A method for integrating chemical chain hydrogen production and carbon pollution removal and its application

Abstract

The present invention provides a method for integrating chemical chain hydrogen production and carbon pollution removal, comprising: (1) introducing pyrolysis gas and oxidized Ca-Fe / Al2O3 oxygen carrier from above a moving bed reactor; (2) adjusting the temperature and residence time of different beds in the reactor so that the pyrolysis gas and the oxidized oxygen carrier pass through the reactor from top to bottom, and decarbonization reaction, desulfurization and dechlorination reaction, and denitration reaction occur in sequence; (3) the reduced oxygen carrier enters a riser from below the reactor and reacts with water vapor to produce hydrogen to obtain hydrogen and oxidized oxygen carrier; (4) after the oxidized oxygen carrier is separated from the hydrogen, it enters the moving bed reactor again to complete the cycle. The present invention realizes the integration of high-purity hydrogen preparation and carbon pollution separation, shortens the process route of traditional carbon pollution removal, not only improves the efficiency of carbon pollution removal and hydrogen production, but also reduces the energy consumption and cost required for carbon pollution removal, greatly improving economic and environmental benefits.

Description

Technical Field

[0001] The present invention belongs to the technical field of gas purification, and specifically relates to a method for integrating chemical chain hydrogen production and carbon pollution removal, and also relates to the application of the above method in a pyrolysis gas hydrogen production process. Background Art

[0002] Energy production and environmental protection are unavoidable issues in human development. Air pollution is a major public health hazard, and energy production and utilization are by far the most important certified source of air pollutant emissions, accounting for 85% of particulate matter and nearly all sulfur oxides and nitrogen oxides. Therefore, finding green energy production methods and waste gas treatment technologies is a constant goal of humanity.

[0003] Pyrolysis gas reforming hydrogen production technology is a method of producing hydrogen from carbon-containing raw materials through a thermochemical process, and is now widely used in the field of hydrogen production. In this process, solid or gaseous carbon-based raw materials are first heated to a high temperature for pyrolysis to produce gaseous carbon monoxide and hydrogen. Subsequently, through the reforming step, these gases react with water vapor to produce additional hydrogen and carbon dioxide. However, the gas produced by this method contains not only hydrogen, but also a large amount of carbon dioxide and various harmful pollutants such as sulfides, nitrogen oxides and chlorides. Therefore, a series of high-energy-consuming processes such as water vapor shift, decarbonization, desulfurization, denitrification, and dechlorination are required to obtain high-purity hydrogen and remove CO2 and pollutants.

[0004] Invention CN116273145A discloses a method for using a supported iron-based catalyst for integrated flue gas removal in coal-fired power plants. This method achieves integrated desulfurization and denitrification, but still suffers from long process routes and high energy consumption. Invention CN1698933A discloses an integrated purifier for desulfurization, denitrification, and dust removal of flue gas from coal-fired boilers. While this invention achieves desulfurization and denitrification within a single device, it has numerous internal subsystems and a large device size. Furthermore, both inventions require additional waste disposal equipment, preventing close integration with production equipment to reduce costs.

[0005] In summary, there is an urgent need for a method that integrates energy production and carbon pollution removal to improve production efficiency and reduce pollutant treatment costs. Summary of the Invention

[0006] One of the objectives of the present invention is to provide an integrated method for chemical chaining hydrogen production and carbon pollution removal.

[0007] A second object of the present invention is to provide an integrated method for chemical chaining hydrogen production and carbon pollution removal for application in a pyrolysis gas hydrogen production process.

[0008] The technical solution adopted by the present invention to achieve one of the objectives is to provide an integrated method for chemical chaining hydrogen production and carbon pollution removal, comprising the following steps:

[0009] S1, introducing pyrolysis gas and oxidized Ca-Fe / Al2O3 oxygen carrier from the top of the moving bed reactor;

[0010] S2. Adjusting the temperature of different bed layers and the residence time of reactants in the moving bed reactor so that the pyrolysis gas and the oxidized Ca-Fe / Al2O3 oxygen carrier pass through the moving bed reactor from top to bottom, and sequentially undergo decarbonization reaction, desulfurization and dechlorination reaction, and denitrification reaction to obtain carbon-removed gas and reduced Ca-Fe / Al2O3 oxygen carrier;

[0011] S3, the reduced Ca-Fe / Al2O3 oxygen carrier enters the riser from the bottom of the moving bed reactor and reacts with the water vapor introduced from the bottom of the riser to produce hydrogen, thereby obtaining hydrogen and oxidized Ca-Fe / Al2O3 oxygen carrier;

[0012] S4. Separating the oxidized Ca-Fe / Al2O3 oxygen carrier from the hydrogen, drying and collecting the hydrogen, and then the oxidized Ca-Fe / Al2O3 oxygen carrier enters the moving bed reactor again to complete the cycle.

