CN116062688A - Solar-driven methane dry reforming hydrogen production system - Google Patents

Solar-driven methane dry reforming hydrogen production system Download PDF

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Publication number
CN116062688A
CN116062688A CN202211689002.7A CN202211689002A CN116062688A CN 116062688 A CN116062688 A CN 116062688A CN 202211689002 A CN202211689002 A CN 202211689002A CN 116062688 A CN116062688 A CN 116062688A
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China
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pipeline
gas
carbon dioxide
mixer
synthesis gas
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CN202211689002.7A
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Chinese (zh)
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吕伟文
苏博生
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Zhejiang Sokete Hydrogen Energy Technology Co ltd
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Zhejiang Sokete Hydrogen Energy Technology Co ltd
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    • 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
    • C01B3/38—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 using catalysts
    • C01B3/384—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 using catalysts the catalyst being continuously externally heated
    • 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
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses a solar-driven methane dry reforming hydrogen production system, which comprises a first mixer, a high Wen Ganchong whole reactor, a solar heat collector, a gas-gas heat exchanger, a flow divider, a second mixer, a medium-temperature shift reactor, a low-pressure steam generator, a water supply deaerator and a pressure swing adsorber, wherein the first mixer is a high-pressure heat exchanger; reinjecting the carbon dioxide separated by the pressure swing adsorber into a high Wen Ganchong whole reactor, wherein heat is provided by concentrated solar heat energy, the molar quantity of the carbon dioxide in the reactor is several times higher than that of methane, the conversion rate of methane and methane is improved, carbon deposition caused by high-temperature pyrolysis of methane is avoided, and the service lives of the reactor and the catalyst are prolonged; the method has the advantages that the carbon dioxide generated in the hydrogen production process is completely recovered and converted into the synthesis gas, the advantages of the two renewable energy sources of solar energy and methane are complemented, and simultaneously hydrogen fuel and synthesis gas fuel are output to the outside, so that the zero emission of the carbon dioxide in the hydrogen production process is realized, and the method has the advantages of simple structure, low production cost and environmental friendliness.

Description

Solar-driven methane dry reforming hydrogen production system
Technical Field
The invention belongs to the technical field of biogas utilization, and particularly relates to a solar-driven biogas dry reforming hydrogen production system.
Background
The biomass resources in China are rich, and the biological biogas becomes an important way for biomass utilization. At present, the biogas utilization technology in China is relatively backward, and the problem of lower biogas utilization efficiency still exists. The complementary utilization of the advantages of the biomass energy and the solar energy is a research hot spot of complementary multiple energy sources in recent years. The methane can be reformed to obtain high-heat-value pollution-free hydrogen fuel, which is the most ideal methane upgrading technical means. Because the main components of the methane are 50% -80% of methane and 20% -40% of carbon dioxide, the methane conversion rate is lower when the methane is subjected to methane carbon dioxide dry reforming reaction, meanwhile, the reforming reaction is a strong endothermic reaction, the methane needs to be carried out at a high temperature above 645 ℃ under the condition of a catalyst, unconverted methane is easy to generate cracking reaction at the high temperature to cause carbon deposition on the surface of the catalyst, and the carbon deposition causes the catalyst to lose activity and even block a reaction tube, so that the service life of the reactor is reduced, and the cost of the catalyst is increased. In order to solve the problem, the currently available method is to add steam into a reforming reactor to make unconverted methane and steam undergo wet reforming reaction, so as to reduce and inhibit carbon deposition, but the steam needs to consume a large amount of heat energy when being heated to high temperature in the reforming reactor, and meanwhile, the requirement on water quality is relatively high, so that the energy consumption and the running cost of the system are increased. In addition, a large amount of carbon dioxide generated in the traditional methane hydrogen production process can cause a greenhouse effect if being directly discharged, so that the recycling of the carbon dioxide is needed to be considered, the complexity of a system is increased, and the popularization and application of the methane reforming hydrogen production technology are restricted. Aiming at the analysis, the invention aims at solving the problems of how to improve the methane conversion rate, reduce the carbon deposition of the reactor and the energy consumption and the operation cost of the system, and finding a new way for recycling the carbon dioxide.
Disclosure of Invention
The invention aims to provide a solar-driven methane dry reforming hydrogen production system which has the advantages of simple structure, low production cost, long service life, environmental friendliness and difficult carbon deposition.
The invention aims at realizing the following technical scheme:
the invention relates to a solar-driven methane dry reforming hydrogen production system, which comprises a first mixer, a solar heat collector, a high Wen Ganchong whole reactor, a gas-gas heat exchanger, a flow divider, a second mixer, a water supply deaerator, a low-pressure steam generator, a medium-temperature shift reactor, a pressure-variable adsorber, a methane input pipeline, a first mixed gas pipeline, a first synthetic gas pipeline, a synthetic gas output pipeline, a second synthetic gas pipeline, a water supply pipeline, a deoxidizing pipeline, a steam pipeline, a second mixed gas pipeline, a shift gas pipeline, a carbon dioxide reinjection pipeline and a hydrogen output pipeline;
the biogas input pipeline is connected with a biogas input port of the first mixer, the carbon dioxide reinjection pipeline is connected with a carbon dioxide inlet of the first mixer, a raw material inlet of the high Wen Ganchong whole reactor is connected with a mixed gas outlet of the first mixer through a mixed gas pipeline I, and a synthesis gas outlet of the high Wen Ganchong whole reactor is connected with a synthesis gas pipeline; the solar heat collector provides concentrated solar heat energy for the high Wen Ganchong whole reactor; the first synthetic gas pipeline is connected with the synthetic gas inlet of the flow divider, the first synthetic gas pipeline passes through the gas-gas heat exchanger in a spiral or zigzag way, and is connected to its hot side, the splitter splitting the synthesis gas into two streams: one strand of synthesis gas outputs product synthesis gas fuel through a synthesis gas output pipeline, the synthesis gas output pipeline passes through the low-pressure steam generator and is connected with the hot side of the low-pressure steam generator, and the other strand of synthesis gas is connected with a synthesis gas inlet of a mixer II through a synthesis gas pipeline II; the water supply is connected with the water vapor inlet of the mixer II through a water supply pipeline, a deoxidization water pipeline and a water vapor pipeline in sequence, wherein a water supply deoxidizer is arranged between the water supply pipeline and the deoxidization water pipeline, and a low-pressure vapor generator is arranged between the deoxidization water pipeline and the water vapor pipeline; the mixed gas outlet of the mixer II is connected with the mixed gas inlet of the medium temperature shift reactor through a mixed gas pipeline II, the shift gas outlet of the medium temperature shift reactor is connected with a hydrogen output pipeline through a shift gas pipeline, and a water supply deaerator and a pressure swing adsorber are sequentially arranged on the shift gas pipeline; the carbon dioxide outlet of the pressure swing absorber is connected with the front section of the carbon dioxide reinjection pipeline; the front section of the carbon dioxide reinjection pipeline is communicated with the carbon dioxide inlet of the gas-gas heat exchanger, and the carbon dioxide outlet of the gas-gas heat exchanger is connected with the carbon dioxide inlet of the first mixer through the rear section of the carbon dioxide reinjection pipeline.
After the scheme is adopted, the invention has the following advantages:
1. improves the methane conversion rate of the marsh gas and reduces carbon deposition in the reactor. Because the carbon dioxide separated by the pressure swing adsorber is reinjected into the reforming reactor, the molar quantity of the carbon dioxide in the reactor is several times higher than that of methane, so that the methane conversion rate is improved to the greatest extent, and meanwhile, carbon deposition caused by high-temperature pyrolysis of the methane is avoided, and the service lives of the reactor and the catalyst are prolonged.
2. Saving water cost and improving the heat economy of the system. Compared with the method of introducing the water vapor into the high-temperature reforming reactor adopted by the traditional technology, the method of introducing the water vapor into the medium-temperature reforming reactor has the advantages of lower temperature of the water vapor in the reactor, reduced water treatment cost and saved water cost. On the other hand, the traditional technology introduces the water vapor into the high-temperature reforming reactor to generate strong endothermic reaction, and the huge heat exchange temperature difference between the water vapor and the heat source causes available energy loss.
3. Realize zero emission of carbon dioxide in the hydrogen production process. The invention completely recovers the carbon dioxide separated by hydrogen production, and reinjects the carbon dioxide to the reforming reaction to be converted into the synthesis gas, thus truly realizing the preparation of hydrogen fuel under the zero emission of carbon dioxide.
4. Realize complementary advantages of various renewable energy sources and coproduction of various products. The invention utilizes the concentrated solar heat energy to provide reaction heat for the dry reforming reaction of the biogas, promotes the low-grade solar heat energy into high-grade fuel chemical energy, and simultaneously upgrades and converts the biogas into the synthetic gas with higher heat value, thereby realizing the complementary advantages of the solar energy and the biological biogas. In addition, the invention outputs two products of hydrogen fuel and synthetic gas fuel at the same time, and the application range is wider.
Drawings
Fig. 1 is a schematic diagram of the system architecture of the present invention.
Detailed Description
As shown in fig. 1, the invention relates to a system for preparing synthetic gas and hydrogen fuel by solar-driven biogas dry reforming, which comprises a mixer I, a solar heat collector 2, a high Wen Ganchong whole reactor 3, a gas-gas heat exchanger 4, a flow divider 5, a mixer II 6, a water supply deaerator 7, a low-pressure steam generator 8, a medium-temperature shift reactor 9, a pressure-variable adsorber 10, a biogas input pipeline 11, a mixed gas pipeline I12, a synthetic gas pipeline I13, a synthetic gas output pipeline 14, a synthetic gas pipeline II 15, a water supply pipeline 16, a deoxidizing water pipeline 17, a steam pipeline 18, a mixed gas pipeline II 19, a shift gas pipeline 20, a carbon dioxide reinjection pipeline 21 and a hydrogen output pipeline 22.
The biogas input pipeline 11 and the carbon dioxide reinjection pipeline 21 are respectively connected with a biogas inlet and a carbon dioxide inlet of the first mixer 1; the mixed gas outlet of the mixer I1 is connected with the raw material inlet of the high-temperature dry reforming reactor 3 through a mixed gas pipeline I12, and the synthesis gas outlet of the high Wen Ganchong reforming reactor 3 is connected with a synthesis gas pipeline I13; the solar heat collector 2 and the high Wen Ganchong whole reactor 3 conduct heat transfer; the first synthesis gas pipeline 13 passes through the gas-gas heat exchanger 4 in a spiral or zigzag manner and then is connected with a synthesis gas inlet of the flow divider 5; the first synthesis gas outlet of the flow divider 5 outputs product synthesis gas outwards through a synthesis gas output pipeline 14, and the second synthesis gas outlet is connected with the synthesis gas inlet of the medium temperature shift reactor 9 through a synthesis gas pipeline II 15; the shift gas outlet of the medium temperature shift reactor 9 is connected with a hydrogen output pipeline 22 through a shift gas pipeline 20, and a water supply deaerator 7 and a pressure swing adsorber 10 are sequentially arranged on the shift gas pipeline 20; the steam outlet of the low-pressure steam generator 5 is connected with the synthesis gas inlet of the medium-temperature shift reactor 9; the water supply inlet of the water supply deaerator 7 is connected with a water supply pipeline 16, and the deaerated water outlet of the water supply deaerator 7 is connected with the deaerated water inlet of the low-pressure steam generator 8 through a deaerated water pipeline 17; the carbon dioxide outlet of the pressure swing absorber 10 is connected with a carbon dioxide reinjection pipeline 21; the carbon dioxide reinjection pipe 21 is connected with the carbon dioxide inlet of the first mixer 1, wherein the carbon dioxide reinjection pipe 21 passes through the gas-gas heat exchanger 4 and is connected with the cold side thereof.
The methane conversion rate of the marsh gas is improved, and carbon deposition in the reactor is reduced; because the carbon dioxide separated by the pressure swing adsorber is reinjected into the reforming reactor, the molar quantity of the carbon dioxide in the reactor is several times higher than that of methane, so that the methane conversion rate is improved to the greatest extent, and meanwhile, carbon deposition caused by high-temperature pyrolysis of the methane is avoided, and the service lives of the reactor and the catalyst are prolonged;
saving water cost and improving the heat economy of the system. Compared with the method of introducing the water vapor into the high-temperature reforming reactor adopted by the traditional technology, the method of introducing the water vapor into the medium-temperature reforming reactor has the advantages of lower temperature of the water vapor in the reactor, reduced water treatment cost and saved water cost. On the other hand, the traditional technology introduces the water vapor into the high-temperature reforming reactor to generate strong endothermic reaction, and the huge heat exchange temperature difference between the water vapor and the heat source causes available energy loss; realize zero emission of carbon dioxide in the hydrogen production process. The invention completely recovers the carbon dioxide separated by hydrogen production, and reinjects the carbon dioxide to the reforming reaction to be converted into the synthesis gas, thus truly realizing the preparation of hydrogen fuel under the zero emission of carbon dioxide.
Realize complementary advantages of various renewable energy sources and coproduction of various products. The invention utilizes the concentrated solar heat energy to provide reaction heat for the dry reforming reaction of the biogas, promotes the low-grade solar heat energy into high-grade fuel chemical energy, and simultaneously upgrades and converts the biogas into the synthetic gas with higher heat value, thereby realizing the complementary advantages of the solar energy and the biological biogas. In addition, the invention outputs two products of hydrogen fuel and synthetic gas fuel at the same time, and the application range is wider.
The working principle of the invention is as follows:
the biogas from the biogas input pipeline 11 and the carbon dioxide gas from the carbon dioxide reinjection pipeline 21 are mixed and then enter the high Wen Ganchong whole reactor 3 to carry out a synthesis reaction, the reaction is carried out under the excessive carbon dioxide atmosphere, and the required heat is provided by the solar heat collector 2. The high-temperature synthesis gas obtained by the high-temperature dry reforming reactor 3 is sent to the gas-gas heat exchanger 4 through the synthesis gas pipeline I13 for waste heat recovery to preheat carbon dioxide. The medium-temperature synthesis gas obtained after releasing heat is divided into two paths: one path of the waste heat is sent to the low-pressure steam generator 8 to recycle the waste heat of the synthesis gas again for generating steam H2O, the obtained steam H2O is sent to the medium-temperature shift reactor 9 through the steam pipeline 18, and the synthesis gas after recycling the waste heat is output to the outside through the synthesis gas output pipeline 14 as a product. The medium temperature shift gas obtained by the medium temperature shift reactor 9 firstly releases heat through the water supply deaerator 7 through the shift gas pipeline 20 to thermally deoxidize the water supply, then the carbon dioxide gas CO2 in the shift gas is separated through the pressure swing adsorber 10, the deoxidized water supply is sent to the low pressure steam generator 8 through the deoxidized water pipeline 17, and the separated high purity hydrogen H2 is output as a product through the hydrogen output pipeline 22. The carbon dioxide gas CO2 separated by the pressure swing absorber 10 is preheated by the gas-gas heat exchanger 4 through the carbon dioxide reinjection pipeline 21 and then sent to the carbon dioxide inlet of the first mixer 1.
The core of the invention is that: the carbon dioxide separated by the pressure swing absorber 10 is reinjected into the high Wen Ganchong whole reactor 3, so that the conversion rate of methane and methane is improved, the carbon deposition problem of the reactor is obviously reduced, and the zero emission of the carbon dioxide is truly realized.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the invention in any way, and any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention falls within the scope of the technical solution of the present invention.

Claims (3)

1. A solar-driven methane dry reforming hydrogen production system is characterized in that: the device comprises a first mixer (1), a solar heat collector (2), a high Wen Ganchong whole reactor (3), a gas-gas heat exchanger (4), a flow divider (5), a second mixer (6), a water supply deaerator (7), a low-pressure steam generator (8), a medium-temperature shift reactor (9), a pressure-variable adsorber (10), a methane input pipeline (11), a first mixed gas pipeline (12), a first synthetic gas pipeline (13), a synthetic gas output pipeline (14), a second synthetic gas pipeline (15), a water supply pipeline (16), a deaeration pipeline (17), a steam pipeline (18), a second mixed gas pipeline (19), a shift gas pipeline (20), a carbon dioxide reinjection pipeline (21) and a hydrogen output pipeline (22);
the biogas input pipeline (11) is connected with a biogas input port of the first mixer (1), the carbon dioxide reinjection pipeline (21) is connected with a carbon dioxide inlet of the first mixer (1), a raw material inlet of the high Wen Ganchong whole reactor (3) is connected with a mixed gas outlet of the first mixer (1) through a first mixed gas pipeline (12), and a synthesis gas outlet of the high Wen Ganchong whole reactor (3) is connected with the first synthesis gas pipeline (13); the first synthesis gas pipeline (13) is connected with a synthesis gas inlet of the splitter (5), the first synthesis gas pipeline (13) passes through the gas-gas heat exchanger (4) and is connected with the hot side of the first synthesis gas pipeline, and the splitter (5) divides the synthesis gas into two parts: one strand of synthesis gas outputs product synthesis gas fuel through a synthesis gas output pipeline, the synthesis gas output pipeline (14) passes through the low-pressure steam generator (8) and is connected with the hot side of the low-pressure steam generator, and the other strand of synthesis gas is connected with a synthesis gas inlet of the mixer II through a synthesis gas pipeline II; the water supply is connected with the water vapor inlet of the mixer II through a water supply pipeline (16), a deoxidization water pipeline (17) and a water vapor pipeline (18) in sequence, wherein a water supply deoxidizer is arranged between the water supply pipeline (16) and the deoxidization water pipeline (17), and a low-pressure vapor generator is arranged between the deoxidization water pipeline and the water vapor pipeline; the mixed gas outlet of the mixer II (6) is connected with the mixed gas inlet of the medium temperature shift reactor through a mixed gas pipeline II, the shift gas outlet of the medium temperature shift reactor (9) is connected with the hydrogen output pipeline through a shift gas pipeline, and a water supply deaerator (7) and a pressure swing adsorber (10) are sequentially arranged on the shift gas pipeline; the carbon dioxide outlet of the pressure swing absorber (10) is connected with the front section of the carbon dioxide reinjection pipeline; the front section of the carbon dioxide reinjection pipeline (21) is communicated with a carbon dioxide inlet of the gas-gas heat exchanger, and a carbon dioxide outlet of the gas-gas heat exchanger (4) is connected with a carbon dioxide inlet of the first mixer through the rear section of the carbon dioxide reinjection pipeline.
2. The solar-driven biogas dry reforming hydrogen production system of claim 1, wherein: the solar collector provides concentrated solar heat energy for the high Wen Ganchong whole reactor.
3. The solar-driven biogas dry reforming hydrogen production system of claim 1, wherein: the synthetic gas pipeline passes through the gas-gas heat exchanger in a spiral or zigzag way.
CN202211689002.7A 2022-12-28 2022-12-28 Solar-driven methane dry reforming hydrogen production system Pending CN116062688A (en)

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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211689002.7A CN116062688A (en) 2022-12-28 2022-12-28 Solar-driven methane dry reforming hydrogen production system

Publications (1)

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CN116062688A true CN116062688A (en) 2023-05-05

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