CN117923570A - Methanation method and equipment for high-water-content organic matters - Google Patents
Methanation method and equipment for high-water-content organic matters Download PDFInfo
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- CN117923570A CN117923570A CN202410102885.XA CN202410102885A CN117923570A CN 117923570 A CN117923570 A CN 117923570A CN 202410102885 A CN202410102885 A CN 202410102885A CN 117923570 A CN117923570 A CN 117923570A
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 249
- 239000003054 catalyst Substances 0.000 claims abstract description 104
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 87
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000001257 hydrogen Substances 0.000 claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 claims abstract description 85
- 238000002407 reforming Methods 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 31
- 239000005416 organic matter Substances 0.000 claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 64
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 239000010813 municipal solid waste Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 244000005700 microbiome Species 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001833 catalytic reforming Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
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- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010806 kitchen waste Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0005—Catalytic processes under superatmospheric pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
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- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The application provides a methanation method of high-water-content organic matters, which comprises the following steps: the high water content organic matter is subjected to reforming hydrogen production reaction under the catalysis of a reforming hydrogen production active catalyst to obtain a mixture containing H 2, CO and CO 2; the mixture containing H 2, CO and CO 2 is subjected to methanation reaction under the catalysis of a methanation active catalyst to obtain methane; the pressure at the reforming hydrogen production reaction is lower than the pressure at the methanation reaction. The application develops how to efficiently utilize the organic matters with high water content, thereby changing waste into valuables.
Description
Technical Field
The application relates to a method and a device for methanation of high-water-content organic matters.
Background
In human social life or production activities, a large amount of high-water-content organic matter such as industrial organic wastewater, sludge, livestock manure, etc. is produced. Because of their different nature and sources, their abatement techniques are also different. Because of the characteristics of large production amount, accompanying peculiar smell, complex components and the like, the rapidity and thoroughness of the treatment process are difficult to realize by adopting a general treatment method, so that the purification treatment, recovery and comprehensive utilization research of the waste water is one of hot research subjects in the environmental field.
Aiming at organic matters or organic wastewater with high water content, a biological treatment method and a physicochemical method are mainly adopted at present. The biological treatment method is to introduce microorganisms, convert organic matters by utilizing the metabolism of the microorganisms, and the product components are different according to the difference of aerobic or anaerobic environments. Due to the upper limit of metabolism of microorganisms, the technology has the problems of long treatment period and large equipment occupation area, and microorganisms cannot effectively treat organic matters which are difficult to degrade or have high toxicity, such as greasy dirt and industrial wastewater.
In the physicochemical method, high-temperature water phase catalytic reforming is to reform organic matters at high temperature by using various catalysts. The high temperature process requires additional heat input and adds additional energy costs.
Disclosure of Invention
The application aims to solve the technical problems in the background art and provides a methanation method and equipment for high-water-content organic matters.
The technical scheme of the application is as follows:
1. a process for methanation of high water content organic matter comprising:
The high water content organic matter is subjected to reforming hydrogen production reaction under the catalysis of a reforming hydrogen production active catalyst to obtain a mixture containing H 2, CO and CO 2;
The mixture containing H 2, CO and CO 2 is subjected to methanation reaction under the catalysis of a methanation active catalyst to obtain methane;
the pressure at the reforming hydrogen production reaction is lower than the pressure at the methanation reaction.
2. The process according to item 1, wherein the reforming hydrogen production active catalyst is M@X-series catalyst, X is a catalyst carrier, M is a catalyst active substance,
M is selected from one or more than two of Pt, pd, cu, fe, preferably Pt and/or Pd.
3. The method according to item 2, wherein,
The X is selected from one or more than two of molecular sieve, zirconia and SiO 2;
preferably, the mass ratio of M to X is 1: (10-100).
4. The method according to item 1, wherein,
The methanation active catalyst is selected from one or more than two of porous nickel, ru-based catalyst, co-based catalyst and Rh-based catalyst.
5. The method according to item 1, wherein,
The heat required by the reforming hydrogen production reaction and the methanation reaction is derived from a photo-thermal conversion material, and the photo-thermal conversion material converts light energy into heat energy and provides the heat energy for the reforming hydrogen production reaction and the methanation reaction.
6. The method according to item 5, wherein,
The temperature of the reforming hydrogen production reaction is 150-350 ℃.
7. The method according to item 5, wherein,
The methanation reaction temperature is 150-350 ℃.
8. The method according to item 5, wherein,
The photo-thermal conversion material is selected from one or more than two of SiC, carbon black, graphite and graphene; siC is preferred.
