CN116873862A - Method and system for preparing hydrogen from garbage leachate biogas - Google Patents
Method and system for preparing hydrogen from garbage leachate biogas Download PDFInfo
- Publication number
- CN116873862A CN116873862A CN202310979045.7A CN202310979045A CN116873862A CN 116873862 A CN116873862 A CN 116873862A CN 202310979045 A CN202310979045 A CN 202310979045A CN 116873862 A CN116873862 A CN 116873862A
- Authority
- CN
- China
- Prior art keywords
- biogas
- gas
- landfill leachate
- steam
- conversion device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 72
- 239000001257 hydrogen Substances 0.000 title claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000000149 chemical water pollutant Substances 0.000 claims abstract description 47
- 238000000629 steam reforming Methods 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000002918 waste heat Substances 0.000 claims abstract description 15
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 11
- 238000003795 desorption Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 50
- 238000006477 desulfuration reaction Methods 0.000 claims description 48
- 230000023556 desulfurization Effects 0.000 claims description 48
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000746 purification Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 238000004056 waste incineration Methods 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000010802 sludge Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000000419 plant extract Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000009280 upflow anaerobic sludge blanket technology Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/48—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 by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method and a system for preparing hydrogen by using landfill leachate biogas. Wherein the method comprises the following steps: desulfurizing biogas; mixing the desulfurized biogas with saturated steam generated by steam drum or steam turbine extraction according to the ratio of (2-4): 1, and introducing into a steam reforming conversion device to obtain a product containing CO 2 CO and H 2 Is a reformed gas of (2); the converted gas is connected to a medium temperature conversion device to obtain converted gas; the shift gas in S3 is connected into CO 2 The trapping device obtains the product CO 2 The method comprises the steps of carrying out a first treatment on the surface of the The product H is prepared by a pressure swing adsorption device 2 And contains CH 4 、CO、H 2 、CO 2 Is not required for the desorption of air. The heat required in the steam reforming conversion device in the step S2 is generated by the combustion of landfill leachate anaerobic biogas, and is provided after entering a combustor at the top of the steam reforming conversion device for combustion through desorption gas in the step S5. The invention utilizes the electric energy and waste heat generated by the garbage incineration facility, and canCan reduce the energy consumption and the economic cost of hydrogen production.
Description
Technical Field
The invention relates to the technical field of hydrogen preparation, in particular to a method and a system for preparing hydrogen from landfill leachate biogas.
Background
Hydrogen energy is an important strategic choice for energy transformation and economic development promotion in China, and is also an important measure for the national coping with climate change and building a low-carbon society. At present, the preparation of hydrogen at home and abroad mainly depends on fossil raw materials, and the ratio of the fossil raw materials is 95% -99%, so that the clean property of hydrogen energy is greatly reduced, and cleaner hydrogen production raw materials are necessary to be developed. Meanwhile, with the development of social economy and the acceleration of urban process, the output of urban domestic garbage is gradually increased year by year, the urban domestic garbage in China is mainly treated by incineration power generation, and the main component of methane generated by anaerobic treatment of garbage leachate in garbage incineration plants is methane, and the component of the methane is more than 60%, so that the methane is very suitable to be used as a raw material for preparing hydrogen. Because the biogas is derived from household garbage, the obtained hydrogen belongs to green hydrogen and is an ideal form for hydrogen energy utilization. At present, the main body of green hydrogen supply in China is to electrolyze water by using renewable energy sources (such as solar energy, wind energy, nuclear energy and the like) to prepare hydrogen, the hydrogen preparation cost is mainly electricity consumption cost, the electricity consumption for preparing 1 kg of hydrogen is about 35-55 ℃, the electricity consumption cost is determined according to electricity price, and the hydrogen preparation cost is still far higher than Yu Lan hydrogen cost, so that the development of green hydrogen is not facilitated.
The landfill leachate is high-concentration organic wastewater with very complex components, which is obtained from a landfill leachate. Biogas is one of the main products of leachate treatment in waste incineration plants, and comprises methane and carbon dioxide as main components, which are both greenhouse gases, and CH 4 The equivalent of the greenhouse effect is CO 2 More than 20 times of (a). At present, the garbage incineration plants in China treat and utilize the biogas in such a way that the garbage percolate biogas is directly sent into a garbage incinerator for incineration and is used as a supplementary heat source in a waste heat boiler, the energy recovery and utilization efficiency is low, and simultaneously CO exists 2 Emission problems, resulting in energy waste.
