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Hydrogen production

February 16, 2024

Hydrogen gas is produced by several industrial methods. Fossil fuels are the dominant source of hydrogen.[1] As of 2020, the majority of hydrogen (~95%) is produced by steam reforming of natural gas and other light hydrocarbons, and partial oxidation of heavier hydrocarbons.[2][need quotation to verify] Other methods of hydrogen production include biomass gasification and methane pyrolysis. Methane pyrolysis and water electrolysis can use any source of electricity including renewable energy.

The production of hydrogen plays a key role in any industrialized society, since hydrogen is required for many chemical processes.[3] In 2020, roughly 87 million tons of hydrogen was produced[4] worldwide for various uses, such as oil refining, in the production of ammonia through the Haber process, and in the production of methanol through reduction of carbon monoxide. The global hydrogen generation market was fairly valued at US$155 billion in 2022, and expected to grow at a compound annual growth rate of 9.3% from 2023 to 2030.[5]

Steam methane reforming edit

Main article: Steam reforming

Steam methane reforming (SMR) produces hydrogen from natural gas, mostly methane (CH4), and water. It is the cheapest source of industrial hydrogen, being the source of nearly 50% of the world's hydrogen.[6] The process consists of heating the gas to 700–1,100 °C (1,300–2,000 °F) in the presence of steam over a nickel catalyst. The resulting endothermic reaction forms carbon monoxide and molecular hydrogen (H2).[7]

In the water-gas shift reaction, the carbon monoxide reacts with steam to obtain further quantities of H2. The WGSR also requires a catalyst, typically over iron oxide or other oxides. The byproduct is CO2.[7] Depending on the quality of the feedstock (natural gas, naphtha, etc.), one ton of hydrogen produced will also produce 9 to 12 tons of CO2, a greenhouse gas that may be captured.[8]

 
Illustrating inputs and outputs of steam reforming of natural gas, a process to produce hydrogen and CO2 greenhouse gas that may be captured with CCS

For this process, high temperature steam (H2O) reacts with methane (CH4) in an endothermic reaction to yield syngas.[9]

CH4 + H2O → CO + 3 H2

In a second stage, additional hydrogen is generated through the lower-temperature, exothermic, water-gas shift reaction, performed at about 360 °C (680 °F):

CO + H2O → CO2 + H2

Essentially, the oxygen (O) atom is stripped from the additional water (steam) to oxidize CO to CO2. This oxidation also provides energy to maintain the reaction. Additional heat required to drive the process is generally supplied by burning some portion of the methane.

Other fossil fuel methods edit

Partial oxidation edit

Hydrogen production from natural gas and heavier hydrocarbons is achieved by partial oxidation. A fuel-air or fuel-oxygen mixture is partially combusted, resulting in a hydrogen- and carbon monoxide-rich syngas. More hydrogen and carbon dioxide are then obtained from carbon monoxide (and water) via the water-gas shift reaction.[7] Carbon dioxide can be co-fed to lower the hydrogen to carbon monoxide ratio.

The partial oxidation reaction occurs when a substoichiometric fuel-air mixture or fuel-oxygen is partially combusted in a reformer or partial oxidation reactor. A distinction is made between thermal partial oxidation (TPOX) and catalytic partial oxidation (CPOX). The chemical reaction takes the general form:

2 CnHm + nO2 → 2n CO + mH2

Idealized examples for heating oil and coal, assuming compositions C12H24 and C24H12 respectively, are as follows:

C12H24 + 6 O2 → 12 CO + 12 H2
C24H12 + 12 O2 → 24 CO + 6 H2

Plasma pyrolysis edit

The Kværner process or Kvaerner carbon black & hydrogen process (CB&H)[10] is a plasma pyrolysis method, developed in the 1980s by a Norwegian company of the same name, for the production of hydrogen and carbon black from liquid hydrocarbons (CnHm). Of the available energy of the feed, approximately 48% is contained in the hydrogen, 40% is contained in activated carbon and 10% in superheated steam.[11] CO2 is not produced in the process.

A variation of this process is presented in 2009 using, plasma arc waste disposal technology for the production of hydrogen, heat and carbon from methane and natural gas in a plasma converter.[12]

Coal edit

For the production of hydrogen from coal, coal gasification is used. The process of coal gasification uses steam and oxygen to break molecular bonds in coal and form a gaseous mixture of hydrogen and carbon monoxide.[13] Carbon dioxide and pollutants may be more easily removed from gas obtained from coal gasification versus coal combustion.[14][15] Another method for conversion is low-temperature and high-temperature coal carbonization.[16]

Coke oven gas made from pyrolysis (oxygen free heating) of coal has about 60% hydrogen, the rest being methane, carbon monoxide, carbon dioxide, ammonia, molecular nitrogen, and hydrogen sulfide (H2S). Hydrogen can be separated from other impurities by the pressure swing adsorption process. Japanese steel companies have carried out production of hydrogen by this method.

Petroleum coke edit

Petroleum coke can also be converted to hydrogen-rich syngas via coal gasification. The produced syngas consists mainly of hydrogen, carbon monoxide and H2S from the sulfur in the coke feed. Gasification is an option for producing hydrogen from almost any carbon source.[17]

Depleted oil wells edit

Injecting appropriate microbes into depleted oil wells allows them to extract hydrogen from the remaining, unrecoverable oil. Since the only inputs are the microbes, production costs are low. The method also produces concentrated CO
2 that could in principle be captured.[18]

From water edit

Main article: Water splitting

Methods to produce hydrogen without the use of fossil fuels involve the process of water splitting, or splitting the water molecule (H2O) into its components oxygen and hydrogen. When the source of energy for water splitting is renewable or low-carbon, the hydrogen produced is sometimes referred to as green hydrogen. The conversion can be accomplished in several ways, but all methods are currently considered more expensive than fossil-fuel based production methods.

