CN115011981A - Hydrogen production equipment and hydrogen production method by coupling electrolyzed water with methane-rich gas - Google Patents
Hydrogen production equipment and hydrogen production method by coupling electrolyzed water with methane-rich gas Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 199
- 239000001257 hydrogen Substances 0.000 title claims abstract description 198
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 195
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000007789 gas Substances 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 96
- 230000008878 coupling Effects 0.000 title claims abstract description 12
- 238000010168 coupling process Methods 0.000 title claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 31
- 230000005611 electricity Effects 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000006057 reforming reaction Methods 0.000 claims abstract description 18
- 238000002407 reforming Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims description 25
- 238000000746 purification Methods 0.000 claims description 21
- 238000010926 purge Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000010248 power generation Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003345 natural gas Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000006477 desulfuration reaction Methods 0.000 claims description 6
- 230000023556 desulfurization Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000002918 waste heat Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract 2
- 239000000047 product Substances 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- 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
- C01B3/36—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 oxygen or mixtures containing oxygen as 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- 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
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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 device and a method for producing hydrogen by coupling electrolyzed water with methane-rich gas. The method uses the heat generated in the step of hydrogen production by water electrolysis for reforming reaction, recycles the waste heat generated in the step of hydrogen production by reforming in a heat exchange and heat extraction manner, and improves the energy efficiency of a hydrogen production system; oxygen generated by hydrogen production through water electrolysis and water generated by heat extraction are used as raw materials for hydrogen production through reforming, so that the by-products of hydrogen production through water electrolysis are efficiently utilized; according to the fluctuation of the external power supply of the water electrolysis hydrogen production system, the reforming hydrogen production system is regulated and controlled, so that the hydrogen production device can stably supply hydrogen under the condition of unstable power. The hydrogen production method provided by the invention solves the problem of unstable power supply in the green electricity hydrogen production process, and efficiently utilizes byproducts and heat.
Description
Technical Field
The invention relates to the technical field of hydrogen production, in particular to hydrogen production equipment and a hydrogen production method by coupling electrolytic water with a methane-rich gas.
Background
Hydrogen is an ideal energy carrier due to its advantages of high energy density, storability, cleanness, no pollution and the like, and has attracted much attention at home and abroad in recent years. At present, the main limiting factors of the development of hydrogen energy come from the cost of hydrogen and environmental requirements.
The hydrogen production by electrolyzing water takes water as raw material, and hydrogen is produced by electrolyzing water under the action of electric energy, so that the whole hydrogen production process is pollution-free, and the method is a hydrogen production approach with great potential. However, the existing water electrolysis hydrogen production technology generally requires a stable power supply system, so that most of the electric energy used by the existing water electrolysis hydrogen production technology comes from power grid power supply, while the power grid power supply in China mainly comes from thermal power generation, a large amount of carbon dioxide is discharged, the electricity price is not high, and the total cost of water electrolysis hydrogen production is high.
The method adopts wind power generation or photovoltaic power generation for hydrogen production by electrolyzing water, can greatly reduce the hydrogen production cost and reduce the emission of carbon dioxide, and has good development prospect. However, wind energy and photovoltaic power generation are influenced by weather, the power supply is unstable, and the hydrogen production device cannot ensure continuous production of hydrogen.
In addition, when hydrogen is prepared by electrolyzing water, most of heat generated by the device is consumed in a heat dissipation mode, so that energy waste is serious, and the system energy efficiency is low; the by-product oxygen of the anode of the electrolytic cell is generally directly discharged to be treated, thereby causing resource waste.
Disclosure of Invention
The invention aims to provide hydrogen production equipment and a hydrogen production method by coupling electrolyzed water with a methane-rich gas, so as to solve the problems of unstable power and resource utilization of waste heat and byproducts in the device in the existing wind-solar-electricity hydrogen production technology.