Accordingly, improvements are needed in the art.
Disclosure of Invention
In the prior art, garbage incineration plants generally send garbage leachate biogas directly into garbage incinerators for incineration, and the biogas is taken as a supplementary heat source in the waste heat boiler, so that the energy recycling efficiency is low, and meanwhile, CO exists 2 The invention provides a method and a system for preparing hydrogen from landfill leachate biogas, which are used for solving the problems.
To achieve the above object, in a first aspect, the present invention provides a method for preparing hydrogen from landfill leachate biogas, comprising the steps of:
s1, methane desulfurization: desulfurizing the biogas generated by anaerobic treatment of the landfill leachate of the waste incineration plant to obtain desulfurized biogas with the hydrogen sulfide content reduced to below 0.5 ppm;
s2, steam reforming conversion: mixing the desulfurized biogas and saturated steam generated by steam drum or steam turbine extraction according to the ratio of (2-4): 1, and introducing the mixture into a steam reforming conversion device for reforming conversion to obtain a mixture containing CO 2 CO and H 2 Is a reformed gas of (2);
s3, medium temperature transformation: the converted gas in S2 is connected into a medium temperature conversion device, and CO and water vapor are converted into CO through the catalyst reaction 2 And H 2 Obtaining a converted gas;
S4、CO 2 and (3) capturing: the shift gas in S3 is connected into CO 2 Trapping device for selectively adsorbing CO in shift gas by adsorbent 2 Adsorbing to obtain the product CO 2 The gas which is not subjected to variable adsorption is used as raw material gas;
s5, pressure swing adsorption purification: the raw material gas in S4 is passed through a pressure swing adsorption device to obtain a product H 2 And contains CH 4 、CO、H 2 、CO 2 The desorption gas of (2) is taken as supplementary fuel to enter step S2;
the heat required in the steam reforming conversion device in the step S2 is generated by combusting landfill leachate anaerobic biogas, and is provided after entering a combustor at the top of the steam reforming conversion device for combustion through desorption gas in the step S5.
In one implementation, S1 specifically includes: pre-desulfurizing methane generated by anaerobic treatment of landfill leachate of a waste incineration plant, reducing the content of hydrogen sulfide in the methane to below 50ppm, and performing fine desulfurization to obtain desulfurized methane with the content of hydrogen sulfide in the methane reduced to below 0.5ppm, wherein the pre-desulfurization step comprises biological desulfurization and iron oxide dry desulfurization, and the fine desulfurization step is zinc oxide dry desulfurization.
In one implementation, in S1, the pre-desulfurization step further includes coarse filtering condensed water and particulate impurities in the biogas.
In one implementation manner, in S2, the saturated steam is formed after the steam drum or the turbine of the garbage incineration plant extracts steam and then is subjected to temperature and pressure reduction.
In one implementation, in S2, the saturated steam is mixed with the desulphurised biogas in a ratio of 3.2:1.
In one implementation, in S2, the reformed gas is further subjected to waste heat recovery and the temperature is reduced to 320-360 ℃, and the reformed gas is partially evacuated through a waste incineration plant chimney.
In one implementation, in S5, the pressure swing adsorption device is a PSA device.
In a second aspect, the invention also provides a system for preparing hydrogen from landfill leachate biogas, which is used for realizing the method for preparing hydrogen from landfill leachate biogas according to any one of the above, and comprises a biogas generating device, a biogas desulfurizing device, a steam reforming conversion device, a medium-temperature conversion device and a CO which are sequentially connected 2 The biogas sequentially passes through the biogas desulfurization device and the steam reforming conversion device to obtain converted gas, passes through the medium-temperature conversion device to obtain converted gas, and then passes through the CO 2 The trapping device and the pressure swing adsorption purification device are used for obtaining a product H 2 And product CO 2 And simultaneously, the gas which is not adsorbed by the pressure swing adsorption purification device enters the steam reforming conversion device again.
In one implementation, the biogas desulfurization apparatus comprises a filtration tower, a biological desulfurization tower, an iron oxide dry desulfurization tower and a zinc oxide dry desulfurization tower which are connected in sequence.
In one implementation mode, the system for preparing hydrogen from landfill leachate biogas further comprises a waste heat recovery device, wherein the waste heat recovery device is connected with the steam reforming conversion device and is used for cooling the conversion gas.