Electrolysis of water edit

Main article: Electrolysis of water
See also: High-temperature electrolysis and High-pressure electrolysis
 
Illustrating inputs and outputs of electrolysis of water, for production of hydrogen and no greenhouse gas

Water electrolysis is using electricity to split water into hydrogen and oxygen. As of 2020, less than 0.1% of hydrogen production comes from water electrolysis.[19]Electrolysis of water is 70–80% efficient (a 20–30% conversion loss)[20][21] while steam reforming of natural gas has a thermal efficiency between 70 and 85%.[22] The electrical efficiency of electrolysis is expected to reach 82–86%[23] before 2030, while also maintaining durability as progress in this area continues apace.[24]

Water electrolysis can operate at 50–80 °C (120–180 °F), while steam methane reforming requires temperatures at 700–1,100 °C (1,300–2,000 °F).[25] The difference between the two methods is the primary energy used; either electricity (for electrolysis) or natural gas (for steam methane reforming). Due to their use of water, a readily available resource, electrolysis and similar water-splitting methods have attracted the interest of the scientific community. With the objective of reducing the cost of hydrogen production, renewable sources of energy have been targeted to allow electrolysis.[13]

There are three main types of electrolytic cells, solid oxide electrolyser cells (SOECs), polymer electrolyte membrane cells (PEM) and alkaline electrolysis cells (AECs).[26] Traditionally, alkaline electrolysers are cheaper in terms of investment (they generally use nickel catalysts), but less-efficient; PEM electrolysers, conversely, are more expensive (they generally use expensive platinum group metal catalysts) but are more efficient and can operate at higher current densities, and can therefore be possibly cheaper if the hydrogen production is large enough.[27]

SOECs operate at high temperatures, typically around 800 °C (1,500 °F). At these high temperatures, a significant amount of the energy required can be provided as thermal energy (heat), and as such is termed high-temperature electrolysis. The heat energy can be provided from a number of different sources, including waste industrial heat, nuclear power stations or concentrated solar thermal plants. This has the potential to reduce the overall cost of the hydrogen produced by reducing the amount of electrical energy required for electrolysis.[28][29][30][31]

PEM electrolysis cells typically operate below 100 °C (212 °F).[28] These cells have the advantage of being comparatively simple and can be designed to accept widely varying voltage inputs, which makes them ideal for use with renewable sources of energy such as photovoltaic solar panels.[32] AECs optimally operate at high concentrations of electrolyte (KOH or potassium carbonate) and at high temperatures, often near 200 °C (392 °F).

Industrial output and efficiency edit

Efficiency of modern hydrogen generators is measured by energy consumed per standard volume of hydrogen (MJ/m3), assuming standard temperature and pressure of the H2. The lower the energy used by a generator, the higher would be its efficiency; a 100%-efficient electrolyser would consume 39.4 kilowatt-hours per kilogram (142 MJ/kg) of hydrogen,[33] 12,749 joules per litre (12.75 MJ/m3). Practical electrolysis typically uses a rotating electrolyser, where centrifugal force helps separate gas bubbles from water.[34] Such an electrolyser at 15 bar pressure may consume 50 kilowatt-hours per kilogram (180 MJ/kg), and a further 15 kilowatt-hours (54 MJ) if the hydrogen is compressed for use in hydrogen cars.[35]

Conventional alkaline electrolysis has an efficiency of about 70%,[36] however advanced alkaline water electrolysers with efficiency of up to 82% are available.[37] Accounting for the use of the higher heat value (because inefficiency via heat can be redirected back into the system to create the steam required by the catalyst), average working efficiencies for PEM electrolysis are around 80%, or 82% using the most modern alkaline electrolysers.[38]

PEM efficiency is expected to increase to approximately 86%[39] before 2030. Theoretical efficiency for PEM electrolysers is predicted up to 94%.[40]

 
H2 production cost ($-gge untaxed) at varying natural gas prices

As of 2020, the cost of hydrogen by electrolysis is around $3–8/kg.[41] Considering the industrial production of hydrogen, and using current best processes for water electrolysis (PEM or alkaline electrolysis) which have an effective electrical efficiency of 70–82%,[42][43][44] producing 1 kg of hydrogen (which has a specific energy of 143 MJ/kg or about 40 kWh/kg) requires 50–55 kWh of electricity. At an electricity cost of $0.06/kWh, as set out in the Department of Energy hydrogen production targets for 2015,[45] the hydrogen cost is $3/kg.

The US DOE target price for hydrogen in 2020 is $2.30/kg, requiring an electricity cost of $0.037/kWh, which is achievable given recent PPA tenders for wind and solar in many regions.[46] The report by IRENA.ORG is an extensive factual report of present-day industrial hydrogen production consuming about 53 to 70 kWh per kg could go down to about 45 kWh/kg H
2.[47] The thermodynamic energy required for hydrogen by electrolysis translates to 33 kWh/kg, which is higher than steam reforming with carbon capture and higher than methane pyrolysis. One of the advantages of electrolysis over hydrogen from steam methane reforming (SMR) is that the hydrogen can be produced on-site, meaning that the costly process of delivery via truck or pipeline is avoided.