9. The method according to item 1, wherein,
The water content of the high-water-content organic matters is more than or equal to 90% and less than 100%;
preferably, the method comprises the steps of,
The high-water-content organic matter is selected from one of organic wastewater, an aqueous solution containing activated sludge, an aqueous solution containing oil stains, kitchen garbage infiltration water, an aqueous solution containing aquatic plants and oily water.
10. The method according to item 1, wherein,
The difference between the pressure of the methanation reaction and the pressure of the reforming hydrogen production reaction is more than or equal to 100kPa.
11. The method according to item 10, wherein,
The pressure of the reforming hydrogen production reaction is more than or equal to 1.0Mpa.
12. The method according to item 10, wherein,
The pressure of the methanation reaction is more than or equal to 1.1Mpa.
13. The method of any one of items 1-12, the method being performed in an apparatus comprising:
The shell body is provided with a plurality of grooves,
The inside of the shell body sequentially comprises a reforming hydrogen production reaction area and a methanation reaction area from top to bottom,
The inner diameter of the shell corresponding to the methanation reaction region is larger than that of the shell corresponding to the reforming hydrogen production reaction region,
The reforming hydrogen production reaction area is provided with a reforming hydrogen production active catalyst,
The methanation reaction area is provided with a methanation active catalyst;
Preferably, the inner diameter of the shell corresponding to the methanation reaction region is more than 2 times of the inner diameter of the shell corresponding to the reforming hydrogen production reaction region.
14. The method according to item 13, wherein,
The outer layer of the shell is coated with a photo-thermal conversion material to form a photo-thermal conversion material coating;
Preferably, before the photothermal conversion material is coated on the outer layer of the shell, the photothermal conversion material is dissolved in an ethanol aqueous solution, and a suspension is formed by ultrasonic waves, and then the photothermal conversion material is coated on the outer layer of the shell;
it is further preferable that the thickness of the coating layer of the photothermal conversion material is 10 μm to 100 μm.
15. The method of item 14, wherein,
The device is placed at 300-1000 ℃ for calcination after the photothermal conversion material is coated on the outer surface of the shell.
16. The method of item 14, wherein,
The shell of the photo-thermal conversion material coating is provided with a jacket for isolating air;
Preferably, the jacket is a quartz jacket.
17. An apparatus for a methanation process of high water content organic matter, wherein the apparatus comprises:
The shell body is provided with a plurality of grooves,
The inside of the shell body sequentially comprises a reforming hydrogen production reaction area and a methanation reaction area from top to bottom,
The inner diameter of the shell corresponding to the methanation reaction region is larger than that of the shell corresponding to the reforming hydrogen production reaction region,
The reforming hydrogen production reaction area is provided with a reforming hydrogen production active catalyst,
The methanation reaction area is provided with a methanation active catalyst;
Preferably, the inner diameter of the shell corresponding to the methanation reaction region is more than 2 times of the inner diameter of the shell corresponding to the reforming hydrogen production reaction region.
18. The apparatus of item 17, wherein,
The outer layer of the shell is coated with a photo-thermal conversion material to form a photo-thermal conversion material coating;
Preferably, before the photothermal conversion material is coated on the outer layer of the shell, the photothermal conversion material is dissolved in an ethanol aqueous solution, and a suspension is formed by ultrasonic waves, and then the photothermal conversion material is coated on the outer layer of the shell;
it is further preferable that the thickness of the coating layer of the photothermal conversion material is 10 μm to 100 μm.
19. The apparatus of item 18, wherein,
The device is placed at 300-1000 ℃ for calcination after the photothermal conversion material is coated on the outer surface of the shell.
20. The apparatus of item 18, wherein,
The shell of the photo-thermal conversion material coating is provided with a jacket for isolating air;
Preferably, the jacket is a quartz jacket.
21. The apparatus according to any one of claims 17-20, wherein a methanation process of high water content organic matter is performed with the apparatus, the process comprising:
The high water content organic matter is subjected to reforming hydrogen production reaction under the catalysis of a reforming hydrogen production active catalyst to obtain a mixture containing H 2, CO and CO 2;
The mixture containing H 2, CO and CO 2 is subjected to methanation reaction under the catalysis of a methanation active catalyst to obtain methane;
the pressure at the reforming hydrogen production reaction is lower than the pressure at the methanation reaction.
22. The apparatus of claim 21, wherein the reforming hydrogen production active catalyst is selected from M@X series catalysts, X is a catalyst support, M is a catalyst active material, and M is one or more selected from Pt, pd, cu, fe, preferably one or more selected from Pt and Pd.
23. The apparatus of item 22, wherein the X is selected from one or more of molecular sieves, zirconia, siO 2;
preferably, the mass ratio of M to X is 1: (10-100).
24. The apparatus according to item 21, wherein the methanation-active catalyst is one or two or more selected from porous nickel, a Ru-based catalyst, a Co-based catalyst, and a Rh-based catalyst.
