WO2022242598A1 - 一种基于新能源消纳的天然气制备含氢产品的装置及方法 - Google Patents

一种基于新能源消纳的天然气制备含氢产品的装置及方法 Download PDF

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Publication number
WO2022242598A1
WO2022242598A1 PCT/CN2022/093069 CN2022093069W WO2022242598A1 WO 2022242598 A1 WO2022242598 A1 WO 2022242598A1 CN 2022093069 W CN2022093069 W CN 2022093069W WO 2022242598 A1 WO2022242598 A1 WO 2022242598A1
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hydrogen
natural gas
unit
preheater
inlet
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English (en)
French (fr)
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刘银河
宋虎潮
林啸龙
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Xian Jiaotong University
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Xian Jiaotong University
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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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • 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; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • 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; Reversible storage 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
    • C01B3/58—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • 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; Reversible storage 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
    • C01B3/58—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/586—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • 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
    • C01B2203/0435—Catalytic purification
    • 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
    • C01B2203/0435—Catalytic purification
    • C01B2203/045—Purification by catalytic desulfurisation
    • 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
    • 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
    • C01B2203/04—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
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • 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
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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

Definitions

  • the invention belongs to the technical field of new energy and hydrogen production from natural gas, and in particular relates to a device and method for preparing hydrogen-containing products from natural gas absorbed by new energy.
  • the natural gas reforming hydrogen production technology has the advantages of low cost and mature technology compared with other technologies, it usually uses part of the natural gas combustion as heat energy supply in the hydrogen production process, which brings a certain degree of carbon emissions.
  • the heat energy cannot be fully utilized; in addition, the existence of the burner and the flue greatly increases the complexity of the system and reduces the stability of the system.
  • the object of the present invention is to provide a device and method for producing hydrogen-containing products from natural gas based on new energy consumption, which solves the problems of high energy consumption and poor device stability in hydrogen production from natural gas.
  • the present invention adopts the following technical solutions to achieve:
  • the invention discloses a device for preparing hydrogen-containing products from natural gas based on new energy consumption, including a natural gas raw material inlet, a refined desulfurization unit, a raw material preheater, a conversion reaction unit, an electrothermal conversion unit, a feed water preheater, a high-temperature heat pump, Hydrogenation inlet, feed water inlet and flow mixer; natural gas preheater is installed in the conversion reaction unit;
  • the inlet of the natural gas raw material is connected to the inlet of the refined desulfurization unit through the natural gas preheater, the outlet of the refined desulfurization unit is connected to the inlet of the cold end of the raw material preheater through the mixer, and the outlet of the hot end of the raw material preheater is connected to the inlet of the electrothermal conversion unit.
  • the outlet of the conversion unit is connected to the inlet of the hot end of the raw material preheater, the outlet of the cold end of the raw material preheater is connected to the inlet of the conversion reaction unit, the outlet of the conversion reaction unit is connected to the inlet of the hot end of the feed water preheater through the steam superheater, and the feed water preheater
  • the outlet of the cold end of the heater is connected with the inlet of the high-temperature side of the high-temperature heat pump, the outlet of the low-temperature side of the high-temperature heat pump is connected with the inlet of the hydrogen splitter through the pressure swing adsorption unit, and the outlet of the hydrogen splitter is connected with the hydrogenation port;
  • the feedwater inlet is connected to the inlet of the cold end of the feedwater preheater, the outlet of the hot end of the feedwater preheater is connected to the inlet of the high temperature side of the high temperature heat pump, and the outlet of the high temperature side of the high temperature heat pump is connected to the mixer through the steam superheater.
  • the outlet of the hydrogen splitter is connected to the inlet of the refining desulfurization unit;
  • a steam compressor is provided on the pipeline between the high temperature side outlet of the high temperature heat pump and the steam superheater;
  • the electrothermal conversion unit is equipped with an electrothermal furnace
  • a hydrogen three-way valve is installed on the pipeline between the outlet of the hydrogen splitter and the hydrogen refueling port, a hydrogen compressor is installed on the pipeline between the outlet of the hydrogen gas splitter and the hydrogen refueling port, and a hydrogen compressor is installed on the pipeline between the hydrogen gas splitter outlet and the hydrogen refueling port.
  • a hydrogen storage unit is installed on the pipeline.
  • a renewable power interface is also included, and the electric furnace, high-temperature heat pump, hydrogen compressor, and steam compressor use external renewable energy through the renewable power interface.
  • the invention discloses a method for using the above-mentioned natural gas based on new energy consumption to prepare hydrogen-containing products, including the following operating steps:
  • the natural gas raw material enters the natural gas preheater to obtain the reaction heat from the shift reaction unit, and the temperature rises to above 300°C; at the same time, the feed water enters the feed water preheater for preliminary preheating until it becomes saturated water;
  • the outlet gas of the electrothermal conversion unit contains CO, H 2 , CO 2 , CH 4 and water vapor, and the temperature is above 700°C.
  • the outlet gas first enters the raw material preheater to preheat the mixed raw material of natural gas and water vapor, and at the same time lower its own temperature In order to take place the shift reaction; the reaction exotherm of the shift reaction will be taken away from the reaction unit through the natural gas preheater;
  • the invention discloses a device for preparing hydrogen-containing products from natural gas based on new energy consumption, including a natural gas raw material inlet, a refined desulfurization unit, a raw material preheater, a conversion reaction unit, an electrothermal conversion unit, a feed water preheater, a high-temperature heat pump, Hydrogen-rich fuel outlet, feed water inlet and flow mixer; the shift reaction unit is equipped with a natural gas preheater;
  • the inlet of the natural gas raw material is connected to the inlet of the refined desulfurization unit through the natural gas preheater, the outlet of the refined desulfurization unit is connected to the inlet of the cold end of the raw material preheater through the mixer, and the outlet of the hot end of the raw material preheater is connected to the inlet of the electrothermal conversion unit.
  • the outlet of the conversion unit is connected to the inlet of the hot end of the raw material preheater, the outlet of the cold end of the raw material preheater is connected to the inlet of the conversion reaction unit, the outlet of the conversion reaction unit is connected to the inlet of the hot end of the feed water preheater through the steam superheater, and the feed water preheater
  • the outlet of the cold end of the heater is connected to the inlet of the high-temperature side of the high-temperature heat pump, and the low-temperature side of the high-temperature heat pump is connected to the product output unit;
  • the low-temperature side of the high-temperature heat pump is connected to the inlet of the hydrogen splitter through the CO 2 removal unit, and the outlet of the hydrogen splitter is connected to the rich The hydrogen fuel outlet is connected;
  • the feedwater inlet is connected to the inlet of the cold end of the feedwater preheater, the outlet of the hot end of the feedwater preheater is connected to the inlet of the high temperature side of the high temperature heat pump, and the outlet of the high temperature side of the high temperature heat pump is connected to the mixer through the steam superheater.
  • the outlet of the hydrogen splitter is connected to the inlet of the refining desulfurization unit;
  • a gas-liquid separation unit is also provided on the pipeline between the CO removal unit and the inlet of the hydrogen splitter;
  • a flash evaporator is provided on the high temperature side of the high temperature heat pump, and a heat storage container is provided on the low temperature side of the high temperature heat pump.
  • a steam compressor is provided on the pipeline between the high temperature side outlet of the high temperature heat pump and the steam superheater;
  • the electrothermal conversion unit is equipped with an electrothermal furnace
  • the device for preparing hydrogen-containing products from natural gas based on new energy consumption also includes a renewable power interface, and the electric furnace, high-temperature heat pump, and steam compressor use external renewable energy through the renewable power interface.
  • the invention discloses a method for using the above-mentioned natural gas based on new energy consumption to prepare hydrogen-containing products, including the following operating steps:
  • the natural gas raw material enters the natural gas preheater to obtain the reaction heat from the shift reaction unit, and the temperature rises to above 300°C; at the same time, the feed water enters the feed water preheater for preliminary preheating until it becomes saturated water;
  • the natural gas raw material enters the mixer and mixes with water vapor, and then enters the electrothermal conversion unit for conversion.
  • the electrothermal conversion unit uses electric energy to heat the furnace to 800-890°C to supply heat for the conversion reaction;
  • the outlet gas of the electrothermal conversion unit contains CO, H 2 , CO 2 , CH 4 and water vapor, and the temperature is above 700°C.
  • the outlet gas first enters the raw material preheater to preheat the mixed raw material of natural gas and water vapor, and at the same time lower its own temperature In order to take place the shift reaction; the reaction exotherm of the shift reaction will be taken away from the reaction unit through the natural gas preheater;
  • the product gas at the outlet of the high-temperature heat pump can enter the CO 2 removal unit and the gas-liquid separation unit after being cooled. After the separation is completed, it will be directly output from the hydrogen-rich fuel outlet as hydrogen-rich fuel without being compressed and stored.
  • the above-mentioned device for producing hydrogen-containing products from natural gas based on new energy consumption also includes a skid box for the equipment accommodation unit, and the natural gas raw material inlet, water supply inlet and renewable power interface are respectively provided on the skid box.
  • the present invention has the following beneficial effects:
  • the invention discloses a device for preparing hydrogen-containing products from natural gas based on new energy consumption. After natural gas passes through a natural gas preheater and a refined desulfurization unit, it mixes with preheated water vapor, and then passes through an electrothermal conversion unit and a conversion reaction unit in sequence. 1.