The beneficial effects are that: according to the method and the system for preparing hydrogen by using the landfill leachate biogas, provided by the invention, the biogas generated by the landfill leachate is used as a hydrogen production raw material, and the electric energy and the waste heat generated by a garbage incineration facility are used for providing the required heat for the steam reforming conversion device, so that the hydrogen production energy consumption and the economic cost can be reduced; meanwhile, the prepared hydrogen is used for garbage collection and transportation vehicles, so that a mode of household garbage treatment, hydrogen production and hydrogen utilization integration is realized; meanwhile, carbon dioxide generated in the hydrogen production process is captured, so that carbon reduction or decarburization in the whole hydrogen production industrial production is realized.
Drawings
FIG. 1 is a flow chart of steps of a method for preparing hydrogen from landfill leachate biogas provided by the invention;
FIG. 2 is a schematic diagram of structural connection of a system for preparing hydrogen from landfill leachate biogas provided by the invention;
fig. 3 is a schematic structural connection diagram of the biogas desulfurization apparatus shown in fig. 2.
Wherein, each reference numeral in the drawings respectively indicates:
10. a biogas generating device; 20. a methane desulfurizing device; 21. a filtering tower; 22. a biological desulfurizing tower; 23. iron oxide dry desulfurizing tower; 24. a zinc oxide dry desulfurizing tower; 30. a temperature and pressure reducing device; 40. a steam reforming conversion device; 50. a waste heat recovery device; 60. a medium temperature conversion device; 70. CO 2 A trapping device; 80. a pressure swing adsorption purification device; 90. CO 2 And a purifying device.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Furthermore, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., described below mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily for the same embodiment or example. The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Referring specifically to fig. 1, fig. 1 is a flow chart of steps of a method for preparing hydrogen from landfill leachate biogas provided by the invention. The invention provides a method for preparing hydrogen from landfill leachate biogas, which comprises the following steps:
s1, methane desulfurization: desulfurizing the biogas generated by anaerobic treatment of the landfill leachate of the waste incineration plant to obtain desulfurized biogas with the hydrogen sulfide content reduced to below 0.5 ppm;
s2, steam reforming conversion: mixing the desulfurized biogas and saturated steam generated by steam drum or steam turbine extraction according to the ratio of (2-4): 1, and introducing the mixture into a steam reforming conversion device for reforming conversion to obtain a mixture containing CO 2 CO and H 2 Is a reformed gas of (2);
s3, medium temperature transformation: the converted gas in S2 is connected into a medium temperature conversion device, and CO and water vapor are converted into CO through the catalyst reaction 2 And H 2 Obtaining a converted gas;
S4、CO 2 and (3) capturing: the shift gas in S3 is connected into CO 2 Trapping device for selectively adsorbing CO in shift gas by adsorbent 2 Adsorbing to obtain the product CO 2 The gas which is not subjected to variable adsorption is used as raw material gas;
s5, pressure swing adsorption purification: the raw material gas in S4 is passed through a pressure swing adsorption device to obtain a product H 2 And contains CH 4 、CO、H 2 、CO 2 The desorption gas of (2) is taken as supplementary fuel to enter step S2;
the heat required in the steam reforming conversion device in the step S2 is generated by combusting landfill leachate anaerobic biogas, and is provided after entering a combustor at the top of the steam reforming conversion device for combustion through desorption gas in the step S5.
Specifically, S1 specifically includes: pre-desulfurizing methane generated by anaerobic treatment of landfill leachate of a waste incineration plant, reducing the content of hydrogen sulfide in the methane to below 50ppm, and performing fine desulfurization to obtain desulfurized methane with the content of hydrogen sulfide in the methane reduced to below 0.5ppm, wherein the pre-desulfurization step comprises biological desulfurization and iron oxide dry desulfurization, and the fine desulfurization step is zinc oxide dry desulfurization.
In the step S1, the pre-desulfurization step is preceded by coarse filtration of condensed water and particulate impurities in the biogas. Furthermore, in the process of generating methane by anaerobic treatment of the landfill leachate of the waste incineration plant, UASB technology is adopted, namely an upflow anaerobic sludge bed reactor is adopted, the landfill leachate enters from the bottom of the upflow anaerobic sludge bed reactor to be mixed and contacted with sludge in a sludge layer, and microorganisms in the sludge decompose organic matters in the landfill leachate to convert the organic matters into methane.