Compared with the prior art, the application has the beneficial effects that:
In the application, the inventor develops a method for efficiently utilizing the organic matters with high water content aiming at the organic matters with high water content, changes waste into valuable, and discovers how to efficiently utilize the organic matters with high water content through repeated exploration.
The prior art converts organic matters to generate methane by means of biological fermentation, and a biological fermentation method has higher requirements on fermentation environment and low conversion speed, but the application realizes the conversion of high-water-content organic matters to generate methane by utilizing thermochemical catalytic conversion, and has universality on raw material disposal and high conversion speed.
The outer layer of the shell is coated with a photo-thermal conversion material to form a photo-thermal conversion material coating; in the reaction process, the light is irradiated to the surface of the photo-thermal conversion material coating by utilizing the light reflecting device, and the light is converted into heat energy due to the excellent photo-thermal conversion effect of the photo-thermal conversion material coating, so that the reaction equipment is heated to reach the reaction temperature.
Drawings
FIG. 1 shows a schematic of a reaction apparatus;
figure 2 shows a schematic of a reaction catalyst packing zone barrier web.
1.A sample injection pump; 2. a flange; a reaction zone; a catalyst packing zone; 5. a quartz jacket; 6. a coating; b catalyst packing zone; a reaction zone B; 9. a device outlet; 10. a collection tank; 11. a collection tank air outlet; 12. a liquid outlet of the collecting tank; 13. an illumination reflection device; 14. a thermocouple; 15. a pressure gauge; 16. a housing; a reaction zone catalyst barrier web; b reaction zone catalyst barrier web.
Detailed Description
The application will be further illustrated with reference to the following examples, which are to be understood as merely further illustrating and explaining the application and are not to be construed as limiting the application.
Unless defined otherwise, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the materials and methods are described herein below. In case of conflict, the present specification, including definitions therein, will control and materials, methods, and examples, will control and be in no way limiting. The application is further illustrated below in connection with specific examples, which are not intended to limit the scope of the application.
The application provides a methanation method of high-water-content organic matters, which comprises the following steps: the high water content organic matter is subjected to reforming hydrogen production reaction under the catalysis of a reforming hydrogen production active catalyst to obtain a mixture containing H 2, CO and CO 2; the mixture containing H 2, CO and CO 2 is subjected to methanation reaction under the catalysis of a methanation active catalyst to obtain methane; the pressure at the reforming hydrogen production reaction is lower than the pressure at the methanation reaction.
In the present application, the inventors found that the water content of the high-water-content organic matter is 90% or more and less than 100%, how to efficiently use the high-water-content organic matter, and how to efficiently use the high-water-content organic matter by repeating the search.
In the present application, the water content of the high water content organic matter may be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, less than 100% or any range therebetween.
In the present application, the source of the high-water-content organic matter is not limited at all, as long as it can be applied to the methanation process in the present application. For example, the high water content organic matter is selected from one of organic wastewater, an aqueous solution containing activated sludge, an aqueous solution containing oil dirt, kitchen waste percolation water, an aqueous solution containing aquatic plants, and an oily water.
In the application, the reforming hydrogen production reaction is to perform the following reaction under the catalysis of a reforming hydrogen production active catalyst to obtain a mixture containing H 2, CO and CO 2;
(1)CnHmOk+(n-k)H2O→nCO+(n+m/2-k)H2
(2)CO+H2O→CO2+H2
in the present application, methanation reaction means that the following reaction is carried out under the catalysis of a methanation active catalyst to obtain methane.
(3)CO+3H2→CH4+H2O；
(4)CO2+4H2→CH4+2H2O。
In some embodiments of the application, the reforming hydrogen production active catalyst is M@X series catalyst, M@X series catalyst refers to catalyst composed of catalyst active material and catalyst carrier, X is catalyst carrier, M is catalyst active material.
In some embodiments of the application, the catalyst active material M is one or more of Pt, pd, cu, fe, preferably Pt and/or Pd.
In some embodiments of the application, the catalyst support X is selected from one or more of molecular sieves, zirconia, siO 2.
In some embodiments of the application, the mass ratio of M to X is 1: (10-100); for example, the mass ratio of M to X may be 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, 1:100, or any range therebetween.
In some embodiments of the present application, the methanation active catalyst is selected from one or more of porous nickel, ru-based catalyst, co-based catalyst, rh-based catalyst.
In some embodiments of the application, the heat required for the reforming hydrogen production reaction and the methanation reaction is derived from a photothermal conversion material that converts light energy into heat energy and provides the heat energy to the reforming hydrogen production reaction and the methanation reaction.
The prior art utilizes biological fermentation to convert organic matters to generate methane, and the biological fermentation method has higher requirements on fermentation environment and low conversion speed.