In order to achieve the purpose, the invention provides the following technical scheme:
the utility model provides an electrolytic water coupling rich methane gas hydrogen manufacturing equipment, including the electrolytic water hydrogen manufacturing module that is used for obtaining damp and hot hydrogen and damp and hot oxygen with the water electrolysis, multiple whole hydrogen manufacturing module that is used for mixing as the raw materials with rich methane gas and damp and hot oxygen and carry out multiple whole reaction and generate the synthetic gas, a heat exchange module for getting wet and hot hydrogen and the reaction product of multiple whole hydrogen manufacturing step together get into the heat exchanger, a separation module for getting rich hydrogen mixed gas is got through the dewatering through gas-liquid separation device after passing through heat transfer step heat transfer treatment with the synthetic gas that multiple whole hydrogen manufacturing step obtained and the damp and hot hydrogen that electrolytic water hydrogen manufacturing step obtained, a hydrogen purification module for carrying out purification with rich hydrogen mixed gas.
The hydrogen purifying module is used for generating hydrogen through power generation equipment, and the generated electricity is returned to the purge gas power generation module on a power supply circuit of an electrolysis bath of the water electrolysis hydrogen production module.
A hydrogen production method by coupling electrolyzed water with methane-rich gas comprises a hydrogen production step by electrolyzed water, a multiple hydrogen production step, a heat exchange step, a separation step, a hydrogen purification step and a purge gas power generation step, and specifically comprises the following steps:
the method comprises the following steps: electrolyzing water to produce hydrogen: water is used as a raw material and is introduced into an electrolytic cell for electrolysis to obtain damp and hot hydrogen and damp and hot oxygen;
step two: multiple integrated hydrogen production: mixing the methane-rich gas and the moist-heat oxygen obtained in the step one as raw materials, and allowing the mixture to enter a reforming reactor for multiple reforming reactions to generate synthesis gas;
step three: heat exchange: the wet and hot hydrogen of the water electrolysis hydrogen production device in the step one and the reaction product of the hydrogen production by multiple reforming in the step two enter a heat exchanger together to exchange heat with cold water, and hot water generated by heat exchange is recycled for the reforming reaction in the step two;
step four: separation: the synthesis gas obtained in the step two and the wet and hot hydrogen obtained in the step one are subjected to heat exchange treatment in the step three and then enter a separation step, a gas-liquid separation device is used for removing water to obtain a hydrogen-rich mixed gas, and meanwhile, the generated water is used as a raw material and is circulated back to the electrolytic cell in the step one for continuous use in electrolytic hydrogen production;
step five: hydrogen purification: and D, purifying and purifying the hydrogen-rich mixed gas obtained in the step four to obtain high-purity hydrogen.
Step six: generating electricity by using purge gas: and (4) generating electricity by using the purge gas generated by the hydrogen gas purifying device in the step (V) through power generation equipment, and returning the generated electricity to a power supply circuit of the electrolytic cell in the step (I) for electrolysis to adjust the unstable power supply condition of green electricity.
Preferably, the step of producing hydrogen by electrolyzing water adopts alkaline electrolyzed water or water electrolyzed by a Proton Exchange Membrane (PEM), the main equipment comprises an electrolytic bath and a heat exchanger, and the produced hydrogen and oxygen carry moisture. When a Proton Exchange Membrane (PEM) is adopted to electrolyze water to produce hydrogen, a heat exchanger is not used, and the heat generated in the electrolytic process of the device is absorbed by increasing the water inflow rate of raw materials, so that the aim of controlling the temperature of an electrolytic bath is fulfilled; one part of the raw material water is used for generating hydrogen and oxygen by electrolysis, and the other part of the redundant water is changed into hot water after passing through the heat of the absorption device and flows out along with the product gas; wherein, the hot water flowing out along with the oxygen does not carry out gas-liquid separation any more, and is mixed with the oxygen to enter multiple hydrogen preparation steps as an oxygen source of reforming reaction. When the alkaline electrolyzed water is used for producing hydrogen, the heat generated by the electrolytic cell is subjected to heat exchange by using a matched heat exchanger to obtain heat, and hot water obtained by heat exchange and oxygen generated by the electrolytic anode enter multiple hydrogen production steps together to serve as an oxygen source of reforming reaction.