  • the pressure swing adsorption unit completes hydrogen production.
  • the hot fluid of the feedwater preheater is connected to the low-temperature side of the steam superheater and the high-temperature heat pump through the pipeline
  • the cold fluid of the feedwater preheater is connected to the inlet of the feedwater (de-salted water) and the high-temperature side of the high-temperature heat pump through the pipeline.
  • the waste heat of the reaction product is obtained through the steam superheater, feed water preheater and high temperature heat pump to reduce the energy consumption of production and preparation.
  • the present invention uses natural gas as fuel in the existing natural gas reforming hydrogen production technology, uses the generated high-temperature flue gas as a heat source and produces a large amount of carbon emissions, and realizes The efficient use of electric energy simplifies the structure of the original device, reduces the start-up and stop time of the device, makes the device more integrated, and improves the overall stability of the device.
  • the original natural gas hydrogen production equipment is improved by using renewable energy and electric energy through electrothermal reformer, high-temperature heat pump, steam compressor and other equipment.
  • Regenerated electric energy provides a solution to the problem of abandoning wind and solar.
  • the invention discloses a hydrogen production method using the above-mentioned device for preparing hydrogen-containing products from natural gas based on new energy consumption. After natural gas passes through a natural gas preheater and a refined desulfurization unit, it mixes with preheated water vapor, and then passes through electric heating in sequence. The conversion unit, shift reaction unit, and pressure swing adsorption unit complete hydrogen production. A solution is given to the problem of insufficient renewable energy consumption capacity and the problem of clean fuel, and at the same time, an efficient utilization method of different grades of heat energy in a highly integrated natural gas reforming hydrogen production system is given.
  • the invention discloses another device for preparing hydrogen-containing products based on natural gas absorbed by new energy sources.
  • the obtained product gas can enter the CO2 removal unit and the gas-liquid separation unit after shift reaction and multi-stage heat exchange cooling. After the separation is completed It is directly output as hydrogen-rich fuel without being compressed and stored.
  • the invention also discloses a hydrogen-rich fuel method using another device for preparing hydrogen-containing products from natural gas based on new energy consumption, which greatly reduces carbon emissions in the process of hydrogen production from natural gas and improves the energy conversion efficiency of fuel gas.
  • the device is a skid-mounted box structure, which can be transported by vehicles.
  • the skid-mounted structure is designed to efficiently integrate the equipment involved in the reaction process, effectively utilize the heat produced or waste heat in the reaction process, and improve the efficiency of the device.
  • the equipment selection and process flow of the present invention are not limited to the skid-mounted structure, and can also be suitable for large-scale hydrogen production by absorbing natural gas with electricity.
  • the device for preparing hydrogen-containing products based on new energy consumption of natural gas has the following advantages: 1. Electrification of gas hydrogen production: by introducing electrothermal conversion units, high-temperature heat pumps and steam compressors, the device can Efficient use of electric energy to participate in the reaction greatly simplifies the structure of the device, and at the same time removes the natural gas combustion link, significantly reducing carbon emissions in the process of hydrogen production from natural gas.
  • the skid-mounted structure integrates the natural gas water vapor hydrogen production device in the container to improve the integration of the device and equipment, which can effectively reduce the production cycle of the device, reduce land costs, and help to improve renewable energy. The flexibility of power consumption.
  • Cascade utilization of waste heat Design multi-stage waste heat recovery devices, including heat exchangers and high-temperature heat pumps, to effectively use the heat produced or waste heat in the reaction process, and improve the efficiency of the device.
  • the device has a renewable power interface, water supply (de-salted water) inlet, natural gas raw material inlet, and hydrogen refueling port.
  • water supply de-salted water
  • natural gas raw material inlet natural gas raw material inlet
  • hydrogen refueling port hydrogen refueling port
  • Fig. 1 is a structural schematic diagram of a skid-mounted natural gas hydrogen production device based on new energy consumption according to the present invention
  • Fig. 2 is a schematic structural diagram of a skid-mounted natural gas hydrogen-rich fuel preparation device based on new energy consumption according to the present invention.
  • 100- skid box 200- refined desulfurization unit; 201- electrothermal conversion unit; 202- conversion reaction unit; 203- pressure swing adsorption unit; 204- gas-liquid separation unit; 205- electric furnace; Removal unit; 300-steam superheater; 301-natural gas preheater; 302-feed water preheater; 303-raw material preheater; 400-high temperature heat pump; 401-flash evaporator; 402-heat storage container; 500-hydrogen split 501-Hydrogen compressor; 502-Hydrogen three-way valve; 503-Hydrogen storage unit; 504-Hydrogen refueling port; ; B-water supply inlet; C-renewable power supply interface.
  • the present invention provides a device for preparing hydrogen-containing products from natural gas based on new energy consumption, which constitutes a skid-mounted natural gas hydrogen production device based on new energy consumption, specifically including:
  • Skid box 100 refined desulfurization unit 200, electrothermal conversion unit 201, shift reaction unit 202, pressure swing adsorption unit 203, gas-liquid separation unit 204, steam superheater 300, natural gas preheater 301, feed water preheater 302, raw material Preheater 303, high temperature heat pump 400, flash evaporator 401, heat storage container 402, hydrogen splitter 500, hydrogen compressor 501, hydrogen three-way valve 502, hydrogen storage unit 503, hydrogenation port 504, flow mixer 600, vapor compression Machine 700, natural gas raw material inlet A, feed water inlet (feed water (de-salted water) inlet) B, and renewable power interface C.
  • the skid box 100 is an equipment accommodation unit; the electrothermal conversion unit 201 is provided with an electrothermal furnace 205 to ensure the reaction temperature; the inlet of the electrothermal conversion unit 201 is connected with the hot end outlet of the raw material preheater 303 through a pipeline, and the electrothermal conversion The outlet of the unit 201 is connected to the inlet of the hot end of the raw material preheater 303 through a pipeline; a natural gas preheater 301 is provided in the shift reaction unit 202 to cool down the temperature of the shift reaction while preheating the raw material; the high temperature side of the high temperature heat pump 400 is equipped with The flash evaporator 401 is used to generate steam.
  • the low temperature side of the high temperature heat pump 400 is provided with a heat storage container 402.
  • the heat storage container 402 is used as the cold end of the high temperature steam heat pump 400 to cool the reaction products and store the thermal energy of the reactants.
  • the outlet of the low temperature side of the high temperature heat pump 400 is connected to the inlet of the hydrogen splitter 500 through the pressure swing adsorption unit 203 , and the outlet of the high temperature side of the high temperature heat pump 400 is connected to the mixer 600 through the steam superheater 300 .
  • a gas-liquid separation unit 204 is also provided on the pipeline between the PSA unit 203 and the inlet of the hydrogen splitter 500 ; the PSA unit 203 is connected to the natural gas preheater 301 .
  • a steam compressor 700 is provided on the pipeline between the hot end of the high temperature heat pump 400 and the steam superheater 300 .
  • the electrothermal furnace 205, high temperature heat pump 400, hydrogen compressor 501, and steam compressor 700 in the electrothermal conversion unit 201 use external renewable energy through the renewable power interface C.
  • the feed water preheater 302 is connected to the high temperature side of the steam superheater 300 and the high temperature heat pump 400 through pipelines, the feed water inlet B is connected to the cold end inlet of the feed water preheater 302, and the hot end outlet of the feed water preheater 302 is connected to the high temperature heat pump
  • the high temperature side inlet at 400 is connected, and the feed water passes through the steam superheater 300 , the feed water preheater 302 , and the high temperature heat pump 400 to obtain the waste heat of the reaction product.
  • the high temperature heat pump 400 uses renewable electric energy, and the heat source is the heat energy of the outlet gas of the pressure swing adsorption unit 203.
  • the high temperature side inlet of the high temperature heat pump 400 is connected to the cold end outlet of the feed water preheater 302 and the flash evaporator 401 through pipelines.
  • the preheated feed water is upgraded to saturated water through the high-temperature heat pump 400, the flash evaporator 401 evaporates the saturated water to form steam, and the steam compressor 700 compresses the generated steam.
  • the high temperature heat pump 400 is provided with a heat storage container 402 to collect the waste heat of the reaction product and cool it down.
  • the hot fluid in the steam superheater 300 is connected to the feedwater preheater 302 and the shift reaction unit 202 through pipelines, and the cold fluid in the steam superheater 300 is connected to the flash evaporator 401 and the flow mixer 600 through pipelines.
  • the heat source of the natural gas preheater 301 in the shift reaction unit 202 is the heat released by the reaction in the shift reaction unit 202 , and the cold end of the natural gas preheater 301 is connected to the inlet A of the natural gas raw material and the inlet of the refined desulfurization unit 200 through pipelines.
  • the outlet of the cold end of the raw material preheater 303 is connected to the inlet of the conversion reaction unit 202, the outlet of the conversion reaction unit 202 is connected to the inlet of the hot end of the feed water preheater 302 through the steam superheater 300, and the hot fluid pipe of the raw material preheater 303 is connected to the electric heater
  • the outlet of the conversion unit 201 is connected to the inlet of the conversion reaction unit 202
  • the raw material preheater 303 is connected to the outlet of the flow mixer 600 and the inlet of the electrothermal conversion unit 201 by a cold fluid pipe.