[0013] The overall idea and inventive principle of the present invention are as follows:

[0014] To address the technical challenges of complex pollutant composition in pyrolysis gas and the long, energy-intensive, and equipment-intensive processes associated with conventional carbon removal methods, the present invention provides a method for integrating hydrogen production and carbon removal by controlling the bed temperature and reactant flow conditions of different layers within a fluidized bed reactor, enabling oxygen carriers to remove different carbon pollutants at different locations within the reactor. This method shortens the process path of existing carbon removal technologies and significantly reduces energy consumption and costs during the carbon removal process following hydrogen production from conventional chemical chaining of pyrolysis gas, offering advantages such as economic reliability, energy conservation, and environmental protection.

[0015] In the present invention, when the oxidized Ca-Fe / Al2O3 oxygen carrier and the pyrolysis gas pass through the moving bed reactor from top to bottom, the following main reactions will occur in sequence:

[0016] CaFeO x +CO→CaFeO x-1 +CO2 (1)

[0017] CaFeO x-1 +HCl / SO2→(CaFe)Cl2 / SO4 (2)

[0018] NO x +CO→N2+CO2 (3)

[0019] The above reaction achieves decarbonization, desulfurization, dechlorination, and denitrification of the pyrolysis gas, resulting in the treated gas and the reduced Ca-Fe / Al2O3 oxygen carrier. Then, in the riser, the reduced Ca-Fe / Al2O3 oxygen carrier reacts with water vapor as follows:

[0020] CaFeO x-1 +H2O→CaFeO x +H2O (4)

[0021] Through the above reaction, hydrogen is produced while the oxidized Ca-Fe / Al2O3 oxygen carrier re-enters the moving bed reactor to complete the cycle. This invention utilizes chemical looping technology to achieve integrated hydrogen production and carbon removal within the same reactor. High-purity hydrogen is directly obtained at the reactor outlet. This hydrogen can directly meet the hydrogen purity requirements of various applications, such as petroleum refining, methanol synthesis, and ammonia synthesis, while meeting ultra-low pollutant emission standards (GB13223-2011).

[0022] Furthermore, in step S1, the pyrolysis gas includes at least CO, SO2, HCl and NO x (x=1 or 2) Preferably, the temperature of the pyrolysis gas is 600-700°C.

[0023] Furthermore, in step S1, the preparation method of the Ca-Fe / Al2O3 oxygen carrier comprises the following steps:

[0024] A1. Dissolve iron salt, calcium salt, aluminum salt and urea in water to obtain a solution;

[0025] A2, adding ethylene glycol to the solution, and ultrasonically treating the solution to obtain a mixed solution;

[0026] A3. Under an inert atmosphere, the mixed solution is heated to react. After the reaction is completed, the product is filtered to obtain a product, and the product is dried to obtain a Ca-Fe / Al2O3 oxygen carrier.

[0027] Furthermore, by maintaining a weakly alkaline environment, controlling the ratio of raw materials, the temperature required for the heating reaction, external conditions and other factors, the crystal structure and performance of the product oxygen carrier can be adjusted, so that it can better adapt to the integrated method of chemical chain hydrogen production and carbon pollution removal.

[0028] Preferably, in step A1 of the above-mentioned method for preparing the Ca-Fe / Al2O3 oxygen carrier, the molar ratio of the iron salt, the calcium salt and the aluminum salt is 3:1:(2-3).

[0029] Preferably, the iron salt, calcium salt and aluminum salt are independently selected from their respective corresponding water-soluble chloride salts or nitrates. More preferably, the iron salt is ferrous chloride tetrahydrate, the calcium salt is calcium chloride hexahydrate, and the aluminum salt is aluminum chloride hexahydrate, and the molar ratio of the three is 3:1:2.

