CN115838157A - Hydrogen storage system for storing and releasing hydrogen and method for storing and releasing hydrogen - Google Patents
Hydrogen storage system for storing and releasing hydrogen and method for storing and releasing hydrogen Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the field of hydrogen storage and discloses a hydrogen storage system for storing and releasing hydrogen and a method for storing and releasing hydrogen, wherein the hydrogen storage system comprises dihydric alcohol, lactone, a hydrogenation catalyst and a dehydrogenation catalyst; under the catalysis of the hydrogenation catalyst, the lactone is subjected to hydrogenation reaction to store hydrogen to obtain the dihydric alcohol; and under the catalysis of the dehydrogenation catalyst, carrying out dehydrogenation reaction on the dihydric alcohol to release hydrogen to obtain the lactone. Compared with the prior art, the hydrogen storage system and the method have the advantages of low cost, wide raw material source and low energy consumption.
Description
Technical Field
The present invention relates to the field of hydrogen storage, and in particular to a hydrogen storage system for storing and releasing hydrogen gas and a method for storing and releasing hydrogen gas.
Background
The existing human energy utilization mode has many problems, such as low utilization efficiency, greenhouse effect caused by greenhouse gas emission, environmental pollution caused by combustion and the like. In order to guarantee the sustainable development of the human society, the search for high-efficiency clean energy with low carbon emission and even no carbon emission is crucial. The hydrogen energy resource is rich, convenient and easy to obtain, has no carbon emission, has incomparable advantages of the traditional fossil energy, and plays an important role in the energy field. Currently, renewable energy sources are adopted to prepare hydrogen, and the breakthrough progress is gradually made on obtaining green hydrogen by adopting wind power, photovoltaic and the like; the problem in the industry is that the output of produced hydrogen is not a problem due to the fluctuation of wind power and photovoltaic power generation, but the hydrogen utilization departments downstream, such as steel, cement, chemical industry and the like, often need relatively stable hydrogen, so that the storage of hydrogen is a very important part of hydrogen economy, and even can be a main technical obstacle restricting the development of hydrogen energy.
Various hydrogen storage technologies have been developed, such as high-pressure hydrogen storage, liquid hydrogen storage, solid-state hydrogen storage, liquid-phase organic hydrogen carrier hydrogen storage, etc., but to date, technologies capable of large-scale application are few and have various problems. For example, the adoption of low-temperature liquid state needs to consume a large amount of energy consumption, and the investment of the compression refrigeration process is large. Among these, organic liquid hydrogen carriers (LOHC) are emerging as an alternative solution to provide hydrogen storage, in the range of 3 to 7wt%, including toluene, acetone, carbazoles, indoles, benzyltoluene, biphenyl, pyridines, and the like.
CN1809505A discloses an organic liquid hydrogen storage medium using N-ethylcarbazole, 1, 2-dimethylindole, 1-ethyl-2-methylindole, etc. as media, creatively, and the dehydrogenation temperature is 200 to 210 deg.C, especially the dehydrogenation energy consumption of N-ethylcarbazole is the lowest, which is about 52KJ/mol H2. However, the method requires more noble metal palladium as a dehydrogenation catalyst, so that the cost of the dehydrogenation catalyst is extremely high, which brings great pressure to commercialization; meanwhile, the price of the N-ethyl carbazole is high, and the price of the unit storage volume is quite low compared with other types such as solid-state hydrogen storage and the like.
CN104812698 discloses dibenzyltoluene as dehydrogenation medium, which has the advantages of low volatility, high stability and high melting point, but its dehydrogenation temperature is high, and it needs 280 deg.C, and at this temperature it can release hydrogen gas at higher rate, but it also needs noble metal platinum as catalyst, and especially its dehydrogenation energy consumption is high, and is over 61 KJ/mol H 2 .
US10435296B2 discloses the use of a mixture of diphenylmethane and biphenyl as an organic liquid hydrogen storage medium, but also requires the use of noble metal palladium as a dehydrogenation catalyst and noble metal ruthenium as a hydrogen storage catalyst, which is costly; the material does not change phase in the hydrogen storage process.
In fact, hydrogenation and dehydrogenation are a long-history and well-controlled reaction type in the chemical industry, but currently, the LOHC has disclosed technology as solving several outstanding problems of wind-solar power generation hydrogen production fluctuation: (1) dehydrogenation temperatures, such as dibenzyltoluene systems; (2) The phase change of the hydrogen storage and dehydrogenation process needs to consume extra energy sources, such as toluene, acetone and the like, (3) noble metals are needed to be used as catalysts for hydrogen storage or dehydrogenation, such as N-ethyl carbazole, biphenyl and the like, (4) the energy consumption of the dehydrogenation process is high, such as a dibenzyl toluene system; (5) The hydrogen storage medium has higher cost or the source is scarce, such as 1-ethyl-2-methylindole and the like.
As is well known, one of the key points in the utilization of hydrogen energy is to convert the energy of hydrogen converted into water into the energy required by the industry as much as possible, so that the LOHC is adopted, and hydrogen is preferably released when the energy is required, namely, the dehydrogenation energy consumption is low; but also can fully utilize the surrounding energy sources nearby, namely temperature grade matching. Another key is the commercially acceptable capital cost, so it is preferable to employ non-noble metal catalysts, using relatively readily available low cost feedstocks as hydrogen storage media.
In conclusion, the development of the organic liquid hydrogen storage system with the advantages of low dehydrogenation energy consumption, low dehydrogenation heat source temperature requirement and low price has important practical significance in solving the harsh problems of cycle stability and phase change.
Disclosure of Invention
The invention aims to overcome the problems of high energy consumption, high cost and the like of a hydrogenation hydrogen storage system and a method in the prior art, and provides a hydrogen storage system for storing and releasing hydrogen and a method for storing and releasing hydrogen, wherein the hydrogen storage system and the method have lower cost and energy consumption.
