Industrial hydrogen-containing gas separation and purification method and device

Abstract

The invention relates to the field of hydrogen energy technology and gas separation, in particular to an industrial hydrogen-containing gas separation and purification method and device. According to the method, industrial hydrogen-containing gas containing impurity gas and valerolactone are subjected to a one-step or multi-step catalytic hydrogenation reaction in the presence of a Cu-based catalyst to provide pentanediol, and hydrogen and impurity gas in the industrial hydrogen-containing gas are separated; the impurity gas at least comprises CO. According to the method, the conversion process of hydrogenation of valerolactone to pentanediol is ingeniously utilized, high-selectivity hydrogenation hydrogen storage is realized by adopting the Cu-based catalyst with relatively high tolerance to CO, and pentanediol can be subjected to catalytic dehydrogenation and release high-purity hydrogen when hydrogen is needed; meanwhile, the temperature interval of CO hydrogenation synthesis of by-products such as methanol is avoided. According to the invention, gas is separated by utilizing multistage chemical hydrogen storage, and efficient utilization of industrial hydrogen-containing gas can be realized.

Description

Technical Field

[0001] The present invention relates to the field of hydrogen energy technology and gas separation, and in particular to a method and device for separating and purifying industrial hydrogen-containing gas. Background Art

[0002] Available hydrogen comes from fossil resource utilization processes such as coal gasification (Formula 1) and natural gas reforming (Formula 2); in addition, industrial waste gas (methanol synthesis, Fischer-Tropsch synthesis, coke oven gas, etc.) is also an important hydrogen resource. The above industrial hydrogen-containing gas resources will be accompanied by a large amount of CO gas impurities (25-50 vol.%), but a very small amount of CO impurities (10 ppm) will poison the Pt, Pd and other precious metal catalysts used in downstream applications (such as hydrogen fuel cells). Therefore, currently, the industry usually uses low-temperature methanation (Formula 3), water vapor shift (Formula 4), alcohol amine absorption, pressure swing adsorption, membrane separation and other processes to extract hydrogen from industrial hydrogen. However, the above process still cannot efficiently utilize industrial hydrogen-containing gas. On the one hand, impurities such as CO and alkanes in the raw gas will be converted into CO2 during the above chemical reaction process; on the other hand, the process involved is complicated and cumbersome, with large investment and high hydrogen loss (such as CN115724402A, CN204039055U, CN210764311U, CN217297309U). Therefore, it is urgent to develop an economical, simple and suitable hydrogen and CO separation technology for industrial hydrogen-containing gas and improve the atomic utilization efficiency of industrial hydrogen-containing gas.

[0003] C+H2O→CO+3H2 (1)

[0004] CH4+H2O→CO+3H2 (2)

[0005] CO+3H2→CH4+H2O (3)

[0006] CO+H2O→CO2+H2 (4) Summary of the invention

[0007] In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a method and device for separating and purifying industrial hydrogen-containing gas, which cleverly utilizes the conversion process of valerolactone hydrogenation to pentanediol, adopts a Cu-based catalyst with strong tolerance to CO, and realizes highly selective hydrogenation and hydrogen storage. Pentanediol can be catalytically dehydrogenated and release high-purity hydrogen when hydrogen is needed; at the same time, the temperature range of CO hydrogenation to synthesize methanol and other byproducts is avoided. The present invention uses multi-stage chemical hydrogen storage to separate gas, which can realize efficient utilization of industrial hydrogen-containing gas.

[0008] The present invention is achieved through the following technical solutions:

[0009] On the one hand, the present invention provides a method for separating and purifying industrial hydrogen-containing gas, comprising the following steps: performing one-step or multi-step catalytic hydrogenation reaction on industrial hydrogen-containing gas containing impurity gas and valerolactone in the presence of a Cu-based catalyst to provide pentanediol capable of storing hydrogen, separating hydrogen and impurity gas in the industrial hydrogen-containing gas; the impurity gas includes at least CO.

[0010] On the other hand, the present invention provides an apparatus for the method for purifying and separating industrial hydrogen-containing gas described in the present invention, comprising a valerolactone storage tank and a crude hydrogen storage tank, and further comprising:

[0011] One-stage or multi-stage hydrogenation reactors, each of the hydrogenation reactors is respectively provided with a valerolactone inlet, an industrial hydrogen-containing gas inlet, a lean hydrogen tail gas outlet and a hydrogenation product outlet; the valerolactone storage tank is communicated with the valerolactone inlet, and the crude hydrogen storage tank is communicated with the industrial hydrogen-containing gas inlet;

[0012] A lean hydrogen gas storage tank, communicated with the lean hydrogen tail gas outlet; for collecting the gas after one-step or multi-step valerolactone hydrogenation purification;

[0013] A hydrogen storage liquid storage tank, the hydrogen storage liquid storage tank is communicated with the hydrogenation product outlet.

[0014] Compared with the prior art, the beneficial effects of the present invention are:

[0015] 1) The present invention utilizes a CO-resistant Cu-based catalyst to catalyze the valerolactone hydrogenation reaction, which can efficiently realize the separation and purification of industrial hydrogen-containing gas containing CO, and reduce the cumbersome steps and costs of hydrogen separation.

[0016] 2) The valerolactone / pentanediol separation and purification crude hydrogen system device and catalyst provided by the present invention have moderate prices and strong application prospects, and almost no side reactions such as methanol synthesis participated by impurity gases such as CO and CO2 occur in the low-temperature reaction process, improving the atomic utilization rate of industrial hydrogen-containing gas and efficiently separating hydrogen.

[0017] 3) The present invention has a multi-stage valerolactone catalytic hydrogenation reaction device with a monitoring system, which is suitable for efficient separation of different industrial hydrogen-containing gases. By dynamically feedback process to control the reactor feed ratio, optimize the process flow, and improve the separation efficiency of industrial hydrogen-containing gas. Description of the Drawings

[0018] Figure 1 It is a schematic structural diagram of the industrial hydrogen-containing gas purification and storage device based on valerolactone catalytic hydrogenation of the present invention.

[0019] Element numbers in the figure:

[0020] 1 Valerolactone storage tank

[0021] 11 Pressurizing unit

[0022] 12 Liquid flow control unit

[0023] 2 Crude hydrogen storage tank

[0024] 21 Hydrogen-containing mixed gas inlet

[0025] 22 Pressure regulation unit

[0026] 23 Gas flow control unit

[0027] 3 Hydrogenation reactor

[0028] 31 Valerolactone inlet

[0029] 32 Industrial hydrogen-containing gas inlet

[0030] 33 Lean hydrogen tail gas outlet

[0031] 34 Hydrogenation product outlet

[0032] 4 Lean hydrogen gas storage tank

[0033] 5 Hydrogen storage liquid storage tank

[0034] 6 Dehydrogenation reactor

[0035] 61 Hydrogen outlet

[0036] 62 Valerolactone outlet

[0037] 7 Monitoring unit

[0038] 8 Pressure transformation unit Specific implementation manner

[0039] Hereinafter, the implementation manners of the method and device for separating and purifying industrial hydrogen-containing gas are specifically described in detail.

[0040] The "range" disclosed in this application is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The ranges defined in this way can include or exclude the end values and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60 - 120 and 80 - 110 are listed for a specific parameter, ranges of 60 - 110 and 80 - 120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all contemplated: 1 - 3, 1 - 4, 1 - 5, 2 - 3, 2 - 4, and 2 - 5. In this application, unless otherwise specified, the numerical range "a - b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0 - 5" means that all real numbers between "0 - 5" are fully listed herein, and "0 - 5" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥2, it is equivalent to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0041] If there is no special instruction, all embodiments and optional embodiments of this application can be combined with each other to form new technical solutions.

[0042] If there is no special instruction, all technical features and optional technical features of this application can be combined with each other to form new technical solutions.

[0043] If there is no special instruction, the "including" and "comprising" mentioned in this application mean open-ended or can also be closed-ended. For example, the "including" and "comprising" can mean that other components not listed can also be included or comprised, or can only include or comprise the listed components.