  • the inlet of the cold end of the raw material preheater 303 is connected to the outlet of the refined desulfurization unit 200 through the mixer 600 , and the natural gas raw material inlet A is connected to the inlet of the refined desulfurization unit 200 through the natural gas preheater 301 .
  • One of the hydrogen outlets of the hydrogen splitter 500 can divert part of the hydrogen to supply the refining desulfurization unit 200 and connect with the inlet of the refining desulfurization unit 200.
  • the other hydrogen outlet of the hydrogen splitter 500 is connected to the hydrogenation port 504.
  • a hydrogen three-way valve 502 is provided on the pipeline between the hydrogen port 504, a hydrogen compressor 501 is provided on the pipeline between the outlet of the hydrogen splitter 500 and the hydrogen three-way valve 502, and a hydrogen compressor 501 is provided on the pipeline between the hydrogen three-way valve 502 and the hydrogenation port 504.
  • a hydrogen storage unit 503 is provided on the pipeline between them, and the hydrogen splitter 500 does not split when the natural gas raw material inlet A is fed with hydrogen-doped natural gas.
  • the hydrogen three-way valve 502 is used to control the external supply of the produced hydrogen or the storage in the device.
  • the present invention provides another device for preparing hydrogen-containing products from natural gas based on new energy consumption, which constitutes a skid-mounted natural gas hydrogen-rich fuel preparation device based on new energy consumption, specifically including:
  • Skid box 100 refined desulfurization unit 200, electrothermal conversion unit 201, shift reaction unit 202, gas-liquid separation unit 204, CO removal unit 206, steam superheater 300, natural gas preheater 301, feed water preheater 302, Raw material preheater 303, high temperature heat pump 400, flash evaporator 401, heat storage container 402, hydrogen splitter 500, hydrogen compressor 501, hydrogen three-way valve 502, hydrogen storage unit 503, hydrogen-rich fuel outlet 505, flow mixer 600, Steam compressor 700, natural gas raw material inlet A, feed water inlet B, and renewable power interface C.
  • the skid box 100 is an equipment accommodation unit; the electrothermal conversion unit 201 is provided with an electrothermal furnace 205 to ensure the reaction temperature; the inlet of the electrothermal conversion unit 201 is connected with the hot end outlet of the raw material preheater 303 through a pipeline, and the electrothermal conversion The outlet of the unit 201 passes through the pipeline and the hot end inlet of the raw material preheater 303; the shift reaction unit 202 is equipped with a natural gas preheater 301 for cooling the shift reaction while preheating the raw material; the high temperature side of the high temperature heat pump 400 is equipped with a flash evaporator 401 is used to generate steam.
  • the low-temperature side of the high-temperature heat pump 400 is provided with a heat storage container 402.
  • the heat storage container 402 is used as the cold end of the high-temperature steam heat pump 400 to cool the reaction products and store the heat energy of the reactants.
  • the low-temperature side outlet of the high-temperature heat pump 400 is connected to the inlet of the hydrogen splitter 500 through the CO removal unit 206
  • the high-temperature side outlet of the high-temperature heat pump 400 is connected to the flow mixer 600 through the steam superheater 300 .
  • a gas-liquid separation unit 204 is also provided on the pipeline between the CO 2 removal unit 206 and the inlet of the hydrogen splitter 500 .
  • a steam compressor 700 is provided on the pipeline between the high temperature side of the high temperature heat pump 400 and the steam superheater 300 .
  • the electrothermal furnace 205, the high temperature heat pump 400, and the steam compressor 700 in the electrothermal conversion unit 201 use external renewable energy through the renewable power interface C.
  • the hot end of the feedwater preheater 302 is connected to the cold end of the steam superheater 300 and the high temperature heat pump 400 through pipelines, the feedwater inlet B is connected to the inlet of the cold end of the feedwater preheater 302, and the outlet of the hot end of the feedwater preheater 302 is connected to and The high temperature side inlet of the high temperature heat pump 400 is connected, and the feed water passes through the steam superheater 300, the feed water preheater 302, and the high temperature heat pump 400 to obtain the waste heat of the reaction product.
  • the high-temperature heat pump 400 uses renewable electric energy, and the heat source is the medium-temperature thermal energy of the outlet gas of the pressure swing adsorption unit 203 .
  • the preheated feed water is upgraded to saturated water through the high-temperature heat pump 400, the flash evaporator 401 evaporates the saturated water to form steam, and the steam compressor 700 compresses the generated steam.
  • the high temperature heat pump 400 is provided with a heat storage container 402 to collect the waste heat of the reaction product and cool it down.
  • the hot fluid in the steam superheater 300 is connected to the feedwater preheater 302 and the shift reaction unit 202 through pipelines, and the cold fluid in the steam superheater 300 is connected to the flash evaporator 401 and the flow mixer 600 through pipelines.
  • the heat source of the natural gas preheater 301 in the shift reaction unit 202 is the heat released by the reaction in the shift reaction unit 202 , and the cold end of the natural gas preheater 301 is connected to the inlet A of the natural gas raw material and the inlet of the refined desulfurization unit 200 through pipelines.
  • the outlet of the cold end of the raw material preheater 303 is connected to the inlet of the conversion reaction unit 202, the outlet of the conversion reaction unit 202 is connected to the inlet of the hot end of the feed water preheater 302 through the steam superheater 300, and the hot end of the raw material preheater 303 is connected to the electrothermal conversion
  • the outlet of the unit 201 is connected to the inlet of the conversion reaction unit 202
  • the cold fluid pipeline of the raw material preheater 303 is connected to the outlet of the flow mixer 600 and the inlet of the electrothermal conversion unit 201 .
  • the inlet of the cold end of the raw material preheater 303 is connected to the outlet of the refined desulfurization unit 200 through the mixer 600 , and the natural gas raw material inlet A is connected to the inlet of the refined desulfurization unit 200 through the natural gas preheater 301 .
  • One of the hydrogen outlets of the hydrogen splitter 500 can divert part of the hydrogen to supply the refined desulfurization unit 200 and connect with the inlet of the refined desulfurization unit 200.
  • the other hydrogen outlet of the hydrogen splitter 500 is connected to the hydrogen-rich fuel outlet 505.
  • the hydrogen gas splitter 500 does not split the flow when the hydrogen-doped natural gas is used.
  • the multiple electrothermal conversion tubes contained in the electrothermal conversion unit 201 are not limited to two. All heat exchangers are arranged according to the heat capacity flow rate matching method, so that the heat capacity flow rates of the hot fluid and the cold fluid in the heat exchanger are as consistent as possible, reducing the heat exchange temperature difference between the cold and hot fluids, and ensuring the efficiency of the heat exchanger. In order to meet the matching of the heat capacity flow rate of the cold and hot flow of the heat exchanger and improve the conversion rate of natural gas, the reaction water-to-carbon ratio should be greater than 4.
  • the device for preparing hydrogen-containing products based on natural gas absorbed by new energy in the present invention
  • the device is a skid-packed box structure that can be transported by vehicles.
  • the equipment selection and process flow of the present invention are not limited to the skid-mounted structure, and are also suitable for large-scale hydrogen production by absorbing natural gas with electricity.
  • the present invention provides a device for preparing hydrogen-containing products based on natural gas absorbed by new energy.
  • the device for preparing hydrogen-containing products based on natural gas absorbed by new energy can realize two preparation modes: 1) including Under the operating strategy with higher purity, that is, to use the device for producing hydrogen-containing products based on new energy consumption natural gas to realize hydrogen production; 2) to use the device for producing hydrogen-containing products based on new energy consumption natural gas to realize production Take hydrogen-rich fuel.
  • the reaction path of each raw material is as follows:
  • the equipment contained in the device can be mainly divided into five modules, among which the skid box 100 is the equipment accommodation unit; the refined desulfurization unit 200, the electrothermal conversion unit 201, the conversion reaction unit 202, the pressure swing adsorption unit 203 and the gas-liquid separation unit 204 constitute the natural gas production unit.
  • Hydrogen module; steam superheater 300, natural gas preheater 301, feed water preheater 302 and raw material preheater 303 constitute a waste heat recovery module in the hydrogen production process;
  • high temperature heat pump 400, flash evaporator 401 and heat storage container 402 constitute a high temperature heat pump Module;
  • hydrogen splitter 500, hydrogen compressor 501, hydrogen three-way valve 502, hydrogen storage unit 503 and hydrogenation port 504 constitute a hydrogen processing module.
  • the reaction path sequence of natural gas raw material is natural gas preheater 301, refining desulfurization unit 200, mixer 600, raw material preheater 303, electrothermal conversion unit 201, raw material preheater 303, shift reaction unit 202, steam superheater 300, Feed water preheater 302, high temperature heat pump 400, pressure swing adsorption unit 203, gas-liquid separation unit 204, hydrogen splitter 500, hydrogen compressor 501, hydrogen three-way valve 502, hydrogenation port 504 or hydrogen storage unit 503.
  • each device is connected through a gas pipeline.
  • the sequence of feed water entering the reactor is feed water preheater 302 , high temperature heat pump 400 , flash evaporator 401 , steam compressor 700 , steam superheater 300 , and flow mixer 600 .
  • the electric heating furnace 205, high temperature heat pump 400, hydrogen compressor 501, and steam compressor 700 in the electrothermal conversion unit 201 all use external renewable energy through the renewable power interface C, and the external electric energy should be general alternating current;
  • the water supply inlet B should be The water after the desalination treatment is connected, and the pressure should not exceed 0.5MPa, so that the saturation temperature is not higher than 150°C to meet the evaporation process of the high-temperature heat pump 400;
  • the steam compressor 700 is preferably a screw-type steam compressor, which can compress water vapor to Above 1.5MPa meets the reaction pressure.