In order to accomplish the above objects, the present invention provides in a first aspect a hydrogen storage system for storing and releasing hydrogen gas, the hydrogen storage system comprising a glycol, a lactone, a hydrogenation catalyst, and a dehydrogenation catalyst;
under the catalysis of the hydrogenation catalyst, the lactone is subjected to hydrogenation reaction to store hydrogen to obtain the dihydric alcohol; and under the catalysis of the dehydrogenation catalyst, carrying out dehydrogenation reaction on the dihydric alcohol to release hydrogen to obtain the lactone.
Preferably, the diol is selected from C4-C5 diols.
Preferably, the diol is one or more selected from the group consisting of 1, 4-butanediol, 1, 4-pentanediol, and 1, 5-pentanediol.
Preferably, the lactone is selected from one or more of gamma-butyrolactone, gamma-valerolactone and cyclopentanolactone.
A second aspect of the invention provides a method of storing and releasing hydrogen gas, the method comprising the steps of:
(1) Carrying out dehydrogenation reaction on dihydric alcohol under the catalysis of a dehydrogenation catalyst to obtain lactone, and realizing the release of hydrogen;
(2) Under the catalysis of a hydrogenation catalyst, the lactone and hydrogen undergo hydrogenation reaction to obtain dihydric alcohol, so that the hydrogen is stored.
Preferably, the diol is selected from C4-C5 diols.
Preferably, the diol is selected from one or more than two of 1, 4-butanediol, 1, 4-pentanediol and 1, 5-pentanediol.
Preferably, the lactone is selected from one or more of gamma-butyrolactone, gamma-valerolactone and cyclopentanolactone.
Preferably, in step (1), the dehydrogenation reaction conditions include: the temperature is 160-200 deg.C, and the pressure is 0.3-0.6MPaG.
Preferably, the dehydrogenation reaction conditions include: the temperature is 170-190 ℃, the pressure is 0.35-0.55MPaG, and the liquid hourly space velocity is 0.1-1h -1 And the vaporization fraction of the dihydric alcohol is less than or equal to 20 percent.
Preferably, in step (2), the conditions of the hydrogenation reaction include: the temperature is 150-220 deg.C, and the pressure is 4-10MPaG.
Preferably, the conditions of the hydrogenation reaction include: the temperature is 150-200 ℃, the pressure is 4-8MPaG, and the liquid hourly space velocity is 0.1-1h -1 。
Preferably, the conditions of the hydrogenation reaction include: the temperature is 160-190 ℃, the pressure is 4-6MPaG, and the liquid hourly space velocity is 0.2-0.8h -1 。
Preferably, the dehydrogenation catalyst comprises a carrier A, and an active component A and an auxiliary agent A which are loaded on the surface of the carrier;
the active component A is copper, and the content of copper in the dehydrogenation catalyst is 20-60 wt%, preferably 25-50 wt%, and more preferably 25-45 wt%.
Preferably, the auxiliary agent a contains one or more of zinc oxide, tin oxide compound, chromium oxide compound, and barium oxide.
Preferably, the auxiliary agent A contains a tin oxide compound and a chromium oxide compound, and the content of the tin oxide compound in the dehydrogenation catalyst is 1-25 wt%, and the content of the chromium oxide compound in the dehydrogenation catalyst is 0.1-15 wt%.
Preferably, the assistant A contains a tin oxide compound, a chromium oxide compound and barium oxide, and the dehydrogenation catalyst contains the tin oxide compound in an amount of 5-20 wt%, the chromium oxide compound in an amount of 0.1-5 wt% and the barium oxide in an amount of 0.1-3 wt%.
Preferably, the carrier a is selected from one or more of silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide.
Preferably, the support a is silica and/or zirconia.
Preferably, the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier;
the active component B contains cobalt;
the auxiliary agent B is an oxide A and/or an oxide B;
the oxide A is selected from one or more of zinc oxide, tin oxide and chromium oxide; the oxide B is potassium oxide and/or barium oxide;
the carrier B is selected from one or more than two of silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide.
Preferably, the content of active component B in the hydrogenation catalyst is 15 to 60 wt%, preferably 20 to 55 wt%.
Preferably, the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier;
the active component B is cobalt;
the auxiliary agent B is an oxide A and an oxide B;
the oxide A is a tin oxide compound;
the oxide B is potassium oxide;
the carrier B is silicon dioxide.
Compared with the prior art, the hydrogen storage system and the method have the advantages of low cost, wide raw material source and low energy consumption.
Drawings
FIG. 1 is a schematic diagram of dehydrogenation and hydrogenation according to the present invention;
FIG. 2 is a gas chromatogram in example 1;
FIG. 3 is a simulation flowchart in example 3;
FIG. 4 is a simulation flowchart in example 3;
fig. 5 is a flowchart simulation in embodiment 5.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides in a first aspect a hydrogen storage system for storing and releasing hydrogen gas, the hydrogen storage system comprising a glycol, a lactone, a hydrogenation catalyst, and a dehydrogenation catalyst;
under the catalysis of the hydrogenation catalyst, the lactone is subjected to hydrogenation reaction to store hydrogen to obtain the dihydric alcohol; and under the catalysis of the dehydrogenation catalyst, carrying out dehydrogenation reaction on the dihydric alcohol to release hydrogen to obtain the lactone.
Preferably, the diol is selected from C4-C5 diols.
In a preferred embodiment, the diol is selected from one or more of 1, 4-butanediol, 1, 4-pentanediol, and 1, 5-pentanediol.
Preferably, the lactone is selected from one or more of gamma-butyrolactone, gamma-valerolactone and cyclopentanolactone.