Chemically assisted electrolysis edit

In addition to reduce the voltage required for electrolysis via the increasing of the temperature of the electrolysis cell it is also possible to electrochemically consume the oxygen produced in an electrolyser by introducing a fuel (such as carbon/coal,[48] methanol,[49][50] ethanol,[51] formic acid,[52] glycerol,[52] etc.) into the oxygen side of the reactor. This reduces the required electrical energy and has the potential to reduce the cost of hydrogen to less than 40~60% with the remaining energy provided in this manner.[53]

Carbon/hydrocarbon assisted water electrolysis (CAWE) has the potential to offer a less energy intensive, cleaner method of using chemical energy in various sources of carbon, such as low-rank and high sulfur coals, biomass, alcohols and methane (Natural Gas), where pure CO2 produced can be easily sequestered without the need for separation.[54][55]

Radiolysis edit

Nuclear radiation can break water bonds through radiolysis.[56][57] In the Mponeng gold mine, South Africa, researchers found bacteria in a naturally occurring high radiation zone. The bacterial community which was dominated by a new phylotype of Desulfotomaculum, was feeding on primarily radiolytically produced hydrogen.[58]

Thermolysis edit

Water spontaneously dissociates at around 2500 °C, but this thermolysis occurs at temperatures too high for usual process piping and equipment resulting in a rather low commercialization potential.[59]

Pyrolysis on biomass edit

Pyrolysis can be divided into different types based on the pyrolysis temperature, namely low-temperature slow pyrolysis, medium-temperature rapid pyrolysis, and high-temperature flash pyrolysis.[60] The source energy is mainly solar energy, with help of photosynthetic microorganisms to decompose water or biomass to produce hydrogen. However, this process has relatively low hydrogen yields and high operating cost. It is not a feasible method for industry.

Nuclear-assisted thermolysis edit

The high-temperature gas-cooled reactor (HTGR) is one of the most promising CO2-free nuclear technique to produce hydrogen by splitting water in a large scale. In this method, iodine-sulfur (IS) thermo-chemical cycle for splitting water and high-temperature steam electrolysis (HTSE) were selected as the main processes for nuclear hydrogen production. The S-I cycle follows three chemical reactions:[61]

Bunsen reaction: I2+SO2+2H2O=H2SO4+2HI

HI decomposition: 2HI=H2+I2

Sulfuric acid decomposition: H2SO4=SO2+1/2O2+H2O

The hydrogen production rate of HTGR with IS cycle is approximately 0.68 kg/s, and the capital cost to build a unit of power plant is $100 million.

Thermochemical cycle edit

Main article: thermochemical cycle

Thermochemical cycles combine solely heat sources (thermo) with chemical reactions to split water into its hydrogen and oxygen components.[62] The term cycle is used because aside from water, hydrogen and oxygen, the chemical compounds used in these processes are continuously recycled. If electricity is partially used as an input, the resulting thermochemical cycle is defined as a hybrid one.

The sulfur-iodine cycle (S-I cycle) is a thermochemical cycle processes which generates hydrogen from water with an efficiency of approximately 50%. The sulfur and iodine used in the process are recovered and reused, and not consumed by the process. The cycle can be performed with any source of very high temperatures, approximately 950 °C, such as by Concentrating solar power systems (CSP) and is regarded as being well suited to the production of hydrogen by high-temperature nuclear reactors,[63] and as such, is being studied in the High-temperature engineering test reactor in Japan.[64][65][66][67] There are other hybrid cycles that use both high temperatures and some electricity, such as the Copper–chlorine cycle, it is classified as a hybrid thermochemical cycle because it uses an electrochemical reaction in one of the reaction steps, it operates at 530 °C and has an efficiency of 43 percent.[68]

Ferrosilicon method edit

Ferrosilicon is used by the military to quickly produce hydrogen for balloons. The chemical reaction uses sodium hydroxide, ferrosilicon, and water. The generator is small enough to fit a truck and requires only a small amount of electric power, the materials are stable and not combustible, and they do not generate hydrogen until mixed.[69] The method has been in use since World War I. A heavy steel pressure vessel is filled with sodium hydroxide and ferrosilicon, closed, and a controlled amount of water is added; the dissolving of the hydroxide heats the mixture to about 93 °C and starts the reaction; sodium silicate, hydrogen and steam are produced.[70]

Photobiological water splitting edit

 
An algae bioreactor for hydrogen production.
Main article: Biological hydrogen production (Algae)

Biological hydrogen can be produced in an algae bioreactor.[71] In the late 1990s it was discovered that if the algae are deprived of sulfur it will switch from the production of oxygen, i.e. normal photosynthesis, to the production of hydrogen. It seems that the production is now economically feasible by surpassing the 7–10 percent energy efficiency (the conversion of sunlight into hydrogen) barrier.[72] with a hydrogen production rate of 10–12 ml per liter culture per hour.[73]

Photocatalytic water splitting edit

Main article: Photocatalytic water splitting

The conversion of solar energy to hydrogen by means of water splitting process is one of the most interesting ways to achieve clean and renewable energy systems. However, if this process is assisted by photocatalysts suspended directly in water instead of using photovoltaic and an electrolytic system the reaction is in just one step, it can be made more efficient.[74][75][76] Current systems, however have low performance for commercial implementation.[77][78]

Biohydrogen routes edit

Biomass and waste streams can in principle be converted into biohydrogen with biomass gasification, steam reforming, or biological conversion like biocatalysed electrolysis[53] or fermentative hydrogen production.[1]

Among hydrogen production methods biological routes are potentially less energy intensive. In addition, a wide variety of waste and low-value materials such as agricultural biomass as renewable sources can be utilized to produce hydrogen via biochemical or thermochemical pathways.[79] Nevertheless, at present hydrogen is produced mainly from fossil fuels, in particular, natural gas which are non-renewable sources. Hydrogen is not only the cleanest fuel but also widely used in a number of industries, especially fertilizer, petrochemical and food ones.[80]

Biochemical routes to hydrogen are classified as dark and photo fermentation processes. In dark fermentation, carbohydrates are converted to hydrogen by fermentative microorganisms including strict anaerobe and facultative anaerobic bacteria. A theoretical maximum of 4 mol H2/mol glucose can be produced.[citation needed] Sugars are convertible to volatile fatty acids (VFAs) and alcohols as by-products during this process. Photo fermentative bacteria are able to generate hydrogen from VFAs. Hence, metabolites formed in dark fermentation can be used as feedstock in photo fermentation to enhance the overall yield of hydrogen.[80]

