commercially mature technologies) for H2
production have been used for years to obtain large scale hydrogen through processes such as steam reforming, coal gasification, and partial oxidation of
hydrocarbons and these are characterized by presenting high operating costs, being energy intensive with low efficiencies and large CO2 discharges.
However, these technologies can be modified and could be considered as a bridge technology, while new sustainable technologies such as photocatalysis,
water electrolysis, biohydrogen, etc., are able to produce H2. Six mayor areas of research have emerged from an important number of scientific publications
and these are: 1. Catalysis. 2. Hydrocarbon decomposition. 3. Steam reforming with CO2 capture. 4. H2S reforming. 5. Water gas shift. 6. Partial oxidation
by metal oxides. Hydrogen Production Techniques: A review 4

Concerning the photocatalysis research towards hydrogen production, this can be encountered in papers related to the following fields: 1.
Photocatalytic water splitting 2. Visible light activated photocatalysis. 3. Mixed oxides photocatalysts. 4. Photocatalytic nanostructures. 5. Photocatalytic thin
films 6. Metallic photocatalyst doping. 7. Novel photoelectrodes. In the field of theoretical studies and systems, the areas where the more active research is
concentrated are: 1. Thermodynamic analyses. 2. Reactor optimization and control. 3. Renewable energy H2 systems 4. Electrolysis and electrolyzers. 5. Solar-
H2 fuel cell systems. 6. Energy and exergy analyses. Furthermore, the contribution of the main activities related to hydrogen production research in Mexico with
respect to the topics involved in the present review is presented in Fig. 3.

Fig. 3Contribution of published papers by main topics of research on hydrogen production.

From this Figure, it can be seen that the distribution of main research activities are reflected in Journal publications and Mexican conference proceedings within
the last seven years. This resulted in the following topics and contributions: Hydrogen production (HP) from biological processes and wastes
Hydrogen Production Techniques: A review 5

40.4%, followed by HP through conventional and non- conventional fuels (CO2 capture & Catalysis) 22.4%, HP by photocatalysis and photoelectrocatalysis
14.1%, HP systems and controls 12.2%, theoretical and thermodynamic studies for HP 7.7%, and HP by electrolysis 3.2%. A wide variety of potential
applications can be followed by these contributions, while the spread of this report can be a key for future national or international collaborations that may
strengthen this important area within the energy sector to take advantage of the upcoming opportunities of research and development.

5. HYDROGEN PRODUCTION METHODS

Hydrogen Production Techniques: A review

5.1. H2 PRODUCTION FROM FOSSIL FUELS

1. Steam Reforming Method Working Principle- The steam changing strategy (SR) is basically a reactant technique transformation of hydrocarbons and steam
into hydrogen and carbon oxides and comprises of the principle steps of changing or amalgamation gas (amalgamation gas) age, water-gas dislodging (WGS)
and methanation or then again gas cleaning. The crude materials range from methane, obviously gas and other methane-containing gases by different blends of
light hydrocarbons, including ethane, propane, butane, pentane and light and hefty naphtha.

Fig.4. Multiple membranes reactor for steam methane reforming Hydrogen Production Techniques: A review 7

Hydrogen produced from the SMR process includes small quantities of carbon monoxide, carbon dioxide, and hydrogen sulfide as impurities and, depending on
use, may require further purification. The primary steps for purification include: Feedstock purification This process removes poisons, including sulfur (S) and
chloride (Cl), to increase the life of the downstream steam reforming and other catalysts. Product purification In a liquid absorption system, CO2 is removed.
The product gas undergoes a methanation step to remove residual traces of carbon oxides. Newer SMR plants utilize a pressure swing absorption (PSA) unit
instead, producing 99.99% pure product hydrogen. High to ultra-high purity hydrogen may be needed for the durable and efficient operation of fuel cells.
Impurities are believed to cause various problems in the current state-of-the-art fuel cell designs, including catalyst poisoning and membrane failure. As such,
additional process steps may be required to purify the hydrogen to meet industry quality standards. Additional steps could also be needed if carbon capture and
sequestration technologies are developed and utilized as part of this method of hydrogen production. Advantage of Steam Reforming Method Steam reforming
of natural gas offers an efficient, economical, and widely used process for hydrogen production, and provides near- and mid-term energy security and
environmental benefits. The efficiency of the steam reforming process is about 65% to 75%, among the highest of current commercially available production
methods. Natural gas is a convenient, easy to handle, hydrogen feedstock with a high hydrogen-to-carbon ratio. Limitation of Steam Reforming Method During
the production of hydrogen, CO2 is also produced. The SMR process in centralized plants emits more than twice the CO2 than hydrogen produced.1 To avoid
emission of CO2 into the atmosphere, CO2 can be concentrated, captured, and sequestered; sequestration concepts and technologies are relatively new and
there is no long-term test evidence to prove that these technologies will be successful. Sequestration in oceans is controversial because of the possible adverse
impact on the aquatic environment by the reduction of ocean water pH.