Further preferably, the diol is 1, 4-butanediol and/or 1, 4-pentanediol.
In a preferred embodiment of the present invention, the diol is 1, 4-butanediol, and the lactone is γ -butyrolactone obtained by dehydrogenation of 1, 4-butanediol.
In the hydrogen storage system, the dehydrogenation catalyst comprises a carrier A, an active component A and an auxiliary agent A, wherein the active component A and the auxiliary agent A are loaded on the surface of the carrier;
the active component a is copper, and the content of copper in the dehydrogenation catalyst is 20 to 60 wt%, preferably 25 to 50 wt%, more preferably 25 to 45 wt%, and specifically may be 25wt%, 30 wt%, 35 wt%, 40wt%, or 45 wt%.
Preferably, the auxiliary agent a contains one or more of zinc oxide, tin oxide compound, chromium oxide compound, and barium oxide.
Preferably, the assistant A contains tin oxide and chromium oxide, and the dehydrogenation catalyst contains 1-25 wt% of tin oxide and 0.1-15 wt% of chromium oxide.
Further preferably, the auxiliary a contains a tin oxide compound, a chromium oxide compound and barium oxide, the dehydrogenation catalyst contains 5 to 20 wt% of the tin oxide compound, 0.1 to 5wt% of the chromium oxide compound and 0.1 to 3wt% of the barium oxide, specifically, the dehydrogenation catalyst contains 5wt%, 10 wt%, 15 wt% or 20 wt% of the tin oxide compound, 0.1 wt%, 1wt%, 2wt%, 3wt%, 4 wt% or 5wt% of the chromium oxide compound and 0.1 wt%, 1wt%, 2wt% or 3wt% of the barium oxide.
Preferably, the carrier a is selected from one or more of silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide.
Further preferably, the carrier a is silica and/or zirconia.
In a preferred embodiment, the dehydrogenation catalyst can be prepared by conventional methods such as coprecipitation (including uniform precipitation such as sequential addition, reverse addition, concurrent flow or ammonia distillation), impregnation loading, sol-gel, precipitation, ball milling, kneading, and even caustic soda extraction after quenching the alloy.
In the hydrogen storage system, the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier;
the active component B contains cobalt;
the auxiliary agent B is an oxide A and/or an oxide B;
the oxide A is selected from one or more of zinc oxide, tin oxide and chromium oxide; the oxide B is potassium oxide and/or barium oxide;
the carrier B is selected from one or more than two of silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide.
In the hydrogen storage system of the present invention, the active component B may further contain other metals, such as copper.
Through a large amount of screening, the inventor of the invention finds that the selection of a proper auxiliary agent can maintain high conversion rate under low temperature and can achieve high selectivity.
Preferably, the auxiliary agent B is an oxide A and an oxide B.
Further preferably, the oxide a is a zinc oxide and/or a tin oxide compound.
Further preferably, the carrier B is silica and/or zirconia.
Preferably, the content of the active component B in the hydrogenation catalyst is 15 to 60 wt%, preferably 20 to 55 wt%, and specifically may be 20 wt%, 25wt%, 30 wt%, 35 wt%, 40wt%, 45 wt%, 50 wt%, or 55 wt%.
In a preferred embodiment, the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier; the active component B is cobalt; the auxiliary agent B is an oxide A and an oxide B; the oxide A is a tin oxide compound; the oxide B is potassium oxide; the carrier B is silicon dioxide.
In the hydrogen storage system of the present invention, when the active component B of the hydrogenation catalyst is cobalt, the oxide a is a tin oxide compound, the oxide B is potassium oxide (i.e., the auxiliary agent B is a tin oxide compound and potassium oxide), and the support B is silica, the hydrogenation catalyst contains 20 to 40wt% of cobalt, 15 to 35 wt% of tin oxide compound, and 0.05 to 1wt% of potassium oxide, specifically, the cobalt content may be 20 wt%, 25wt%, 30 wt%, 35 wt%, or 40wt%, the tin oxide compound content may be 15 wt%, 20 wt%, 25wt%, 30 wt%, or 35 wt%, and the potassium oxide content may be 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5wt%, 0.6wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt%.
In a preferred embodiment, the hydrogenation catalyst can be prepared by a common method such as coprecipitation (including a uniform precipitation method such as sequential addition, reverse addition, parallel flow or ammonia distillation), an impregnation loading method, a sol-gel method, deposition, ball milling, kneading and the like, and can be obtained by caustic soda extraction after alloy quenching.
A second aspect of the present invention provides a method of storing and releasing hydrogen gas, the method comprising the steps of:
(1) Carrying out dehydrogenation reaction on dihydric alcohol under the catalysis of a dehydrogenation catalyst to obtain lactone, and realizing the release of hydrogen;
(2) Under the catalysis of a hydrogenation catalyst, the lactone and hydrogen undergo hydrogenation reaction to obtain dihydric alcohol, so that the hydrogen is stored.
The schematic diagram of the hydrogenation and dehydrogenation method in the invention is shown in figure 1.
In the present invention, the liquid hourly space velocity refers to the amount of feed (m) to the reactor per hour 3 H) and the catalyst loading volume in the reactor (m) 3 ) In-line with the above and (4) the ratio.
In the method of the present invention, the diol is preferably selected from C4-C5 diols.
In a preferred embodiment of the method of the present invention, the diol is one or more selected from the group consisting of 1, 4-butanediol, 1, 4-pentanediol, and 1, 5-pentanediol.
Preferably, the lactone is selected from one or more of gamma-butyrolactone, gamma-valerolactone and cyclopentanolactone.
Further preferably, in the method of the present invention, the diol is 1, 4-butanediol and/or 1, 4-pentanediol.