Fermentative hydrogen production edit

Main articles: fermentative hydrogen production and dark fermentation

Fermentative hydrogen production converts organic substrates to hydrogen. A diverse group of bacteria promote this transformation. Photofermentation differs from dark fermentation because it only proceeds in the presence of light. For example, photo-fermentation with Rhodobacter sphaeroides SH2C can be employed to convert some fatty acids into hydrogen.[81]

Fermentative hydrogen production can be done using direct biophotolysis by green algae, indirect biophotolysis by cyanobacteria, photo-fermentation by anaerobic photosynthetic bacteria and dark fermentation by anaerobic fermentative bacteria. For example, studies on hydrogen production using H. salinarium, an anaerobic photosynthetic bacteria, coupled to a hydrogenase donor like E. coli, are reported in literature.[82] Enterobacter aerogenes is another hydrogen producer.[83]

Enzymatic hydrogen generation edit

Diverse enzymatic pathways have been designed to generate hydrogen from sugars.[84]

Biocatalysed electrolysis edit

 
A microbial electrolysis cell
Main articles: electrohydrogenesis and microbial fuel cell

Besides dark fermentation, electrohydrogenesis (electrolysis using microbes) is another possibility. Using microbial fuel cells, wastewater or plants can be used to generate power. Biocatalysed electrolysis should not be confused with biological hydrogen production, as the latter only uses algae and with the latter, the algae itself generates the hydrogen instantly, where with biocatalysed electrolysis, this happens after running through the microbial fuel cell and a variety of aquatic plants[85] can be used. These include reed sweetgrass, cordgrass, rice, tomatoes, lupines and algae.[86]

 
Nano-galvanic aluminum-based powder developed by the U.S. Army Research Laboratory

Nanogalvanic aluminum alloy powder edit

Main article: Aluminum based nanogalvanic alloys

Aluminum alloy powder reacts with water to produce hydrogen gas upon contact with water. It reportedly generates hydrogen at 100 percent of the theoretical yield.[87][88] Cost-effective routes for generating the aluminum alloy remain elusive.

CC-HOD edit

Main article: CC-HOD

CC-HOD (Catalytic Carbon - Hydrogen On Demand) is a low-temperature process in which carbon and aluminium are submerged and heated to about 80 °C (176 °F), causing a chemical reaction which produces hydrogen.

Natural hydrogen edit

 
Mid-continental Rift System
Main article: Natural hydrogen

Hydrogen is also present naturally underground. This natural hydrogen, also called white hydrogen, can be extracted from wells in a similar manner as fossil fuels such as oil and natural gas.[89][90]

White hydrogen could be found or produced in the Mid-continental Rift System at scale for a renewable hydrogen economy. Water could be pumped down to hot iron-rich rock to produce hydrogen and the hydrogen could be extracted.[91]

Environmental impact edit

As of 2020, most hydrogen is produced from fossil fuels, resulting in carbon dioxide emissions.[92] Hydrogen produced by this technology has been described as grey hydrogen when emissions are released to the atmosphere, and blue hydrogen when emissions are captured through carbon capture and storage (CCS).[93][94] Blue hydrogen has been estimated to have a carbon footprint 20% greater than burning gas or coal for heat and 60% greater when compared to burning diesel for heat, assuming US up- and mid-stream methane leakage rates and production via steam methane reformers (SMR) retrofitted with carbon dioxide capture.[95]

The use of autothermal reformers (ATR) with integrated capture of carbon dioxide allows higher capture rates at satisfactory energy efficiencies and life cycle assessments have shown lower greenhouse gas emissions for such plants compared to SMRs with carbon dioxide capture.[96] Application of ATR technology with integrated capture of carbon dioxide in Europe has been assessed to have a lower greenhouse gas footprint than burning natural gas, e.g. for the H21 project with a reported reduction of 68% due to a reduced carbon dioxide intensity of natural gas combined with a more suitable reactor type for capture of carbon dioxide.[97]

Hydrogen produced from renewable energy sources is often referred to as green hydrogen. Two ways of producing hydrogen from renewable energy sources are claimed to be practical. One is to use power to gas, in which electric power is used to produce hydrogen from electrolysis of water, and the other is to use landfill gas to produce hydrogen in a steam reformer. Hydrogen fuel, when produced by renewable sources of energy like wind or solar power, is a renewable fuel.[98][99] Hydrogen produced from nuclear energy via electrolysis is sometimes viewed as a subset of green hydrogen, but can also be referred to as pink hydrogen. The Oskarshamn Nuclear Power Plant made an agreement in January 2022 to supply commercial pink hydrogen in the order of kilograms per day.[100]

As of 2020, estimated costs of production are $1–1.80/kg for grey hydrogen and blue hydrogen,[101] and $2.50–6.80 for green hydrogen.[101]

94 million tonnes of grey hydrogen are produced globally using fossil fuels as of 2022, primarily natural gas, and are therefore a significant source of greenhouse gas emissions.[102][103][104][105]

Hydrogen uses edit

See also: Hydrogen economy

Hydrogen is used for the conversion of heavy petroleum fractions into lighter ones via hydrocracking. It is also used in other processes including the aromatization process, hydrodesulfurization and the production of ammonia via the Haber process, the primary industrial method for the production of synthetic nitrogen fertilizer for growing 47 percent of food worldwide.[106]

Hydrogen may be used in fuel cells for local electricity generation or potentially as a transportation fuel.

Hydrogen is produced as a by-product of industrial chlorine production by electrolysis. Although requiring expensive technologies, hydrogen can be cooled, compressed and purified for use in other processes on site or sold to a customer via pipeline, cylinders or trucks. The discovery and development of less expensive methods of production of bulk hydrogen is relevant to the establishment of a hydrogen economy.[1]

See also edit

 
Wikimedia Commons has media related to Hydrogen production.