Preferably, the multiple hydrogen production steps mainly comprise a reforming reaction, a desulfurization reaction and a medium-low temperature shift reaction, and the multiple hydrogen production modules comprise a reforming reactor, a desulfurization reactor, a high-low temperature shift reactor, a corresponding catalyst and a matched flow control system. The reforming flow control system mainly comprises a methane flow controller, an air flow controller and a feed water pump. The multiple reforming reaction comprises one or more of partial oxidation of methane, steam reforming of methane, autothermal reforming of methane, plasma reforming of methane and the like.
Preferably, the oxygen/methane ratio in the multiple reforming reaction is 0.1-2, the reaction temperature is 750-950 ℃, the pressure is 0.05-3.0MPa,the space velocity is 500-8000h -1 。
Preferably, the methane-rich gas is natural gas, methane gas, coal bed gas or shale gas.
Preferably, the heat source in the heat exchange step is hot water carried by the cathode product hydrogen in the water electrolysis hydrogen production device, high-temperature gas of reforming reaction in the multiple hydrogen production steps, and heat release of medium-low temperature shift reaction.
Preferably, the hydrogen purification step adopts one or a combination of two modes of membrane separation and pressure swing adsorption to remove methane, carbon monoxide, carbon dioxide and other trace impurities in the hydrogen-rich mixed gas obtained in the fourth step, so as to obtain high-purity hydrogen.
Preferably, in the step of generating electricity by using the purge gas generated by the hydrogen purification device as a fuel, the electricity generation is performed by the power generation equipment, and the generated energy can be controlled by regulating and controlling the composition and the gas quantity of the purge gas, so that the power supply of the water electrolysis hydrogen production device is kept in a stable state. The purge gas component can be regulated and controlled by controlling multiple integral reaction temperature, methane conversion rate, hydrogen purification device yield and other modes.
Compared with the prior art, the invention has the beneficial effects that:
(1) the hydrogen production method maintains the stability of the power supply of the water electrolysis hydrogen production device by regulating and controlling the composition and the gas quantity of the purge gas, and realizes the aim of stably and efficiently producing hydrogen by wind, light and electricity.
(2) The hydrogen production method of the invention prepares hydrogen by renewable energy sources such as wind energy, solar energy and the like, can greatly reduce the emission of carbon dioxide, effectively utilizes the methane-rich gas and reduces the greenhouse effect problem of the methane-rich gas.
(3) The hydrogen production method of the invention uses wind, light and electricity to produce hydrogen, and simultaneously efficiently utilizes the by-products and waste heat of the system, and can also reduce the hydrogen production cost.
Drawings
FIG. 1 is a schematic diagram of a process flow of an apparatus and a method for producing hydrogen by coupling electrolysis water with a methane-rich gas according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, an apparatus for producing hydrogen by coupling electrolyzed water with methane-rich gas comprises a hydrogen production module for electrolyzing water to obtain humid hot hydrogen and humid hot oxygen, a multiple hydrogen production module for mixing the methane-rich gas and the humid hot oxygen as raw materials to perform multiple reactions to generate synthesis gas, a heat exchange module for introducing the humid hot hydrogen and the reaction product of the multiple hydrogen production steps into a heat exchanger, a separation module for performing heat exchange treatment on the synthesis gas obtained in the multiple hydrogen production steps and the humid hot hydrogen obtained in the hydrogen production step by the heat exchange step and then performing dehydration by a gas-liquid separation device to obtain hydrogen-rich gas mixture, a hydrogen purification module for purifying the hydrogen-rich gas mixture, and a purge gas generation module for generating electricity by the hydrogen purification module through power generation equipment, wherein the generated electricity is returned to a purge gas generation module on a power supply line of an electrolytic cell of the hydrogen production module, the method specifically comprises the following steps:
the method comprises the following steps: electrolyzing water to produce hydrogen: water is used as a raw material and is introduced into an electrolytic cell, direct current is introduced into the electrolytic cell, water molecules are subjected to electrochemical reaction on electrodes to generate hydrogen and oxygen, and at the moment, the hydrogen and the oxygen contain moisture and are called as damp-heat hydrogen and damp-heat oxygen;
step two: multiple integrated hydrogen production: firstly, mixing natural gas and the moist heat oxygen obtained in the first step as raw materials, feeding the mixture into a reforming reactor, and carrying out multiple reforming reaction to generate synthesis gas, wherein the synthesis gas mainly comprises H 2 、CO、CO 2 、H 2 O、H 2 S and other small amounts of impurities; then the synthetic gas enters a desulfurization reactor, sulfur-containing gas is removed through an adsorbent, and then the synthetic gas enters a medium-low temperature shift reactor to convert most CO into CO 2 And is produced in combinationGenerating hydrogen, wherein the temperature of the reforming reaction is controlled to be 750-950 ℃, the pressure is controlled to be 0.05-3.0MPa, and the airspeed is controlled to be 500-8000h -1 The oxygen/methane ratio is 0.1 to 2.