The biological desulfurization in the pre-desulfurization utilizes microorganisms or enzymes contained in the microorganisms to catalyze sulfur-containing compounds including H2S, organic sulfur and the like, and the sulfur contained in the compounds is released to realize desulfurization. The dry desulfurization of iron oxide uses active iron oxide as desulfurizing agent to make H in gas 2 S is fully contacted with active ferric oxide, and generates ferric sulfide and ferrous sulfide, thereby removing H 2 S, S. The zinc oxide dry desulfurization realizes the desulfurization effect by reacting the zinc oxide with sulfur dioxide in the biogas, and adsorbing the sulfur dioxide to generate sulfate. Zinc oxide desulfurization effectively removes hydrogen sulfide and sulfur dioxide in methane through higher adsorption efficiency and faster adsorption rate, and realizes effective desulfurization of methane.
In S2, the saturated steam is formed by temperature and pressure reduction after steam extraction of a steam drum or a steam turbine of the garbage incineration plant. In this embodiment, the steam turbine may be of a primary or secondary modulation extraction type. The high-temperature and high-pressure steam is generated after the steam drum or the steam turbine of the waste incineration plant extracts steam, and is subjected to pressure reduction and temperature reduction through a temperature reduction and pressure reduction step, so that the high-temperature and high-pressure steam reaches the safe use standard. Specifically, in this embodiment, the saturated steam and the desulfurized biogas are mixed according to a ratio of 3.2:1, so as to effectively convert the desulfurized biogas into a mixture containing CO 2 CO and H 2 Is a conversion gas of (a). It should be noted thatIn S2, however, the converted gas is also subjected to waste heat recovery and the temperature is reduced to 320-360 ℃. More specifically, the temperature of the converted gas can be reduced to 340 ℃ through waste heat recovery, and then the subsequent operation is carried out.
In S3, the converted gas enters a medium temperature conversion device to undergo a conversion reaction under the action of a catalyst, and CO and water vapor are converted into CO 2 And H 2 Obtaining a change gas, wherein H in the change gas 2 About 70% of the content of CO 2 The content is about 20%.
In S4, the converted gas is passed through CO 2 Trapping device, under the selective adsorption of adsorbent, and through CO 2 Purification device for forming product CO 2 . The non-absorbed conversion gas enters a pressure swing adsorption purification device. Specifically, in S5, the pressure swing adsorption apparatus is a PSA apparatus, and the difference in adsorption performance of molecular sieves on different gas molecules is used to separate the gas mixture, thereby obtaining the product H 2 。
Referring to fig. 2 and 3 in combination, fig. 2 is a schematic structural connection diagram of a system for preparing hydrogen from landfill leachate biogas, and fig. 3 is a schematic structural connection diagram of a biogas desulfurization apparatus shown in fig. 2. On the other hand, the invention also provides a system for preparing hydrogen by using landfill leachate biogas, which is used for the method for preparing hydrogen by using the landfill leachate biogas, and comprises a biogas generating device 10, a biogas desulfurizing device 20, a steam reforming conversion device 40, a medium-temperature conversion device 60 and CO which are sequentially connected 2 A trapping device 70 and a pressure swing adsorption purification device 80.
Specifically, biogas generated by anaerobic treatment of landfill leachate of a refuse incineration plant sequentially passes through a biogas desulfurization device 20 and a steam reforming conversion device 40 to obtain a wastewater containing CO 2 CO and H 2 Is passed through a medium temperature shift device 60 to obtain a CO-containing gas 2 And H 2 Is passed through the CO 2 Trapping device 70 and pressure swing adsorption purification device 80 to obtain product H 2 And product CO 2 While the gas not adsorbed by the pressure swing adsorption purification apparatus 80 is again introduced into the steam reforming conversion apparatus.
Further, the biogas desulfurization apparatus 20 comprises a filtering tower 21, a biological desulfurization tower 22, an iron oxide dry desulfurization tower 23 and a zinc oxide dry desulfurization tower 24 which are sequentially connected.