References edit

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Further reading edit

  • Francesco Calise; et al., eds. (2019). Solar Hydrogen Production. Academic Press. ISBN 978-0-12-814853-2.

February 16, 2024
hydrogen, production, hydrogen, produced, several, industrial, methods, fossil, fuels, dominant, source, hydrogen, 2020, majority, hydrogen, produced, steam, reforming, natural, other, light, hydrocarbons, partial, oxidation, heavier, hydrocarbons, need, quota. Hydrogen gas is produced by several industrial methods Fossil fuels are the dominant source of hydrogen 1 As of 2020 the majority of hydrogen 95 is produced by steam reforming of natural gas and other light hydrocarbons and partial oxidation of heavier hydrocarbons 2 need quotation to verify Other methods of hydrogen production include biomass gasification and methane pyrolysis Methane pyrolysis and water electrolysis can use any source of electricity including renewable energy The production of hydrogen plays a key role in any industrialized society since hydrogen is required for many chemical processes 3 In 2020 roughly 87 million tons of hydrogen was produced 4 worldwide for various uses such as oil refining in the production of ammonia through the Haber process and in the production of methanol through reduction of carbon monoxide The global hydrogen generation market was fairly valued at US 155 billion in 2022 and expected to grow at a compound annual growth rate of 9 3 from 2023 to 2030 5 Contents 1 Steam methane reforming 2 Other fossil fuel methods 2 1 Partial oxidation 2 2 Plasma pyrolysis 2 3 Coal 2 4 Petroleum coke 2 5 Depleted oil wells 3 From water 3 1 Electrolysis of water 3 1 1 Industrial output and efficiency 3 2 Chemically assisted electrolysis 3 3 Radiolysis 3 4 Thermolysis 3 4 1 Pyrolysis on biomass 3 4 2 Nuclear assisted thermolysis 3 5 Thermochemical cycle 3 6 Ferrosilicon method 3 7 Photobiological water splitting 3 8 Photocatalytic water splitting 3 9 Biohydrogen routes 3 9 1 Fermentative hydrogen production 3 9 2 Enzymatic hydrogen generation 3 9 3 Biocatalysed electrolysis 3 10 Nanogalvanic aluminum alloy powder 3 11 CC HOD 4 Natural hydrogen 5 Environmental impact 6 Hydrogen uses 7 See also 8 References 9 Further readingSteam methane reforming editMain article Steam reforming Steam methane reforming SMR produces hydrogen from natural gas mostly methane CH4 and water It is the cheapest source of industrial hydrogen being the source of nearly 50 of the world s hydrogen 6 The process consists of heating the gas to 700 1 100 C 1 300 2 000 F in the presence of steam over a nickel catalyst The resulting endothermic reaction forms carbon monoxide and molecular hydrogen H2 7 In the water gas shift reaction the carbon monoxide reacts with steam to obtain further quantities of H2 The WGSR also requires a catalyst typically over iron oxide or other oxides The byproduct is CO2 7 Depending on the quality of the feedstock natural gas naphtha etc one ton of hydrogen produced will also produce 9 to 12 tons of CO2 a greenhouse gas that may be captured 8 nbsp Illustrating inputs and outputs of steam reforming of natural gas a process to produce hydrogen and CO2 greenhouse gas that may be captured with CCSFor this process high temperature steam H2O reacts with methane CH4 in an endothermic reaction to yield syngas 9 CH4 H2O CO 3 H2In a second stage additional hydrogen is generated through the lower temperature exothermic water gas shift reaction performed at about 360 C 680 F CO H2O CO2 H2Essentially the oxygen O atom is stripped from the additional water steam to oxidize CO to CO2 This oxidation also provides energy to maintain the reaction Additional heat required to drive the process is generally supplied by burning some portion of the methane Other fossil fuel methods editPartial oxidation edit Hydrogen production from natural gas and heavier hydrocarbons is achieved by partial oxidation A fuel air or fuel oxygen mixture is partially combusted resulting in a hydrogen and carbon monoxide rich syngas More hydrogen and carbon dioxide are then obtained from carbon monoxide and water via the water gas shift reaction 7 Carbon dioxide can be co fed to lower the hydrogen to carbon monoxide ratio The partial oxidation reaction occurs when a substoichiometric fuel air mixture or fuel oxygen is partially combusted in a reformer or partial oxidation reactor A distinction is made between thermal partial oxidation TPOX and catalytic partial oxidation CPOX The chemical reaction takes the general form 2 CnHm nO2 2n CO mH2Idealized examples for heating oil and coal assuming compositions C12H24 and C24H12 respectively are as follows C12H24 6 O2 12 CO 12 H2 C24H12 12 O2 24 CO 6 H2Plasma pyrolysis edit The Kvaerner process or Kvaerner carbon black amp hydrogen process CB amp H 10 is a plasma pyrolysis method developed in the 1980s by a Norwegian company of the same name for the production of hydrogen and carbon black from liquid hydrocarbons CnHm Of the available energy of the feed approximately 48 is contained in the hydrogen 40 is contained in activated carbon and 10 in superheated steam 11 CO2 is not produced in the process A variation of this process is presented in 2009 using plasma arc waste disposal technology for the production of hydrogen heat and carbon from methane and natural gas in a plasma converter 12 Coal edit For the production of hydrogen from coal coal gasification is used The process of coal gasification uses steam and oxygen to break molecular bonds in coal and form a gaseous mixture of hydrogen and carbon monoxide 13 Carbon dioxide and pollutants may be more easily removed from gas obtained from coal gasification versus coal combustion 14 15 Another method for conversion is low temperature and high temperature coal carbonization 16 Coke oven gas made from pyrolysis oxygen free heating of coal has about 60 hydrogen the rest being methane carbon monoxide carbon dioxide ammonia molecular nitrogen and hydrogen sulfide H2S Hydrogen can be separated from other impurities by the pressure swing adsorption process Japanese steel companies have carried out production of hydrogen by this method Petroleum coke edit Petroleum coke can also be converted to hydrogen rich syngas via coal gasification The produced syngas consists mainly of hydrogen carbon monoxide and H2S from the sulfur in the coke feed Gasification is an option for producing hydrogen from almost any carbon source 17 Depleted oil wells edit Injecting appropriate microbes into depleted oil wells allows them to extract hydrogen from the remaining unrecoverable oil Since the only inputs are the microbes production costs are low The method also produces concentrated CO2 that could in principle be captured 18 From water editMain article Water splitting Methods to produce hydrogen without the use of fossil fuels involve the process of water splitting or splitting the water molecule H2O into its components oxygen and hydrogen When the source of energy for water splitting is renewable or low carbon the hydrogen produced is sometimes referred to as green hydrogen The conversion can be accomplished in several ways but all methods are currently considered more expensive than fossil fuel based production methods Electrolysis of water edit Main article Electrolysis of water See also High temperature electrolysis and High pressure electrolysis nbsp Illustrating inputs and outputs of electrolysis of water for production of hydrogen and no greenhouse gasWater electrolysis is using electricity to split water into hydrogen and oxygen As of 2020 less than 0 1 of hydrogen production comes from water electrolysis 19 Electrolysis of water is 70 80 efficient a 20 30 conversion loss 20 21 while steam reforming of natural gas has a thermal efficiency between 70 and 85 22 The electrical efficiency of electrolysis is expected to reach 82 86 23 before 2030 while also maintaining durability as progress in this area continues apace 24 Water electrolysis can operate at 50 80 C 120 180 F while steam methane reforming requires temperatures at 700 1 100 C 1 300 2 000 F 25 The difference between the two methods is the primary energy used either electricity for electrolysis or natural gas for steam methane reforming Due to their use of water a readily available resource electrolysis and similar water splitting methods have attracted the interest of the scientific community With the objective of reducing the cost of hydrogen production renewable sources of energy have been targeted to allow electrolysis 13 There are three main types of electrolytic cells solid oxide electrolyser cells SOECs polymer electrolyte membrane cells PEM and alkaline electrolysis cells AECs 26 Traditionally alkaline electrolysers are cheaper in terms of investment they generally use nickel catalysts but less efficient PEM electrolysers conversely are more expensive they generally use expensive platinum group metal catalysts but are more efficient and can operate at higher current densities and can therefore be possibly cheaper if the hydrogen production is large enough 27 SOECs operate at high temperatures typically around 800 C 1 500 F At these high temperatures a significant amount of the energy required can be provided as thermal energy heat and as such is termed high temperature electrolysis The heat energy can be provided from a number of different sources including waste industrial heat nuclear power stations or concentrated solar thermal plants This has the potential to reduce the overall cost of the hydrogen produced by reducing the amount of electrical energy required for electrolysis 28 29 30 31 PEM electrolysis cells typically operate below 100 C 212 F 28 These cells have the advantage of being comparatively simple and can be designed to accept widely varying voltage inputs which makes them ideal for use with renewable sources of energy such as photovoltaic solar panels 32 AECs optimally operate at high concentrations of electrolyte KOH or potassium carbonate and at high temperatures often near 200 C 392 F Industrial output and efficiency edit Efficiency of modern hydrogen generators is measured by energy consumed per standard volume of hydrogen MJ m3 assuming standard temperature and pressure of the H2 The lower the energy used by a generator the higher would be its efficiency a 100 efficient electrolyser would consume 39 4 kilowatt hours per kilogram 142 MJ kg of hydrogen 33 12 749 joules per litre 12 75 MJ m3 Practical electrolysis typically uses a rotating electrolyser where centrifugal force helps separate gas bubbles from water 34 Such an electrolyser at 15 bar pressure may consume 50 kilowatt hours per kilogram 180 MJ kg and a further 15 kilowatt hours 54 MJ if the hydrogen is compressed for use in hydrogen cars 35 Conventional alkaline electrolysis has an efficiency of about 70 36 however advanced alkaline water electrolysers with efficiency of up to 82 are available 37 Accounting for the use of the higher heat value because inefficiency via heat can be redirected back into the system to create the steam required by the catalyst average working efficiencies for PEM electrolysis are around 80 or 82 using the most modern alkaline electrolysers 38 PEM efficiency is expected to increase to approximately 86 39 before 2030 Theoretical efficiency for PEM electrolysers is predicted up to 94 40 nbsp H2 production cost gge untaxed at varying natural gas pricesAs of 2020 the cost of hydrogen by electrolysis is around 3 8 kg 41 Considering the industrial production of hydrogen and using current best processes for water electrolysis PEM or alkaline electrolysis which have an effective electrical efficiency of 70 82 42 43 44 producing 1 kg of hydrogen which has a specific energy of 143 MJ kg or about 40 kWh kg requires 50 55 kWh of electricity At an electricity cost of 0 06 kWh as set out in the Department of Energy hydrogen production targets for 2015 45 the hydrogen cost is 3 kg The US DOE target price for hydrogen in 2020 is 2 30 kg requiring an electricity cost of 0 037 kWh which is achievable given recent PPA tenders for wind and solar in many regions 46 The report by IRENA ORG is an extensive factual report of present day industrial hydrogen production consuming about 53 to 70 kWh per kg could go down to about 45 kWh kg H2 47 The thermodynamic energy required for hydrogen by electrolysis translates to 33 kWh kg which is higher than steam reforming with carbon capture and higher than methane pyrolysis One of the advantages of electrolysis over hydrogen from steam methane reforming SMR is that the hydrogen can be produced on site meaning that the costly process of delivery via truck or pipeline is avoided Chemically assisted electrolysis edit In addition to reduce the voltage required for electrolysis via the increasing of the temperature of the electrolysis cell it is also possible to electrochemically consume the oxygen produced in an electrolyser by introducing a fuel such as carbon coal 48 methanol 49 50 ethanol 51 formic acid 52 glycerol 52 etc into the oxygen side of the reactor This reduces the required electrical energy and has the potential to reduce the cost of hydrogen to less than 40 60 