Hydrogen Production Techniques: A review

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2. Hydrocarbon Pyrolysis Working Principle- Hydrocarbon (CHs) pyrolysis is a well-known process in which the only source of hydrogen is the hydrocarbon
itself, which undergoes thermal decomposition through the following general reaction:

Thermo-catalytic decomposition of light liquid hydrocarbons (boiling point between 50 and 200 °C), is carried out with the production of elemental carbon and
hydrogen, whereas in the case of heavy residual fractions (boiling point higher than 350 °C), hydrogen is produced in a two-step scheme namely,
hydrogasification and cracking of methane.

Production ProcessThermo-catalytic decomposition of light liquid hydrocarbons (boiling point between 50 and 200 °C), is carried out with the production of
elemental carbon and hydrogen, whereas in the case of heavy residual fractions (boiling point higher than 350 °C), hydrogen is produced in a two-step scheme
namely, hydrogasification and cracking of methane.

Fig.5. Flow diagram of the Methane Pyrolysis Process.

Direct de-carbonization of natural gas (CH4), is effected in an air and water free environment, at temperature up to 980 °C and atmospheric pressure as
illustrated in Fig. The energy requirement per mole of hydrogen produced (37.6 kJ/mol), is less than that for the SMR method (63.3 kJ/mol) and could be
covered by combustion of approximately 1520% of hydrogen produced in the process Moreover, pyrolysis does not include WGS and CO2 removal steps, and
the energy intensive stage of CCS is replaced from carbon management which could be used in the metallurgy and
Hydrogen Production Techniques: A review
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chemical industries or even can be stored underwater or on land for future use. Hence, capital investments for large plants are lower than for the processes of
steam conversion or partial oxidation resulting in 2530% lower hydrogen production cost. Continuous removal of hydrogen by membrane separation should
increase the de-carbonization conversion for a given temperature. Pd-Ag alloys are typically used for H2 separation, allowing operation at lower temperatures
and reducing the coke formation. The main drawbacks of this technology are related to the hydrogen separation weakness due to the low H2 partial pressures in
the reaction mixture and membrane durability affected by high temperatures needed for the decarbonization equilibrium. COMPARATIVE ANALYSIS OF
REFORMING TECHNOLOGIES Hydrogen Production Techniques: A review

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5.2. H2 PRODUCTION FROM RENEWABLE SOURCES

Although hydrocarbons are currently the main feedstock used for H2 production, the need to increase the integration of renewable technologies will become
unavoidable. As the fossil fuels are declining and Greenhouse effect is attracting greater attention, the share of renewable technologies will increase in the near
future while in long term, is expected to dominate over conventional technologies. There are many processes for H2 production from renewable resources and a
brief description of some biomass-based technologies, along with approaches related to water splitting, is included here.

1.Thermolysis Working Principle- Thermolysis or thermochemical water splitting is the process at which water is heated to a high
temperature until decomposed to hydrogen and oxygen.

Production Process- The decomposition of water is not effected until the temperature is very high, generally over 2500 °C, in order the Gibbs function (G) to
become zero and the separation of hydrogen from the equilibrium mixture become feasible Since such expenditures of considerable primary energy could not
be achieved by sustainable heat sources, several thermochemical watersplitting cycles have been proposed to lower the temperature and improve the overall
efficiency. Thermochemical cycles consist of a series of chemical reactions at different temperatures and constitute one of the most promising process through
which heat is converted into chemical energy in the form of hydrogen. Two examples of thermochemical cycle, represented by the chemical reactions
respectively, are shown below enabling the comparison with the single-stage water decomposition of Eq. Hydrogen Production Techniques: A review

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2. Hydrogen Production from Glycerol Using Microbial Electrolysis Cell

Working Principle- In MEC, electrochemically active microbes growing on the surface of the anode break down organic matter into CO2, electrons and protons.
The electrons and protons travel through the external circuit and solution, respectively, and combine at the cathode to generate hydrogen. The anode process of
MEC is the same as that of a Microbial Fuel Cell (MFC) and the cathode process is the same as that of a water electrolyzer. In MFC, oxygen is used as the
electron acceptor at the cathode, instead of protons in the solution.