In some embodiments of the application, the reforming hydrogen production reaction temperature is 150-350 ℃. For example, the temperature of the reforming hydrogen production reaction may be 150 ℃,200 ℃, 250 ℃,300 ℃, 350 ℃, or any range therebetween.
In some embodiments of the application, the methanation reaction has a temperature of 150 to 350 ℃. For example, the methanation reaction may be at a temperature of 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, or any range therebetween.
In the present application, the photothermal conversion material is not limited at all as long as it can convert light energy into heat energy.
In some embodiments of the application, the photothermal conversion material is selected from one or more of SiC, carbon black, graphite, graphene; siC is preferred.
In some embodiments of the application, the difference between the pressure of the methanation reaction and the pressure of the reforming hydrogen production reaction is greater than or equal to 100kPa. For example, the difference between the pressure of the methanation reaction and the pressure of the reforming hydrogen production reaction may be 100kPa、150kPa、200kPa、250kPa、300kPa、350kPa、400kPa、450kPa、500kPa、550kPa、600kPa、650kPa、700kPa、750kPa、800kPa、850kPa、900kPa、950kPa、1000kPa and above, or any range therebetween.
In the present application, the difference between the pressure of the methanation reaction and the pressure of the reforming hydrogen production reaction may be controlled in a manner well known to those skilled in the art, as long as the above difference is obtained.
In some embodiments of the application, the pressure of the reforming hydrogen production reaction is 1.0Mpa or greater. For example, the pressure of the reforming reaction may be 1.0Mpa, 1.5Mpa, 2.0Mpa, 2.5Mpa, 3.0Mpa, 3.5Mpa, 4.0Mpa, 4.5Mpa, 5.0Mpa and above, or any range therebetween.
In some embodiments of the application, the methanation reaction has a pressure of 1.1Mpa or greater; for example, the methanation reaction pressure may be 1.1Mpa, 1.5Mpa, 2.0Mpa, 2.5Mpa, 3.0Mpa, 3.5Mpa, 4.0Mpa, 4.5Mpa, 5.0Mpa, 5.5Mpa, 6.0Mpa and above, or any range therebetween.
The application provides a device for a methanation process of high water content organic matter, wherein the device comprises the following components:
The shell (16) comprises a reforming hydrogen production reaction region and a methanation reaction region from top to bottom in sequence, wherein the inner diameter of the shell corresponding to the methanation reaction region is larger than that of the shell corresponding to the reforming hydrogen production reaction region, the reforming hydrogen production reaction region is provided with a reforming hydrogen production active catalyst, and the methanation reaction region is provided with a methanation active catalyst.
The device for the methanation method of the high-water-content organic matters is shown in fig. 1, wherein the device is vertically arranged, a shell (16) is provided with a device liquid outlet (9), and a reforming hydrogen production reaction area or an A reaction area (3), a methanation reaction area or a B reaction area (8) are sequentially arranged from top to bottom.
Under the conditions of high temperature and high pressure, the gas and the water are in a mutual dissolution state, the sub/supercritical water is converted from strong polarity at normal temperature and normal pressure to low polarity, the liquid medium and the gas are mutually dissolved, and the gas and the liquid flow directions are consistent, so that the device of the application avoids the phenomenon that the gas walks upwards at normal temperature and normal pressure.
As shown in fig. 1, the reaction zone a (3) and the reaction zone B (8) are both provided with catalyst packing regions, and barrier nets (31 or 32) are arranged at both ends of the packing regions to fix the catalyst, thereby preventing the catalyst from being lost. The minimum width of the holes of the barrier net is smaller than the particle size of the catalyst. For example, as shown in fig. 2, catalyst-blocking nets (31) are disposed at both ends of the catalyst-packing region of the a reaction region (3), and catalyst-blocking nets (32) are disposed at both ends of the catalyst-packing region of the B reaction region (8).
As shown in fig. 1, the catalyst filling area (4) of the area a is filled with a catalyst M@X series of reforming hydrogen production active catalyst, such as pt@x series catalyst, and the specific reaction of the area a is as follows:
(1)CnHmOk+(n-k)H2O→nCO+(n+m/2-k)H2
(2)CO+H2O→CO2+H2
As shown in fig. 1, the catalyst filling area (7) of the area B is filled with methanation active catalyst to catalyze the methanation active catalyst of CO and CO 2, and the specific reaction of the area B is as follows:
(1)CO+3H2→CH4+H2O；
(2)CO2+4H2→CH4+2H2O；
As shown in FIG. 1, the length of the shell (16) is greater than or equal to 5m, the inner diameter of the shell corresponding to the methanation reaction region is greater than the inner diameter of the shell corresponding to the reforming hydrogen production reaction region, namely the inner diameter of the reaction region B is greater than the inner diameter of the reaction region A, and the inner diameter of the reaction region B is more than 2 times of the inner diameter of the reaction region A.
In the present application, the control of the pressure is mainly achieved by controlling the inner diameter size and the reactor length. According to Bernoulli's equationIt can be seen that, taking two points 1 and 2 in the reaction zone a (3) and the reaction zone B (8), when the fluid is in the same streamline and the height is unchanged (potential energy is unchanged), the formula can be deformed to p 1+1/2ρ1v1 2＝p2+1/2ρ2v2 2, and since the inner diameter of the reaction zone B (8) is increased, the flow velocity v 2 is smaller than v 1, and therefore p 2 is larger than p 1. In addition, the vertically placed reactors have a liquid level pressure difference. Thus, the above-described inner diameter and reactor apparatus arrangement can achieve a pressure differential between the two reaction zones.
As shown in fig. 1, thermocouples (14) and pressure gauges (15) are distributed inside the apparatus for detecting temperature and pressure.
As shown in fig. 1, the outer layer of the shell (16) is coated with a photo-thermal conversion material to form a photo-thermal conversion material coating (6); in the reaction process, the light is irradiated to the surface of the photo-thermal conversion material coating by utilizing the light reflecting device (13), and the light is converted into heat energy due to the excellent photo-thermal conversion effect of the photo-thermal conversion material coating, so that the reaction equipment is heated to reach the reaction temperature.
In some embodiments of the application, the photothermal conversion material is dissolved in an aqueous ethanol solution and a suspension is formed by ultrasound before the photothermal conversion material is applied to the outer layer of the housing (16), and then applied to the outer layer of the housing.
In some embodiments of the application, the coating of the photothermal conversion material has a thickness of from 10 μm to 100 μm. For example, the thickness of the coating of the photothermal conversion material may be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm or any range therebetween.
In some embodiments of the application, the device is calcined at 300-1000 ℃ after the photothermal conversion material is applied to the outer surface of the housing. For example, calcination may be performed at 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or any range therebetween.
For example, siC layer preparation method: adding nano SiC particles into a solution with the volume ratio of ethanol to water=2:1, and performing ultrasonic dispersion for 30min to form a stable dispersion suspension. Then sprayed onto the wall surface of zone A, and then the reactor was placed in a tube furnace and calcined in an air atmosphere at 500℃for 1 hour.
The shell of the photo-thermal conversion material coating (6) is provided with an air-isolating jacket (5), and the photo-thermal conversion material coating is mainly used for isolating air and prolonging the service life of the coating. The jacket is a quartz jacket. The quartz jacket is positioned outside the reaction equipment shell, and two ends of the quartz jacket are sealed by flanges (2).
The whole process is that high water content organic matters enter the equipment under the action of a sample injection pump (1), firstly flow through an A reaction zone (3), and are converted under the action of a reforming cracking active catalyst to generate products mainly comprising CO and H 2; the material stream then passes through the B reaction zone (8) to form methane under the action of the methanation active catalyst. Finally, the material flow enters a collecting tank (10) to finish gas-liquid separation, and the collecting tank (10) is provided with a collecting tank air outlet (11) and a collecting tank liquid outlet (12).
The equipment provided by the application is continuous equipment, and methane can be continuously produced. The continuous operation is easy to realize the automatic control of the height, and the product quality is stable; continuous operation shortens the overall reaction time and achieves energy savings.
The methanation process of the high water content organic matter in the present application is carried out in an apparatus as described in FIG. 1.
Examples
The raw materials in the following examples are oily sewage, and the composition analysis thereof is shown in Table 1;
TABLE 1 analysis of oily wastewater Components
| Project | Numerical value |
| Moisture content | 96％ |
| Ash content | 0.7％ |
| Volatile matters | 2.3％ |
| Fixed carbon | 0.9％ |
Example 1:
the apparatus, as shown in fig. 1, comprises the following:
The shell (16) is vertically arranged, the length of the shell (16) is greater than or equal to 5m, the shell (16) is provided with a tank gas outlet (11), a tank liquid outlet (12) and a liquid outlet (9), the shell comprises a reforming hydrogen production reaction region or A reaction region (3), a methanation reaction region or B reaction region (8), the inner diameter of the B reaction region is greater than that of the A reaction region, and the inner diameter of the B reaction region is more than 2 times that of the A reaction region; the A area (3) and the B area (8) are both provided with catalyst filling areas, and barrier nets (31 or 32) are arranged at two ends of the filling areas to fix the catalyst, so that the catalyst is prevented from losing. The minimum width of the holes of the barrier net is smaller than the particle size of the catalyst. The catalyst filling area A (4) is filled with a reforming hydrogen production active catalyst Pt/ZSM-5, and the specific reaction of the area A is as follows:
(1)CnHmOk+(n-k)H2O→nCO+(n+m/2-k)H2
(2)CO+H2O→CO2+H2
the preparation method of 2wt% Pt/ZSM-5 comprises the following steps: the impregnation sintering method can be obtained by a commercially available or conventional preparation method, and is specifically as follows:
the catalyst filling area (7) of the area B is filled with methanation active catalyst porous nickel so as to catalyze the methanation active catalyst of CO and CO 2, and the specific reaction of the area B is as follows:
(1)CO+3H2→CH4+H2O；
(2)CO2+4H2→CH4+2H2O；
wherein the dosage of Pt/ZSM-5 is 10g, and the mass ratio of Pt to ZSM-5 in the Pt/ZSM-5 is 2%. The porous nickel was used in an amount of 10g.