[0030] Preferably, in step A1 of the method for preparing the Ca-Fe / Al2O3 oxygen carrier, the content of urea in the solution is 10 wt.%-12 wt.%.

[0031] Preferably, in step A3, the heating reaction temperature is 95-100° C., and the heating reaction time is 42-54 h.

[0032] After testing, it was found that the structure, active sites, reaction temperature and mechanical strength of the Ca-Fe / Al2O3 oxygen carrier prepared under the above conditions can better adapt to the requirements of the treatment process.

[0033] Preferably, in step A2 of the preparation method of the Ca-Fe / Al2O3 oxygen carrier, the volume ratio of ethylene glycol to solution is 1:(100-300), the frequency of ultrasonic treatment is 20-40kHz, and the time is 3-5min. Studies have found that ethylene glycol as a solvent can affect the adhesion and surface tension of the solution, thereby affecting the formation of the precipitate. By adding a certain proportion of ethylene glycol during the preparation process of the oxygen carrier, the crystal growth rate and crystal shape can be effectively controlled, and the morphology, particle size and dispersibility of the precipitate can be regulated, thereby obtaining uniform, size-controlled composite oxide particles with a specific microstructure.

[0034] Furthermore, in step S2, the temperature of the bed layer of the decarburization reaction is 750-850°C, and the residence time of the reactants in the bed layer is 20-30s.

[0035] Furthermore, in step S2, the temperature of the bed for the desulfurization and dechlorination reaction is 400-600°C, and the residence time of the reactants in the bed is 10-15s.

[0036] Furthermore, in step S2, the temperature of the bed layer of the denitration reaction is 300-400°C, and the residence time of the reactants in the bed layer is 60-90s.

[0037] Furthermore, in step S3, the temperature of the hydrogen production reaction is 700-800° C., and the pressure of the hydrogen production reaction is 0.5-1 MPa.

[0038] Furthermore, in step S4, a cyclone separator is used to separate the oxidized Ca-Fe / Al2O3 oxygen carrier and the hydrogen.

[0039] The technical solution adopted by the present invention to achieve the second purpose is: to provide an application of the method according to one of the purposes of the present invention in a pyrolysis gas hydrogen production process.

[0040] Furthermore, the pyrolysis gas includes at least CO, SO2, HCl and NO x (x=1 or 2).

[0041] Furthermore, in the pyrolysis gas, the volume percentage of CO is 20%-30%, the volume percentage of SO2 is 0.05%-0.1%, the volume percentage of NOx is 0.5%-1%, the volume percentage of HCl is 0.01%-0.05%, and the rest is CO2.

[0042] Preferably, the mass ratio of the Ca-Fe / Al2O3 oxygen carrier to the pyrolysis gas circulating in the reactor is (3-5):1.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] (1) The present invention provides a method for integrating chemical chain hydrogen production and carbon pollution removal, which is suitable for containing CO, SO2, HCl and NO x The pyrolysis gas of the components realizes the integration of hydrogen preparation and carbon pollution removal through a chemical chain cycle, shortens the process of traditional carbon pollution removal, and effectively solves the problem of high energy consumption in the traditional carbon pollution removal process. Compared with the existing process, the energy consumption of carbon dioxide and pollutant removal is reduced by 60%.

[0045] (2) The present invention provides an integrated method for chemical chain hydrogen production and carbon pollution removal. By controlling the reactions in different areas within the reactor, the graded removal of pollutants, the purification and capture of carbon dioxide, and the preparation of high-purity hydrogen are achieved. The hydrogen and carbon dioxide obtained can directly meet industrial needs and generate huge economic benefits.