Production Process- Electrogenic microorganisms consuming an energy source (such as acetic acid) release electrons and protons, creating an electrical
potential of up to 0.3 volts. In a conventional MFC, this voltage is used to generate electrical power. In a MEC, an additional voltage is supplied to the cell from
an outside source. The combined voltage is sufficient to reduce protons, producing hydrogen gas. As part of the energy for this reduction is derived from
bacterial activity, the total electrical energy that has to be supplied is less than for electrolysis of water in the absence of Hydrogen Production Techniques: A
review

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Showing 2 of 2 found references: depends on which organic substances are used. Lactic and acetic acid achieve 82% efficiency, while the values for unpretreated cellulose
or
https://www.researchgate.net/publication/308309135_A_comparative_overview_of_hydrogen_production_processes glucose are close to 63%. The efficiency of normal water
electrolysis is 60 to 70 percent. As MEC's convert unusable biomass into usable https://www.scribd.com/document/368820385/1-s2-0-S1364032116305366-main
microbes. Hydrogen production has reached up to 3.12 m3H2/m3d with an input voltage of 0.8 volts. The efficiency of hydrogen production

hydrogen, they can produce 144% more usable energy than they consume as electrical energy. Depending on the organisms present at the cathode, MECs can
also produce methane by a related mechanism. Calculations Overall hydrogen recovery was calculated as RH2 = CERCat. The Coulombic efficiency is
CE=(nCE/nth), where nth is the moles of hydrogen that could be theoretically produced and nCE = CP/(2F) is the moles of hydrogen that could be produced
from the measured current, CP is the total coulombs calculated by integrating the current over time, F is Faraday's constant, and 2 is the moles of electrons per
mole of hydrogen. The cathodic hydrogen recovery was calculated as RCat = nH2/nCE, where nH2 is the total moles of hydrogen produced. Hydrogen yield
(YH2) was calculated as YH2 = nH2 /ns, where ns is substrate removal calculated on the basis of chemical oxygen demand.
Hydrogen Production Techniques: A review

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6. COMPARISON OF THE DIFFERENT HYDROGEN PRODUCTION PROCESSES.

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SMR is currently the most cost-effective process for H2 production followed by CG. SR possess the lowest operating temperature requiring no oxygen, followed
by ATR and POX, while hydrocarbon pyrolysis provides the advantage of reduced-step and emission-free procedure, with carbon being the only byproduct that
requires treatment. Referring to Table , these methods occur more advantageous in that, they constitute a mature and highly developed technique for H2
generation through infrastructures that already exist.

7.CONCLUSIONS
Hydrogen has become one of the most promising alternative energy carriers in the country, this in view to decentralize the today's energy production based on
oil. Hydrogen versatility of new applications, high calorific value, and the fact that can be used as a clean fuel are some examples of the high potential in
research and development activities. The most active area of report for hydrogen production in deals with biological related processes (40% of published papers)
with interesting topics such as bioreactors; their operation and specific applications, microalgae as source for photosynthetic hydrogen, bacteria and
microorganisms, fermentation of organic matter and microbial electrolysis cells (MEC). These research activities have been enhanced by the actual trend to
make use of a vast industrial and agroindustrial organic wastes that the country currently produce in many areas of economic activities where biomass can be
obtained in a regular basis. Hydrogen Production Techniques: A review

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References
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for sustainable development. Energy 2007;32(6):9129. [3] Blok K. Enhanced policies for the improvement of electricity efficiencies. Energy Policy
2005;33(13):163541. [4] Lior N. Thoughts about future power generation systems and the role of exergy analysis in their development. Energy Convers Manag
2002;43(9 [5]. Hydrogen production research in Mexico: A review/ A. Lo pez Ortiz, M.J. Mel endez Zaragoza, V. Collins-Mart´nez/ Departamento de
Ingenier´a y Qu´mica de Materiales, Centro de Investigacio n en Materiales Avanzados, S.C., Miguel de Cervantes 120, Chihuahua, Chih., 31136, Mexico. [6]
Hall PJ, Bain EJ. Energy-storage technologies and electricity generation. Energy Policy 2008;36(12):43525. [7] Hadjipaschalis I, Poullikkas A, Efthimiou V.
Overview of current and future energy storage technologies for electric power applications. Renew Sustain Energy Rev 2009;13(67):151322. [8] Dell RM, Rand
D a J. Energy storage a key technology for global energy sustainability. J Power Sources 2001;100(12):217. [9] Marbán G, Valdés-Solís T. Towards the
hydrogen economy? Int J Hydrog Energy 2007;32(12):1625 37. [10] Shinnar R. The hydrogen economy, fuel cells, and electric cars. Technol Soc
2003;25(4):45576. [11]
Granovskii M, Dincer I, Rosen MA. Economic and environmental comparison of conventional, hybrid, electric and hydrogen fuel cell vehicles. J Power
Sources 2006;59(2):118693. [12] Van Mierlo J, Maggetto G, Lataire P. Which energy source for road transport in the future? A comparison of battery, hybrid
and fuel cell vehicles Energy Convers Manag 2006;47(17):274860. Hydrogen Production Techniques: A review

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