Step three: heat exchange: the wet and hot hydrogen of the water electrolysis hydrogen production device in the step one and the reaction product of the multiple hydrogen production in the step two enter a heat exchanger tube pass together, a cooling medium adopts cold water and flows through a shell pass of the heat exchanger, the shell pass cold water is changed into hot water with a certain temperature after heat exchange, and the hot water is used as a raw material for the multiple integral reaction in the step two;
step four: separation: the synthesis gas obtained in the step two and the wet and hot hydrogen obtained in the step one enter a separation device together after being subjected to heat exchange treatment in the step three, a gas-liquid separator can be selected, water vapor is removed through gas-liquid separation, the outlet at the upper end of the gas-liquid separator is hydrogen-rich mixed gas, the outlet at the lower end of the gas-liquid separator is liquid water, the hydrogen-rich mixed gas enters a hydrogen purification system, and the liquid water is recycled to a raw material water pipeline to be used as a raw material;
step five: hydrogen purification: and D, purifying and purifying the hydrogen-rich mixed gas obtained in the step four to obtain high-purity hydrogen.
Step six: generating electricity by using purge gas: and (4) generating electricity by using the purge gas generated by the hydrogen gas purification device in the step (V) through power generation equipment, and returning the generated electricity to a power circuit of the electrolytic cell in the step (I) for electrolysis to adjust the unstable power supply condition of green electricity.
The present invention will be further explained with reference to examples, but the present invention is not limited thereto.
The embodiment of the invention is established in a set of 6Nm 3 6Nm on the basis of a hydrogen production device 3 The hydrogen production device comprises main equipment including water electrolysis hydrogen production equipment, multiple hydrogen production equipment, heat exchange equipment, separation equipment, hydrogen purification equipment and power generation equipment, wherein the equipment corresponds to the steps in the attached drawing 1, and the connection mode of the equipment is consistent with the flow trend in the attached drawing 1.
Example 1
The power supply of the water electrolysis device supplies power to full load, and at the moment, hydrogen production by reforming and exhausted gas generationThe electric equipment is in a closed state, the water electrolysis device adopts alkaline electrolyzed water, and the alkaline liquor returns to the electrolytic bath in a circulating mode. Injecting softened water into an electrolytic cell through a pump at the speed of 5.63kg/h, and controlling the temperature of the electrolytic cell to be about 80 ℃; electrolyzing water in an electrolytic bath to generate damp and hot hydrogen carrying certain moisture; the wet and hot hydrogen enters a pressure swing adsorption separation and purification device after being cooled and separated, and the hydrogen-rich gas is further purified to obtain high-purity hydrogen; detecting and measuring the hydrogen purity and the product hydrogen flow at the product gas outlet of the pressure swing adsorption device, wherein the product hydrogen purity is more than 99.99 percent, and the flow is 6.0Nm 3 /h。
Example 2
The experiment is carried out on the same hydrogen production device as the embodiment 1, the power supply of the water electrolysis device provides 50 percent of power supply load, and the specific operation steps are as follows:
the method comprises the following steps: injecting softened water into an electrolytic cell at the speed of 3.25kg/h through a pump, wherein the temperature of the electrolytic cell is controlled to be about 80 ℃; electrolyzing the water in the electrolytic bath to generate damp and hot hydrogen and damp and hot oxygen carrying certain moisture, and introducing the damp and hot oxygen generated by the anode into the multiple integral reactor in the second step; and (4) the damp and hot hydrogen generated by the cathode and the synthesis gas generated by the multiple integration in the second step enter a heat exchanger together.