[0046] (3) The present invention provides a method for integrating chemical chain hydrogen production and carbon pollution removal, which closely combines hydrogen production with carbon pollution removal, greatly reducing the volume of production equipment, reducing floor space, and reducing production costs. This method can be directly applied to the production of products containing CO, SO2, HCl and NO. x In the post-processing step of the pyrolysis gas of the components, carbon pollution can be removed and hydrogen can be produced, which has a prospect for promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 A schematic diagram of a method for integrating chemical chaining hydrogen production and carbon pollution removal provided by the present invention;

[0048] Figure 2A process route comparison diagram of the traditional pyrolysis gas reforming hydrogen production method and the integrated chemical chaining hydrogen production and carbon pollution removal method provided by the present invention. DETAILED DESCRIPTION

[0049] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0050] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0051] like Figure 1 As shown, an embodiment of the present invention provides an integrated method for chemical chaining hydrogen production and carbon pollution removal, comprising the following steps:

[0052] Step 1: introducing pyrolysis gas and oxidized Ca-Fe / Al2O3 oxygen carrier from the top of the moving bed reactor; wherein the Ca-Fe / Al2O3 oxygen carrier is prepared by a co-precipitation method, comprising the following steps:

[0053] (1) Weigh 1.49 g of ferrous chloride tetrahydrate, 0.52 g of calcium chloride hexahydrate, 1.21 g of aluminum chloride hexahydrate, and 100 g of urea and dissolve them in 1000 ml of distilled water;

[0054] (2) Add 5 ml of ethylene glycol to the prepared solution and treat under ultrasonic conditions at a frequency of 30 kHz for 3 minutes;

[0055] (3) Transfer the treated solution to a flask, place the flask in an oil bath, introduce nitrogen gas into the flask at a rate of 2 L / min, and connect a condenser to the flask;

[0056] (4) Set the temperature of the oil bath to 97°C, place a rotor in the oil bath, and stir at a speed of 200 r / min. Maintain the temperature of the solution at 97°C for 48 h.

[0057] (5) After completing step (4), turn off the heating and allow the mixture to cool naturally, while continuing to introduce nitrogen and stirring;

[0058] (6) The cooled solution was filtered using a filter membrane with a pore size of 1 μm;

[0059] (7) The solid obtained by filtration was dried in a vacuum drying oven at 60°C for 10 h to obtain Ca-Fe / Al2O3 oxygen carrier.

[0060] Step 2: Adjust the temperature of different bed layers and the residence time of the reactants in the moving bed reactor so that the pyrolysis gas and the oxidized Ca-Fe / Al2O3 oxygen carrier pass through the moving bed reactor from top to bottom, and sequentially undergo decarbonization reaction, desulfurization and dechlorination reaction, and denitrification reaction to obtain carbon-removed gas and reduced Ca-Fe / Al2O3 oxygen carrier; specifically:

[0061] The bed temperature required for the decarbonization reaction is 750-850°C, and the pyrolysis gas and the oxidized Ca-Fe / Al2O3 oxygen carrier stay in the bed for 20-30 seconds. The main reactions that occur are as follows:

[0062] CaFeO x +CO→CaFeO x-1 +CO2 (1)

[0063] The bed temperature required for the desulfurization and dechlorination reaction is 400-600°C, and the pyrolysis gas and the reduced Ca-Fe / Al2O3 oxygen carrier stay in the bed for 20-30 seconds. The main reactions that occur are as follows:

[0064] CaFeO x-1 +HCl / SO2→(CaFe)Cl2 / SO4 (2)

[0065] The bed temperature required for the denitration reaction is 300-400°C. At this time, only carbon monoxide and nitrogen oxides remain in the pyrolysis gas. The main reactions that occur are as follows:

[0066] NO x +CO→N2+CO2 (3)

[0067] Step 3: The reduced Ca-Fe / Al2O3 oxygen carrier enters the riser from the bottom of the moving bed reactor and reacts with the water vapor introduced from the bottom of the riser to produce hydrogen and oxidized Ca-Fe / Al2O3 oxygen carrier. The hydrogen production reaction temperature is 700-800°C and the pressure is 0.5-1MPa. The main reactions that occur are as follows:

[0068] CaFeO x-1 +H2O→CaFaO x +H2 (4)

[0069] Step 4: Separate the oxidized Ca-Fe / Al2O3 oxygen carrier from the hydrogen, dry and collect the hydrogen, and the oxidized Ca-Fe / Al2O3 oxygen carrier enters the moving bed reactor again to complete the cycle.

[0070] The present invention will be further described below with reference to specific examples, but they are not intended to limit the present invention.

[0071] Example 1

[0072] like Figure 1 As shown in the figure, the integrated method of chemical chain hydrogen production and carbon pollution removal mainly includes four reactions. The laboratory test gas is used as the treatment object, the pyrolysis gas temperature is 650℃, the SO2 concentration is 930ppm, the HCl concentration is 120ppm, and the NO x The concentration is 7100ppm and the CO concentration is 242310ppm.