[0044] If there is no special instruction, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); or both A and B are true (or exist).

[0045] After extensive research, the applicant of the present invention unexpectedly found that to solve the problem of separating and purifying industrial hydrogen-containing gases containing CO, the present invention uses a cheap, abundant, and CO-tolerant Cu-based catalyst to catalyze the reaction of hydrogen with valerolactone in industrial hydrogen-containing gases, and highly selectively stores hydrogen in pentanediol at a temperature of 140-200 °C. When hydrogen is needed, high-purity hydrogen is obtained by catalyzing the dehydrogenation of pentanediol at a temperature of 140-200 °C. At this temperature, CO is not likely to react with hydrogen to form methanol as a side reaction, and CO will be enriched in the hydrogen-deficient tail gas. On this basis, a multi-stage hydrogenation reaction device is used to catalyze the hydrogenation reaction of valerolactone in the hydrogen-deficient gas after hydrogen storage multiple times. By monitoring the system to count data such as liquid yield and gas ratio, an intelligent data-model library is established, and the process flow is optimized based on the intelligent output parameters to finely adjust the multi-stage reactor to achieve the purpose of efficient gas separation and realize the separation and purification of industrial hydrogen-containing gases. On this basis, this application was completed.

[0046] Industrial hydrogen-containing gas separation and purification method

[0047] On the one hand, the present invention provides a method for separating and purifying industrial hydrogen-containing gases, including the following steps: performing one-step or multi-step catalytic hydrogenation reactions on industrial hydrogen-containing gases containing impurity gases and valerolactone in the presence of a Cu-based catalyst to provide pentanediol capable of storing hydrogen, separating hydrogen and impurity gases in industrial hydrogen-containing gases, and realizing the separation of industrial hydrogen-containing gases, the purification of CO, and catalytic hydrogen storage. The impurity gases include at least CO, and the impurity gases may optionally include CH4, CO2, etc.

[0048] In the method for separating and purifying industrial hydrogen-containing gases provided by the present invention, valerolactone is selected from γ-valerolactone and / or δ-valerolactone. The concentration of valerolactone is 16.7 wt% - 100 wt%. In valerolactone, the solvent is one or more of methanol, ethanol, glycerol, 1,4-dioxane, tetrahydrofuran, and dodecane.

[0049] In the method for separating and purifying industrial hydrogen-containing gases provided by the present invention, optionally, the pentanediol is catalytically dehydrogenated to provide hydrogen. The hydrogen is high-purity hydrogen with a purity of ≥99 vol%.

[0050] In the method for separating and purifying industrial hydrogen-containing gases provided by the present invention, the reaction formulas for the catalytic hydrogenation and catalytic dehydrogenation are as follows:

[0051]

[0052] In the method for separating and purifying industrial hydrogen-containing gas provided by the present invention, the volume concentration of the impurity gas CO in the industrial hydrogen-containing gas is 0.1% to 95%. Optionally, the volume concentration of the impurity gas CO in the industrial hydrogen-containing gas can be, for example, 0.1% to 35%, 35% to 100%, 0.1% to 20%, 20% to 35%, 35% to 50%, 50% to 75%, or 75% to 100%, etc.

[0053] In the method for separating and purifying industrial hydrogen-containing gas provided by the present invention, the Cu-based catalyst comprises Cu and a carrier, and the mass ratio of Cu to the carrier is (10 - 70):(30 - 90). Optionally, the mass ratio of Cu to the carrier can be, for example, (10 - 60):(40 - 90), (10 - 50):(50 - 90), (10 - 40):(60 - 90), (10 - 30):(70 - 90), or (10 - 20):(80 - 90), etc. Further optionally, the carrier is selected from one or more of SiO2, ZnO, Cr2O3, ZrO2, Al2O3, and MgO. Further, the carrier can be, for example, SiO2, ZnO, SiO2-ZrO2, Al2O3-ZrO2, ZrO2, MgO, Cr2O3, ZnO-Cr2O3, Cr2O3-ZrO2, etc.

[0054] In the method for separating and purifying industrial hydrogen-containing gas provided by the present invention, the catalytic hydrogenation reaction is carried out under certain temperature and pressure. In some embodiments, the temperature of the catalytic hydrogenation reaction is 140°C to 200°C. Optionally, the temperature of the catalytic hydrogenation reaction can be, for example, 140°C to 160°C, 160°C to 180°C, or 180°C to 200°C, etc. The pressure of the catalytic hydrogenation reaction is 0.1 to 10 MPa. Optionally, the pressure of the catalytic hydrogenation reaction can be, for example, 0.1 to 5 MPa, 5 to 10 MPa, 0.1 to 3 MPa, 3 to 5 MPa, 5 to 8 MPa, or 8 to 10 MPa, etc.

[0055] In the method for separating and purifying industrial hydrogen-containing gas provided by the present invention, the catalytic dehydrogenation reaction is carried out under certain temperature and pressure. In some embodiments, the temperature of the catalytic dehydrogenation reaction is 140°C to 200°C. Optionally, the temperature of the catalytic dehydrogenation reaction can be, for example, 140°C to 160°C, 160°C to 180°C, or 180°C to 200°C, etc. The pressure of the catalytic dehydrogenation reaction is 0.1 MPa to 5 MPa. Optionally, the pressure of the catalytic dehydrogenation reaction can be, for example, 0.1 MPa to 3 MPa, 3 MPa to 5 MPa, 0.1 MPa to 1.5 MPa, 1.5 MPa to 3 MPa, 3 MPa to 4 MPa, or 4 MPa to 5 MPa, etc.

[0056] Industrial hydrogen-containing gas purification and separation device

[0057] On the other hand, the present invention provides an apparatus for the purification and separation method of industrial hydrogen-containing gas described in the first aspect of the present invention. As Figure 1 shown, the apparatus includes: a crude hydrogen storage tank 2, a valerolactone storage tank 1, one or more hydrogenation reactors 3, a hydrogen-depleted gas storage tank 4, and a hydrogenation product storage tank.

[0058] In the industrial hydrogen-containing gas purification and separation apparatus provided by the present invention, the valerolactone storage tank 1 is used to store valerolactone. Wherein, a pressurizing unit 11 and a liquid flow control unit 12 are provided at the outlet of the valerolactone storage tank 1. Both the pressurizing unit 11 and the liquid flow control unit 12 can be obtained through commercial purchase. The pressurizing unit 11 is, for example, a pressure pump and needs to input liquid into the pipeline. The liquid flow control unit 12 can be, for example, a plunger pump for regulating the flow rate.

[0059] Further, the concentration of valerolactone stored in the valerolactone storage tank 1 can be, for example, 16.7% - 100 wt%. It can be optionally 16.7% - 33 wt%, 16.7% - 33 wt%, 33% - 50 wt%, 50% - 66.7 wt% or 66.7% - 100 wt% etc.

[0060] In the industrial hydrogen-containing gas purification and separation apparatus provided by the present invention, the crude hydrogen storage tank 2 includes a hydrogen-containing mixed gas inlet 21 for communicating with the hydrogen production section, for example, it can be connected through a pipeline. At the outlet of the crude hydrogen storage tank 2, there is a pressure regulating unit 22 and a gas flow control unit 23. Among them, the pressure regulating unit 22 can be obtained through commercial purchase. For example, a fixed-bed reactor controls the pipeline pressure through a back-pressure valve; a batch reactor controls it through an electronic pressure gauge and a valve. The gas flow control unit 23 can be an mfc, a mass flow controller, electronically control the specific flow rate, or use a throttle valve and a rotameter.

[0061] In the industrial hydrogen-containing gas purification and separation apparatus provided by the present invention, for one or more hydrogenation reactors 3, each hydrogenation reactor 3 is respectively provided with a valerolactone inlet 31, an industrial hydrogen-containing gas inlet 32, a hydrogen-depleted tail gas outlet 33, and a hydrogenation product outlet 34; the valerolactone storage tank 1 is communicated with the valerolactone inlet 31, and the crude hydrogen storage tank 2 is communicated with the industrial hydrogen-containing gas inlet 32. Specifically, the outlet of the valerolactone storage tank 1 is communicated with the valerolactone inlet 31, the outlet of the crude hydrogen storage tank 2 is communicated with the industrial hydrogen-containing gas inlet 32, and between adjacent hydrogenation reactors 3, the hydrogen-depleted tail gas outlet 33 of the upper stage is communicated with the industrial hydrogen-containing gas inlet 32 of the lower stage.

[0062] Further, the connecting pipelines between the crude hydrogen storage tank 2, one or more hydrogenation reactors 3, and the hydrogen-depleted gas storage tank 4 are connected in series, wherein the connecting pipelines are gas paths, that is, the crude hydrogen and hydrogen-depleted gas paths are in series form.

[0063] Furthermore, the γ-valerolactone storage tank 1 is respectively connected to each stage of the hydrogenation reactor 3 through γ-valerolactone pipelines, and the γ-valerolactone pipelines are connected in parallel.

[0064] Furthermore, the hydrogenation reactor 3 is a gas series-type multiphase catalytic continuous flow reactor or a multiphase catalytic autoclave reactor. Each stage of the hydrogenation reactor 3 is provided with a heating module, a catalyst module, a temperature sensor, a pressure sensor, and a safety relief device. Among them, the heating module is an electric heater, such as a heating jacket; the catalyst module is catalyst powder or particles in the autoclave and a packed particle bed layer in the fixed-bed reactor; the safety relief device is a bursting safety valve that will burst and relieve pressure when the air pressure is too high.

[0065] Furthermore, at the γ-valerolactone inlet 31 and the industrial hydrogen-containing gas inlet 32 of each stage of the hydrogenation reactor 3, there is a feed ratio control system, including a gas pressure control valve, an electronic pressure detection meter, a liquid piston pump, and a balance to detect the substrate mass. By adjusting the gas pressure and the liquid feed flow rate, the content of pentanediol and solvent in the liquid and the feed ratio can be changed.

[0066] Furthermore, at the lean hydrogen tail gas outlet 33 and the hydrogenation product outlet 34 of each stage of the hydrogenation reactor 3, a monitoring unit 7 is connected, mainly using gas chromatography to detect the hydrogen consumption of the gas and the product content in the liquid on-line or off-line.

[0067] Furthermore, the intermediate gas pipeline of each stage of the hydrogenation reactor 3 is connected to a pressure transformation unit 8 to adjust the tail gas pressure of the reactor to an appropriate value to adapt to the next stage of the reactor or the gas storage tank. The pressure transformation unit 8 includes an air booster pump and an electronic pressure gauge.

[0068] Furthermore, each stage of the hydrogenation reactor 3 is provided with a product feedback mechanism. According to the monitored tail gas and product data, the feed ratio is regulated to optimize the hydrogenation reaction result of each stage. Specifically, according to the analysis of the gas / liquid product data of each stage of the hydrogenation reactor 3 by the monitoring unit 7, the feed ratio of the reactor can be automatically / manually adjusted to adapt to the dynamic change of the gas composition, and the substrate conversion rate and product selectivity of each stage of the reactor can be regulated.

[0069] In the industrial hydrogen-containing gas purification and separation device provided by the present invention, the lean hydrogen gas storage tank 4 is communicated with the lean hydrogen tail gas outlet 33 of the last stage of the hydrogenation reactor 3; it is used to collect the gas after one-step or multi-step γ-valerolactone hydrogenation purification.

[0070] In the industrial hydrogen-containing gas purification and separation device provided by the present invention, the hydrogen storage liquid storage tank 5 is communicated with the hydrogenation product outlet 34, for example, through a pipeline, to realize the storage of the hydrogen storage product.

[0071] In the industrial hydrogen-containing gas purification and separation device provided by the present invention, a dehydrogenation reactor 6 is further included. The dehydrogenation reactor 6 is communicated with the hydrogen storage liquid storage tank 5. The dehydrogenation reactor 6 includes a hydrogen outlet 61 and a valerolactone outlet 62. The valerolactone outlet 62 is communicated with the valerolactone storage tank 1. High-purity hydrogen is prepared by dehydrogenation, and valerolactone is recovered to the valerolactone storage tank 1.

[0072] The working process of the present invention:

[0073] As Figure 1 , the industrial hydrogen-containing gas is communicated with the inlet of the crude hydrogen storage tank 2 through a pipeline. After pressure regulation in the crude hydrogen storage tank 2 unit, it is transported to the hydrogenation reactor 3 together with valerolactone. The valerolactone catalytic hydrogenation reactor 3 is a gas series-type multiphase catalytic continuous flow reactor or a multiphase catalytic kettle type. The catalytic hydrogenation reactor 3 is equipped with a heating module, a catalyst module, a temperature sensor, a pressure sensor, and a safety relief device. Each stage of the reactor is provided with an industrial hydrogen-containing gas inlet, a valerolactone inlet 31, a lean hydrogen tail gas outlet 33, and a hydrogenation product outlet 34. The crude hydrogen and lean hydrogen gas paths are in series form, and the valerolactone pipeline is in parallel form, and the valerolactone raw material can be input into each stage of the reactor at the same time. The crude hydrogen and valerolactone raw materials undergo a hydrogenation reaction under the action of a catalytic module containing a Cu catalyst at a temperature of 140-200°C to obtain a hydrogen storage liquid product and lean hydrogen tail gas. Subsequently, the liquid product is input from the liquid outlet of the hydrogenation reactor 3 to the hydrogen storage liquid storage tank 5, and the lean hydrogen tail gas enters the next-stage hydrogenation reaction tank or the lean hydrogen gas storage tank 4. A feed ratio control system is installed at the gas / liquid feed port of each stage of the reactor, and the gas / liquid outlet of the reactor is connected to a gas and liquid monitoring system. The intermediate gas pipeline of each stage of the hydrogenation reactor 3 is connected to a pressure swing unit 8. The one-stage or multi-stage hydrogenation reactor 3 has a product feedback mechanism. According to the analysis of the gas / liquid product data of each stage of the hydrogenation reactor 3 by the monitoring system, parameters such as the reactor feed ratio and gas input pressure can be automatically / manually adjusted to adapt to the dynamic changes in the composition of the industrial hydrogen-containing gas / lean hydrogen gas, and the substrate conversion rate and product selectivity of each stage of the reactor can be regulated. The hydrogen storage liquid enters the dehydrogenation reactor 6 from the hydrogen storage liquid storage tank 5, and high-purity hydrogen is prepared by dehydrogenation at a temperature of 140-200°C, and valerolactone is recovered to the valerolactone storage tank 1.

[0074] The beneficial effects of the present invention:

[0075] 1) The present invention uses a CO-resistant Cu-based catalyst to catalyze the hydrogenation reaction of valerolactone, which can efficiently separate and purify the CO-containing industrial hydrogen-containing gas, reducing the cumbersome steps and costs of hydrogen separation.

[0076] 2) The device and catalyst for separating and purifying crude hydrogen system of valerolactone / valerol are provided by the present invention, with moderate prices and strong application prospects. Moreover, in this low-temperature reaction process, side reactions such as methanol synthesis involving impurity gases such as CO and CO2 are hardly accompanied, improving the atomic utilization rate of industrial hydrogen-containing gases and efficiently separating hydrogen.

[0077] 3) The present invention has a multi-stage valerolactone catalytic hydrogenation reaction device with a monitoring system, which is applicable to the efficient separation of different industrial hydrogen-containing gases. By regulating the feed ratio of the reactor through a dynamic feedback process, the process flow is optimized, and the separation efficiency of industrial hydrogen-containing gases is improved.

[0078] The beneficial effects of the present invention are further described below in conjunction with embodiments.

[0079] In order to make the invention purpose, technical solution and beneficial technical effects of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. For the embodiments without specific experimental conditions or operation conditions indicated, they are made according to conventional conditions or according to the conditions recommended by the material suppliers.

[0080] In addition, it should be understood that one or more process steps mentioned in the present invention do not exclude the existence of other process steps before and after the combined steps or the insertion of other process steps between these clearly mentioned steps, unless otherwise specified; it should also be understood that the combined connection relationship between one or more devices / apparatuses mentioned in the present invention does not exclude the existence of other devices / apparatuses before and after the combined devices / apparatuses or the insertion of other devices / apparatuses between these two clearly mentioned devices / apparatuses, unless otherwise specified. Moreover, unless otherwise specified, the numbers of each process step are only convenient tools for identifying each process step, rather than limiting the arrangement order of each process step or the scope of the present invention that can be implemented. The change or adjustment of their relative relationship, without substantial change in technical content, should also be regarded as the scope that the present invention can be implemented.

[0081] In the following embodiments, the reagents, materials and instruments used, if not specifically stated, can all be obtained commercially.

[0082] Example 1

[0083] Industrial hydrogen-containing gas (with a CO content of 40 vol%, a CH4 content of 10 vol%, a H2 content of 50 vol%, and a pressure of 0.1 MPa) is mixed and reacted with γ-valerolactone (with a concentration of 16.7 wt% and a solvent of 1,4-dioxane) in a hydrogenation reactor 3, where the hydrogenation reactor 3 is a kettle reactor filled with a Cu / SiO2 catalyst, with a Cu mass fraction of 30% and the rest being SiO2. Before use, the Cu / SiO2 catalyst is activated under a H2 atmosphere at 250 °C. The reaction is carried out at 180 °C for 1 hour to obtain tail gas (with a H2 content ratio of 43.1 vol%, a CH4 content of 11 vol%, and a CO content of 45.9 vol%) and a hydrogen storage liquid. By adjusting the valerolactone concentration, the crude hydrogen pressure, and the reaction time, its conversion rate, the corresponding hydrogen storage capacity, and the carbon-hydrogen ratio in the tail gas can be adjusted.

[0084] The hydrogen storage liquid is dehydrogenated in a dehydrogenation reactor 6 filled with a Cu / SiO2 catalyst, with a Cu mass fraction of 30% and the rest being SiO2. Before use, the Cu / SiO2 catalyst is activated under a H2 atmosphere at 250 °C. After the reaction at 200 °C for 1 hour, tail gas (with a H2 content ratio of 99 vol%.) and valerolactone liquid are obtained. By adjusting the flow rate of the hydrogen storage liquid and the reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0085] Example 2

[0086] Industrial hydrogen-containing gas (with a CO content of 25 vol%, a CO2 content of 25 vol%, a H2 content of 50 vol%, and a total pressure of 6 MPa) and δ-valerolactone (with a concentration of 33.4 wt% and a solvent of tetrahydrofuran) are mixed and reacted in a hydrogenation reactor 3, where the hydrogenation reactor 3 is a fixed-bed reactor filled with a Cu / SiO2-ZrO2 catalyst, with a Cu mass fraction of 10% and the rest being 45 wt% SiO2 and 45 wt% ZrO2 (the mass ratio of the two oxides is 1:1). The upper and lower voids are filled with quartz sand. Before use, the Cu / SiO2-ZrO2 catalyst is activated under a H2 atmosphere at 250 °C. The reaction is carried out at 140 °C to obtain tail gas (with a H2 content ratio of 46.3 vol%, a CO content of 27.7 vol%, and a CO2 content of 26 vol%) and a hydrogen storage liquid. By adjusting the valerolactone concentration, the crude hydrogen pressure, and the reaction time, its conversion rate, the corresponding hydrogen storage capacity, and the carbon-hydrogen ratio in the tail gas can be adjusted.

[0087] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / SiO2-ZrO2 catalyst, where the mass fraction of Cu is 10%, and the rest is 45wt% SiO2 and 45wt% ZrO2. Before use, the Cu / SiO2-ZrO2 catalyst is activated under the conditions of H2 atmosphere and 250°C. After reacting at 140°C for 1 hour, tail gas (the proportion of H2 content is 99vol%.) and valerolactone liquid are obtained. The conversion rate and hydrogen production rate can be adjusted by adjusting the flow rate of the hydrogen storage liquid and the reaction time.

[0088] Example 3

[0089] Industrial hydrogen-containing gas (where the CO content is 95vol%, the H2 content is 5vol%, and the pressure is 5MPa) and δ-valerolactone (the concentration is 16.7wt%, and the solvent is 1,4-dioxane) are mixed and reacted in the hydrogenation reactor 3, where the hydrogenation reactor 3 is a kettle reactor filled with Cu / ZnO catalyst, where the mass fraction of Cu is 70%, and the rest is ZnO. Before use, the Cu / ZnO catalyst is activated under the conditions of H2 atmosphere and 250°C. Reacting at 200°C for 2 hours, tail gas (the proportion of H2 content is 3.3vol%, and the CO content is 96.7vol%) and hydrogen storage liquid are obtained. The conversion rate, the corresponding hydrogen storage amount, and the carbon-hydrogen ratio in the tail gas can be adjusted by adjusting the valerolactone concentration, the crude hydrogen pressure, and the reaction time.

[0090] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / SiO2 catalyst, where the mass fraction of Cu is 30%, and the rest is SiO2. Before use, the Cu / SiO2 catalyst is activated under the conditions of H2 atmosphere and 250°C. After reacting at 160°C for 3 hours, tail gas (the proportion of H2 content is 99vol%.) and valerolactone liquid are obtained. The conversion rate and hydrogen production rate can be adjusted by adjusting the flow rate of the hydrogen storage liquid and the reaction time.

[0091] Example 4

[0092] Industrial hydrogen-containing gas (with a CO content of 20 vol%, a CO2 content of 15 vol%, a CH4 content of 15 vol%, a H2 content of 50 vol%, and a pressure of 10 MPa) and γ-valerolactone (with a concentration of 33.4 wt% and a solvent of dodecane) are mixed and reacted in a hydrogenation reactor 3, where the hydrogenation reactor 3 is a fixed-bed reactor filled with a Cu / SiO2-ZrO2 catalyst, with a Cu mass fraction of 10%, and the rest being 45 wt% SiO2 and 45 wt% ZrO2 (the mass ratio of the two oxides is 1:1), and the voids on its upper and lower sides are filled with quartz sand. Before use, the Cu / SiO2-ZrO2 catalyst is activated under a H2 atmosphere at 250 °C. The reaction is carried out at 160 °C to obtain tail gas (with a H2 content ratio of 45.2 vol%, a CO content of 22 vol%, a CO2 content of 16.4 vol%, and a CH4 content of 16.4 vol%) and a hydrogen storage liquid. By adjusting the valerolactone concentration, the crude hydrogen pressure, and the reaction time, the conversion rate, the corresponding hydrogen storage capacity, and the carbon-hydrogen ratio in the tail gas can be adjusted.

[0093] The hydrogen storage liquid is dehydrogenated in a dehydrogenation reactor 6 filled with a Cu / SiO2-ZrO2 catalyst, with a Cu mass fraction of 10%, and the rest being 45 wt% SiO2 and 45 wt% ZrO2. Before use, the Cu / SiO2-ZrO2 catalyst is activated under a H2 atmosphere at 250 °C. After reacting at 200 °C for 3 hours, tail gas (with a H2 content ratio of 99 vol%.) and valerolactone liquid are obtained. By adjusting the hydrogen storage liquid flow rate and the reaction time, the conversion rate and the hydrogen production rate can be adjusted.