  • the design and layout of the heat exchanger follows the heat capacity flow rate matching.
  • the specific heat capacity of the reaction product is higher than the specific heat capacity of the raw material and feed water. In order to make the heat capacity of the cold and hot fluids in the heat exchanger closer, the inlet water-to-carbon ratio should be greater than 4.
  • the heat source of the high temperature heat pump 400 is the heat accumulated in the heat storage container 402.
  • the heat comes from the heat energy of the output product after the heat exchange of the feed water preheater 302.
  • the internal temperature of the heat storage container 402 should be higher than 80°C.
  • the hot end of the high-temperature heat pump 400 is connected to the feedwater preheater 302 and the flash evaporator 401 through pipelines.
  • the internal working medium of the high-temperature heat pump 400 has an evaporation temperature of around 80°C on the low-pressure side, and a high-pressure condensation temperature of 150°C; the high-temperature heat pump module includes a flash evaporator 401,
  • the flash evaporator can flash saturated water at 150°C into steam for output.
  • the high-temperature heat pump 400 improves the thermal energy grade, heats the preheated feed water into saturated water, and the flash evaporator 401 evaporates the saturated water to form steam.
  • the heat source of the natural gas preheater 301 in the shift reaction unit 202 is the heat released by the reaction in the shift reaction unit 202 , and the cold end is connected to the natural gas raw material inlet A and the refined desulfurization unit 200 through pipelines. Part of the heat of the shift reaction unit is taken away by the raw natural gas to realize the cooling of the shift reaction, which is conducive to the positive progress of the shift reaction and can realize the preheating of the natural gas raw material.
  • Hydrogen is separated from the hydrogen splitter 500 including hydrogen, and part of the hydrogen is supplied to the refining desulfurization unit 200, because the reaction in the refining desulfurization unit requires hydrogen to participate.
  • One of the reactions includes olefin saturation reactions. Due to the presence of olefin double bonds, the molecular carbon-hydrogen ratio is high. Carbon deposition is easy to form during the high-temperature conversion reaction. Converting olefins to alkanes can help reduce the carbon deposition of the catalyst in the reformer, increase the service life of the catalyst and reduce the difficulty of catalyst replacement.
  • hydrogen reacts with olefins Produces alkanes.
  • the second reaction is the conversion reaction of organic sulfur-containing compounds.
  • Hydrogen reacts with organic sulfur-containing compounds including mercaptan, sulfide, disulfide, thiophene, carbon oxysulfide, carbon disulfide, etc. under catalytic action to form H 2 S , and then solidify the sulfur by reacting with ZnO (solid).
  • the hydrogen splitter 500 does not supply hydrogen to the refining desulfurization unit 200 .
  • the hydrogen three-way valve 502 is used to control the external supply or internal storage of the produced hydrogen, which depends on the work performed by the skid-mounted device and the environment provided on site. When the hydrogen storage equipment is provided on site, it can be output externally. Hydrogen storage equipment not provided will be stored in hydrogen storage tanks in the unit.
  • the product gas can enter the CO 2 removal unit 206 and the gas-liquid separation unit 204 after the transformation reaction and multi-stage heat exchange cooling. It is directly output as hydrogen-rich fuel without being compressed and stored.
  • the invention also provides the operation steps of the device for preparing hydrogen-containing products from natural gas based on new energy consumption. It also corresponds to the operation steps in the two modes of hydrogen production and hydrogen-rich fuel production. Therefore, the specific Methods include the following:
  • the natural gas raw material enters the natural gas preheater 301 to obtain the reaction heat from the shift reaction unit 202, and the temperature rises to above 300°C; at the same time, the feed water (de-salted water) enters the feed water preheater 302 for preliminary preheating until it becomes saturated water .
  • Carbon oxysulfide COS+H 2 ⁇ CO+H 2 S
  • the natural gas raw material enters the mixer 600 to mix with water vapor, and then enters the electrothermal conversion unit 201 for conversion.
  • the electrothermal conversion unit 201 uses electric energy to heat the furnace to 800-890°C to supply the conversion reaction to absorb heat.
  • the conversion reaction equation As follows:
  • the outlet gas of the electrothermal conversion unit 201 mainly contains CO, H 2 , CO 2 , CH 4 and water vapor, and the temperature is above 700°C. After the outlet gas flows out, it first enters the raw material preheater 303 to preheat the mixed raw material of natural gas and water vapor. heat while lowering its own temperature for the shift reaction to take place. Enter conversion reaction unit 202 and take place following reaction:
  • the reaction temperature ranges from 320-420°C. This reaction is an exothermic reaction, and low temperature is conducive to the reaction. Therefore, the exothermic heat of the shift reaction will be taken away from the reaction unit through the natural gas preheater 301 .
  • the product gas after the shift reaction enters the steam superheater 300 and the feedwater preheater 302 to release heat, and then releases the heat in the heat storage container 402 provided by the high temperature heat pump 400 as a heat source for the high temperature heat pump 400 .
  • the high-temperature heat pump 400 extracts heat and uses electric energy to improve the energy grade and evaporate the saturated water at the outlet of the feed water preheater 302 .
  • the hydrogen gas enters the gas-liquid separation unit 204 after pressure swing adsorption to realize gas-liquid separation. Then enter the hydrogen splitter 500 to divert part of the hydrogen for refining and desulfurization, and most of the hydrogen enters the hydrogen compressor 501 to be compressed and then exported or stored.
  • the natural gas inlet is supplied with hydrogen-doped natural gas, it does not divert to the refined desulfurization unit 200 .
  • the working principle of the present invention is:
  • the natural gas has undergone a preheating and a prereaction before entering the electrothermal conversion unit 201.
  • the first preheating is to absorb the transformation reaction heat release in the natural gas preheater 301, and the first prereaction is to enter the refining desulfurization unit 200 to complete desulfurization;
  • Before entering the electrothermal conversion unit 201 it undergoes four stages of heating, and the required heat comes from the waste heat of the reaction process and the work of the steam compressor 700. Two of them are heated in the steam superheater 300 and the feed water preheater 302 respectively.
  • the heat source is the product waste heat of the conversion reaction unit 202.
  • the third is to use the high-temperature heat pump 400 to use the low-temperature waste heat of the product to obtain heat to complete evaporation.
  • the fourth is to use the steam compressor 700 to pressurize the steam to meet the needs of the reaction.
  • the natural gas and steam are mixed, and undergo a preheating in the raw material preheater 303 , and the heat source is the waste heat of the product of the electrothermal conversion unit 201 . After preheating, it enters the electrothermal reformer to complete the conversion. The gas at the outlet of the electrothermal conversion unit 201 undergoes four temperature drops and one exothermic reaction after being discharged.
  • the steam heated by the device 300 completes the second temperature drop; then enters the feed water preheater 302 to exchange heat with the feed water to complete the third temperature drop; then enters the high-temperature heat pump 400 to transfer heat to the feed water to complete the fourth temperature drop.
  • the lower hydrogen temperature in the gas-liquid separation unit 204 can ensure that more water can be removed and the purity of hydrogen can be improved.

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Abstract

本发明公开了一种基于新能源消纳的天然气制备含氢产品的装置及方法，属于新能源与天然气制氢技术领域。所述基于新能源消纳的天然气制备含氢产品的装置中，天然气在经过天然气预热器和精制脱硫单元后与预热完成的水蒸气混流，依次经过电热转化单元、变换反应单元、变压吸附单元完成氢气或富氢燃料的生产。本发明可及时消纳新能源电力，大大降低天然气制氢过程中的碳排放，与此同时给出天然气重整制氢系统在高度集成下不同品位热能的高效利用方法。

Description

一种基于新能源消纳的天然气制备含氢产品的装置及方法 技术领域
本发明属于新能源与天然气制氢技术领域，具体涉及一种基于新能源消纳的天然气制备含氢产品的装置及方法。
 背景技术
大规模发展风能、太阳能等可再生清洁能源，推进能源消费结构向低碳化和清洁化方向转型已成为能源发展的新风向。然而以现有技术角度看，可再生能源的供需协同仍存在矛盾，风能光能产生的电无法及时消纳与传输，弃风弃电现状依然严重。另一方面氢能作为真正的清洁燃料受到广泛关注与研究，灵活地将富余可再生能源发电与氢能生产结合起来将成为解决可再生能源消纳问题和终端燃料清洁化的有力解决方案。
在制氢技术中天然气重整制氢技术虽然相比其他技术具有成本低、技术成熟等优点，但其在制氢过程中通常使用部分天然气燃烧作为热能供给，在带来一定程度碳排放的同时不能做到热能的充分利用；此外，燃烧器以及烟道的存在大大增加了系统的复杂程度，降低了系统的稳定性。
此外，现有天然气重整制氢厂往往规模较大，集成度不高，同时现有装置运输不便、占地面积大，不适合跟随风光资源的波动即用即走，难以实现资源的实时消纳；且天然气重整制氢厂建设周期长，土建成本高、现场调试周期长，不利于装置整体的投资回收。
 技术问题
为了克服上述现有技术的缺点，本发明的目的在于提供一种基于新能源消纳的天然气制备含氢产品的装置及方法，解决了天然气制氢中高能耗成本、且装置稳定性差的问题。
 技术解决方案
为了达到上述目的，本发明采用以下技术方案予以实现：
本发明公开了一种基于新能源消纳的天然气制备含氢产品的装置，包括天然气原料入口、精制脱硫单元、原料预热器、变换反应单元、电热转化单元、给水预热器、高温热泵、加氢口、给水入口和混流器；变换反应单元内设有天然气预热器；
天然气原料入口通过天然气预热器与精制脱硫单元进口接通，精制脱硫单元出口通过混流器与原料预热器冷端入口接通，原料预热器热端出口与电热转化单元进口接通，电热转化单元出口与原料预热器热端入口接通，原料预热器冷端出口与变换反应单元进口接通，变换反应单元出口通过蒸汽过热器与给水预热器热端入口接通，给水预热器冷端出口与和高温热泵高温侧入口接通，高温热泵低温侧出口经过变压吸附单元与氢气分流器进口接通，氢气分流器出口与加氢口接通；
给水入口与给水预热器冷端入口接通，给水预热器热端出口与和高温热泵高温侧入口接通，高温热泵高温侧出口通过蒸汽过热器与混流器接通。
优选地，氢气分流器出口与精制脱硫单元进口接通；
变压吸附单元与氢气分流器进口之间的管路上还设有气液分离单元；变压吸附单元与天然气预热器接通；
高温热泵高温侧设有闪蒸器，高温热泵低温侧设有蓄热容器。
优选地，高温热泵高温侧出口与蒸汽过热器之间的管路上设有蒸汽压缩机；
电热转化单元内设有电热炉膛；
氢气分流器出口与加氢口之间的管路上设有氢气三通阀，氢气分流器出口与氢气三通阀之间的管路上设有氢气压缩机，氢气三通阀与加氢口之间的管路上设有氢气储存单元。
进一步优选地，还包括可再生电源接口，电热炉膛、高温热泵、氢气压缩机、蒸汽压缩机通过可再生电源接口使用外接可再生能源电能。
本发明公开了一种利用上述基于新能源消纳的天然气制备含氢产品的装置的方法，包括以下运行步骤：
1）天然气原料进入天然气预热器，获取来自变换反应单元的反应放热，温度升高至300℃以上；同时给水进入给水预热器进行初步预热到成饱和水；
2）初步预热后天然气原料与循环氢气同时进入精制脱硫单元，发生烯烃饱和反应以及有机含硫物脱硫反应；
3）脱硫后天然气原料进入混流器与水蒸气混合，之后进入电热转化单元进行转化，电热转化单元使用电能将炉膛加热到800-890℃用来供给转化反应吸热；
4）电热转化单元出口气包含CO、H 2、CO 2、CH 4以及水蒸气，温度在700℃以上，出口气先进入原料预热器对天然气和水蒸气混合原料预热，同时降低自身温度以便发生变换反应；变换反应的反应放热将通过天然气预热器带离反应单元；
5）变换反应之后的产物气体进入蒸汽过热器和给水预热器放热，之后将热量释放于高温热泵设有的蓄热容器中，作为高温热泵的热源；高温热泵将热量提取用电能将能源品位提升，使给水预热器出口的饱和水蒸发；
6）高温热泵出口的产物进入变压吸附装置对除氢气外气体进行吸附得到高纯度氢气。
本发明公开了一种基于新能源消纳的天然气制备含氢产品的装置，包括天然气原料入口、精制脱硫单元、原料预热器、变换反应单元、电热转化单元、给水预热器、高温热泵、富氢燃料出口、给水入口和混流器；变换反应单元内设有天然气预热器；
天然气原料入口通过天然气预热器与精制脱硫单元进口接通，精制脱硫单元出口通过混流器与原料预热器冷端入口接通，原料预热器热端出口与电热转化单元进口接通，电热转化单元出口与原料预热器热端入口接通，原料预热器冷端出口与变换反应单元进口接通，变换反应单元出口通过蒸汽过热器与给水预热器热端入口接通，给水预热器冷端出口与和高温热泵高温侧入口接通，高温热泵低温侧与产物产出单元连接；高温热泵低温侧经过CO 2脱除单元与氢气分流器进口接通，氢气分流器出口与富氢燃料出口接通；
给水入口与给水预热器冷端入口接通，给水预热器热端出口与和高温热泵高温侧入口接通，高温热泵高温侧出口通过蒸汽过热器与混流器接通。
优选地，氢气分流器出口与精制脱硫单元进口接通；
CO 2脱除单元与氢气分流器进口之间的管路上还设有气液分离单元；
高温热泵高温侧设有闪蒸器，高温热泵低温侧设有蓄热容器。
优选地，高温热泵高温侧出口与蒸汽过热器之间的管路上设有蒸汽压缩机；
电热转化单元内设有电热炉膛；
所述基于新能源消纳的天然气制备含氢产品的装置中还包括可再生电源接口，电热炉膛、高温热泵、蒸汽压缩机通过可再生电源接口使用外接可再生能源电能。
本发明公开了一种利用上述基于新能源消纳的天然气制备含氢产品的装置的方法，包括以下运行步骤：
1）天然气原料进入天然气预热器，获取来自变换反应单元的反应放热，温度升高至300℃以上；同时给水进入给水预热器进行初步预热到成饱和水；
2）初步预热后天然气原料与循环氢气同时进入精制脱硫单元，发生烯烃饱和反应以及有机含硫物脱硫反应；
3）脱硫后天然气原料进入混流器与水蒸气混合，之后进入电热转化单元进行转化，电热转化单元使用电能将炉膛加热到800-890℃用来供给转化反应吸热；
4）电热转化单元出口气包含CO、H 2、CO 2、CH 4以及水蒸气，温度在700℃以上，出口气先进入原料预热器对天然气和水蒸气混合原料预热，同时降低自身温度以便发生变换反应；变换反应的反应放热将通过天然气预热器带离反应单元；
5）变换反应之后的产物气体进入蒸汽过热器和给水预热器放热，之后将热量释放于高温热泵设有的蓄热容器中，作为高温热泵的热源；高温热泵将热量提取用电能将能源品位提升，使给水预热器出口的饱和水蒸发；
6）高温热泵出口的产品气经降温后可进入CO 2脱除单元、气液分离单元，分离完成后不经过压缩储存，直接从富氢燃料出口输出为富氢燃料。
优选地，上述基于新能源消纳的天然气制备含氢产品的装置，还包括用于设备容纳单元的撬装箱，天然气原料入口、给水入口和可再生电源接口分别设于撬装箱上。
 有益效果
与现有技术相比，本发明具有以下有益效果：
本发明公开了一种基于新能源消纳的天然气制备含氢产品的装置，天然气在经过天然气预热器和精制脱硫单元后与预热完成的水蒸气混流，依次经过电热转化单元、变换反应单元、变压吸附单元完成氢气生产。其中，给水预热器热流体通过管路与蒸汽过热器和高温热泵的低温侧接通，给水预热器冷流体通过管路与给水（去盐水）入口和高温热泵的高温侧接通，给水通过蒸汽过热器、给水预热器、高温热泵获取反应产物余热，降低生产制备能耗。其中，本发明通过改变现有天然气重整制氢技术中以天然气为燃料，利用生成的高温烟气为热源并产生大量碳排放的现状，通过耦合高温热泵、电热转化炉与蒸汽压缩机，实现电能高效利用的同时简化原有装置的结构，降低装置启停时间，使装置更加集成化，提升装置的整体稳定性。
进一步地，通过电热转化炉、高温热泵、蒸汽压缩机等设备利用可再生能源电能对原有天然气制氢设备进行改进，通过将可再生电能引入天然气重整制氢技术中，灵活地消纳可再生电能，为解决弃风弃光问题提供方案。
本发明公开了利用上述一种基于新能源消纳的天然气制备含氢产品的装置的制氢方法，天然气在经过天然气预热器和精制脱硫单元后与预热完成的水蒸气混流，依次经过电热转化单元、变换反应单元、变压吸附单元完成氢气生产。针对可再生能源消纳能力不足问题与燃料清洁化问题给出解决方案，与此同时给出天然气重整制氢系统在高度集成下不同品位热能的高效利用方法。
本发明公开了另一种基于新能源消纳的天然气制备含氢产品的装置，所得产品气在变换反应、经过多段换热降温后可进入CO 2脱除单元、气液分离单元，分离完成后不经过压缩储存，直接输出为富氢燃料。
本发明还公开了利用上述另一种基于新能源消纳的天然气制备含氢产品的装置的富氢燃料方法，大大降低天然气制氢过程中的碳排放，提升燃料气能量转化效率。
进一步地，在上述撬装式天然气制氢装置中，装置为撬装箱式结构，可以供车辆运输。同时，以撬装式结构设计高效集成参与反应流程的设备，有效利用反应过程中的产热或余热，提升装置的效率。
其中，本发明设备选取、工艺流程不局限于撬装式结构，同样能够适合于大规模的电力消纳天然气制氢。
综上所述，本发明所述基于新能源消纳的天然气制备含氢产品的装置，具有以下优点：1、燃气制氢电气化：通过引入电热转化单元、高温热泵以及蒸汽压缩机，本装置可以高效利用电能参与反应，大大简化了装置结构，同时去除天然气燃烧环节，显著降低了天然气制氢过程中的碳排放。
2、装置设备集成化：以撬装式结构将天然气水蒸气制氢装置高度集成在集装箱内，提升装置设备的集成度，可有效降低装置生产周期，降低土地成本，同时有助于提升可再生电能消纳的灵活性。
3、余热利用梯级化：设计多级余热回收装置，包括换热器，高温热泵，有效利用反应过程中的产热或余热，提升装置的效率。
4、制氢工具模块化：所述装置拥有可再生电源接口、给水（去盐水）入口、天然气原料入口、加氢口。在实际生产中作为模块化的生产工具可以满足即插即用，大大提升制氢装置便利性。
 附图说明
图1为本发明所述基于新能源消纳的撬装式天然气制氢装置的结构示意图；
图2为本发明所述基于新能源消纳的撬装式天然气富氢燃料制备装置的结构示意图。
其中：100-撬装箱；200-精制脱硫单元；201-电热转化单元；202-变换反应单元；203-变压吸附单元；204-气液分离单元；205-电热炉膛；206-CO 2脱除单元；300-蒸汽过热器；301-天然气预热器；302-给水预热器；303-原料预热器；400-高温热泵；401-闪蒸器；402-蓄热容器；500-氢气分流器；501-氢气压缩机；502-氢气三通阀；503-氢气储存单元；504-加氢口；505-富氢燃料出口；600-混流器；700-蒸汽压缩机；A-天然气原料入口；B-给水入口；C-可再生电源接口。
本发明的实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
需要说明的是，本发明的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本发明的实施例能够以除了在这里图示或描述的那些以外的顺序实施。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
下面结合附图和具体实施例对本发明做进一步详细描述：
实施例1
如图1所示，本发明提供了一种基于新能源消纳的天然气制备含氢产品的装置，构成基于新能源消纳的撬装式天然气制氢装置，具体包括：
撬装箱100、精制脱硫单元200、电热转化单元201、变换反应单元202、变压吸附单元203、气液分离单元204、蒸汽过热器300、天然气预热器301、给水预热器302、原料预热器303、高温热泵400、闪蒸器401、蓄热容器402、氢气分流器500、氢气压缩机501、氢气三通阀502、氢气储存单元503、加氢口504、混流器600、蒸汽压缩机700、天然气原料入口A、给水入口（给水（去盐水）入口）B以及可再生电源接口C。
其中，撬装箱100为设备容纳单元；电热转化单元201内设有电热炉膛205用于保证反应温度；电热转化单元201的进口通过管路与原料预热器303的热端出口连通，电热转化单元201的出口通过管路与原料预热器303的热端入口接通；变换反应单元202内设有天然气预热器301用于为变换反应降温同时预热原料；高温热泵400高温侧设有闪蒸器401用于产生蒸汽，高温热泵400低温侧设有蓄热容器402，蓄热容器402作为高温蒸汽热泵400的冷端用于冷却反应产物并蓄积反应物热能。高温热泵400低温侧出口经过变压吸附单元203与氢气分流器500进口接通，高温热泵400高温侧出口通过蒸汽过热器300与混流器600接通。变压吸附单元203与氢气分流器500进口之间的管路上还设有气液分离单元204；变压吸附单元203与天然气预热器301接通。高温热泵400热端与蒸汽过热器300之间的管路上设有蒸汽压缩机700。
电热转换单元201内电热炉膛205、高温热泵400、氢气压缩机501、蒸汽压缩机700通过可再生电源接口C使用外接可再生能源电能。
给水预热器302通过管路与蒸汽过热器300和高温热泵400的高温侧接通，给水入口B与给水预热器302冷端入口接通，给水预热器302热端出口与和高温热泵400高温侧入口接通，给水通过蒸汽过热器300、给水预热器302、高温热泵400获取反应产物余热。
高温热泵400使用可再生电能，热源为变压吸附单元203出口气体的热能，高温热泵400的高温侧入口通过管道连接给水预热器302冷端出口和闪蒸器401。
预热给水通过高温热泵400将热能品位提升为饱和水，闪蒸器401将饱和水蒸发形成蒸汽，蒸汽压缩机700对产生蒸汽进行压缩。高温热泵400中设有蓄热容器402收集反应产物余热并将其冷却。
蒸汽过热器300中热流体通过管路与给水预热器302和变换反应单元202接通，蒸汽过热器300中冷流体通过管路与闪蒸器401和混流器600接通。
变换反应单元202内天然气预热器301的热源为变换反应单元202内反应放出的热量，天然气预热器301冷端通过管道连接天然气原料入口A与精制脱硫单元200进口。
原料预热器303冷端出口与变换反应单元202进口接通，变换反应单元202出口通过蒸汽过热器300与给水预热器302热端入口接通，原料预热器303的热流体管道连接电热转化单元201的出口与变换反应单元202的入口，原料预热器303冷流体管道连接混流器600的出口与电热转化单元201的入口。原料预热器303冷端入口通过混流器600与精制脱硫单元200出口接通，天然气原料入口A通过天然气预热器301与精制脱硫单元200进口接通。
氢气分流器500其中一个氢气出口可以分流部分氢气供给精制脱硫单元200、与精制脱硫单元200进口接通，氢气分流器500另一氢气出口与加氢口504接通，氢气分流器500出口与加氢口504之间的管路上设有氢气三通阀502，氢气分流器500出口与氢气三通阀502之间的管路上设有氢气压缩机501，氢气三通阀502与加氢口504之间的管路上设有氢气储存单元503，当天然气原料入口A通入掺氢天然气时氢气分流器500则不分流。
氢气三通阀502用于控制所产氢气向外供给或是装置内储存。
实施例2
如图2所示，本发明提供了另一种基于新能源消纳的天然气制备含氢产品的装置，构成基于新能源消纳的撬装式天然气富氢燃料制备装置，具体包括：
撬装箱100、精制脱硫单元200、电热转化单元201、变换反应单元202、气液分离单元204、CO 2脱除单元206、蒸汽过热器300、天然气预热器301、给水预热器302、原料预热器303、高温热泵400、闪蒸器401、蓄热容器402、氢气分流器500、氢气压缩机501、氢气三通阀502、氢气储存单元503、富氢燃料出口505、混流器600、蒸汽压缩机700、天然气原料入口A、给水入口B以及可再生电源接口C。
其中，撬装箱100为设备容纳单元；电热转化单元201内设有电热炉膛205用于保证反应温度；电热转化单元201的进口通过管路与原料预热器303的热端出口连通，电热转化单元201的出口通过管路与原料预热器303的热端进口；变换反应单元202内设有天然气预热器301用于为变换反应降温同时预热原料；高温热泵400高温侧设有闪蒸器401用于产生蒸汽，高温热泵400低温侧设有蓄热容器402，蓄热容器402作为高温蒸汽热泵400的冷端用于冷却反应产物并蓄积反应物热能。高温热泵400低温侧出口经过CO 2脱除单元206与氢气分流器500进口接通，高温热泵400高温侧出口通过蒸汽过热器300与混流器600接通。CO 2脱除单元206与氢气分流器500进口之间的管路上还设有气液分离单元204。高温热泵400高温侧与蒸汽过热器300之间的管路上设有蒸汽压缩机700。
电热转换单元201内电热炉膛205、高温热泵400、蒸汽压缩机700通过可再生电源接口C使用外接可再生能源电能。
给水预热器302热端通过管路与蒸汽过热器300和高温热泵400的冷端接通，给水入口B与给水预热器302冷端入口接通，给水预热器302热端出口与和高温热泵400高温侧入口接通，给水通过蒸汽过热器300、给水预热器302、高温热泵400获取反应产物余热。
高温热泵400使用可再生电能，热源为变压吸附单元203出口气体的中温热能，高温热泵400高温侧入口通过管道连接给水预热器302冷端出口和闪蒸器401。
预热给水通过高温热泵400将热能品位提升为饱和水，闪蒸器401将饱和水蒸发形成蒸汽，蒸汽压缩机700对产生蒸汽进行压缩。高温热泵400中设有蓄热容器402收集反应产物余热并将其冷却。
蒸汽过热器300中热流体通过管路与给水预热器302和变换反应单元202接通，蒸汽过热器300中冷流体通过管路与闪蒸器401和混流器600接通。
变换反应单元202内天然气预热器301的热源为变换反应单元202内反应放出的热量，天然气预热器301冷端通过管道连接天然气原料入口A与精制脱硫单元200进口。
原料预热器303冷端出口与变换反应单元202进口接通，变换反应单元202出口通过蒸汽过热器300与给水预热器302热端入口接通，原料预热器303的热端连接电热转化单元201的出口与变换反应单元202的入口，原料预热器303冷流体管道通过连接混流器600的出口与电热转化单元201的入口。原料预热器303冷端入口通过混流器600与精制脱硫单元200出口接通，天然气原料入口A通过天然气预热器301与精制脱硫单元200进口接通。
氢气分流器500其中一个氢气出口可以分流部分氢气供给精制脱硫单元200、与精制脱硫单元200进口接通，氢气分流器500另一氢气出口与富氢燃料出口505，，当天然气原料入口A通入掺氢天然气时氢气分流器500则不分流。
针对上述本发明的具体实施例，以及本发明的任意具体实施方式中：
电热转化单元201内所含的多路电热转化管不仅限于2根。所有换热器根据热容流率匹配的方法布置，使换热器中热流体与冷流体的热容流率尽量一致，降低冷热流体换热温差，保障换热器效率。为满足换热器冷热流热容流率的匹配以及提升天然气转化率，反应水碳比应大于4。
本发明所述基于新能源消纳的天然气制备含氢产品的装置中，所述装置为撬装箱式结构，可以供车辆运输。此外，本发明设备选取、工艺流程不局限于撬装式结构，同样能够适合于大规模的电力消纳天然气制氢。
本发明提供了一种基于新能源消纳的天然气制备含氢产品的装置，利用所述基于新能源消纳的天然气制备含氢产品的装置，能够实现两种制备模式：1）包括当在制取纯度较高的运行策略下，即利用所述基于新能源消纳的天然气制备含氢产品的装置实现制氢；2）利用所述基于新能源消纳的天然气制备含氢产品的装置实现制取富氢燃料。其两种模式中，各个原料的反应路径具体如下：
装置所含设备主要可分为五个模块，其中撬装箱100为设备容纳单元；精制脱硫单元200、电热转化单元201、变换反应单元202、变压吸附单元203和气液分离单元204构成天然气制氢模块；蒸汽过热器300、天然气预热器301、给水预热器302和原料预热器303构成制氢过程中的余热回收模块；高温热泵400、闪蒸器401和蓄热容器402构成高温热泵模块；氢气分流器500、氢气压缩机501、氢气三通阀502、氢气储存单元503和加氢口504构成氢气处理模块。
天然气原料的反应路径顺序依次为天然气预热器301、精制脱硫单元200、混流器600、原料预热器303、电热转化单元201、原料预热器303、变换反应单元202、蒸汽过热器300、给水预热器302、高温热泵400、变压吸附单元203、气液分离单元204、氢气分流器500、氢气压缩机501、氢气三通阀502、加氢口504或氢气储存单元503。其间每个设备均通过气体管路接通。
给水进入反应器的路径顺序依次为给水预热器302、高温热泵400、闪蒸器401、蒸汽压缩机700、蒸汽过热器300、混流器600。
电热转换单元201内电热炉膛205、高温热泵400、氢气压缩机501、蒸汽压缩机700用电设备均通过可再生电源接口C使用外接可再生能源电能，外接电能应为通用交流电；给水入口B应接入去盐处理后的水，压力不应超过0.5MPa，使得饱和温度不高于150℃来满足高温热泵400蒸发过程；蒸汽压缩机700优选为螺杆式蒸汽压缩机，可以将水蒸气压缩至1.5MPa以上满足反应压力。换热器设计布置遵循热容流率匹配，反应产物比热容高于原料与给水比热容，为使换热器中冷热流体的热容更加接近，入口水碳比应大于4。
高温热泵400热源为蓄热容器402中蓄积热量，热量来自给水预热器302换热后出口产物的热能，蓄热容器402内部温度应高于80℃。高温热泵400热端通过管道连接给水预热器302和闪蒸器401，高温热泵400内部工质在低压侧蒸发温度为80℃附近，高压冷凝温度可达到150℃；高温热泵模块包含闪蒸器401，闪蒸器可以将150℃的饱和水闪蒸为蒸汽进行输出。整体来说，高温热泵400提升热能品位，将预热给水加热为饱和水，闪蒸器401将饱和水蒸发形成蒸汽。
变换反应单元202内天然气预热器301的热源为变换反应单元202内反应放热，冷端通过管道连接天然气原料入口A与精制脱硫单元200。变换反应单元的部分热量被原料天然气带走实现变换反应降温，有利于变换反应的正向进行，同时可以实现天然气原料的预热。
氢气与包括氢气的氢气分流器500分离部分氢气供给精制脱硫单元200，是由于精制脱硫单元中反应需要氢气参与，反应其一包括烯烃饱和反应，由于烯烃双键存在，分子碳氢比较高，在高温转化反应过程中容易形成积碳，将烯烃转换为烷烃有助于减轻转化炉内催化剂的积碳情况，增加催化剂使用寿命且降低催化剂换装难易程度，在精制脱硫单元中氢气与烯烃反应生成烷烃。反应其二是有机含硫物的转化反应，氢气与包括硫醇、硫醚、二硫醚、噻吩、氧硫化碳、二硫化碳等在内的有机含硫物在催化作用下发生反应形成H 2S，再通过ZnO（固）与其进行反应对硫进行固化。当天然气入口（A）供给为天然气掺氢燃料时氢气分流器500不向精制脱硫单元200供氢。
氢气三通阀502用于控制所产氢气向外供给或是装置内储存，这取决于本撬装式装置所执行的工作以及现场所提供环境，当现场提供储氢设备可向外输出，若不提供储氢设备将储存入装置中的储氢罐。
1）制氢：当在制取纯度较高的运行策略下，高温热泵400出口产物进入变压吸附单元203对除氢气外气体进行吸附得到高纯度氢气，变压吸附单元203温度应在40℃，变压吸附单元203中解析气经过脱除CO 2后通过天然气管道进入装置再次反应，提升转化效率。
2）制取富氢燃料：当在制取富氢燃料的运行策略下，产品气在变换反应、经过多段换热降温后可进入CO 2脱除单元206、气液分离单元204，分离完成后不经过压缩储存，直接输出为富氢燃料。
本发明同时提供基于新能源消纳的天然气制备含氢产品的装置的运行步骤。同样对应于制氢和制取富氢燃料两种模式下的运行步骤，因此，利用基于新能源消纳的天然气制备含氢产品的装置制氢或制取富氢燃料两种模式下，其具体方法包括如下：
1、天然气原料进入天然气预热器301，获取来自变换反应单元202的反应放热，温度升高至300℃以上；同时给水（去盐水）进入给水预热器302进行初步预热到成饱和水。
2、初步预热后天然气原料与循环氢气同时进入精制脱硫单元200，发生烯烃饱和反应以及有机含硫物脱硫反应，反应方程如下：
烯烃饱和：C nH 2n＋H 2→C nH 2 n +2
硫醇:        RSH+H 2→RH+H 2S
硫醚:        R 1SR 2+2H 2→R 1H+R 2H+H 2S
二硫醚:      R 1SSR 2+3H 2→R 1H+R 2H+2H 2S
噻吩:        C 4H 4S+4H 2→C 4H 10+H 2S
氧硫化碳:    COS+H 2→CO+H 2S
二硫化碳:    CS 2+4H 2→CH 4+2H 2S
在烯烃饱和反应以及有机含硫物脱硫反应之后在催化剂作用下通过氧化锌进行固硫，发生如下反应：
ZnO(固)+H 2S → ZnS(固)+H 2O
3、精制脱硫后天然气原料进入混流器600与水蒸气混合，之后进入电热转化单元201进行转化，电热转化单元201使用电能将炉膛加热到800-890℃用来供给转化反应吸热，转换反应方程如下所示：
CH 4 +H 2O →CO + 3H 2      H R = 205 kJ/mol
4、电热转化单元201出口气主要包含CO、H 2、CO 2、CH 4以及水蒸气，温度在700℃以上，出口气气体流出后首先进入原料预热器303对天然气和水蒸气混合原料预热，同时降低自身温度以便发生变换反应。进入变换反应单元202发生如下反应：
CO + H 2O → H 2 + CO 2      H R = -41.3 kJ/mol
该反应温度范围在320-420℃，该反应为放热反应，低温有利于反应进行，故变换反应的反应放热将通过天然气预热器301带离反应单元。
5、变换反应之后的产物气体进入蒸汽过热器300和给水预热器302放热，之后将热量释放于高温热泵400设有的蓄热容器402中，作为高温热泵400的热源。高温热泵400将热量提取用电能将能源品位提升，使给水预热器302出口的饱和水蒸发。
1）制氢：当在制取纯度较高的运行策略下，高温热泵400出口的产物进入变压吸附装置203对除氢气外气体进行吸附得到高纯度氢气，变压吸附单元203温度应在40℃，变压吸附单元203中解析气经过脱除CO 2后再次通过天然气管道进入装置反应。
2）制取富氢燃料：当在制取富氢燃料的运行策略下，高温热泵400出口的产品气在变换反应、经过多段换热降温后可进入CO 2脱除单元206、气液分离单元204，分离完成后不经过压缩储存，直接从富氢燃料出口505输出为富氢燃料。
6、氢气在变压吸附后进入气液分离单元204，实现气液分离。随后进入氢气分流器500分流部分氢气进行精制脱硫，大部分氢气进入氢气压缩机501压缩后输出或储存。当天然气入口供给的是掺氢天然气，则不向精制脱硫单元200分流。
根据上述一种基于新能源消纳的天然气制备含氢产品的装置的运行步骤，本发明的工作原理在于：
天然气在进入电热转化单元201前经历了一次预热和一次预反应，一次预热是在天然气预热器301中吸收变换反应放热，一次预反应是进入精制脱硫单元200完成脱硫；水蒸气在进入电热转化单元201前共经历了四段加热，其所需热量来自反应过程的余热与蒸汽压缩机700做工。其中两段分别在蒸汽过热器300和给水预热器302加热，热源为变换反应单元202的产物余热，其三是使用高温热泵400利用产物中低温余热获得热量完成蒸发。其四是通过蒸汽压缩机700对蒸汽进行增压来满足反应使用。
天然气与水蒸气完成预热及预处理后混合，在原料预热器303中经历一次预热，热源为电热转化单元201的产物余热。预热之后进入电热转化炉完成转化。电热转化单元201出口气体在排出后经历四次温降和一次放热反应。首先进入原料预热器303加热天然气水蒸气混合原料，完成第一次温降；后进入变换反应单元202发生放热反应，将反应热量通过原料预热器303传输给天然气原料；后进入蒸汽过热器300加热蒸汽完成第二次温降；后进入给水预热器302向给水换热，完成第三次温降；后进入高温热泵400向给水传输热量，完成第四次温降。在气液分离单元204中更低的氢气温度可以保证能够脱除更多的水分，提升氢气的纯度。
最后应说明的是：以上各实施例仅仅为本发明的较优实施例用以说明本发明的技术方案，而非对其限制，当然更不是限制本发明的专利范围；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围；也就是说，但凡在本发明的主体设计思想和精神上做出的毫无实质意义的改动或润色，其所解决的技术问题仍然与本发明一致的，均应当包含在本发明的保护范围之内；另外，将本发明的技术方案直接或间接的运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

  1. 一种基于新能源消纳的天然气制备含氢产品的装置，其特征在于，包括天然气原料入口（A）、精制脱硫单元（200）、原料预热器（303）、变换反应单元（202）、电热转化单元（201）、给水预热器（302）、高温热泵（400）、加氢口（504）、给水入口（B）和混流器（600）；变换反应单元（202）内设有天然气预热器（301）；
    天然气原料入口（A）通过天然气预热器（301）与精制脱硫单元（200）进口接通，精制脱硫单元（200）出口通过混流器（600）与原料预热器（303）冷端入口接通，原料预热器（303）热端出口与电热转化单元（201）进口接通，电热转化单元（201）出口与原料预热器（303）热端入口接通，原料预热器（303）冷端出口与变换反应单元（202）进口接通，变换反应单元（202）出口通过蒸汽过热器（300）与给水预热器（302）热端入口接通，给水预热器（302）冷端出口与和高温热泵（400）高温侧入口接通，高温热泵（400）低温侧出口经过变压吸附单元（203）与氢气分流器（500）进口接通，氢气分流器（500）出口与加氢口（504）接通；
    给水入口（B）与给水预热器（302）冷端入口接通，给水预热器（302）热端出口与和高温热泵（400）高温侧入口接通，高温热泵（400）高温侧出口通过蒸汽过热器（300）与混流器（600）接通。
  2. 根据权利要求1所述的一种基于新能源消纳的天然气制备含氢产品的装置，其特征在于，氢气分流器（500）出口与精制脱硫单元（200）进口接通；
    变压吸附单元（203）与氢气分流器（500）进口之间的管路上还设有气液分离单元（204）；变压吸附单元（203）与天然气预热器（301）接通；
    高温热泵（400）高温侧设有闪蒸器（401），高温热泵（400）低温侧设有蓄热容器（402）。
  3. 根据权利要求1所述的一种基于新能源消纳的天然气制备含氢产品的装置，其特征在于，高温热泵（400）高温侧出口与蒸汽过热器（300）之间的管路上设有蒸汽压缩机（700）；
    电热转化单元（201）内设有电热炉膛（205）；
    氢气分流器（500）出口与加氢口（504）之间的管路上设有氢气三通阀（502），氢气分流器（500）出口与氢气三通阀（502）之间的管路上设有氢气压缩机（501），氢气三通阀（502）与加氢口（504）之间的管路上设有氢气储存单元（503）。
  4. 根据权利要求3所述的一种基于新能源消纳的天然气制备含氢产品的装置，其特征在于，还包括可再生电源接口（C），电热炉膛（205）、高温热泵（400）、氢气压缩机（501）、蒸汽压缩机（700）通过可再生电源接口（C）使用外接可再生能源电能。
  5. 一种利用权利要求1~4任意一项所述基于新能源消纳的天然气制备含氢产品的装置的方法，其特征在于，包括以下运行步骤：
    1）天然气原料进入天然气预热器（301），获取来自变换反应单元（202）的反应放热，温度升高至300℃以上；同时给水进入给水预热器（302）进行初步预热到成饱和水；
    2）初步预热后天然气原料与循环氢气同时进入精制脱硫单元（200），发生烯烃饱和反应以及有机含硫物脱硫反应；
    3）脱硫后天然气原料进入混流器（600）与水蒸气混合，之后进入电热转化单元（201）进行转化，电热转化单元（201）使用电能将炉膛加热到800-890℃用来供给转化反应吸热；
    4）电热转化单元（201）出口气包含CO、H 2、CO 2、CH 4以及水蒸气，温度在700℃以上，出口气先进入原料预热器（303）对天然气和水蒸气混合原料预热，同时降低自身温度以便发生变换反应；变换反应的反应放热将通过天然气预热器（301）带离反应单元；
    5）变换反应之后的产物气体进入蒸汽过热器（300）和给水预热器（302）放热，之后将热量释放于高温热泵（400）设有的蓄热容器（402）中，作为高温热泵（400）的热源；高温热泵（400）将热量提取用电能将能源品位提升，使给水预热器（302）出口的饱和水蒸发；
    6）高温热泵（400）出口的产物进入变压吸附装置（203）对除氢气外气体进行吸附得到高纯度氢气。
  6. 一种基于新能源消纳的天然气制备含氢产品的装置，其特征在于，包括天然气原料入口（A）、精制脱硫单元（200）、原料预热器（303）、变换反应单元（202）、电热转化单元（201）、给水预热器（302）、高温热泵（400）、富氢燃料出口（505）、给水入口（B）和混流器（600）；变换反应单元（202）内设有天然气预热器（301）；
    天然气原料入口（A）通过天然气预热器（301）与精制脱硫单元（200）进口接通，精制脱硫单元（200）出口通过混流器（600）与原料预热器（303）冷端入口接通，原料预热器（303）热端出口与电热转化单元（201）进口接通，电热转化单元（201）出口与原料预热器（303）热端入口接通，原料预热器（303）冷端出口与变换反应单元（202）进口接通，变换反应单元（202）出口通过蒸汽过热器（300）与给水预热器（302）热端入口接通，给水预热器（302）冷端出口与和高温热泵（400）高温侧入口接通，高温热泵（400）低温侧与产物产出单元连接；高温热泵（400）低温侧经过CO 2脱除单元（206）与氢气分流器（500）进口接通，氢气分流器（500）出口与富氢燃料出口（505）接通；
    给水入口（B）与给水预热器（302）冷端入口接通，给水预热器（302）热端出口与和高温热泵（400）高温侧入口接通，高温热泵（400）高温侧出口通过蒸汽过热器（300）与混流器（600）接通。
  7. 根据权利要求6所述的一种基于新能源消纳的天然气制备含氢产品的装置，其特征在于，氢气分流器（500）出口与精制脱硫单元（200）进口接通；
    CO 2脱除单元（206）与氢气分流器（500）进口之间的管路上还设有气液分离单元（204）；
    高温热泵（400）高温侧设有闪蒸器（401），高温热泵（400）低温侧设有蓄热容器（402）。
  8. 根据权利要求6所述的一种基于新能源消纳的天然气制备含氢产品的装置，其特征在于，高温热泵（400）高温侧出口与蒸汽过热器（300）之间的管路上设有蒸汽压缩机（700）；
    电热转化单元（201）内设有电热炉膛（205）；
    所述基于新能源消纳的天然气制备含氢产品的装置中还包括可再生电源接口（C），电热炉膛（205）、高温热泵（400）、蒸汽压缩机（700）通过可再生电源接口（C）使用外接可再生能源电能。
  9. 一种利用权利要求6~8任意一项所述基于新能源消纳的天然气制备含氢产品的装置的方法，其特征在于，包括以下运行步骤：
    1）天然气原料进入天然气预热器（301），获取来自变换反应单元（202）的反应放热，温度升高至300℃以上；同时给水进入给水预热器（302）进行初步预热到成饱和水；
    2）初步预热后天然气原料与循环氢气同时进入精制脱硫单元（200），发生烯烃饱和反应以及有机含硫物脱硫反应；
    3）脱硫后天然气原料进入混流器（600）与水蒸气混合，之后进入电热转化单元（201）进行转化，电热转化单元（201）使用电能将炉膛加热到800-890℃用来供给转化反应吸热；
    4）电热转化单元（201）出口气包含CO、H 2、CO 2、CH 4以及水蒸气，温度在700℃以上，出口气先进入原料预热器（303）对天然气和水蒸气混合原料预热，同时降低自身温度以便发生变换反应；变换反应的反应放热将通过天然气预热器（301）带离反应单元；
    5）变换反应之后的产物气体进入蒸汽过热器（300）和给水预热器（302）放热，之后将热量释放于高温热泵（400）设有的蓄热容器（402）中，作为高温热泵（400）的热源；高温热泵（400）将热量提取用电能将能源品位提升，使给水预热器（302）出口的饱和水蒸发；
    6）高温热泵（400）出口的产品气经降温后可进入CO 2脱除单元（206）、气液分离单元（204），分离完成后不经过压缩储存，直接从富氢燃料出口（505）输出为富氢燃料。
  10. 根据权利要求1~4任意一项或权利要求6~8任意一项所述基于新能源消纳的天然气制备含氢产品的装置，其特征在于，还包括用于设备容纳单元的撬装箱（100），天然气原料入口（A）、给水入口（B）和可再生电源接口（C）分别设于撬装箱（100）上。
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