[0073] Ca-Fe / Al2O3 oxygen carrier was added to the chemical chain reaction, and the decarbonization reaction bed temperature was controlled at 800°C, the desulfurization and dechlorination reaction bed temperature was controlled at 500°C, and the denitrification reaction bed temperature was controlled at 350°C. After the reaction stabilized, the gas at the outlet was sampled and analyzed.

[0074] When the oxygen carrier circulation rate is 0.9 kg / h, the results show that the removal rate of SO2 is 97.8%, the removal rate of HCl is 96.5%, and the removal rate of NO x The removal rate is 94.9%, and the purity of the obtained hydrogen is 99.7%.

[0075] Example 2

[0076] like Figure 1 As shown in the figure, the integrated method of chemical chain hydrogen production and carbon pollution removal mainly includes four reactions. The laboratory test gas is used as the treatment object, the pyrolysis gas temperature is 650℃, the SO2 concentration is 930ppm, the HCl concentration is 120ppm, and the NO x The concentration is 7100ppm and the CO concentration is 242310ppm.

[0077] Ca-Fe / Al2O3 oxygen carrier was added to the chemical chain reaction, and the decarbonization reaction bed temperature was controlled at 760°C, the desulfurization and dechlorination reaction bed temperature was controlled at 450°C, and the denitrification reaction bed temperature was controlled at 310°C. After the reaction stabilized, the gas at the outlet was sampled and analyzed.

[0078] When the oxygen carrier circulation rate is 0.9 kg / h, the results show that the removal rate of SO2 is 96.9%, the removal rate of HCl is 95.9%, and the removal rate of NO x The removal rate is 94.1%, and the purity of the obtained hydrogen reaches 99.2%.

[0079] Example 3

[0080] like Figure 1 As shown in the figure, the integrated method of chemical chain hydrogen production and carbon pollution removal mainly includes four reactions. The laboratory test gas is used as the treatment object, the pyrolysis gas temperature is 650℃, the SO2 concentration is 874ppm, the HCl concentration is 111ppm, and the NO xThe concentration is 6540ppm and the CO concentration is 282310ppm.

[0081] Ca-Fe / Al2O3 oxygen carrier was added to the chemical chain reaction, and the decarbonization reaction bed temperature was controlled at 800°C, the desulfurization and dechlorination reaction bed temperature was controlled at 500°C, and the denitrification reaction bed temperature was controlled at 350°C. After the reaction stabilized, the gas at the outlet was sampled and analyzed.

[0082] When the oxygen carrier circulation rate is 0.9 kg / h, the results show that the SO2 removal rate is 98.9%, the HCl removal rate is 97.1%, the NOx removal rate is 95.2%, and the obtained hydrogen purity reaches 99.9%.

[0083] Comparative Example

[0084] like Figure 2 As shown, this comparative example provides a method for producing hydrogen by traditional pyrolysis gas reforming. Unlike the embodiment of the present invention (completion of chemical chain hydrogen production and carbon pollution removal in one set of equipment), this comparative example adopts the method for producing hydrogen by traditional pyrolysis gas reforming, which requires five steps and five types of equipment.

[0085] The laboratory test gas is used as the object, the pyrolysis gas temperature is 650℃, the SO2 concentration is 930ppm, the HCl concentration is 120ppm, and the NO x The concentration is 710ppm, and the CO concentration is 242310ppm. Applying the traditional carbon pollution removal process route, the energy consumption of the water vapor shift process is measured to be 4.2MJ / kg carbon monoxide conversion, the energy consumption of the decarbonization process is 3.7MJ / kg carbon dioxide removal, the energy consumption of the desulfurization process is 0.5MJ / kg sulfur dioxide removal, the energy consumption of the denitrification process is 1.9MJ / kg nitrogen oxide removal, and the energy consumption of the dechlorination process is 0.2MJ / kg hydrogen chloride removal. The energy consumption of purifying 1kg of laboratory test gas through the traditional carbon pollution removal process route is 1.05MJ, of which the removal rate of SO2 is 94%, the removal rate of HCl is 91%, and the removal rate of NO x The removal rate is 90%, and the purity of the obtained hydrogen is 96%.