The outer layer of the shell (16) is coated with a photo-thermal conversion material on the illumination reflecting device (13) to form a SiC coating (6); wherein the thickness of the SiC coating (6) is 10um.
Wherein, before the photothermal conversion material is coated on the outer layer of the shell (16), the SiC layer is prepared by the following method: adding nano SiC particles into a solution with the volume ratio of ethanol to water=2:1, and performing ultrasonic dispersion for 30min to form a stable dispersion suspension. Then sprayed onto the shell surface of the reaction zone A, and then the reactor was placed in a tube furnace and calcined in an air atmosphere at 500 ℃ for 1 hour.
The shell of the SiC coating (6) is provided with a jacket (5) for isolating air, the quartz jacket is positioned outside the reactor wall, and the two ends of the quartz jacket are sealed by flanges (2).
The specific implementation process is as follows:
Firstly, the oily sewage is injected into the reaction equipment by a sample injection pump (1), the reaction is carried out under the condition of illumination, the conveying speed of the pump is 100L/h, and the oily sewage firstly flows through the reaction zone A (3) and then flows through the reaction zone B (8) for reaction. In the reaction process, light irradiates the surface of the photo-thermal conversion material SiC coating, and the light is converted into heat energy, so that the reaction temperature of reforming hydrogen production reaches 260 ℃. The pressure of the reaction zone A (3) is 4.7Mpa, the pressure of the reaction zone B (8) is 4.8Mpa, and the difference between the pressure of methanation reaction and the pressure of reforming hydrogen production reaction is 0.1Mpa. Finally, the product enters a collecting tank (10), and after 2 hours of reaction, the product gas is analyzed.
The product gas was analyzed qualitatively and quantitatively by hydrogen flame ionization detector-gas chromatography (GC-FID), thermal conductivity detector-gas chromatography (GC-TCD) and gas chromatography-mass spectrometry (GC-MS), and no gas was generated by detection.
Example 1 produced a large amount of gaseous product and effectively achieved conversion of oily wastewater to methane.
Example 2:
the conditions for the specific implementation were the same as in example 1, except that in example 2, the light was not introduced, and the reaction gas components and contents were as shown in Table 2. As shown in table 2, example 2 did not generate gas compared to example 1.
Examples 3-10 differ only in the parameters in Table 2, the remainder being the same as example 1.
Examples 11-12 differ only in the parameters in Table 3, mainly in the reforming hydrogen production reaction temperature due to the thickness of the SiC coating.
Comparative example 4
With the apparatus used in example 1, methanation reaction was performed in zone A, reforming hydrogen production reaction was performed in zone B, and the hydrogen production reaction was fed from below the apparatus so that the pressure of the reforming hydrogen production reaction was greater than that of the methanation reaction.
TABLE 2
TABLE 3 Table 3
Application example
The product gas was qualitatively and quantitatively analyzed by hydrogen flame ionization detector-gas chromatography (GC-FID), thermal conductivity detector-gas chromatography (GC-TCD) and gas chromatography-mass spectrometry (GC-MS), and the results are shown in table 4 below.
The results in Table 4 are derived from H 2、CO、CO2、CH4 collected on the premise that the pump feed rate was 100L/H, and the product gas, i.e., 200L of oily wastewater, was analyzed after 2 hours of reaction. Wherein, the calculation formula of the volume collected by H 2、CO、CO2、CH4 is as follows: v x＝Vtotal x percent gas content, x is H 2、CO、CO2、CH4,Vtotal is the total volume measured by the flow meter, and the percent of each gas content is determined by the combination of gas chromatography and standard curve method.