In a preferred embodiment of the process of the present invention, the diol is 1, 4-butanediol, and the lactone is γ -butyrolactone which is obtained by dehydrogenation of 1, 4-butanediol.
In the method of the present invention, in order to obtain a good dehydrogenation and hydrogenation effect, it is necessary to control the conditions of the dehydrogenation reaction and the hydrogenation reaction within a reasonable range.
In the method of the present invention, in order to further reduce the energy consumption of the reaction, the dehydrogenation reaction is performed in a liquid phase dehydrogenation manner, so that the temperature and pressure of the reaction need to be reasonably controlled to ensure that the dehydrogenation reaction is liquid phase dehydrogenation.
Thus preferably, in step (1), the dehydrogenation reaction conditions include: the temperature is 160-200 deg.C, and the pressure is 0.3-0.6MPaG.
In the process of the present invention, the temperature and pressure of the dehydrogenation reaction are controlled within the above ranges so that the glycol is subjected to the liquid-phase dehydrogenation reaction, while further controlling the vaporization fraction of the glycol within a suitable range.
In the present invention, the vaporization fraction refers to a proportion of a vapor phase of a substance in a vapor-liquid equilibrium state.
Further preferably, in the step (1), the dehydrogenation reaction conditions include: the temperature is 170-190 ℃, the pressure is 0.35-0.55MPaG, and the liquid hourly space velocity is 0.1-1h -1 The vaporization fraction of the dihydric alcohol is less than or equal to 20 percent.
In a preferred embodiment, in step (1), the vaporization fraction of the glycol is 15% or less, more preferably 10% or less, and still more preferably 8% or less.
In a specific embodiment, in step (1), the temperature of the dehydrogenation reaction may be 170 ℃, 175 ℃, 180 ℃, 185 ℃ or 190 ℃, the pressure of the dehydrogenation reaction may be 0.35MPaG, 0.4MPaG, 0.45MPaG, 0.5MPaG or 0.55MPaG, and the liquid hourly space velocity of the dehydrogenation reaction may be 0.1h -1 、0.2h -1 、0.3h -1 、0.4h -1 、0.5h -1 、0.6h -1 、0.7h -1 、0.8h -1 、0.9h -1 Or 1h -1 。
In particular embodiments, in step (1), the partial vaporization fraction of the glycol may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8%.
In the method of the present invention, in step (1), there is no particular requirement on the reactor used for the dehydrogenation reaction, and the reactor may be a dehydrogenation reactor conventionally used in the art, and in a specific embodiment, the dehydrogenation reaction is performed using a tubular fixed bed reactor or a slurry bed reactor, and further preferably, the dehydrogenation reaction is performed in a tubular fixed bed reactor.
In a preferred embodiment, in step (1), when the dehydrogenation reaction is carried out using a tubular fixed bed reactor, the glycol of the present invention is passed through the tubular fixed bed reactor from top to bottom, i.e., under the action of gravity, to carry out the dehydrogenation reaction.
In a preferred embodiment, in step (1), to ensure the liquid phase dehydrogenation, the temperature of the glycol entering the dehydrogenation reactor is controlled to be T 1 The temperature of the dehydrogenation reactor (i.e., the temperature of the dehydrogenation reaction) is T 2 ，T 2 -T 1 = Δ T, in a preferred case, Δ T-5 to 20 ℃,in particular embodiments, Δ T may be-5 ℃, 0 ℃,5 ℃, 10 ℃, 15 ℃ or 20 ℃.
Preferably, in step (2), the conditions of the hydrogenation reaction include: the temperature is 150-220 deg.C, and the pressure is 4-10MPaG.
Further preferably, in step (2), the conditions of the hydrogenation reaction include: the temperature is 150-200 ℃, the pressure is 4-8MPaG, and the liquid hourly space velocity is 0.1-1h -1 。
More preferably, in step (2), the conditions of the hydrogenation reaction include: the temperature is 160-190 ℃, the pressure is 4-6MPaG, and the liquid hourly space velocity is 0.2-0.8h -1 。
In a specific embodiment, in the step (2), the temperature of the hydrogenation reaction may be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ or 190 ℃, the pressure of the hydrogenation reaction may be 4MPaG, 4.5MPaG, 5MPaG, 5.5MPaG or 6MPaG, and the liquid hourly space velocity of the hydrogenation reaction may be 0.2h -1 、0.3h -1 、0.4h -1 、0.5h -1 、0.6h -1 、0.7h -1 Or 0.8h -1 。
In a preferred embodiment, in step (2), the molar ratio of hydrogen to lactone is from 20 to 60.
In the method of the present invention, in the step (2), there is no particular requirement for the reactor used for the hydrogenation reaction, and the reactor may be a reactor for hydrogenation reaction conventionally used in the art, and in a specific embodiment, a tubular fixed bed reactor is used for the hydrogenation reaction.
In a preferred embodiment, in step (2), when the hydrogenation reaction is carried out using a tubular fixed bed reactor, the lactone and hydrogen are passed through the tubular fixed bed reactor from top to bottom, i.e., under the action of gravity, to carry out the hydrogenation reaction.
In the method of the present invention, in order to further obtain better dehydrogenation and hydrogenation effects, besides reasonable control of dehydrogenation and hydrogenation process conditions, a suitable hydrogenation catalyst and a suitable dehydrogenation catalyst also need to be further selected.
In step (1) of the method, the dehydrogenation catalyst comprises a carrier A, and an active component A and an auxiliary agent A which are loaded on the surface of the carrier;
the active component a is copper, and the content of copper in the dehydrogenation catalyst is 20 to 60 wt%, preferably 25 to 50 wt%, more preferably 25 to 45 wt%, and specifically may be 25wt%, 30 wt%, 35 wt%, 40wt%, or 45 wt%.