[0086] In contrast, the integrated method of chemical chain hydrogen production and carbon pollution removal provided in Example 1 of the present invention consumes only 0.41 MJ of energy to purify 1 kg of laboratory test gas, with a SO2 removal rate of 97.8%, a HCl removal rate of 96.5%, and a NO x The removal rate is 94.9%, and the purity of the obtained hydrogen reaches 99.7%. This shows that the method provided by the present invention not only has a better purification effect, but also saves 60% of energy consumption compared with traditional carbon pollution removal technology.

[0087] The above are only preferred embodiments of the present invention and do not limit the implementation mode and protection scope of the present invention. For those skilled in the art, it should be aware that all solutions obtained by equivalent substitutions and obvious changes made using the contents of the present invention specification should be included in the protection scope of the present invention.

Claims

1. A method for integrating chemical chain hydrogen production and carbon pollution removal, characterized in that: The following steps are involved: S1, introducing pyrolysis gas and oxidized Ca-Fe / Al2O3 oxygen carrier from the top of the moving bed reactor; S2. Adjusting the temperature of different bed layers and the residence time of reactants in the moving bed reactor so that the pyrolysis gas and the oxidized Ca-Fe / Al2O3 oxygen carrier pass through the moving bed reactor from top to bottom, and sequentially undergo decarbonization reaction, desulfurization and dechlorination reaction, and denitrification reaction to obtain carbon-removed gas and reduced Ca-Fe / Al2O3 oxygen carrier; S3, the reduced Ca-Fe / Al2O3 oxygen carrier enters the riser from the bottom of the moving bed reactor and reacts with the water vapor introduced from the bottom of the riser to produce hydrogen, thereby obtaining hydrogen and oxidized Ca-Fe / Al2O3 oxygen carrier; S4. Separating the oxidized Ca-Fe / Al2O3 oxygen carrier from the hydrogen, drying and collecting the hydrogen, and then the oxidized Ca-Fe / Al2O3 oxygen carrier enters the moving bed reactor again to complete the cycle.

2. The method according to claim 1, characterized in that The preparation method of the Ca-Fe / Al2O3 oxygen carrier comprises the following steps: A1. Dissolve iron salt, calcium salt, aluminum salt and urea in water to obtain a solution; A2, adding ethylene glycol to the solution, and ultrasonically treating the solution to obtain a mixed solution; A3. Under an inert atmosphere, the mixed solution is heated to react. After the reaction is completed, the product is filtered to obtain the product, and the product is dried to obtain a Ca-Fe / Al2O3 oxygen carrier.

3. The method according to claim 2, characterized in that In step A1, the molar ratio of the iron salt, the calcium salt and the aluminum salt is 3:1:(2-3).

4. The method according to claim 2, characterized in that In step A1, the content of urea in the solution is 10 wt.%-12 wt.%.

5. The method according to claim 2, characterized in that In step A2, the volume ratio of ethylene glycol to the solution is 1:(100-300), the frequency of ultrasonic treatment is 20-40 kHz, and the time of ultrasonic treatment is 3-5 min.

6. The method according to claim 2, characterized in that In step A3, the heating reaction temperature is 95-100°C.

7. The method according to claim 1, characterized in that In step S2, the temperature of the bed layer of the decarbonization reaction is 750-850°C, and the residence time of the reactants in the bed layer is 20-30s; the temperature of the bed layer of the desulfurization and dechlorination reaction is 400-600°C, and the residence time of the reactants in the bed layer is 10-15s; the temperature of the bed layer of the denitrification reaction is 300-400°C, and the residence time of the reactants in the bed layer is 60-90s.

8. The method according to claim 1, characterized in that In step S3, the temperature of the hydrogen production reaction is 700-800° C., and the pressure of the hydrogen production reaction is 0.5-1 MPa.

9. The method according to claim 1, characterized in that In step S4, a cyclone separator is used to separate the oxidized Ca-Fe / Al2O3 oxygen carrier and hydrogen.

10. Application of the method according to any one of claims 1 to 9 in a pyrolysis gas hydrogen production process, characterized in that: The pyrolysis gas includes at least CO, SO2, HCl and NO x , x=1 or 2.

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