TABLE 4 Table 4
| H2(L) | CO(L) | CO2(L) | CH4(L) | Others (L) | |
| Example 1 | 2.5 | 0.0 | 13.7 | 46.9 | 3.7 |
| Example 2 | / | / | / | / | / |
| Example 3 | 1.1 | 0.0 | 12.2 | 42.8 | 1.5 |
| Example 4 | 0.5 | 0.8 | 11.7 | 26.5 | 0.5 |
| Example 5 | 1.3 | 0.0 | 15.5 | 34.8 | 0.6 |
| Example 6 | 3.6 | 0.0 | 20.2 | 46.8 | 1.4 |
| Example 7 | 1.1 | 0.0 | 12.3 | 27.6 | 0.4 |
| Example 8 | 0.9 | 0.0 | 14.8 | 16.3 | 0.1 |
| Example 9 | 2.1 | 0.0 | 13.8 | 47.0 | 2.6 |
| Comparative example 1 | 0.2 | 0.0 | 10.9 | 24.0 | 1.5 |
| Comparative example 2 | 40.5 | 11.7 | 13.6 | 0.4 | 0.2 |
| Comparative example 3 | 3.2 | 0.0 | 4.6 | 1.1 | 0.2 |
| Comparative example 4 | 6.2 | 2.3 | 11.1 | 36.6 | 2.3 |
As can be seen from Table 2, either the A reaction zone uses no catalyst or the B reaction zone uses no catalyst, which results in poor methanation results.
As shown in comparative example 3, the reforming hydrogen production reaction and the methanation reaction solution can be performed without using a catalyst, and the thermal cracking reaction derived from the raw material itself is low in efficiency. In comparative example 1, only the B-zone catalyst is provided with porous nickel, and some catalytic reforming hydrogen production and methanation reactions also occur because porous nickel also has catalytic reforming hydrogen production activity, but the catalytic efficiency is far lower than Pt/ZSM. In comparative example 2, only zone A catalyst was provided with Pt/ZSM-5, resulting in lower CH 4 yield. Since both reactions occur in comparative example 2, hydrogen is further consumed in the second reaction.
When the reaction process was not illuminated, the whole reaction was rendered impossible as shown in example 2.
From examples 1 and 3 to 4, it can be seen that the effect is better than Cu when the catalyst active material M is Pt or Pd in the catalyst in the zone A.
It can be seen from example 1 and comparative example 4 that when the pressure at the reforming hydrogen production reaction is higher than that at the methanation reaction, the CH 4 yield is reduced from 46.9L to 36.6L.
As can be seen from Table 4, when the thickness of the SiC coating is less than 10. Mu.m, such as 5. Mu.m, the reaction temperature for reforming hydrogen production is 206℃and the reaction temperature is lowered, resulting in low reaction efficiency and lower methanation. However, when the thickness of the SiC coating layer exceeds 10 μm, for example, 100 μm, the effect of the SiC coating layer is much as that of example 1, and the effect of the SiC coating layer is not further improved.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but rather is capable of modification and variation without departing from the spirit and scope of the present invention as defined in the following claims.
Claims (24)
1. A process for methanation of high water content organic matter comprising:
The high water content organic matter is subjected to reforming hydrogen production reaction under the catalysis of a reforming hydrogen production active catalyst to obtain a mixture containing H 2, CO and CO 2;
The mixture containing H 2, CO and CO 2 is subjected to methanation reaction under the catalysis of a methanation active catalyst to obtain methane;
the pressure at the reforming hydrogen production reaction is lower than the pressure at the methanation reaction.
2. The process of claim 1, wherein the reforming hydrogen production active catalyst is M@X series catalyst, X is catalyst carrier, M is catalyst active substance,
M is selected from one or more than two of Pt, pd, cu, fe, preferably Pt and/or Pd.
3. The method of claim 2, wherein,
The X is selected from one or more than two of molecular sieve, zirconia and SiO 2;
preferably, the mass ratio of M to X is 1: (10-100).
4. The method of claim 1, wherein,
The methanation active catalyst is selected from one or more than two of porous nickel, ru-based catalyst, co-based catalyst and Rh-based catalyst.
5. The method of claim 1, wherein,
The heat required by the reforming hydrogen production reaction and the methanation reaction is derived from a photo-thermal conversion material, and the photo-thermal conversion material converts light energy into heat energy and provides the heat energy for the reforming hydrogen production reaction and the methanation reaction.
6. The method of claim 5, wherein,
The temperature of the reforming hydrogen production reaction is 150-350 ℃.
7. The method of claim 5, wherein,
The methanation reaction temperature is 150-350 ℃.
8. The method of claim 5, wherein,
The photo-thermal conversion material is selected from one or more than two of SiC, carbon black, graphite and graphene; siC is preferred.
9. The method of claim 1, wherein,
The water content of the high-water-content organic matters is more than or equal to 90% and less than 100%;
preferably, the method comprises the steps of,
The high-water-content organic matter is selected from one of organic wastewater, an aqueous solution containing activated sludge, an aqueous solution containing oil stains, kitchen garbage infiltration water, an aqueous solution containing aquatic plants and oily water.