with the remaining energy provided in this manner 53 Carbon hydrocarbon assisted water electrolysis CAWE has the potential to offer a less energy intensive cleaner method of using chemical energy in various sources of carbon such as low rank and high sulfur coals biomass alcohols and methane Natural Gas where pure CO2 produced can be easily sequestered without the need for separation 54 55 Radiolysis edit Nuclear radiation can break water bonds through radiolysis 56 57 In the Mponeng gold mine South Africa researchers found bacteria in a naturally occurring high radiation zone The bacterial community which was dominated by a new phylotype of Desulfotomaculum was feeding on primarily radiolytically produced hydrogen 58 Thermolysis edit Water spontaneously dissociates at around 2500 C but this thermolysis occurs at temperatures too high for usual process piping and equipment resulting in a rather low commercialization potential 59 Pyrolysis on biomass edit Pyrolysis can be divided into different types based on the pyrolysis temperature namely low temperature slow pyrolysis medium temperature rapid pyrolysis and high temperature flash pyrolysis 60 The source energy is mainly solar energy with help of photosynthetic microorganisms to decompose water or biomass to produce hydrogen However this process has relatively low hydrogen yields and high operating cost It is not a feasible method for industry Nuclear assisted thermolysis edit The high temperature gas cooled reactor HTGR is one of the most promising CO2 free nuclear technique to produce hydrogen by splitting water in a large scale In this method iodine sulfur IS thermo chemical cycle for splitting water and high temperature steam electrolysis HTSE were selected as the main processes for nuclear hydrogen production The S I cycle follows three chemical reactions 61 Bunsen reaction I2 SO2 2H2O H2SO4 2HIHI decomposition 2HI H2 I2Sulfuric acid decomposition H2SO4 SO2 1 2O2 H2OThe hydrogen production rate of HTGR with IS cycle is approximately 0 68 kg s and the capital cost to build a unit of power plant is 100 million Thermochemical cycle edit Main article thermochemical cycle Thermochemical cycles combine solely heat sources thermo with chemical reactions to split water into its hydrogen and oxygen components 62 The term cycle is used because aside from water hydrogen and oxygen the chemical compounds used in these processes are continuously recycled If electricity is partially used as an input the resulting thermochemical cycle is defined as a hybrid one The sulfur iodine cycle S I cycle is a thermochemical cycle processes which generates hydrogen from water with an efficiency of approximately 50 The sulfur and iodine used in the process are recovered and reused and not consumed by the process The cycle can be performed with any source of very high temperatures approximately 950 C such as by Concentrating solar power systems CSP and is regarded as being well suited to the production of hydrogen by high temperature nuclear reactors 63 and as such is being studied in the High temperature engineering test reactor in Japan 64 65 66 67 There are other hybrid cycles that use both high temperatures and some electricity such as the Copper chlorine cycle it is classified as a hybrid thermochemical cycle because it uses an electrochemical reaction in one of the reaction steps it operates at 530 C and has an efficiency of 43 percent 68 Ferrosilicon method edit Ferrosilicon is used by the military to quickly produce hydrogen for balloons The chemical reaction uses sodium hydroxide ferrosilicon and water The generator is small enough to fit a truck and requires only a small amount of electric power the materials are stable and not combustible and they do not generate hydrogen until mixed 69 The method has been in use since World War I A heavy steel pressure vessel is filled with sodium hydroxide and ferrosilicon closed and a controlled amount of water is added the dissolving of the hydroxide heats the mixture to about 93 C and starts the reaction sodium silicate hydrogen and steam are produced 70 Photobiological water splitting edit nbsp An algae bioreactor for hydrogen production Main article Biological hydrogen production Algae Biological hydrogen can be produced in an algae bioreactor 71 In the late 1990s it was discovered that if the algae are deprived of sulfur it will switch from the production of oxygen i e normal photosynthesis to the production of hydrogen It seems that the production is now economically feasible by surpassing the 7 10 percent energy efficiency the conversion of sunlight into hydrogen barrier 72 with a hydrogen production rate of 10 12 ml per liter culture per hour 73 Photocatalytic water splitting edit Main article Photocatalytic water splitting The conversion of solar energy to hydrogen by means of water splitting process is one of the most interesting ways to achieve clean and renewable energy systems However if this process is assisted by photocatalysts suspended directly in water instead of using photovoltaic and an electrolytic system the reaction is in just one step it can be made more efficient 74 75 76 Current systems however have low performance for commercial implementation 77 78 Biohydrogen routes edit Biomass and waste streams can in principle be converted into biohydrogen with biomass gasification steam reforming or biological conversion like biocatalysed electrolysis 53 or fermentative hydrogen production 1 Among hydrogen production methods biological routes are potentially less energy intensive In addition a wide variety of waste and low value materials such as agricultural biomass as renewable sources can be utilized to produce hydrogen via biochemical or thermochemical pathways 79 Nevertheless at present hydrogen is produced mainly from fossil fuels in particular natural gas which are non renewable sources Hydrogen is not only the cleanest fuel but also widely used in a number of industries especially fertilizer petrochemical and food ones 80 Biochemical routes to hydrogen are classified as dark and photo fermentation processes In dark fermentation carbohydrates are converted to hydrogen by fermentative microorganisms including strict anaerobe and facultative anaerobic bacteria A theoretical maximum of 4 mol H2 mol glucose can be produced citation needed Sugars are convertible to volatile fatty acids VFAs and alcohols as by products during this process Photo fermentative bacteria are able to generate hydrogen from VFAs Hence metabolites formed in dark fermentation can be used as feedstock in photo fermentation to