Preferably, the auxiliary agent a contains one or more of zinc oxide, tin oxide compound, chromium oxide compound, and barium oxide.
Preferably, the auxiliary agent A contains a tin oxide compound and a chromium oxide compound, and the content of the tin oxide compound in the dehydrogenation catalyst is 1-25 wt%, and the content of the chromium oxide compound in the dehydrogenation catalyst is 0.1-15 wt%.
Further preferably, the auxiliary a contains a tin oxide compound, a chromium oxide compound and barium oxide, the dehydrogenation catalyst contains 5 to 20 wt% of the tin oxide compound, 0.1 to 5wt% of the chromium oxide compound and 0.1 to 3wt% of the barium oxide, specifically, the dehydrogenation catalyst contains 5wt%, 10 wt%, 15 wt% or 20 wt% of the tin oxide compound, 0.1 wt%, 1wt%, 2wt%, 3wt%, 4 wt% or 5wt% of the chromium oxide compound and 0.1 wt%, 1wt%, 2wt% or 3wt% of the barium oxide.
Preferably, the carrier a is selected from one or more of silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide.
Further preferably, the carrier a is silica and/or zirconia.
In a preferred embodiment, the dehydrogenation catalyst can be prepared by conventional methods such as coprecipitation (including uniform precipitation such as sequential addition, reverse addition, concurrent flow or ammonia distillation), impregnation loading, sol-gel, precipitation, ball milling, kneading, and even caustic soda extraction after quenching the alloy.
In the present invention, the dehydrogenation catalyst needs to be reduced to make the active composition of the dehydrogenation catalyst in a metallic state or a partial metallic state in a reaction state, and then catalytic dehydrogenation is performed, wherein the reduction operation usually employs a reducing substance such as hydrogen.
For the dehydrogenation catalyst, hydrogen or a mixed gas of nitrogen and hydrogen is adopted for reduction, the reduction temperature is 210 to 300 ℃, and the reduction space velocity is 100 to 2000h -1 。
In step (2) of the method, the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier;
the active component B contains cobalt;
the auxiliary agent B is an oxide A and/or an oxide B;
the oxide A is selected from one or more of zinc oxide, tin oxide and chromium oxide; the oxide B is potassium oxide and/or barium oxide;
the carrier B is selected from one or more than two of silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide.
In the present invention, the active component B may also contain other metals, such as copper.
Through a large amount of screening, the inventor of the invention finds that the selection of a proper auxiliary agent can maintain high conversion rate under low temperature and can achieve high selectivity.
Preferably, the auxiliary agent B is an oxide A and an oxide B.
Further preferably, the oxide a is a zinc oxide and/or a tin oxide compound.
Further preferably, the carrier B is silica and/or zirconia.
Preferably, the content of the active component B in the hydrogenation catalyst is 15 to 60 wt%, preferably 20 to 55 wt%, and specifically may be 20 wt%, 25wt%, 30 wt%, 35 wt%, 40wt%, 45 wt%, 50 wt%, or 55 wt%.
In a preferred embodiment, the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier; the active component B is cobalt; the auxiliary agent B is an oxide A and an oxide B; the oxide A is a tin oxide compound; the oxide B is potassium oxide; the carrier B is silicon dioxide.
In the method of the present invention, when the active component B of the hydrogenation catalyst is cobalt, the oxide a is a tin oxide compound, the oxide B is potassium oxide (i.e., the auxiliary agent B is a tin oxide compound and potassium oxide), and the carrier B is silica, the hydrogenation catalyst contains 20 to 40wt% of cobalt, 15 to 35 wt% of tin oxide compound, and 0.05 to 1wt% of potassium oxide, specifically, the cobalt content may be 20 wt%, 25wt%, 30 wt%, 35 wt%, or 40wt%, the tin oxide compound content may be 15 wt%, 20 wt%, 25wt%, 30 wt%, or 35 wt%, and the potassium oxide content may be 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5wt%, 0.6wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt%.
In a preferred embodiment, the hydrogenation catalyst can be prepared by a common method such as coprecipitation (including a uniform precipitation method such as sequential addition, reverse addition, parallel flow or ammonia distillation), an impregnation loading method, a sol-gel method, deposition, ball milling, kneading and the like, and can be obtained by caustic soda extraction after alloy quenching.
In the invention, the hydrogenation catalyst needs to be subjected to reduction treatment firstly, so that the active composition of the hydrogenation catalyst is in a metallic state or a partial metallic state in a reaction state, and then catalytic hydrogenation is carried out, wherein reducing substances such as hydrogen and the like are usually adopted in the reduction operation.
For the hydrogenation catalyst, hydrogen or a mixed gas of nitrogen and hydrogen is adopted for reduction, the reduction temperature is 260 to 400 ℃, and the reduction space velocity is 100 to 2000h -1 。
In the method of the invention, the hydrogen released in the dehydrogenation reaction in the step (1) can be used for synthesizing ammonia with nitrogen or CO x And (4) synthesizing methanol.
In a preferred embodiment, the hydrogen released by the dehydrogenation reaction in step (1) can be used subsequently in the synthesis of ammonia from nitrogen, wherein the gas needs to be purged before the ammonia synthesis reaction is carried out.
When the hydrogen obtained by the dehydrogenation reaction in the step (1) is used for synthesizing ammonia with nitrogen, because the dehydrogenation process is actually accompanied with a process lacking energy, namely heat absorption and energy consumption, and the temperature of the secondary synthesis ammonia is higher than 300 ℃, the heat energy of the byproduct of the synthesis ammonia can be returned to the dehydrogenation reaction to provide reaction heat energy for the dehydrogenation reaction.
In the present invention, the gas purification operation comprises the adsorption or absorption removal of organic matter (lactone, tetrahydrofuran, n-butanol, butanediol, etc.) vapors, the removal of CO and CO 2 In which CO and CO are removed 2 One of pressure swing adsorption desorption (PSA), temperature swing adsorption desorption (TSA) or methanation may be employed.
The method of the invention can store and release hydrogen for a plurality of cycles, but in practical process operation, in combination with specific working conditions and process conditions, impurities (components with boiling points lower than that of lactone, such as ethane, butane and N) can be generated in dehydrogenation reaction and hydrogenation reaction 2 Tetrahydrofuran, n-butanol, etc.), and the content of impurities is gradually increased after a plurality of cycles, and the lactone is not completely converted into the diol due to thermodynamic equilibrium, and in order to ensure the dehydrogenation effect, when the dehydrogenation reaction is performed after a plurality of cycles, it is necessary to reasonably control the content of impurities in the raw material subjected to the dehydrogenation reaction, and therefore, in a preferred embodiment, in the raw material subjected to the dehydrogenation reaction after a plurality of cycles, the content of the diol is 80 to 95 wt%, the content of the lactone is 1 to 19 wt%, the content of impurities is 0.01 to 5wt%, and the total vaporization fraction of the diol and the lactone is 0.1 to 5% in the dehydrogenation reaction, and more preferably, the content of the diol is 80 to 95 wt%, the content of the lactone is 1 to 19 wt%, and the content of the impurities is 0.01 to 4 wt%, based on 100wt% of the total weight of the diol, the lactone, and the impurities.
In the operation of an actual working condition, when the content of impurities is too high, the impurities can be removed through rectification operation, so that the content of the impurities in the raw materials for dehydrogenation reaction is not higher than 4 wt%, the operation pressure of the rectification operation is negative pressure, and the vacuum degree is minus 90 to minus 20kpa.
The method has the advantages of low cost, no toxicity, no corrosion, wide raw material source, dehydrogenation temperature lower than 210 ℃, no need of a noble metal catalyst for dehydrogenation, low required dehydrogenation energy consumption and particular suitability for site-based hydrogen storage.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
The acidic silica sol (model SW 15) and the neutral silica sol (model NS 20) used in the following examples were obtained from Li Xin micro-nano technology, inc., zhejiang.
The ordinary temperature hereinafter means 25 ℃.
EXAMPLE 1 liquid phase dehydrogenation of 1, 4-Butanediol (BDO) to give gamma-butyrolactone (GBL)
(1) Dissolving 1000g of copper nitrate trihydrate, 122g of chromium nitrate nonahydrate and 9 g of barium nitrate in 4000ml of pure water, heating to 80 ℃ to obtain an acidic aqueous solution, and keeping the temperature constant at the temperature for later use; 525g of KOH are subsequently added to 1000ml of water and the temperature is raised to 80 ℃ until complete dissolution is achieved, giving a KOH solution, and 60g of metastannic acid (H) 2 SnO 3 88 wt%) of the acid-soluble polymer is slowly added into KOH solution, stirred for 6 hours at 110 ℃ under a closed condition to obtain suspended colloidal matter, the suspended colloidal matter is dripped into an acid aqueous solution with the temperature of 80 ℃, and 950g of acid silica Sol (SiO) is added after the dripping is finished 2 40 wt%), heating to 90 ℃ under the conditions of sealing and stirring, reacting for 2 hours at 90 ℃, filtering, washing the obtained filter residue with hot water at 80 ℃ for 3 times to obtain about 1100g of product, drying, roasting for 2 hours at 400 ℃ to obtain 768g of roasted product, tabletting, molding, crushing, sieving with 5-40 mesh sieve, collecting 5-40 mesh material to obtain dehydrogenation catalyst, wherein the particle size of the dehydrogenation catalyst is 0.4-4.0 mm, the dehydrogenation catalyst is irregular, XRF test shows that the active component in the dehydrogenation catalyst is copper, the auxiliary agents are tin oxide, chromium oxide and barium oxide, the carrier is silicon dioxide, the copper content in the dehydrogenation catalyst is 33.6wt%, and the tin oxide is tin oxide6wt% of chromium oxide, 3wt% of barium oxide and the balance of silicon dioxide;
(2) 100g of the dehydrogenation catalyst was loaded into a tubular fixed bed reactor and reduced in a mixed gas of hydrogen and nitrogen (hydrogen content 5 vol%) (temperature 250 ℃, time 2 hours, space velocity 300h -1 ) Then, 1, 4-butanediol (the temperature of the 1, 4-butanediol is 185 ℃) is added, and the 1, 4-butanediol flows through a tubular fixed bed reactor from top to bottom under the action of gravity to carry out dehydrogenation reaction, wherein the dehydrogenation reaction conditions comprise: the temperature is 180 ℃, the pressure is 0.5MPaG, and the liquid hourly space velocity is 0.25h -1 The vaporization fraction of 1, 4-butanediol was 0.03%, gas-liquid separation was carried out after condensing the outlet product to-10 deg.C, and the gas composition was analyzed by gas chromatography, as shown in FIG. 2 (wherein 1 is N) 2 2 is CO, 3 is CH 4 And 4 is CO 2 5 is THF,6 is H 2 ) The content of hydrogen in the gas phase was 99.97vol%, wherein the content of methane was 0.012vol%, the content of CO was 0.006vol%, and CO was 2 The content was 0.002vol%, and others (ethane, butane and N) 2 Content) was 0.01vol%; the liquid phase composition was analyzed and calculated from the results to give a BDO conversion of 87%, a gamma-butyrolactone (GBL) selectivity of 99.8mol%, a tetrahydrofuran and n-butanol selectivity of 0.19mol%, and a reduced BDO single dehydrogenation efficiency (single dehydrogenation efficiency = (weight of hydrogen obtained by dehydrogenation)/(weight of hydrogen-rich liquid entering the dehydrogenation reactor) × 100%) of 3.87wt%;
(3) Pressurizing the gas after gas-liquid separation to 0.8MPaG, then carrying out normal-temperature adsorption, adopting porous silicon dioxide and 13X molecular sieve as adsorbents, and ensuring that the gas airspeed is 800h -1 The gas adsorbed at the outlet was analyzed by gas chromatography to find that the hydrogen content was 99.995vol%.
Example 2 liquid phase hydrogenation of GBL to BDO
(1) Dissolving 820g of cobalt nitrate hexahydrate in 2000ml of pure water, heating to 70 ℃ to obtain an acidic aqueous solution, and keeping the temperature constant at the temperature for later use; 260g of NaOH are then added to 800ml of water, the temperature is raised to 90 ℃ until complete dissolution is obtained, a NaOH solution is obtained, and 150g of metastannic acid (H) are then added 2 SnO 3 Content 88 wt.%) was slowly dosedAdding into NaOH solution, stirring at 110 deg.C for 3 hr under sealed condition to obtain suspended colloid, adding dropwise into 70 deg.C acidic aqueous solution, adding 800g neutral silica Sol (SiO) 2 40 wt%), heating to 90 ℃ under the conditions of sealing and stirring, reacting for 2 hours at 90 ℃, filtering, washing the obtained filter residue with hot water at 80 ℃ for 2 times to obtain about 850g of a product, drying for 5 hours at 120 ℃ in an oven, grinding to obtain dried powder, dissolving 6g of potassium carbonate in 60g of water to obtain a potassium carbonate solution, slowly adding the potassium carbonate solution into the dried powder, uniformly stirring to obtain modified powder, roasting the modified powder for 3 hours at 450 ℃ to obtain 645g of a roasted product, crushing by tabletting, sieving with a 10-20-mesh sieve, collecting a 10-20-mesh material to obtain a hydrogenation catalyst, wherein the hydrogenation catalyst is irregular in shape, and is tested by XRF, active components in the hydrogenation catalyst are cobalt, auxiliaries are a tin oxide compound and potassium oxide, a carrier is silicon dioxide, the cobalt content in the hydrogenation catalyst is 25wt%, the tin oxide compound content is 18wt%, the potassium oxide content is 0.5wt%, and the balance is silicon dioxide;
(2) 60g of the hydrogenation catalyst precursor is loaded into a tubular fixed bed reactor and reduced in pure hydrogen (the temperature is 350 ℃, the time is 2h, and the space velocity is 300 h) -1 ) Then, adding gamma-butyrolactone (GBL) and hydrogen (the molar ratio of hydrogen to GBL is 50: the temperature is 175 ℃, the pressure is 6MPaG, and the liquid hourly space velocity is 0.24h -1 And condensing the outlet product to 40 ℃, performing gas-liquid separation, analyzing the liquid phase composition, and calculating according to the result to obtain that the GBL conversion rate is 91%, the BDO selectivity is 99.20mol%, and the tetrahydrofuran and n-butanol selectivity is 0.79mol%.
Example 3
Technological process scheme for establishing BDO-GBL circulating hydrogen storage
Firstly, a process flow for preparing GBL by BDO liquid phase dehydrogenation is established based on the process conditions of the embodiment 1, aspen plus is adopted to carry out full-flow simulation,as shown in FIG. 3, the design scale is 6000NM 3 A dehydrogenation rate,/h; wherein 13900kg/h BDO is preheated by E202 and then enters E201 to be heated to 180 ℃ (the pressure is 0.55MPa, the vaporization fraction of BDO is<1%), the temperature of the reactor is set to be an isothermal reactor (heat is supplied by heat-conducting oil), the temperature of the reactor is 180 ℃, the conversion rate and the selectivity of the reaction are determined according to the results of the example 1, the heat exchange is carried out by E202, then the reaction is condensed to 40 ℃ by an E203 circulating water condenser, the obtained hydrogen is pressurized to 0.5MPa by a gas-liquid separation tank V201 and then is sent to a hydrogen using device, and the amount of the hydrogen released in the actual dehydrogenation reaction is 6003NM 3 H,; the total energy consumption of the reactor and preheater is calculated to be 933.5Kcal/s, which is converted to 3920Kw, i.e. about 0.653KWh/Nm 3 Hydrogen (i.e. each yield of 1 NM) 3 Hydrogen ambient needs to be replenished with about 0.653KWh of energy);
then, a process flow for preparing BDO by GBL liquid phase hydrogenation is established based on the process conditions of example 2, aspen plus is adopted to perform a full-flow simulation, and the design scale is 6000NM as shown in FIG. 4 3 A hydrogenation rate of/h; 13354kg/h of the above dehydrogenation product (mainly GBL, wherein the GBL content is 86.47wt%, the BDO content is 13.51wt%, and the total content of impurities such as tetrahydrofuran is 0.02wt%, based on the total weight of GBL, BDO and impurities being 100 wt%), and 6025NM 3 The hydrogen/h is mixed in M101 and heated to 175 ℃ by preheating E102 and heating E101, the liquid entering the reactor has a vaporization fraction of 9%, the conversion and selectivity are according to the result of example 2, wherein the heat produced by the R101 side of the hydrogenation reactor is 653Kcal/s, which is greater than 257Kcal/s of the external supplementary heat source required by the E101, so that practically no external energy source is consumed in the hydrogenation process and at least 396Kcal/s is abundant.
The process is a GBL-BDO circulation process, and is calculated according to carrier decomposition, the content of impurities such as tetrahydrofuran and the like after one circulation is 0.37wt%, the content reaches 3.7wt% after 10 circulations according to calculation, the carrier vacuum rectification regeneration impurity removal is carried out for one time, the operation pressure of the rectification operation is negative pressure, the vacuum degree is-50 kpa, a hydrogen-rich medium (the content of light components is controlled below 0.5 wt%) with BDO as a main body is extracted from a measurement line of a tower kettle, the light components such as tetrahydrofuran and water are extracted from the tower top, the energy required by the tower kettle of the rectification is K289 cal/s, and the heat required by the product circulation purification in the hydrogenation process can be met by a byproduct heat source.
Example 4
The hydrogenation was carried out as in example 2, except that the hydrogenation catalyst used was a Cu-Mn-Al catalyst prepared in US5395990A, and the GBL conversion was 42% and the BDO selectivity was 93mol%, and the by-products were more tetrahydrofuran and n-butanol with a selectivity of 6.7mol% or more, as calculated from the results.
According to the results, the hydrogenation catalyst used in this example has low-temperature activity and insufficient selectivity, and has better hydrogenation effect compared with the hydrogenation catalyst used in the method.
Example 5
Adopting BDO gas phase dehydrogenation process, designing 6000NM according to the prior art 3 The hydrogen release rate/h, the whole flow simulation is carried out by Aspen plus, specifically as shown in fig. 5, the catalyst is the catalyst used in example 2 of patent application 202211029145.5, the vaporization fraction of BDO is 100%, the pressure of dehydrogenation reaction is 0.08MPaG, the conversion rate of BDO in the reactor is 99.8%, the GBL selectivity is 99.0mol%, the energy consumption of dehydrogenation reactor and superheated vaporization is 345+832+223+455= 5Kcal/s, the energy consumption is 7766KW, namely the dehydrogenation energy consumption is 1.294Kwh/Nm 3 And 1.897 times higher than that of example 3 on the same scale.
From the results, the gas phase dehydrogenation mode in the prior art has higher energy consumption, and the liquid phase dehydrogenation mode adopted in the method can effectively reduce the energy consumption.
Comparative example 1
According to the literature (energy efficiency analysis of hydrogen energy storage system based on organic liquid hydrogen storage carrier, new energy development, 2017), dibenzyl toluene is adopted for hydrogen storage, the corresponding energy loss proportion (the ratio of the amount of lost energy divided by the total consumption of energy) of hydrogen in the dehydrogenation stage is 0.38, and the heat value of hydrogen is 10.8MJ/NM 3 According to 6000NM 3 The hydrogen storage scale is 1628Kcal/s, which is converted to 6837KW, which is converted to 1.14Kwh/Nm 3 Hydrogen, which is 1.75 times the equivalent scale of example 3.
The results show that the method of the invention has lower cost, does not need to adopt noble metal catalysts, has low required dehydrogenation energy consumption, and is particularly suitable for site-based hydrogen storage.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A hydrogen storage system for storing and releasing hydrogen gas, wherein the hydrogen storage system comprises a glycol, a lactone, a hydrogenation catalyst, and a dehydrogenation catalyst;
under the catalysis of the hydrogenation catalyst, the lactone is subjected to hydrogenation reaction to store hydrogen to obtain the dihydric alcohol; and under the catalysis of the dehydrogenation catalyst, carrying out dehydrogenation reaction on the dihydric alcohol to release hydrogen to obtain the lactone.
2. The hydrogen storage system of claim 1 wherein the glycol is selected from the group consisting of C4-C5 glycols.
3. A method of storing and releasing hydrogen gas, the method comprising the steps of:
(1) Carrying out dehydrogenation reaction on dihydric alcohol under the catalysis of a dehydrogenation catalyst to obtain lactone, and realizing the release of hydrogen;
(2) Under the catalysis of a hydrogenation catalyst, the lactone and hydrogen undergo hydrogenation reaction to obtain dihydric alcohol, so that the hydrogen is stored.
4. The method of claim 3, wherein the glycol is selected from the group consisting of C4-C5 glycols.
5. The process according to claim 3 or 4, wherein in step (1), the dehydrogenation reaction conditions comprise: the temperature is 160-200 deg.C, and the pressure is 0.3-0.6MPaG.
6. The process according to claim 3 or 4, wherein in step (2), the conditions of the hydrogenation reaction comprise: the temperature is 150-220 deg.C, and the pressure is 4-10MPaG.
7. The method according to claim 3, wherein the dehydrogenation catalyst comprises a carrier A, and an active component A and an auxiliary agent A which are loaded on the surface of the carrier;
the active component A is copper, and the content of copper in the dehydrogenation catalyst is 20-60 wt%.
8. The method of claim 7, wherein the additive A comprises one or more of zinc oxide, tin oxide compound, chromium oxide compound, and barium oxide.
9. The process according to claim 7 or 8, wherein the carrier A is selected from one or more of silica, alumina, zirconia and titania.
10. The method according to claim 3, wherein the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier;
the active component B contains cobalt;
the auxiliary agent B is an oxide A and/or an oxide B;
the oxide A is selected from one or more of zinc oxide, tin oxide and chromium oxide; the oxide B is potassium oxide and/or barium oxide;
the carrier B is selected from one or more than two of silicon dioxide, aluminum oxide, zirconium dioxide and titanium dioxide.
11. The process according to claim 10, characterized in that the content of active component B in the hydrogenation catalyst is between 15 and 60% by weight.
12. The method according to claim 10, wherein the hydrogenation catalyst comprises a carrier B, and an active component B and an auxiliary agent B which are loaded on the surface of the carrier;
the active component B is cobalt;
the auxiliary agent B is an oxide A and an oxide B;
the oxide A is a tin oxide compound;
the oxide B is potassium oxide;
the carrier B is silicon dioxide.
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