10. The method of claim 1, wherein,
The difference between the pressure of the methanation reaction and the pressure of the reforming hydrogen production reaction is more than or equal to 100kPa.
11. The method of claim 10, wherein,
The pressure of the reforming hydrogen production reaction is more than or equal to 1.0Mpa.
12. The method of claim 10, wherein,
The pressure of the methanation reaction is more than or equal to 1.1Mpa.
13. The method according to any one of claims 1-12, which is carried out in an apparatus comprising:
The shell body is provided with a plurality of grooves,
The inside of the shell body sequentially comprises a reforming hydrogen production reaction area and a methanation reaction area from top to bottom,
The inner diameter of the shell corresponding to the methanation reaction region is larger than that of the shell corresponding to the reforming hydrogen production reaction region,
The reforming hydrogen production reaction area is provided with a reforming hydrogen production active catalyst,
The methanation reaction area is provided with a methanation active catalyst;
Preferably, the inner diameter of the shell corresponding to the methanation reaction region is more than 2 times of the inner diameter of the shell corresponding to the reforming hydrogen production reaction region.
14. The method of claim 13, wherein,
The outer layer of the shell is coated with a photo-thermal conversion material to form a photo-thermal conversion material coating;
Preferably, before the photothermal conversion material is coated on the outer layer of the shell, the photothermal conversion material is dissolved in an ethanol aqueous solution, and a suspension is formed by ultrasonic waves, and then the photothermal conversion material is coated on the outer layer of the shell;
it is further preferable that the thickness of the coating layer of the photothermal conversion material is 10 μm to 100 μm.
15. The method of claim 14, wherein,
The device is placed at 300-1000 ℃ for calcination after the photothermal conversion material is coated on the outer surface of the shell.
16. The method of claim 14, wherein,
The shell of the photo-thermal conversion material coating is provided with a jacket for isolating air;
Preferably, the jacket is a quartz jacket.
17. An apparatus for a methanation process of high water content organic matter, wherein the apparatus comprises:
The shell body is provided with a plurality of grooves,
The inside of the shell body sequentially comprises a reforming hydrogen production reaction area and a methanation reaction area from top to bottom,
The inner diameter of the shell corresponding to the methanation reaction region is larger than that of the shell corresponding to the reforming hydrogen production reaction region,
The reforming hydrogen production reaction area is provided with a reforming hydrogen production active catalyst,
The methanation reaction area is provided with a methanation active catalyst;
Preferably, the inner diameter of the shell corresponding to the methanation reaction region is more than 2 times of the inner diameter of the shell corresponding to the reforming hydrogen production reaction region.
18. The apparatus of claim 17, wherein,
The outer layer of the shell is coated with a photo-thermal conversion material to form a photo-thermal conversion material coating;
Preferably, before the photothermal conversion material is coated on the outer layer of the shell, the photothermal conversion material is dissolved in an ethanol aqueous solution, and a suspension is formed by ultrasonic waves, and then the photothermal conversion material is coated on the outer layer of the shell;
it is further preferable that the thickness of the coating layer of the photothermal conversion material is 10 μm to 100 μm.
19. The apparatus of claim 18, wherein,
The device is placed at 300-1000 ℃ for calcination after the photothermal conversion material is coated on the outer surface of the shell.
20. The apparatus of claim 18, wherein,
The shell of the photo-thermal conversion material coating is provided with a jacket for isolating air;
Preferably, the jacket is a quartz jacket.
21. The apparatus according to any one of claims 17-20, wherein a methanation process of high water content organic matter is carried out with the apparatus, the process comprising:
The high water content organic matter is subjected to reforming hydrogen production reaction under the catalysis of a reforming hydrogen production active catalyst to obtain a mixture containing H 2, CO and CO 2;
The mixture containing H 2, CO and CO 2 is subjected to methanation reaction under the catalysis of a methanation active catalyst to obtain methane;
the pressure at the reforming hydrogen production reaction is lower than the pressure at the methanation reaction.
22. The apparatus of claim 21 wherein the reforming hydrogen production active catalyst is selected from M@X series catalysts, X is a catalyst support, M is a catalyst active material, and M is one or more selected from Pt, pd, cu, fe, preferably one or more selected from Pt and Pd.
23. The apparatus of claim 22, wherein X is selected from one or more of molecular sieves, zirconia, siO 2;
preferably, the mass ratio of M to X is 1: (10-100).
24. The apparatus according to claim 21, wherein the methanation active catalyst is selected from one or two or more of porous nickel, ru-based catalyst, co-based catalyst, rh-based catalyst.
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