enhance the overall yield of hydrogen 80 Fermentative hydrogen production edit Main articles fermentative hydrogen production and dark fermentation Fermentative hydrogen production converts organic substrates to hydrogen A diverse group of bacteria promote this transformation Photofermentation differs from dark fermentation because it only proceeds in the presence of light For example photo fermentation with Rhodobacter sphaeroides SH2C can be employed to convert some fatty acids into hydrogen 81 Fermentative hydrogen production can be done using direct biophotolysis by green algae indirect biophotolysis by cyanobacteria photo fermentation by anaerobic photosynthetic bacteria and dark fermentation by anaerobic fermentative bacteria For example studies on hydrogen production using H salinarium an anaerobic photosynthetic bacteria coupled to a hydrogenase donor like E coli are reported in literature 82 Enterobacter aerogenes is another hydrogen producer 83 Enzymatic hydrogen generation edit Diverse enzymatic pathways have been designed to generate hydrogen from sugars 84 Biocatalysed electrolysis edit nbsp A microbial electrolysis cellMain articles electrohydrogenesis and microbial fuel cell Besides dark fermentation electrohydrogenesis electrolysis using microbes is another possibility Using microbial fuel cells wastewater or plants can be used to generate power Biocatalysed electrolysis should not be confused with biological hydrogen production as the latter only uses algae and with the latter the algae itself generates the hydrogen instantly where with biocatalysed electrolysis this happens after running through the microbial fuel cell and a variety of aquatic plants 85 can be used These include reed sweetgrass cordgrass rice tomatoes lupines and algae 86 nbsp Nano galvanic aluminum based powder developed by the U S Army Research LaboratoryNanogalvanic aluminum alloy powder edit Main article Aluminum based nanogalvanic alloys Aluminum alloy powder reacts with water to produce hydrogen gas upon contact with water It reportedly generates hydrogen at 100 percent of the theoretical yield 87 88 Cost effective routes for generating the aluminum alloy remain elusive CC HOD edit Main article CC HOD CC HOD Catalytic Carbon Hydrogen On Demand is a low temperature process in which carbon and aluminium are submerged and heated to about 80 C 176 F causing a chemical reaction which produces hydrogen Natural hydrogen edit nbsp Mid continental Rift SystemMain article Natural hydrogen Hydrogen is also present naturally underground This natural hydrogen also called white hydrogen can be extracted from wells in a similar manner as fossil fuels such as oil and natural gas 89 90 White hydrogen could be found or produced in the Mid continental Rift System at scale for a renewable hydrogen economy Water could be pumped down to hot iron rich rock to produce hydrogen and the hydrogen could be extracted 91 Environmental impact editAs of 2020 most hydrogen is produced from fossil fuels resulting in carbon dioxide emissions 92 Hydrogen produced by this technology has been described as grey hydrogen when emissions are released to the atmosphere and blue hydrogen when emissions are captured through carbon capture and storage CCS 93 94 Blue hydrogen has been estimated to have a carbon footprint 20 greater than burning gas or coal for heat and 60 greater when compared to burning diesel for heat assuming US up and mid stream methane leakage rates and production via steam methane reformers SMR retrofitted with carbon dioxide capture 95 The use of autothermal reformers ATR with integrated capture of carbon dioxide allows higher capture rates at satisfactory energy efficiencies and life cycle assessments have shown lower greenhouse gas emissions for such plants compared to SMRs with carbon dioxide capture 96 Application of ATR technology with integrated capture of carbon dioxide in Europe has been assessed to have a lower greenhouse gas footprint than burning natural gas e g for the H21 project with a reported reduction of 68 due to a reduced carbon dioxide intensity of natural gas combined with a more suitable reactor type for capture of carbon dioxide 97 Hydrogen produced from renewable energy sources is often referred to as green hydrogen Two ways of producing hydrogen from renewable energy sources are claimed to be practical One is to use power to gas in which electric power is used to produce hydrogen from electrolysis of water and the other is to use landfill gas to produce hydrogen in a steam reformer Hydrogen fuel when produced by renewable sources of energy like wind or solar power is a renewable fuel 98 99 Hydrogen produced from nuclear energy via electrolysis is sometimes viewed as a subset of green hydrogen but can also be referred to as pink hydrogen The Oskarshamn Nuclear Power Plant made an agreement in January 2022 to supply commercial pink hydrogen in the order of kilograms per day 100 As of 2020 update estimated costs of production are 1 1 80 kg for grey hydrogen and blue hydrogen 101 and 2 50 6 80 for green hydrogen 101 94 million tonnes of grey hydrogen are produced globally using fossil fuels as of 2022 primarily natural gas and are therefore a significant source of greenhouse gas emissions 102 103 104 105 Hydrogen uses editSee also Hydrogen economy Hydrogen is used for the conversion of heavy petroleum fractions into lighter ones via hydrocracking It is also used in other processes including the aromatization process hydrodesulfurization and the production of ammonia via the Haber process the primary industrial method for the production of synthetic nitrogen fertilizer for growing 47 percent of food worldwide 106 Hydrogen may be used in fuel cells for local electricity generation or potentially as a transportation fuel Hydrogen is produced as a by product of industrial chlorine production by electrolysis Although requiring expensive technologies hydrogen can be cooled compressed and purified for use in other processes on site or sold to a customer via pipeline cylinders or trucks The discovery and development of less expensive methods of production of bulk hydrogen is relevant to the establishment of a hydrogen economy 1 See also edit nbsp Wikimedia Commons has media related to Hydrogen production Ammonia production Artificial photosynthesis Biohydrogen Hydrogen analyzer Hydrogen compressor Hydrogen economy Color codes Hydrogen embrittlement Hydrogen leak testing Hydrogen pipeline transport Hydrogen purifier Hydrogen purity Hydrogen safety Hydrogen sensor 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