Reaction type industrial byproduct hydrogen purification system

Abstract

The utility model discloses a reaction type industrial byproduct hydrogen purification system, the purification system comprises a hydrogenation reaction unit, a gas-liquid separation unit and a dehydrogenation reaction unit which are connected in sequence, the input end of the hydrogenation reaction unit is used for inputting a byproduct hydrogen mixture, the hydrogenation reaction unit is filled with a catalyst and a purifying agent, and the gas-liquid separation unit is connected with the dehydrogenation reaction unit. The catalyst is used for carrying out hydrogenation reaction with the byproduct hydrogen mixture to generate a hydrogenation product; the gas-liquid separation unit is used for carrying out gas-liquid separation on the hydrogenated product; the output end of the dehydrogenation reaction unit is used for outputting hydrogen, and the dehydrogenation reaction unit is also filled with a catalyst and a purifying agent and used for carrying out dehydrogenation reaction on a hydrogenation product to generate hydrogen; the hydrogenation reaction unit, the gas-liquid separation unit and the dehydrogenation reaction unit of the purification system disclosed by the utility model realize the collection and separation of hydrogen through chemical reaction, and the system is simple in structure, lower in cost, convenient and applicable.

Description

Technical Field

[0001] The present application relates to the technical field of hydrogen processing, and in particular to a reactive industrial by-product hydrogen purification system. Background Art

[0002] By-product hydrogen refers to hydrogen generated as a by-product in the industrial production process. This hydrogen is not the main target of the production process, but is naturally produced in the process of manufacturing steel, petrochemical products, chemicals, etc. Since by-product hydrogen exists in the coal chemical industry, petrochemical industry, and Fischer-Tropsch synthesis, its purity is relatively low, generally between 85% and 95%, and contains impurities such as CH4, CO, CO2, O2, N2, olefins, NOx, etc., so it is greatly restricted in subsequent applications. For example, it cannot be directly supplied to fuel cells, otherwise it may cause damage to the fuel cells; it cannot be directly supplied to many chemical processes, and many impurities contained therein may affect the reaction process or cause the product purity to decrease. Therefore, in production, by-product hydrogen is often used as heating fuel or directly burned, resulting in a huge waste of resources.

[0003] In the prior art, the purification methods for by-product hydrogen include cryogenic separation, cryogenic adsorption, pressure swing adsorption, cryogenic absorption, membrane separation and chemical reaction. Each of these purification methods has its own advantages and disadvantages, either because of high cost, large equipment, or because of complex system, high regeneration energy consumption, etc. At present, there are different methods and equipment for purifying by-product hydrogen. For example, a Chinese patent with publication number CN116177493A and titled "A method for deep purification of industrial by-product hydrogen" proposes a method for purifying by-product hydrogen that combines the above-mentioned various purification methods. By combining different purification methods, impurities in by-product hydrogen are gradually separated to obtain hydrogen with higher purity. However, this technology has the problems of cumbersome purification process and high cost, which is not conducive to the efficiency of inputting by-product hydrogen into the regeneration cycle, and the purification process cannot be effectively simplified to cope with the continuous need for by-product hydrogen input. Utility Model Content

[0004] The main purpose of the present application is to provide a reactive by-product hydrogen purification system, which aims to solve the complex and high-cost technical problems caused by the need to improve the purity of existing by-product hydrogen purification methods or equipment.

[0005] To achieve the above-mentioned purpose, the present application proposes a reactive industrial by-product hydrogen purification system, characterized in that the purification system comprises: a hydrogenation reaction unit, a gas-liquid separation unit and a dehydrogenation reaction unit connected in sequence, wherein:

[0006] The input end of the hydrogenation reaction unit is used to input a by-product hydrogen mixture, and the hydrogenation reaction unit is filled with a catalyst and the purifying agent, and the catalyst and the purifying agent are used to react with the by-product hydrogen mixture to produce a hydrogenated product;

[0007] The gas-liquid separation unit is used to separate the hydrogenation product into gas and liquid;

[0008] The output end of the dehydrogenation reaction unit is used to output hydrogen. The dehydrogenation reaction unit is filled with the catalyst and the purifying agent. The catalyst and the purifying agent are used for the hydrogenation product to undergo a dehydrogenation reaction to generate hydrogen.

[0009] Optionally, the hydrogenation reaction unit includes several hydrogenation reaction vessels, the dehydrogenation reaction unit includes several dehydrogenation reaction vessels, the output ends of the several hydrogenation reaction vessels are connected to the gas-liquid separation unit through a converging valve, and the gas-liquid separation unit is connected to the input ends of the several dehydrogenation reaction vessels through a diverter valve.

[0010] Optionally, the purification system further comprises a waste gas treatment unit, which is connected to the gas-liquid separation unit and processes the gaseous compounds separated by the gas-liquid separation unit.

[0011] Optionally, the exhaust gas treatment unit treats the exhaust gas by RTO, RCO or liquid absorption.

[0012] Optionally, the purification system further comprises a circulation storage unit connected between the hydrogenation reaction unit and the dehydrogenation reaction unit.

[0013] Optionally, the output end of the dehydrogenation reaction unit is further provided with a purity detection unit for detecting the purity of the output hydrogen.

[0014] Optionally, the hydrogenation reaction unit and the dehydrogenation reaction unit are also respectively configured with a temperature detection unit for detecting reaction temperature conditions.

[0015] Optionally, the purification system further comprises a desulfurization unit, the output end of the desulfurization unit is connected to the input end of the hydrogenation reaction unit, and is used for desulfurizing the by-product hydrogen mixture.

[0016] Compared with the existing by-product hydrogen purification methods and equipment systems, the utility model has at least the following beneficial effects: through the hydrogenation reaction unit, the hydrogen in the by-product hydrogen mixture and the unsaturated compound, that is, the purifying agent, undergo an organic chemical reaction under the action of a catalyst, that is, a hydrogenation reaction, to produce a hydrogenated product; through the gas-liquid separation unit, the impurity gas is separated from the hydrogenated product and transferred to the dehydrogenation reaction unit, and the dehydrogenation reaction is again carried out through the purifying agent and the catalyst to produce hydrogen to purify the by-product hydrogen. Compared with the existing by-product hydrogen purification methods or devices, this purification system eliminates the link facilities required for filtering and separating various impurities, and purifies the hydride as the main or only reaction object, breaking through the traditional purification idea of ​​passive separation of impurities to purify the target product, and realizing the active extraction of the target product, simplifying the overall purification system, reducing economic costs, and ensuring purification efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0018] Figure 1 This is a schematic diagram of the structure of an embodiment of the purification system of the utility model;

[0019] Figure 2 This is a schematic structural diagram of another embodiment of the purification system of the utility model;

[0020] Figure 3 This is a schematic structural diagram of another embodiment of the purification system of the utility model;

[0021] Figure numerals: 1. hydrogenation reaction unit; 2. gas-liquid separation unit; 3. dehydrogenation reaction unit; 4. exhaust gas treatment unit; 5. circulation storage unit; 6. purity detection unit; 7. temperature detection unit; 8. desulfurization unit; 9. hydrogenation reaction vessel; 10. dehydrogenation reaction vessel.

[0022] The realization of the purpose, functional features and advantages of the utility model will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0023] The following will be combined with the drawings in the embodiments of the utility model to clearly and completely describe the technical solutions in the embodiments of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model, not all of the embodiments. Based on the embodiments of the utility model, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the utility model.

[0024] It should be noted that all directional indications in the embodiments of the present invention (such as up, down, left, right, front, back...) are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0025] In the present invention, unless otherwise clearly specified and limited, the terms "connection", "fixation", etc. should be understood in a broad sense. For example, "fixation" can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0026] In addition, if there are descriptions involving "first", "second", etc. in the embodiments of the utility model, the descriptions of "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes. Taking "A and / or B" as an example, it includes scheme A, or scheme B, or a scheme that satisfies both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in this field to implement. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the utility model.

[0027] like Figure 1The figure shows a reaction-type industrial by-product hydrogen purification system, which comprises: a hydrogenation reaction unit 1, a gas-liquid separation unit 2 and a dehydrogenation reaction unit 3 connected in sequence, wherein the input end of the hydrogenation reaction unit 1 is used to input a by-product hydrogen mixture, the hydrogenation reaction unit 1 is filled with a catalyst and a purifying agent, the catalyst and the purifying agent are used to react with the by-product hydrogen mixture to produce a hydrogenated product; the gas-liquid separation unit 2 is used to separate the gas and liquid of the hydrogenated product; the output end of the dehydrogenation reaction unit 3 is used to output hydrogen, the dehydrogenation reaction unit 3 is filled with the catalyst and the purifying agent, the catalyst and the purifying agent are used for the hydrogenated product to undergo a dehydrogenation reaction to produce hydrogen.

[0028] As a basic embodiment of the present invention, the simplest structure or unit of the reaction type purification system is provided above, and the hydrogen element or hydrogen gas in the by-product hydrogen mixture is combined and transferred out by the hydrogenation reaction unit 1 and the dehydrogenation reaction unit 3, and the specific process is as follows:

[0029] After the by-product hydrogen mixture is input into the hydrogenation reaction unit 1 through the input end, the hydrogen in the by-product hydrogen mixture reacts with the purifying agent under the action of the catalyst and other reaction conditions (hydrogenation reaction) to generate a hydrogenation product;

[0030] Wherein, the purifying agent can be liquid unsaturated aromatic compounds and mixtures thereof, such as benzene, toluene or mixtures thereof, or liquid unsaturated heterocyclic compounds, such as N-methylindole, N-ethylcarbazole, dimethylindole, 7-methylindole, N-propylcarbazole and mixtures thereof; and the catalyst loaded in the hydrogenation reaction unit 1 can be a granular supported catalyst, whose carrier is activated carbon, alumina or molecular sieve, cordierite and other adsorption materials, and the active component is a metal such as Pd, Pt, Ni or a mixture of the above metals and metal oxides such as NiO, ZnO, MgO, CuO, etc., which can make the selective conversion rate of the addition (hydrogenation) reaction, that is, reacting with hydrogen element or hydrogen gas to generate products, reach a higher level under specific temperature conditions. In this reaction process, other compounds in the impurities still exist in gaseous form because they cannot react with the purifying agent.

[0031] The hydrogenated product enters the gas-liquid separation unit 2, which can perform gas-liquid separation on this part of the mixture. The liquid unsaturated aromatic compounds (mixture) and heterocyclic compounds (mixture) carry hydrogen elements through addition reaction, and other impurities are separated from the hydrogenated product through gas-liquid separation operation.

[0032] The dehydrogenation reaction unit 3 is also loaded with the purifying agent and catalyst as described above. By adjusting the reaction temperature, the reverse process of the addition (hydrogenation) reaction, the dehydrogenation reaction, can be achieved; specifically, the reaction temperature conditions of the addition (hydrogenation) reaction are within 80°C to 150°C, and the reaction temperature conditions of the dehydrogenation reaction are within 130°C to 270°C. Although there is an overlapping range of temperature conditions for the above two reactions, in actual applications, the two reactions should be distinguished based on the selected catalyst conversion efficiency curve. However, it should be understood that the selection of purifying agents and catalysts is not the core invention of the present invention. With the use of these two substances, the purification system provided by the present invention can be simplified.

[0033] It should be noted that for the purification agent, catalyst and its conversion efficiency, reference can be made to the disclosure of the Chinese patent with publication number CN117643897B, entitled "Selective semi-hydrogenation catalyst for N-heterocycle and preparation method thereof" or publication number CN118079969A, entitled "A core-shell type Ru-RuC catalyst and its preparation method and application". It should be understood that this part is preferably used in the present utility model as the prior art.

[0034] The utility model uses a hydrogenation reaction unit 1 to cause the hydrogen in the by-product hydrogen mixture to react with an unsaturated compound, i.e., a purifying agent, under the action of a catalyst to undergo an organic chemical reaction to produce a hydrogenation product; the impurity gas is separated from the hydrogenation product through a gas-liquid separation unit 2 and transferred to a dehydrogenation reaction unit 3, and a dehydrogenation reaction is again carried out through the purifying agent and the catalyst to produce hydrogen to purify the by-product hydrogen. Compared with the existing by-product hydrogen purification methods or devices, the link facilities required for filtering and separating various impurities are omitted, and the hydride is used as the main or only reaction object for purification, breaking through the traditional purification idea of ​​purifying the target product by passive separation of impurities, and realizing the active extraction of the target product, simplifying the overall purification system, reducing economic costs, and ensuring purification efficiency.