Step two: at 1.66Nm 3 The natural gas is led into the reforming reactor at the speed of/h, and the space velocity of the natural gas is 1660h -1 And (3) keeping the reforming reaction temperature at 800 ℃, keeping the reaction pressure at 0.1MPa, and keeping the oxygen/methane ratio at 1.2, wherein the reforming reaction product sequentially passes through a desulfurization reactor and a medium-low temperature shift reactor to obtain synthesis gas, and the synthesis gas and the wet and hot hydrogen obtained in the step one pass through a heat exchanger to exchange heat and obtain heat.
Step three: and the gas after heat exchange directly enters a gas-liquid separation device, water vapor is removed through gas-liquid separation, the outlet at the upper end of the gas-liquid separator is hydrogen-rich mixed gas, the outlet at the lower end of the gas-liquid separator is liquid water, the hydrogen-rich mixed gas enters a hydrogen purification system, and the liquid water is circulated back to a raw material water pipeline to be used as a raw material.
Step four: introducing the hydrogen-rich mixed gas into a pressure swing adsorption separation purification device for purification treatment to obtain high-purity hydrogen and simultaneously generating partial purge gas; and the generated purge gas is introduced into power generation equipment to generate power, the generated power of the purge gas is monitored in real time, the generated power is within the range of 3.9-4.0 kW, and the generated power returns to a power circuit of the electrolytic cell in the first step.
Step five: detecting and measuring the hydrogen purity and the product hydrogen flow at the product gas outlet of the pressure swing adsorption device, wherein the product hydrogen purity is more than 99.99 percent, and the flow is 6.0Nm 3 /h。
Example 3
The experiment was carried out on the same hydrogen production apparatus as in example 1, and the power supply of the water electrolysis apparatus was applied with a load of 0, and the specific operation steps were the operation steps in example 2. Wherein the feeding amount of the softened water in the first step is 1.22 kg/h; the natural gas feed amount in the second step was set to 3.90Nm at the initial start-up stage of the reaction apparatus 3 H, after the power generation step of the purge gas is started, the feeding amount of the natural gas is reduced to 3.06Nm 3 The space velocity of natural gas is kept to 3060h -1 The reforming reaction temperature was maintained at 800 ℃, the reaction pressure was 0.1MPa, and the oxygen/methane ratio was 1.2. The third to fifth operation steps are consistent with the embodiment, monitoring shows that the generated energy is within the range of 6.5 to 6.6kW, the detected product hydrogen purity is more than 99.99 percent, and the flow rate is 6.02Nm 3 /h。
As can be seen from the embodiments 1 to 3, the hydrogen production method provided by the invention has very small fluctuation range of hydrogen production amount, and the whole hydrogen production system can stably operate within the range of 0-100% of the power supply load of the water electrolysis device.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The utility model provides an electrolytic water coupling rich methane gas hydrogen manufacturing equipment which characterized in that: the device comprises an electrolytic water hydrogen production module for electrolyzing water to obtain damp-heat hydrogen and damp-heat oxygen, a multiple integral hydrogen production module for mixing methane-rich gas and the damp-heat oxygen together as raw materials to carry out multiple integral reaction to generate synthesis gas, a heat exchange module for enabling the damp-heat hydrogen and reaction products of the multiple integral hydrogen production steps to enter a heat exchanger together, a separation module for carrying out water removal on the synthesis gas obtained in the multiple integral hydrogen production step and the damp-heat hydrogen obtained in the electrolytic water hydrogen production step through a gas-liquid separation device after heat exchange treatment in the heat exchange step to obtain hydrogen-rich mixed gas, and a hydrogen purification module for purifying and purifying the hydrogen-rich mixed gas.