The system for preparing hydrogen from landfill leachate biogas further comprises a waste heat recovery device 50, wherein the waste heat recovery device 50 is connected with the steam reforming conversion device 40 and is used for cooling the converted gas. The system for preparing hydrogen from the landfill leachate biogas further comprises a temperature and pressure reduction device 30, wherein the temperature and pressure reduction device 30 is connected with the steam reforming conversion device 40 and is used for carrying out subsequent operation on saturated steam which is produced by steam drum or turbine extraction and can be safely used after being cooled and reduced in pressure.
The temperature and pressure reducing device 30 includes a pressure reducing valve, a desuperheater, and a cooler. The pressure reducing valve automatically adjusts the pressure of steam through a set pressure value, so that the aim of reducing pressure is fulfilled. The desuperheater reduces the temperature of the steam to within a safe range by contacting the steam with a cooling medium. The cooler cools the steam through cooling water, so that the purpose of temperature reduction is achieved.
In general, the method and the system for preparing hydrogen by using the landfill leachate biogas provided by the invention have the advantages that the biogas generated by the landfill leachate is used as a hydrogen production raw material, and the electric energy and the waste heat generated by a garbage incineration facility are used for providing the required heat for the steam reforming conversion device, so that the hydrogen production energy consumption and the economic cost can be reduced; meanwhile, the prepared hydrogen is used for garbage collection and transportation vehicles, so that a mode of household garbage treatment, hydrogen production and hydrogen utilization integration is realized; meanwhile, carbon dioxide generated in the hydrogen production process is captured, so that carbon reduction or decarburization in the whole hydrogen production industrial production is realized.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures or equivalent processes disclosed herein or in the alternative, which may be employed directly or indirectly in other related arts.
Claims (10)
1. The method for preparing hydrogen by using landfill leachate biogas is characterized by comprising the following steps of:
s1, methane desulfurization: desulfurizing the biogas generated by anaerobic treatment of the landfill leachate of the waste incineration plant to obtain desulfurized biogas with the hydrogen sulfide content reduced to below 0.5 ppm;
s2, steam reforming conversion: mixing the desulfurized biogas and saturated steam generated by steam drum or steam turbine extraction according to the ratio of (2-4): 1, and introducing the mixture into a steam reforming conversion device for reforming conversion to obtain a mixture containing CO 2 CO and H 2 Is a reformed gas of (2);
s3, medium temperature transformation: the converted gas in S2 is connected into a medium temperature conversion device, and CO and water vapor are converted into CO through the catalyst reaction 2 And H 2 Obtaining a converted gas;
S4、CO 2 and (3) capturing: the shift gas in S3 is connected into CO 2 Trapping device for selectively adsorbing CO in shift gas by adsorbent 2 Adsorbing to obtain the product CO 2 The gas which is not subjected to variable adsorption is used as raw material gas;
s5, pressure swing adsorption purification: the raw material gas in S4 is passed through a pressure swing adsorption device to obtain a product H 2 And contains CH 4 、CO、H 2 、CO 2 The desorption gas of (2) is taken as supplementary fuel to enter step S2;
the heat required in the steam reforming conversion device in the step S2 is generated by combusting landfill leachate anaerobic biogas, and is provided after entering a combustor at the top of the steam reforming conversion device for combustion through desorption gas in the step S5.
2. The method for preparing hydrogen by landfill leachate biogas according to claim 1, wherein the method specifically comprises the following steps in S1: pre-desulfurizing methane generated by anaerobic treatment of landfill leachate of a waste incineration plant, reducing the content of hydrogen sulfide in the methane to below 50ppm, and performing fine desulfurization to obtain desulfurized methane with the content of hydrogen sulfide in the methane reduced to below 0.5ppm, wherein the pre-desulfurization step comprises biological desulfurization and iron oxide dry desulfurization, and the fine desulfurization step is zinc oxide dry desulfurization.
3. The method for producing hydrogen from landfill leachate biogas according to claim 2, wherein in S1, the pre-desulphurisation step is preceded by coarse filtration of condensed water and particulate impurities in the biogas.
4. The method for preparing hydrogen from landfill leachate biogas according to claim 1, wherein in the step S2, the saturated steam is formed by reducing temperature and pressure after steam extraction of a steam drum or a steam turbine of a garbage incineration plant.
5. The method for producing hydrogen from landfill leachate biogas according to claim 4, wherein in S2, the saturated steam and the desulphurized biogas are mixed according to a ratio of 3.2:1.