[0035] As an implementation method, see Figure 2 The hydrogenation reaction unit 1 includes a plurality of hydrogenation reaction vessels 9, and the dehydrogenation reaction unit 3 includes a plurality of dehydrogenation reaction vessels 10. The output ends of the plurality of hydrogenation reaction vessels 9 are connected to the gas-liquid separation unit 2 through a confluence valve, and the gas-liquid separation unit 2 is connected to the input ends of the plurality of dehydrogenation reaction vessels 10 through a diverter valve.

[0036] In actual use, the source of the by-product hydrogen mixture is not unique, and it may come from multiple equipment or factories. It is very costly to establish a complete purification system specifically for each by-product hydrogen source. Therefore, the hydrogenation reaction unit 1 can be placed in each source point in the form of a hydrogenation reaction container 9 for reaction, and the intermediate products can be concentrated through a converging valve (not shown in the figure), which can effectively reduce the construction cost of the purification system of the utility model and is also conducive to the improvement of economic benefits.

[0037] Similarly, the dehydrogenation reaction unit 3 serves as a hydrogen output unit, and the hydrogen it outputs can be used directly. Therefore, it can also be diverted to various demand points in the form of multiple dehydrogenation reaction vessels 10 through a diverter valve (not shown in the figure). After purification, it can be directly used in hydrogen refueling stations, industrial hydrogen points and other locations, reducing the intermediate transportation cost of hydrogen energy.

[0038] It can be understood that the concepts of the hydrogenation reaction unit 1, the gas-liquid separation unit 2, the dehydrogenation reaction unit 3 and various "units" mentioned later are relative to the "purification system". In application, they can all be realized through specific physical objects. For example, the hydrogenation reaction unit 1, the gas-liquid separation unit 2, and the dehydrogenation reaction unit 3 can all be realized in the form of containers, storage tanks, reactors, etc. that can realize corresponding functions; "connection" can be achieved through pipeline connection.

[0039] As an embodiment, the purification system further includes a waste gas treatment unit 4 , which is connected to the gas-liquid separation unit 2 and processes the gaseous compounds separated by the gas-liquid separation unit 2 .

[0040] The gas-liquid separation unit 2 separates the hydrogenation product and the impurity gas after the reaction and discharges them out of the purification system. In order to prevent the impurity gas from polluting the environment or harming the health of users, a waste gas treatment unit 4 is added to treat the waste gas before discharging it. Optionally, the waste gas treatment unit 4 treats the waste gas by RTO, RCO or liquid absorption.

[0041] Specifically, the treatment method can be selected according to the main impurity gas components in the exhaust gas, such as RTO (Regenerative Thermal Oxidizer)-regenerative thermal incinerator or RCO (Regenerative Catalytic Oxidizer)-regenerative catalytic oxidizer and liquid absorption method through solvent dissolution absorption to treat the exhaust gas.

[0042] As an embodiment, the circulation storage unit 5 is connected between the hydrogenation reaction unit 1 and the dehydrogenation reaction unit 3 .

[0043] See also Figure 3One end of the circulation storage unit 5 is connected to the input end of the hydrogenation reaction unit 1, and the other end is connected to the output end of the dehydrogenation reaction unit 3. Its function is to store or reflux the liquid unsaturated aromatic compounds and their mixtures or liquid unsaturated heterocyclic compounds through the circulation storage unit 5 to the hydrogenation reaction unit 1 for purification again when the dehydrogenation reaction is incomplete and the purity of the produced hydrogen is not high. This process will hardly cause the above-mentioned liquid unsaturated aromatic compounds and their mixtures or liquid unsaturated heterocyclic compounds to deteriorate, and can achieve repeated and efficient utilization of the purifier and the catalyst and continuous and stable purification of the by-product hydrogen.

[0044] As an implementation method, see Figure 3 The output end of the dehydrogenation reaction unit 3 is also provided with a purity detection unit 6 for detecting the purity of the output hydrogen.

[0045] The purification system of the utility model finally outputs hydrogen with high purity. Different hydrogen energy usage scenarios have different purity requirements, most of which require a purity of ≥ 99%. In order to avoid safety hazards caused by poor purity of the output hydrogen, a purity detection unit 6 is configured to detect the output hydrogen to ensure the quality of the output product.

[0046] As an implementation method, see Figure 3 The hydrogenation reaction unit 1 and the dehydrogenation reaction unit 3 are also respectively provided with a temperature detection unit 7 for detecting the reaction temperature conditions.

[0047] As explained in the above embodiments, in the process of using specific purifying agents and catalysts to purify the by-product hydrogen mixture, certain requirements are placed on the reaction temperature and real-time monitoring may be required. This purpose is achieved by configuring a temperature detection unit 7 in the hydrogenation reaction unit 1 and the dehydrogenation reaction unit 3. Specifically, the temperature detection unit 7 can be connected to the central control system through a temperature detection sensor for monitoring.

[0048] As an implementation method, see Figure 3 The purification system further includes a desulfurization unit 8, the output end of the desulfurization unit 8 is connected to the input end of the hydrogenation reaction unit 1, and is used for desulfurizing the by-product hydrogen mixture.

[0049] The reaction purification process performed by the purification system of the utility model cannot directly process by-product hydrogen with a high sulfide content. If the sulfide content in the by-product hydrogen is high (>2%), the by-product hydrogen needs to be pretreated first, for example, by setting a desulfurization unit 8, first undergoing desulfurization treatment at the front end and then purification to ensure that the purified product does not contain other impurities.

[0050] The above description is only an optional embodiment of the present application, and does not limit the patent scope of the present application. All equivalent structural transformations made by using the contents of the present application specification and drawings under the inventive concept of the present application, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present application.

Claims

1. A reactive industrial by-product hydrogen purification system, characterized in that: The purification system comprises: a hydrogenation reaction unit, a gas-liquid separation unit and a dehydrogenation reaction unit connected in sequence, wherein: The input end of the hydrogenation reaction unit is used to input a by-product hydrogen mixture, and the hydrogenation reaction unit is filled with a catalyst and a purifying agent, and the catalyst and the purifying agent are used to react with the by-product hydrogen mixture to produce a hydrogenated product; The gas-liquid separation unit is used to separate the hydrogenation product into gas and liquid; The output end of the dehydrogenation reaction unit is used to output hydrogen. The dehydrogenation reaction unit is filled with the catalyst and the purifying agent. The catalyst and the purifying agent are used for the hydrogenation product to undergo a dehydrogenation reaction to generate hydrogen.

2. The purification system according to claim 1, characterized in that The hydrogenation reaction unit includes a plurality of hydrogenation reaction vessels, and the dehydrogenation reaction unit includes a plurality of dehydrogenation reaction vessels. The output ends of the plurality of hydrogenation reaction vessels are connected to the gas-liquid separation unit through a confluence valve, and the gas-liquid separation unit is connected to the input ends of the plurality of dehydrogenation reaction vessels through a diversion valve.

3. The purification system according to claim 1, characterized in that: The purification system further comprises a waste gas treatment unit, which is connected to the gas-liquid separation unit and processes the gaseous compounds separated by the gas-liquid separation unit.

4. The purification system according to claim 3, characterized in that: The exhaust gas treatment unit treats the exhaust gas by RTO, RCO or liquid absorption.

5. The purification system according to claim 1, characterized in that: The purification system further includes a circulation storage unit connected between the hydrogenation reaction unit and the dehydrogenation reaction unit.

6. The purification system according to claim 1, characterized in that: The output end of the dehydrogenation reaction unit is also provided with a purity detection unit for detecting the purity of the output hydrogen.

7. The purification system according to claim 1, characterized in that: The hydrogenation reaction unit and the dehydrogenation reaction unit are also respectively configured with a temperature detection unit for detecting reaction temperature conditions.

8. The purification system according to claim 1, characterized in that: The purification system further comprises a desulfurization unit, the output end of which is connected to the input end of the hydrogenation reaction unit for desulfurizing the by-product hydrogen mixture.

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