2. The apparatus for producing hydrogen by electrolyzing water-coupled methane-rich gas as claimed in claim 1, wherein: the hydrogen purifying module is used for generating hydrogen through power generation equipment, and the generated electricity is returned to the purge gas power generation module on a power supply circuit of an electrolysis bath of the water electrolysis hydrogen production module.
3. The method for producing hydrogen by coupling electrolyzed water with methane-rich gas as claimed in claim 1, characterized in that: the multiple hydrogen production modules comprise reforming reactors, desulfurization reactors, medium-low temperature shift reactors, corresponding catalysts and matched flow control systems, wherein the reforming reactor feed flow control system comprises a methane gas flow controller, an air flow controller and a feed water pump.
4. A method for producing hydrogen by the apparatus for producing hydrogen by electrolyzing water-coupled methane-rich gas according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
the method comprises the following steps: electrolyzing water to produce hydrogen: water is used as a raw material and is introduced into an electrolytic cell for electrolysis to obtain damp and hot hydrogen and damp and hot oxygen;
step two: multiple integrated hydrogen production: mixing the methane-rich gas and the moist-heat oxygen obtained in the step one as raw materials, and allowing the mixture to enter a reforming reactor for multiple reforming reactions to generate synthesis gas;
step three: heat exchange: the wet and hot hydrogen of the water electrolysis hydrogen production device in the step one and the reaction product of the hydrogen production by multiple reforming in the step two enter a heat exchanger together to exchange heat with cold water, and hot water generated by heat exchange is recycled for the reforming reaction in the step two;
step four: separation: the synthesis gas obtained in the step two and the wet and hot hydrogen obtained in the step one are subjected to heat exchange treatment in the step three and then enter a separation step, a gas-liquid separation device is used for removing water to obtain a hydrogen-rich mixed gas, and meanwhile, the generated water is used as a raw material and is circulated back to the electrolytic cell in the step one for continuous use in electrolytic hydrogen production;
step five: hydrogen purification: and D, purifying and purifying the hydrogen-rich mixed gas obtained in the step four to obtain high-purity hydrogen.
Step six: generating electricity by using purge gas: and (4) generating electricity by using the purge gas generated by the hydrogen gas purification device in the step (V) through power generation equipment, and returning the generated electricity to a power circuit of the electrolytic cell in the step (I) for electrolysis to adjust the unstable power supply condition of green electricity.
5. The method for producing hydrogen by electrolyzing water coupled with methane-rich gas as claimed in claim 4, wherein: the step of producing hydrogen by electrolyzing water adopts alkaline electrolyzed water or proton exchange membrane electrolyzed water.
6. The method for producing hydrogen by coupling electrolyzed water with methane-rich gas as claimed in claim 4, characterized in that: the multiple reforming hydrogen production steps mainly comprise reforming reaction, desulfurization reaction and medium-low temperature shift reaction.
7. The method for producing hydrogen by electrolyzing water coupled with methane-rich gas as claimed in claim 4, wherein: the methane-rich gas raw material is natural gas or methane or coal bed gas or shale gas.
8. The method for producing hydrogen by electrolyzing water coupled with methane-rich gas as claimed in claim 4, wherein: the oxygen/methane ratio in the multiple reforming reaction is 0.1-2, the reaction temperature is 750- -1 Wherein the oxygen is the sum of oxygen and oxygen element in water.
9. The method for producing hydrogen by electrolyzing water coupled with methane-rich gas as claimed in claim 4, wherein: and in the hydrogen purification step, one or two modes of membrane separation and pressure swing adsorption separation are combined, and methane, carbon monoxide, carbon dioxide and trace impurities in the hydrogen-rich mixed gas obtained in the fourth step are removed to obtain high-purity hydrogen.
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Application publication date: 20220906 |