[0094] Example 5

[0095] Industrial hydrogen-containing gas (with a CO content of 50 vol%, an H₂ content of 50 vol%, and a pressure of 8 MPa) is mixed and reacted with δ-valerolactone (with a concentration of 16.7 wt% and ethanol as the solvent) in a hydrogenation reactor 3. The hydrogenation reactor 3 is a stirred-tank reactor filled with a Cu / Al₂O₃-ZrO₂ catalyst, where the mass fraction of Cu is 30%, and the rest is 35 wt% Al₂O₃ and 35 wt% ZrO₂. Before use, the Cu / Al₂O₃-ZrO₂ catalyst is activated under a H₂ atmosphere at 250 °C. The reaction is carried out at 180 °C for 1 hour to obtain tail gas (with an H₂ content ratio of 43.1 vol% and a CO content of 56.9 vol%) and a hydrogen storage liquid. The above-obtained tail gas is input as a reaction gas into the next reaction kettle and mixed and reacted with δ-valerolactone (with a concentration of 16.7 wt% and ethanol as the solvent) in the hydrogenation reactor 3. The activated Cu / Al₂O₃-ZrO₂ catalyst is filled, and the reaction is carried out at 180 °C for 1 hour to obtain tail gas (with an H₂ content ratio of 39.1 vol% and a CO content of 60.9 vol%) and a hydrogen storage liquid. By adjusting the valerolactone concentration, crude hydrogen pressure, and reaction time, its conversion rate and corresponding hydrogen storage capacity can be adjusted. By controlling the number of reaction times experienced by the hydrogen-deficient tail gas, the gas concentration can be adjusted and the gas can be separated.

[0096] The hydrogen storage liquid is dehydrogenated in a dehydrogenation reactor 6 filled with a Cu / SiO₂-ZrO₂ catalyst, where the mass fraction of Cu is 10%, and the rest is 45 wt% SiO₂ and 45 wt% ZrO₂. Before use, the Cu / SiO₂-ZrO₂ catalyst is activated under a H₂ atmosphere at 250 °C. After reacting at 200 °C for 3 hours, tail gas (with an H₂ content ratio of 99 vol%.) and valerolactone liquid are obtained. By adjusting the hydrogen storage liquid flow rate and reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0097] Example 6

[0098] Industrial hydrogen-containing gas (with a CO content of 50 vol%, an H₂ content of 50 vol%, and a pressure of 6 MPa) is mixed and reacted with γ-valerolactone (with a concentration of 50 wt% and 1,4-dioxane as the solvent) in a hydrogenation reactor 3. The hydrogenation reactor 3 is a stirred-tank reactor filled with a Cu / ZrO₂ catalyst, where the mass fraction of Cu is 10%, and the rest is ZrO₂. Before use, the Cu / ZrO₂ catalyst is activated under a H₂ atmosphere at 250 °C. The reaction is carried out at 200 °C for 1 hour to obtain tail gas (with an H₂ content ratio of 44.1 vol% and a CO content of 55.9 vol%) and a hydrogen storage liquid. By adjusting the valerolactone concentration, crude hydrogen pressure, and reaction time, its conversion rate, corresponding hydrogen storage capacity, and the carbon-hydrogen ratio in the tail gas can be adjusted.

[0099] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / SiO2-ZrO2 catalyst, where the mass fraction of Cu is 10%, and the rest are 45wt% SiO2 and 45wt% ZrO2. Before use, the Cu / SiO2-ZrO2 catalyst is activated under the conditions of H2 atmosphere and 250°C. After reacting at 200°C for 1 hour, tail gas (the proportion of H2 content is 99vol%.) and valerolactone liquid are obtained. By adjusting the flow rate of the hydrogen storage liquid and the reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0100] Example 7

[0101] Industrial hydrogen-containing gas (where the CO content is 35vol%, the H2 content is 65vol%, and the pressure is 3MPa) is mixed and reacted with δ-valerolactone (the concentration is 16.7wt%, and the solvent is ethanol) in the hydrogenation reactor 3. The hydrogenation reactor 3 is a kettle reactor filled with Cu / MgO catalyst, where the mass fraction of Cu is 70%, and the rest is MgO. Before use, the Cu / MgO catalyst is activated under the conditions of H2 atmosphere and 250°C. Reacting at 200°C for 2 hours, tail gas (the proportion of H2 content is 55.6vol%, and the CO content is 44.4vol%) and hydrogen storage liquid are obtained. By adjusting the valerolactone concentration, the crude hydrogen pressure and the reaction time, its conversion rate, the corresponding hydrogen storage capacity and the carbon-hydrogen ratio in the tail gas can be adjusted.

[0102] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / SiO2-ZrO2 catalyst, where the mass fraction of Cu is 10%, and the rest are 45wt% SiO2 and 45wt% ZrO2. Before use, the Cu / SiO2-ZrO2 catalyst is activated under the conditions of H2 atmosphere and 250°C. After reacting at 140°C for 20 hours, tail gas (the proportion of H2 content is 99vol%.) and valerolactone liquid are obtained. By adjusting the flow rate of the hydrogen storage liquid and the reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0103] Example 8

[0104] Industrial hydrogen-containing gas (where the CO content is 95vol%, the H2 content is 5vol%, and the pressure is 10MPa) is mixed and reacted with γ-valerolactone (the concentration is 100wt%) in the hydrogenation reactor 3. The hydrogenation reactor 3 is a kettle reactor filled with Cu / Cr2O3 catalyst, where the mass fraction of Cu is 50%, and the rest is Cr2O3. Before use, the Cu / Cr2O3 catalyst is activated under the conditions of H2 atmosphere and 250°C. Reacting at 200°C for 1 hour, tail gas (the proportion of H2 content is 3.0vol%, and the CO content is 97.0vol%) and hydrogen storage liquid are obtained. By adjusting the valerolactone concentration, the crude hydrogen pressure and the reaction time, its conversion rate, the corresponding hydrogen storage capacity and the carbon-hydrogen ratio in the tail gas can be adjusted.

[0105] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / Cr₂O₃ catalyst, where the mass fraction of Cu is 50%, and the rest is Cr₂O₃. Before use, the Cu / Cr₂O₃ catalyst is activated under the conditions of H₂ atmosphere and 250 °C. After reacting at 200 °C for 2 hours, tail gas (the proportion of H₂ content is 99 vol%.) and valerolactone liquid are obtained. The conversion rate and hydrogen production rate can be adjusted by regulating the flow rate of the hydrogen storage liquid and the reaction time.

[0106] Example 9

[0107] Industrial hydrogen-containing gas (where the CO content is 95 vol%, the H₂ content is 5 vol%, and the pressure is 3 MPa) is mixed and reacted with γ-valerolactone (the concentration is 33.4 wt%, and the solvent is glycerol) in the hydrogenation reactor 3. The hydrogenation reactor 3 is a kettle reactor filled with Cu / ZnO catalyst, where the mass fraction of Cu is 70%, and the rest is ZnO. Before use, the Cu / ZnO catalyst is activated under the conditions of H₂ atmosphere and 250 °C. Reacting at 200 °C for 2 hours, tail gas (the proportion of H₂ content is 2.2 vol%, and the CO content is 97.8 vol%) and hydrogen storage liquid are obtained. The conversion rate, the corresponding hydrogen storage amount, and the carbon-hydrogen ratio in the tail gas can be adjusted by regulating the valerolactone concentration, the crude hydrogen pressure, and the reaction time.

[0108] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / Cr₂O₃ catalyst, where the mass fraction of Cu is 50%, and the rest is Cr₂O₃. Before use, the Cu / Cr₂O₃ catalyst is activated under the conditions of H₂ atmosphere and 250 °C. After reacting at 200 °C for 1 hour, tail gas (the proportion of H₂ content is 99 vol%.) and valerolactone liquid are obtained. The conversion rate and hydrogen production rate can be adjusted by regulating the flow rate of the hydrogen storage liquid and the reaction time.

[0109] Example 10

[0110] Industrial hydrogen-containing gas (where the CO content is 95 vol%, the H₂ content is 5 vol%, and the pressure is 6 MPa) is mixed and reacted with γ-valerolactone (the concentration is 33.4 wt%, and the solvent is ethanol) in the hydrogenation reactor 3. The hydrogenation reactor 3 is a kettle reactor filled with Cu / ZnO-Cr₂O₃ catalyst, where the mass fraction of Cu is 70%, and the rest is 15 wt% ZnO and 15 wt% Cr₂O₃. Before use, the Cu / ZnO-Cr₂O₃ catalyst is activated under the conditions of H₂ atmosphere and 250 °C. Reacting at 200 °C for 2 hours, tail gas (the proportion of H₂ content is 2.9 vol%, and the CO content is 97.1 vol%) and hydrogen storage liquid are obtained. The conversion rate, the corresponding hydrogen storage amount, and the carbon-hydrogen ratio in the tail gas can be adjusted by regulating the valerolactone concentration, the crude hydrogen pressure, and the reaction time.

[0111] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / Cr₂O₃ catalyst, where the mass fraction of Cu is 50%, and the rest is Cr₂O₃. Before use, the Cu / Cr₂O₃ catalyst is activated under the conditions of H₂ atmosphere and 250 °C. After reacting at 200 °C for 2 hours, tail gas (the proportion of H₂ content is 99 vol%.) and valerolactone liquid are obtained. The conversion rate and hydrogen production rate can be adjusted by regulating the flow rate of the hydrogen storage liquid and the reaction time.

[0112] Example 11

[0113] Industrial hydrogen-containing gas (where the CO content is 35 vol%, the H₂ content is 65 vol%, and the pressure is 8 MPa) is mixed and reacted with γ-valerolactone (the concentration is 16.7 wt%, and the solvent is methanol) in the hydrogenation reactor 3. The hydrogenation reactor 3 is a kettle reactor filled with Cu / Cr₂O₃-ZrO₂ catalyst, where the mass fraction of Cu is 30%, and the rest is 35 wt% Cr₂O₃ and 35 wt% ZrO₂. Before use, the Cu / Cr₂O₃-ZrO₂ catalyst is activated under the conditions of H₂ atmosphere and 250 °C. React at 200 °C for 10 hours to obtain tail gas (the proportion of H₂ content is 40.1 vol%, and the CO content is 59.9 vol%) and hydrogen storage liquid. The above-obtained tail gas is input into the next reaction kettle as the reaction gas and mixed and reacted with γ-valerolactone (the concentration is 16.7 wt%, and the solvent is methanol) in the hydrogenation reactor 3. After filling with the activated Cu / Cr₂O₃-ZrO₂ catalyst and reacting at 200 °C for 10 hours, tail gas (the proportion of H₂ content is 30.1 vol%, and the CO content is 69.9 vol%) and hydrogen storage liquid are obtained. The conversion rate and the corresponding hydrogen storage amount can be adjusted by regulating the valerolactone concentration, the crude hydrogen pressure, and the reaction time. The gas concentration can be adjusted and the gas can be separated by controlling the number of reaction times that the hydrogen-deficient tail gas experiences.

[0114] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / Cr₂O₃ catalyst, where the mass fraction of Cu is 50%, and the rest is Cr₂O₃. Before use, the Cu / Cr₂O₃ catalyst is activated under the conditions of H₂ atmosphere and 250 °C. After reacting at 200 °C for 2 hours, tail gas (the proportion of H₂ content is 99 vol%.) and valerolactone liquid are obtained. The conversion rate and hydrogen production rate can be adjusted by regulating the flow rate of the hydrogen storage liquid and the reaction time.

[0115] Example 12

[0116] Industrial hydrogen-containing gas (with a CO content of 50 vol%, an H2 content of 50 vol%, and a pressure of 6 MPa) is mixed and reacted with δ-valerolactone (concentration of 33.4 wt%, solvent is 1,4-dioxane) in a hydrogenation reactor 3, where the hydrogenation reactor 3 is a kettle reactor filled with a Cu / ZrO2 catalyst, with a Cu mass fraction of 50% and the remaining 50 wt% being ZrO2. Before use, the Cu / ZrO2 catalyst is activated under a H2 atmosphere at 250 °C. React at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 37.0 vol%, CO content is 63.0 vol%) and a hydrogen storage liquid.

[0117] The above-obtained tail gas is used as a reaction gas and input into the next reaction kettle, where it is mixed and reacted with γ-valerolactone (concentration of 33.4 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst (the same as the previous reaction device) is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 27.5 vol%, CO content is 72.5 vol%) and a hydrogen storage liquid.

[0118] Continue to use the above-obtained tail gas as a reaction gas and input it into the next reaction kettle, where it is mixed and reacted with δ-valerolactone (concentration of 33.4 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 20.0 vol%, CO content is 80.0 vol%) and a hydrogen storage liquid.

[0119] Continue to use the above-obtained tail gas as a reaction gas and input it into the next reaction kettle, where it is mixed and reacted with δ-valerolactone (concentration of 33.4 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 13.0 vol%, CO content is 87.0 vol%) and a hydrogen storage liquid.

[0120] Continue to use the above-obtained tail gas as a reaction gas and input it into the next reaction kettle, where it is mixed and reacted with δ-valerolactone (concentration of 33.4 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 8.5 vol%, CO content is 91.5 vol%) and a hydrogen storage liquid.

[0121] Continue to input the above-obtained tail gas as the reaction gas into the next reaction kettle, mix and react it with δ-valerolactone (concentration is 33.4 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3, charge the activated Cu / ZrO2 catalyst, and react at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 6.5 vol%, CO content is 93.5 vol%) and hydrogen storage liquid.

[0122] Continue to input the above-obtained tail gas as the reaction gas into the next reaction kettle, mix and react it with δ-valerolactone (concentration is 33.4 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3, charge the activated Cu / ZrO2 catalyst, and react at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 4.2 vol%, CO content is 95.8 vol%) and hydrogen storage liquid.

[0123] Continue to input the above-obtained tail gas as the reaction gas into the next reaction kettle, mix and react it with δ-valerolactone (concentration is 33.4 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3, charge the activated Cu / ZrO2 catalyst, and react at 200 °C for 1 hour to obtain tail gas (H2 content accounts for 1.7 vol%, CO content is 98.3 vol%) and hydrogen storage liquid.

[0124] The CO proportion can be adjusted from 50.0 vol% to 98.3 vol% through 8 consecutive processes (a total of 8 hours). By controlling the number of reaction times that the hydrogen-deficient tail gas experiences, the gas concentration can be adjusted and the gas can be separated.

[0125] The hydrogen storage liquid is dehydrogenated in the dehydrogenation reactor 6 filled with the Cu / Cr2O3 catalyst, where the mass fraction of Cu is 50%, and the rest is Cr2O3. The Cu / Cr2O3 catalyst is activated in a H2 atmosphere at 250 °C before use. After reacting at 200 °C for 2 hours, tail gas (H2 content accounts for 99 vol%.) and valerolactone liquid are obtained. By adjusting the flow rate of the hydrogen storage liquid and the reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0126] Example 13

[0127] Industrial hydrogen-containing gas (with a CO content of 50 vol%, an H2 content of 50 vol%, and a pressure of 6 MPa) is mixed and reacted with γ-valerolactone (concentration of 16.7 wt%, solvent is 1,4-dioxane) in a hydrogenation reactor 3, where the hydrogenation reactor 3 is a stirred tank reactor filled with a Cu / ZrO2 catalyst, with a Cu mass fraction of 30% and the remaining 70 wt% being ZrO2. Before use, the Cu / ZrO2 catalyst is activated under a H2 atmosphere at 250 °C. The reaction is carried out at 200 °C for 1 hour to obtain tail gas (with an H2 content ratio of 32.7 vol% and a CO content of 67.3 vol%) and a hydrogen storage liquid.

[0128] The above-obtained tail gas is input as a reaction gas into the next reaction kettle, where it is mixed and reacted with γ-valerolactone (concentration of 16.7 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst (the same as in the previous reaction device) is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (with an H2 content ratio of 28.7 vol% and a CO content of 71.3 vol%) and a hydrogen storage liquid.

[0129] Continue to input the above-obtained tail gas as a reaction gas into the next reaction kettle, where it is mixed and reacted with γ-valerolactone (concentration of 16.7 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (with an H2 content ratio of 23.6 vol% and a CO content of 76.4 vol%) and a hydrogen storage liquid.

[0130] Continue to input the above-obtained tail gas as a reaction gas into the next reaction kettle, where it is mixed and reacted with γ-valerolactone (concentration of 16.7 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (with an H2 content ratio of 20.0 vol% and a CO content of 80.0 vol%) and a hydrogen storage liquid.

[0131] Continue to input the above-obtained tail gas as a reaction gas into the next reaction kettle, where it is mixed and reacted with γ-valerolactone (concentration of 16.7 wt%, solvent is 1,4-dioxane) in the hydrogenation reactor 3. The activated Cu / ZrO2 catalyst is filled, and the reaction is carried out at 200 °C for 1 hour to obtain tail gas (with an H2 content ratio of 15.5 vol% and a CO content of 84.5 vol%) and a hydrogen storage liquid.

[0132] Continue to input the above-obtained tail gas as the reaction gas into the next reaction kettle, mix and react it with γ-valerolactone (concentration: 16.7 wt%, solvent: 1,4-dioxane) in the hydrogenation reactor 3. Load the activated Cu / ZrO₂ catalyst and react at 200 °C for 1 hour to obtain tail gas (H₂ content: 10.4 vol%, CO content: 89.6 vol%) and hydrogen storage liquid.

[0133] Continue to input the above-obtained tail gas as the reaction gas into the next reaction kettle, mix and react it with γ-valerolactone (concentration: 16.7 wt%, solvent: 1,4-dioxane) in the hydrogenation reactor 3. Load the activated Cu / ZrO₂ catalyst and react at 200 °C for 1 hour to obtain tail gas (H₂ content: 5.9 vol%, CO content: 94.1 vol%) and hydrogen storage liquid.

[0134] Continue to input the above-obtained tail gas as the reaction gas into the next reaction kettle, mix and react it with γ-valerolactone (concentration: 16.7 wt%, solvent: 1,4-dioxane) in the hydrogenation reactor 3. Load the activated Cu / ZrO₂ catalyst and react at 200 °C for 1 hour to obtain tail gas (H₂ content: 5.0 vol%, CO content: 95.0 vol%) and hydrogen storage liquid.

[0135] The CO proportion can be adjusted from 50.0 vol% to 95.0 vol% through 8 consecutive processes (8 hours in total). By controlling the number of reactions that the hydrogen-deficient tail gas undergoes, the gas concentration can be adjusted and the gas can be separated.

[0136] The hydrogen storage liquid is dehydrogenated in the dehydrogenation reactor 6 loaded with the Cu / Al₂O₃ catalyst, where the mass fraction of Cu is 50% and the rest is Al₂O₃. The Cu / Al₂O₃ catalyst is activated under the conditions of H₂ atmosphere and 250 °C before use. After reacting at 200 °C for 2 hours, tail gas (H₂ content: 99 vol%.) and valerolactone liquid are obtained. By adjusting the flow rate of the hydrogen storage liquid and the reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0137] Example 14

[0138] Industrial hydrogen-containing gas (with a CO content of 50 vol%, an H2 content of 50 vol%, and a pressure of 6 MPa) is mixed and reacted with δ-valerolactone (with a concentration of 16.7 wt% and a solvent of tetrahydrofuran) in a hydrogenation reactor 3, where the hydrogenation reactor 3 is a stirred tank reactor filled with a Cu / ZnO-ZrO2 catalyst, with a Cu mass fraction of 30%, and the rest being 35 wt% ZnO and 35 wt% ZrO2. Before use, the Cu / ZnO-ZrO2 catalyst is activated under a H2 atmosphere at 250 °C. The reaction is carried out at 200 °C for 2 hours to obtain tail gas (with an H2 content ratio of 33.5 vol% and a CO content of 66.5 vol%) and a hydrogen storage liquid.

[0139] The above-obtained tail gas is used as the reaction gas and input into the next reaction kettle, where it is mixed and reacted with δ-valerolactone (with a concentration of 16.7 wt% and a solvent of tetrahydrofuran) in the hydrogenation reactor 3. The activated Cu / ZnO-ZrO2 catalyst (same as the previous reaction device) is filled, and the reaction is carried out at 200 °C for 2 hours to obtain tail gas (with an H2 content ratio of 26.3 vol% and a CO content of 73.7 vol%) and a hydrogen storage liquid.

[0140] Continue to use the above-obtained tail gas as the reaction gas and input it into the next reaction kettle, where it is mixed and reacted with δ-valerolactone (with a concentration of 16.7 wt% and a solvent of tetrahydrofuran) in the hydrogenation reactor 3. The activated Cu / ZnO-ZrO2 catalyst (same as the previous reaction device) is filled, and the reaction is carried out at 200 °C for 2 hours to obtain tail gas (with an H2 content ratio of 20.2 vol% and a CO content of 79.8 vol%) and a hydrogen storage liquid.

[0141] Continue to use the above-obtained tail gas as the reaction gas and input it into the next reaction kettle, where it is mixed and reacted with δ-valerolactone (with a concentration of 16.7 wt% and a solvent of tetrahydrofuran) in the hydrogenation reactor 3. The activated Cu / ZnO-ZrO2 catalyst (same as the previous reaction device) is filled, and the reaction is carried out at 200 °C for 2 hours to obtain tail gas (with an H2 content ratio of 15.0 vol% and a CO content of 75.0 vol%) and a hydrogen storage liquid.

[0142] Continue to use the above-obtained tail gas as the reaction gas and input it into the next reaction kettle, where it is mixed and reacted with δ-valerolactone (with a concentration of 16.7 wt% and a solvent of tetrahydrofuran) in the hydrogenation reactor 3. The activated Cu / ZnO-ZrO2 catalyst (same as the previous reaction device) is filled, and the reaction is carried out at 200 °C for 2 hours to obtain tail gas (with an H2 content ratio of 9.8 vol% and a CO content of 90.2 vol%) and a hydrogen storage liquid.

[0143] The CO proportion can be adjusted from 50.0 vol% to 90.2 vol% through 5 consecutive processes (10 hours in total). By controlling the number of reactions experienced by the hydrogen-deficient tail gas, the gas concentration can be adjusted and the gas can be separated.

[0144] The hydrogen storage liquid dehydrogenates in the dehydrogenation reactor 6 filled with Cu / Al2O3 catalyst, where the mass fraction of Cu is 50%, and the rest is Al2O3. Before use, the Cu / Al2O3 catalyst is activated under the conditions of H2 atmosphere and 250 °C. After reacting at 200 °C for 2 hours, tail gas (the proportion of H2 content is 99 vol%.) and valerolactone liquid are obtained. By adjusting the flow rate of the hydrogen storage liquid and the reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0145] Comparative Example 1

[0146] Comparing the first step of the hydrogen storage separation reaction process in Example 12, industrial hydrogen-containing gas (where the CO content is 50 vol%, the H2 content is 50 vol%, and the pressure is 6 MPa) is mixed and reacted with γ-butyrolactone (concentration is 33.4 wt%, and the solvent is 1,4-dioxane) in the hydrogenation reactor 3. The hydrogenation reactor 3 is a kettle reactor filled with Cu / ZrO2 catalyst, where the mass fraction of Cu is 50%, and the rest is 50 wt% ZrO2. Before use, the Cu / ZrO2 catalyst is activated under the conditions of H2 atmosphere and 250 °C. Reacting at 200 °C for 1 hour, tail gas (the proportion of H2 content is 47.7 vol%, and the CO content is 52.3 vol%) and hydrogen storage liquid are obtained. The conversion rate of γ-butyrolactone in the hydrogen storage liquid is 7.6%, while the conversion rate of valerolactone in the δ-valerolactone hydrogen storage system can reach 52.7% under the same reaction conditions. Although the conversion rate and the corresponding hydrogen storage amount can be adjusted by adjusting the concentration of butyrolactone, the pressure of crude hydrogen, and the reaction time, the conversion efficiency of butyrolactone is significantly lower than that of the δ-valerolactone system under the same reaction conditions.

[0147] The hydrogen storage liquid produced by the above butyrolactone can dehydrogenate in the dehydrogenation reactor 6 filled with Cu / Cr2O3 catalyst, where the mass fraction of Cu is 50%, and the rest is Cr2O3. Before use, the Cu / Cr2O3 catalyst is activated under the conditions of H2 atmosphere and 250 °C. After reacting at 200 °C for 2 hours, tail gas (the proportion of H2 content is 99 vol%.) and butyrolactone liquid are obtained. Among them, by adjusting the flow rate of the hydrogen storage liquid and the reaction time, its conversion rate and hydrogen production rate can be adjusted.

[0148] Comparative Example 2

[0149] For the first step of the hydrogen storage separation reaction process in Comparative Example 14, an industrial hydrogen-containing gas (with a CO content of 50 vol%, an H2 content of 50 vol%, and a pressure of 6 MPa) is mixed and reacted with γ-butyrolactone (concentration of 16.7 wt%, solvent is tetrahydrofuran) in a hydrogenation reactor 3, where the hydrogenation reactor 3 is a stirred tank reactor filled with a Cu / ZnO-ZrO2 catalyst, with the Cu mass fraction being 30%, and the rest being 35 wt% ZnO and 35 wt% ZrO2. Before use, the Cu / ZnO-ZrO2 catalyst is activated under a H2 atmosphere at 250 °C. The reaction is carried out at 200 °C for 2 hours to obtain tail gas (H2 content accounts for 43.3 vol%, CO content is 56.7 vol%) and a hydrogen storage liquid. The conversion rate of γ-butyrolactone in the hydrogen storage liquid is 35.5%, while under the same reaction conditions, the conversion rate of valerolactone in the δ-valerolactone hydrogen storage system can reach 74.4%. Although the conversion rate and the corresponding hydrogen storage capacity can be adjusted by adjusting the concentration of butyrolactone, the pressure of crude hydrogen, and the reaction time, the conversion efficiency of butyrolactone is significantly lower than that of the δ-valerolactone system under the same reaction conditions.

[0150] The hydrogen storage liquid produced by the above butyrolactone can be dehydrogenated in a dehydrogenation reactor 6 filled with a Cu / Al2O3 catalyst, with the Cu mass fraction being 50% and the rest being Al2O3. Before use, the Cu / Al2O3 catalyst is activated under a H2 atmosphere at 250 °C. After reacting at 200 °C for 2 hours, tail gas (H2 content accounts for 99 vol%.) and butyrolactone liquid are obtained. Among them, the conversion rate and hydrogen production rate can be adjusted by adjusting the flow rate of the hydrogen storage liquid and the reaction time.

[0151] The above description of the embodiments is for the convenience of those of ordinary skill in the art to understand and apply the present application. Those skilled in the art can obviously make various modifications to these embodiments easily and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present application is not limited to the embodiments herein, and the improvements and modifications made by those skilled in the art within the scope and spirit of the present application disclosed are within the scope of the present application.

Claims

1. A method for separating and purifying industrial hydrogen-containing gas, characterized in that, It includes the following steps: Carry out one-step or multi-step catalytic hydrogenation reaction on industrial hydrogen-containing gas containing impurity gas and valerolactone in the presence of a Cu-based catalyst to provide pentanediol capable of storing hydrogen, separate hydrogen and impurity gas in the industrial hydrogen-containing gas; catalytically dehydrogenate the pentanediol to provide hydrogen; wherein, the impurity gas at least includes CO.

2. The method for separating and purifying industrial hydrogen-containing gas according to claim 1, characterized in that, The volume concentration of impurity gas CO in the industrial hydrogen-containing gas is 0.1% - 95%.

3. The method for separating and purifying industrial hydrogen-containing gas according to claim 1, characterized in that, It also includes any one or more of the following features: A1) The valerolactone is selected from γ-valerolactone and / or δ-valerolactone; A2) The concentration of the valerolactone is 16.7 wt% - 100 wt%; A3) The temperature of the catalytic hydrogenation reaction is 140°C - 200°C; the reaction pressure is 0.1 MPa - 10 MPa; A4) The purity of the hydrogen obtained by catalytically dehydrogenating the pentanediol is ≥99 vol%.

4. The method for separating and purifying industrial hydrogen-containing gas according to claim 3, characterized in that, The reaction formulas of the catalytic hydrogenation and catalytic dehydrogenation are:

5. The method for separating and purifying industrial hydrogen-containing gas according to claim 3, characterized in that, The temperature of the catalytic dehydrogenation reaction is 140°C - 200°C, and the reaction pressure is 0.1 MPa - 5 MPa.

6. The method for separating and purifying industrial hydrogen-containing gas according to claim 1, characterized in that, The Cu-based catalyst includes Cu and a carrier, and the mass ratio of Cu to the carrier is (10 - 70):(30 - 90).

7. The method for separating and purifying industrial hydrogen-containing gas according to claim 6, characterized in that, The carrier is selected from one or more of SiO2, Cr2O3, ZnO, Al2O3, ZrO2, MgO, etc.

8. An apparatus for the method of separating and purifying industrial hydrogen-containing gas according to any one of claims 1 to 7, characterized in that, The device includes a valerolactone storage tank (1) and a crude hydrogen storage tank (2), and also includes: One-stage or multi-stage hydrogenation reactors (3), each of the hydrogenation reactors (3) is respectively provided with a valerolactone inlet (31), an industrial hydrogen-containing gas inlet (32), a lean hydrogen tail gas outlet (33) and a hydrogenation product outlet (34); the valerolactone storage tank (1) is communicated with the valerolactone inlet (31), and the crude hydrogen storage tank (2) is communicated with the industrial hydrogen-containing gas inlet (32); A lean hydrogen gas storage tank (4), which is communicated with the lean hydrogen tail gas outlet (33) of the last-stage hydrogenation reactor (3); used to collect the gas after one-step or multi-step valerolactone hydrogenation purification; A hydrogen storage liquid storage tank (5), and the hydrogen storage liquid storage tank (5) is communicated with the hydrogenation product outlet (34).

9. The apparatus for the method of separating and purifying industrial hydrogen-containing gas according to claim 8, characterized in that, It also includes a dehydrogenation reactor (6), the dehydrogenation reactor (6) is communicated with the hydrogen storage liquid storage tank (5), the dehydrogenation reactor (6) includes a hydrogen outlet (61) and a valerolactone outlet (62), and the valerolactone outlet (62) is communicated with the valerolactone storage tank (1).

10. The apparatus for the method of separating and purifying industrial hydrogen-containing gas according to claim 8, characterized in that, It also includes any one or more of the following conditions: B1) The concentration of valerolactone in the valerolactone storage tank (1) is 16.7% - 100 wt%; B2) A pressurizing unit (11) and a liquid flow control unit (12) are provided at the outlet of the valerolactone storage tank (1); B3) The crude hydrogen storage tank (2) includes a hydrogen-containing mixed gas inlet (21) for communicating with the hydrogen production section, and a pressure regulating unit (22) is provided at the outlet of the crude hydrogen storage tank (2); B4) The connecting pipelines between the crude hydrogen storage tank (2), the one-stage or multi-stage hydrogenation reactors (3) and the lean hydrogen gas storage tank (4) are connected in series; B5) The γ-valerolactone storage tank (1) is respectively connected to each stage of hydrogenation reactor (3) through γ-valerolactone pipelines, and each of the γ-valerolactone pipelines is connected in parallel; B6) The hydrogenation reactor (3) is a gas series type multiphase catalytic continuous flow reactor or a multiphase catalytic kettle reactor; B7) The hydrogenation reactor (3) is provided with a heating module, a catalyst module, a temperature sensor, a pressure sensor, and a safety relief device; B8) A monitoring unit (7) is connected to the lean hydrogen tail gas outlet (33) and the hydrogenation product outlet (34) of each stage of the hydrogenation reactor (3); B9) The intermediate gas pipeline of each stage of the hydrogenation reactor (3) is connected to a pressure swing unit (8).

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