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New technology of hydrogen production from methanol and water in liquid phase
2017-04-141114
Recently, in view of the characteristics of methanol and water liquid phase hydrogen production, platinum molybdenum carbide dual functional catalyst was used to realize the efficient activation of water and methanol, and high hydrogen production efficiency was obtained at low temperature (150-190 ℃). This catalytic system is expected to be used as the next generation of high efficient hydrogen storage and desorption system.
To solve the problem of hydrogen storage, a possible solution is to store hydrogen in liquid methanol, and generate hydrogen in situ through the liquid-phase reforming reaction of water and methanol for fuel cell use. While releasing hydrogen stored in methanol, it also activates equimolar water to release additional hydrogen.
Current hydrogen production methods
Hydrogen production by water electrolysis: hydrogen production by water electrolysis is one of the most widely used and mature methods. The process of hydrogen production from water is the reverse process of hydrogen and oxygen combustion to produce water, so as long as a certain form of energy is provided, water can be decomposed. The efficiency of hydrogen production from water decomposition by electricity is generally 75-85%. The process is simple and pollution-free, but the consumption of electricity is large, so its application is limited. Generally, the power consumption per cubic meter of hydrogen is about 4.5-5.5kwh, and the power can be provided by various primary energy sources, including fossil fuel, nuclear energy, solar energy, water energy, wind energy and marine energy, etc. Nuclear energy, water energy and ocean energy are rich in resources and can be used for a long time, and they are still in the development stage.
Hydrogen production from natural gas conversion: this method is to produce hydrogen through natural gas filtration device in the presence of catalyst. The reaction was carried out at 800-820 ℃. In the gas composition obtained by this method, the volume content of hydrogen can reach 74%. Most large-scale ammonia to methanol plants use natural gas as raw material to catalyze the conversion of water vapor to hydrogen. China has done a lot of effective research work in this field and built a large number of industrial production units. In China, the intermittent natural gas steam conversion process was developed to produce raw materials for small-scale ammonia plant. This method does not need to use high-temperature alloy converter, and the investment cost of the device is low. The production cost mainly depends on the source of raw materials. The distribution of natural gas in China is uneven, so the use of this method is limited.
Hydrogen production from gasoline reforming: the existing perfect infrastructure can be used for hydrogen production from gasoline reforming. Gasoline contains different types of hydrocarbons, including alkanes, cycloalkanes, olefins and aromatics, and gasoline also contains many sulfur compounds and a small amount of additives, sometimes even oxidants and ethanol. When aromatic compounds are not considered, the hydrocarbon composition of gasoline has similar reforming performance, and oxidation additives are helpful to improve the reforming reaction.
Hydrogen production from biomass gasification: biomass raw materials such as firewood, sawdust, wheat straw, straw, etc. are pressed into shape, and hydrogen containing fuel gas can be produced by gasification or cracking reaction in the gasifier. Some achievements have been made in the field of biomass gasification technology in China. Guangzhou Energy Institute of Chinese Academy of Sciences has carried out the research of biomass gasification for many years. In its gasification products, H2 accounts for about 10%, and its calorific value reaches 11mj / m3, which can be used as rural fuel, but the hydrogen content is still low. In foreign countries, due to the improvement of conversion technology, biomass gasification has been able to produce water gas on a large scale, and its H2 content has been greatly increased.
Comparison of hydrogen production processes: from various hydrogen production methods, it can be seen that, at present, Methanol Autothermal hydrogen production, gasoline reforming hydrogen production and biological hydrogen production do not have the conditions for industrialization; from the perspective of production cost, water electrolysis hydrogen production has no obvious advantages; from the perspective of cracked gas composition, methanol decomposition hydrogen production is not suitable for fuel cells.
Water gas hydrogen plant needs huge equipment investment, covers a large area and causes relatively large environmental pollution, so it is not suitable to be built in cities. If we use water gas to produce hydrogen, we must use pipeline transportation, which will be a huge project, so we will not use water gas to produce hydrogen in the early stage of the development of hydrogen fuel cell vehicles.
The advantages of natural gas conversion to hydrogen production lie in the small land occupation of the unit and the small investment of the equipment. Due to the uneven distribution of natural gas, the unit has great limitations. If natural gas is used for hydrogen production, special natural gas transmission pipeline is required, which is troublesome.
Hydrogen production by steam reforming of methanol is an industrial unit with mature technology, which occupies a small area, operates safely and reliably, and has no pollution. Methanol can be synthesized from coal, which is easy to store and transport. It is an ideal hydrogen source for hydrogen fuel cell vehicles. However, Martin et al. Provided a new idea for hydrogen production technology by using platinum molybdenum carbide bifunctional catalyst methanol and water in liquid phase.
According to Matthias Baylor, director and scientist of Leibniz catalysis Institute in Germany, this research is a "major breakthrough" in the field of hydrogen storage and transportation. Such catalysts are also expected to play an advantageous role in other water phase reforming hydrogen production processes, such as domestic wastewater, ethanol and other raw materials.
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