6. The method for preparing hydrogen from landfill leachate biogas according to claim 1, wherein in the step S2, the converted gas is subjected to waste heat recovery and the temperature is reduced to 320-360 ℃, and the converted gas is partially emptied through a chimney of a garbage incineration plant.
7. The method for producing hydrogen from landfill leachate biogas according to claim 1, wherein in S5, the pressure swing adsorption device is a PSA device.
8. A system for preparing hydrogen from landfill leachate biogas, which is characterized by being used for realizing the method for preparing hydrogen from landfill leachate biogas according to any one of claims 1-7, and comprising a biogas generating device, a biogas desulfurizing device, a steam reforming conversion device, a medium-temperature conversion device and a CO which are sequentially connected 2 The biogas sequentially passes through the biogas desulfurization device and the steam reforming conversion device to obtain converted gas, passes through the medium-temperature conversion device to obtain converted gas, and then passes through the CO 2 The trapping device and the pressure swing adsorption purification device are used for obtaining a product H 2 And product CO 2 And simultaneously, the gas which is not adsorbed by the pressure swing adsorption purification device enters the steam reforming conversion device again.
9. The system for preparing hydrogen from landfill leachate biogas according to claim 8, wherein the biogas desulfurization apparatus comprises a filtration tower, a biological desulfurization tower, an iron oxide dry desulfurization tower and a zinc oxide dry desulfurization tower which are sequentially connected.
10. The system for producing hydrogen from landfill leachate biogas according to claim 9, further comprising a waste heat recovery device connected to the steam reforming conversion device for cooling the converted gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310979045.7A CN116873862A (en) | 2023-08-04 | 2023-08-04 | Method and system for preparing hydrogen from garbage leachate biogas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310979045.7A CN116873862A (en) | 2023-08-04 | 2023-08-04 | Method and system for preparing hydrogen from garbage leachate biogas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116873862A true CN116873862A (en) | 2023-10-13 |
Family
ID=88256857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310979045.7A Pending CN116873862A (en) | 2023-08-04 | 2023-08-04 | Method and system for preparing hydrogen from garbage leachate biogas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116873862A (en) |
-
2023
- 2023-08-04 CN CN202310979045.7A patent/CN116873862A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Khan et al. | Current status of biogas upgrading for direct biomethane use: A review | |
| Awe et al. | A review of biogas utilisation, purification and upgrading technologies | |
| Papacz | Biogas as vehicle fuel | |
| CN107758617B (en) | Method for producing hydrogen by using biogas biomass | |
| JP4187851B2 (en) | Biomass-based carbon production equipment | |
| CN202322831U (en) | Methane and landfill gas utilization system | |
| CN112159063A (en) | Sludge pyrolysis safe resource utilization process | |
| CN101245262A (en) | Gas-steam combined cycle system and technique based on coal gasification and methanation | |
| CN107129818A (en) | A kind of integrated conduct method of solid waste and nickel-plating waste water | |
| CN103373705B (en) | Method and device for improving grade of medium-and-low-temperature solar thermal power and integrally separating CO2 | |
| EP0942067B1 (en) | Carbon producing apparatus utilizing biomass | |
| CN220537493U (en) | System for preparing hydrogen from landfill leachate biogas | |
| CN102464544A (en) | Method for hydrothermally reducing CO2 or CO into methane by using porous nickel catalyst | |
| WO2020082377A1 (en) | Process for using garbage to prepare liquid-state fuel and chemical products, and garbage catalytic pyrolysis system | |
| CN216191073U (en) | Hydrogen production device for urban wet garbage | |
| CN116873862A (en) | Method and system for preparing hydrogen from garbage leachate biogas | |
| KR102368058B1 (en) | Biogas purification system and purification method using the same | |
| CN205856262U (en) | Biogas electricity generation apparatus in technique for treating industrial wastewater | |
| Deng et al. | Biogas cleaning and upgrading | |
| CN114100688A (en) | Preparation of immobilized biomimetic enzyme and application thereof in flue gas carbon dioxide capture | |
| CN111500333A (en) | Solid waste and alkali liquor circulating desulfurization and decarburization system and working method thereof | |
| CN220684688U (en) | Coupling system for garbage incineration and methane hydrogen production | |
| Kabeyi et al. | Biogas treatment and upgrading techniques | |
| CN216274083U (en) | High-purity biogas generation and biogas residue utilization device | |
| JP2001137691A (en) | Device for carbon dioxide fixation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |