CN112531185A - Power generation system and method using methanol as raw material - Google Patents

Power generation system and method using methanol as raw material Download PDF

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Publication number
CN112531185A
CN112531185A CN202011524719.7A CN202011524719A CN112531185A CN 112531185 A CN112531185 A CN 112531185A CN 202011524719 A CN202011524719 A CN 202011524719A CN 112531185 A CN112531185 A CN 112531185A
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China
Prior art keywords
hydrogen
raw material
methanol
tank
power generation
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Chinese (zh)
Inventor
曹道帆
江锋浩
梅豫杰
吴昌宁
刘科
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Zhonghe smart energy technology (Shenzhen) Co.,Ltd.
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Southwest University of Science and Technology
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Priority to CN202011524719.7A priority Critical patent/CN112531185A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
    • 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
    • Y02E60/50—Fuel cells
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a hydrogen energy power generation system using methanol as a raw material. The invention can adjust the composition of raw materials, only needs to allocate one raw material, and can give the raw material concentration meeting the catalytic conversion and the raw material concentration required by the electrochemical conversion by adjusting the water-carbon ratio; and the ratio of the two sources in the final hydrogen product can be adjusted. If a catalytic conversion route is adopted, only heat energy needs to be input; if electrochemical conversion is adopted, electric energy is input, and renewable electric energy can be introduced through the way; the system can have two different hydrogen sources, and the purification of the hydrogen is realized without technologies such as membrane separation, pressure swing adsorption and the like under a proper proportion so as to meet the requirements of a fuel cell or other hydrogen fuel power generation equipment; the water generated in the system is further recovered in the water collecting tank, and is partially recycled to the raw material water tank for reuse, so that the utilization rate of the system materials is effectively improved, and the possible emissions of methanol, formaldehyde and the like in the tail gas are reduced.

Description

Power generation system and method using methanol as raw material
Technical Field
The invention relates to the technical field of power generation, in particular to a power generation system and method using methanol as a raw material.
Background
At present, coal-fired or gas-fired boilers are mainly adopted in the energy and power industry for large-scale centralized power generation, and internal combustion engines such as gasoline engines and diesel engines are mainly adopted for distributed power generation. The raw materials for these power generation systems are derived from non-renewable fossil energy sources (coal, oil, natural gas) and emit significant amounts of CO during energy use2Sulfur Oxide (SO)X) And Nitrogen Oxides (NO)X). With the further improvement of national economy and the gradual increase of energy demand, the traditional power generation method not only can aggravate the consumption of natural resources such as coal, petroleum, natural gas and the like, but also can cause ecological problems such as greenhouse effect, environmental pollution and the like. In order to maintain national energy safety and meet the requirements of environmental protection, the development of green and efficient clean alternative energy application technology and the adoption of clean energy for power generation are inevitable trends of future energy and power industries.
Hydrogen (H)2) The material is considered as an energy material with a future prospect, and can be widely applied to a plurality of fields such as energy, electric power, chemical industry and the like. The hydrogen can be prepared from the existing coal and natural gas, can also be prepared from green hydrogen-containing gas liquid such as methanol and the like, and can also be prepared by adopting renewable energy sources (such as wind energy and electric energy) through a method of electrolyzing water and methanol. The existing hydrogen power generation technology mainly utilizes methods such as a hydrogen fuel cell, a hydrogen turbine power generation method, a hydrogen internal combustion engine power generation method and the like. The hydrogen fuel cell is realized by a Proton Exchange Membrane Fuel Cell (PEMFC), and hydrogen and oxygen in the air undergo a combustion reaction to release electric energy based on an electrochemical principle. The hydrogen turbine and the hydrogen internal combustion engine utilize the heat energy output generated after the hydrogen fuel is combusted as mechanical energy, so as to drive the generator to generate electricity. However, the main reason limiting the widespread use of hydrogen energy is the storage and transportation problems of hydrogen gas. The specific reasons are: (1) the volume energy density of the hydrogen is low, about 12.7MJ/m at normal temperature and normal pressure3. It is necessary to increase the energy density by compression or liquefaction, e.g. by liquefying hydrogen at-253 deg.CThe volume energy density of the hydrogen is increased to about 10027MJ/m3. However, a large amount of energy is lost in the compression and liquefaction process, and it is estimated that 30-33% of the total energy carried by hydrogen is used to liquefy hydrogen. The high pressure cylinder materials used for storing hydrogen gas require special manufacturing, which is costly to process and transport. (2) Due to the hydrogen molecules and the easy dissipation thereof, 0.1-1% of evaporation loss is generated every day, which brings unnecessary waste. (3) From the viewpoint of safety, the explosion limit of hydrogen is 4.0 v% to 75.6 v%, and particularly in a closed space, the safety of hydrogen is far lower than that of other fuels.
In order to solve the problems, the existing proposal adopts methanol as a hydrogen storage carrier, and hydrogen is produced on line through catalytic cracking or catalytic reforming, thereby solving the problem of storage and transportation of hydrogen energy. However, in the actual use process, the purity of the hydrogen gas is difficult to directly meet the requirement of hydrogen fuel power generation. If wind energy, solar energy, water electrolysis or methanol is adopted to generate hydrogen, the purity can meet the requirement, but the yield and the continuity are difficult to guarantee.
Therefore, a process and a system technology for producing hydrogen-rich gas by using methanol as a raw material and using the hydrogen-rich gas for power generation are urgently needed, and the process and the system technology have the function of flexibly adjusting an operation process and meeting the requirements of different hydrogen products.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a power generation system using methanol as a raw material, and the system conversion route of the present invention is flexible and controllable, and has low cost.
The invention provides a power generation system using methanol as a raw material, which comprises:
the system comprises a methanol solution storage tank, a raw material liquid first storage tank, a water collecting tank, an evaporator, a reactor, a purification chamber, a hydrogen buffer tank, a combustion chamber, a solution preparation tank, a static mixer, a raw material liquid second storage tank, an electrolytic bath, a hydrogen buffer tank and a power generation system;
a liquid outlet of the methanol solution storage tank is connected with a methanol inlet of the raw material liquid first storage tank through a first valve;
the water outlet of the water collecting tank is connected with the water inlet of the raw material liquid storage tank through a second valve;
the raw material liquid storage tank is connected with the inlet of the evaporator through a discharge pipe;
the gas outlet of the evaporator is connected with the inlet of the reactor;
the outlet of the reactor is connected with the inlet of the purification chamber;
the hydrogen outlet of the purification chamber is connected with the reformed hydrogen inlet of the hydrogen buffer tank;
the pressure relief outlet of the hydrogen buffer tank is connected with the inlet of the combustion chamber, and the combustion chamber provides a heat source for the evaporator and the reactor;
the liquid outlet of the raw material liquid storage tank is connected with the raw material liquid inlet of the solution preparation tank through a third valve; a second water outlet of the water collecting tank is connected with a water inlet of the solution preparation tank through a fourth valve;
the liquid outlet of the solution preparation tank is connected with the inlet of the static mixer through a fifth valve;
the outlet of the static mixer is connected with the second raw material liquid storage tank through a sixth valve;
the raw material liquid storage tank II is connected with the electrolytic cell through a discharge pipe, and an electrolytic power supply supplies power to the electrolytic cell;
the hydrogen outlet of the electrolytic cell is connected with the electrolytic hydrogen inlet of the hydrogen buffer tank;
and the second outlet of the hydrogen buffer tank is connected with the power generation system.
Preferably, a tail gas drain pipe in the power generation system is connected with a first water inlet of the water collecting tank;
the evaporator water outlet is connected with the second water inlet of the water collecting tank.
Preferably, the tail gas outlet of the power generation system is connected with the inlet of the combustion chamber;
the combustion chamber can be an independent fuel combustion device which heats the evaporator through heat transfer oil heat exchange, or can be a shell sleeved outside the evaporator and forms a whole with the evaporator;
the combustion chamber can be an independent fuel combustion device which heats the reactor through heat transfer oil heat exchange, or can be a shell sleeved outside the reactor and forms a whole with the reactor;
the combustion chamber can be an independent fuel combustion device, the heat conduction oil heat exchange reactor and the evaporator are used for heating, and the heat conduction oil firstly provides heat for the reactor and then provides heat for the evaporator.
Preferably, the raw material liquid storage tank is used for storing raw materials for the hydrogen production reaction by methanol reforming; the molar ratio of water to methanol in the raw material liquid storage tank is 1-5;
the raw material liquid two storage tank is used for storing a hydrolysis methanol hydrogen production reaction raw material; the molar concentration of the methanol water solution in the raw material liquid two storage tank is 4 mol/L.
Preferably, a methanol reforming catalyst is provided in the reactor.
Preferably, the pressure of the hydrogen in the buffer tank is 3.5atm to 6 atm.
Preferably, the electrolytic power source is selected from solar energy, wind energy or other external electric energy.
Preferably, the purification chamber comprises hopcalite or copper-loaded activated carbon monoxide adsorbent.
The invention provides a method for generating power by adopting the system in any one of the technical schemes, which comprises the following steps:
a catalytic conversion mode and/or an electrochemical conversion mode;
the catalytic conversion mode is specifically as follows: mixing methanol in the methanol solution storage tank with water in the water collection tank, heating and evaporating the mixture, then feeding the mixture into a reactor for methanol reforming hydrogen production reaction, purifying the obtained hydrogen, feeding the purified hydrogen into a hydrogen buffer tank, and feeding the purified hydrogen into a power generation system for power generation;
the electrochemical conversion mode is specifically as follows: diluting and preparing the solution in the raw material solution I storage tank to obtain a diluted methanol solution; and electrolyzing the diluted methanol solution by an electrolytic bath to obtain hydrogen, and feeding the hydrogen into a power generation system to generate power.
Preferably, the concentration of hydrogen in the hydrogen buffer tank is not higher than the concentration of hydrogen in the purification chamber.
Preferably, the concentration of carbon monoxide in the hydrogen in the purification chamber is 1ppm or less; the concentration of carbon monoxide in the buffer tank is below 0.2 ppm.
Preferably, the flow rate of the raw materials in the catalytic conversion mode is 18-25 g/min; the flow rate of the raw materials in the electrochemical conversion mode is 30-50 g/min; the ratio of the flow rate of the raw material in the catalytic conversion mode to the flow rate of the raw material in the electrochemical conversion mode is preferably 0.35-0.8.
Compared with the prior art, the invention provides a power generation system taking methanol as a raw material, which comprises: the system comprises a methanol solution storage tank, a raw material liquid first storage tank, a water collecting tank, an evaporator, a reactor, a purification chamber, a hydrogen buffer tank, a combustion chamber, a solution preparation tank, a static mixer, a raw material liquid second storage tank, an electrolytic bath, a hydrogen buffer tank and a power generation system; a liquid outlet of the methanol solution storage tank is connected with a methanol inlet of the raw material liquid first storage tank through a first valve; the water outlet of the water collecting tank is connected with the water inlet of the raw material liquid storage tank through a second valve; the raw material liquid storage tank is connected with the inlet of the evaporator through a discharge pipe; the gas outlet of the evaporator is connected with the inlet of the reactor; the outlet of the reactor is connected with the inlet of the purification chamber; the hydrogen outlet of the purification chamber is connected with the reformed hydrogen inlet of the hydrogen buffer tank; the pressure relief outlet of the hydrogen buffer tank is connected with the inlet of the combustion chamber, and the combustion chamber provides a heat source for the evaporator and the reactor; the liquid outlet of the raw material liquid storage tank is connected with the raw material liquid inlet of the solution preparation tank through a third valve; a second water outlet of the water collecting tank is connected with a water inlet of the solution preparation tank through a fourth valve; the liquid outlet of the solution preparation tank is connected with the inlet of the static mixer through a fifth valve; the outlet of the static mixer is connected with the second raw material liquid storage tank through a sixth valve; the raw material liquid storage tank II is connected with the electrolytic cell through a discharge pipe, and an electrolytic power supply supplies power to the electrolytic cell; the hydrogen outlet of the electrolytic cell is connected with the electrolytic hydrogen inlet of the hydrogen buffer tank; and the second outlet of the hydrogen buffer tank is connected with the power generation system. The invention can adjust the composition of raw materials, can provide the raw material concentration meeting the catalytic reforming reaction and adjust the water-carbon ratio according to the process requirement, and can also provide the raw material concentration required by the electrolytic methanol; the source of the desired hydrogen can be selected. If a catalytic conversion route is adopted, only heat energy needs to be input, and the heat in the tail gas can be fully recovered through the method; if electrochemical conversion is adopted, the electric energy is input, and renewable electric energy can be introduced from the electric energy input route; the hydrogen purification device can have two different hydrogen sources, and can realize the purification of hydrogen without technologies such as membrane separation, pressure swing adsorption and the like under a proper proportion so as to meet the requirement of a fuel cell; water generated in the hydrogen power generation process is further recovered in the water collecting tank and is partially pumped back to the raw material water tank for reuse, so that the utilization rate of system materials is effectively improved. On the other hand, incompletely combusted methanol possibly existing in the tail gas and part of impurities such as formaldehyde generated by methanol oxidation can be recovered along with moisture in the tail gas, so that the emission is reduced.
Drawings
FIG. 1 is a schematic diagram of a power generation system using methanol as a raw material according to the present invention.
Detailed Description
The invention provides a power generation system and method using methanol as a raw material, and a person skilled in the art can use the content for reference and appropriately improve the process parameters to realize the purpose. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a power generation system using methanol as a raw material, which comprises:
the system comprises a methanol solution storage tank, a raw material liquid first storage tank, a water collecting tank, an evaporator, a reactor, a purification chamber, a hydrogen buffer tank, a combustion chamber, a solution preparation tank, a static mixer, a raw material liquid second storage tank, an electrolytic bath, a hydrogen buffer tank and a power generation system;
a liquid outlet of the methanol solution storage tank is connected with a methanol inlet of the raw material liquid first storage tank through a first valve;
the water outlet of the water collecting tank is connected with the water inlet of the raw material liquid storage tank through a second valve;
the raw material liquid storage tank is connected with the inlet of the evaporator through a discharge pipe;
the gas outlet of the evaporator is connected with the inlet of the reactor;
the outlet of the reactor is connected with the inlet of the purification chamber;
the hydrogen outlet of the purification chamber is connected with the reformed hydrogen inlet of the hydrogen buffer tank;
the pressure relief outlet of the hydrogen buffer tank is connected with the inlet of the combustion chamber, and the combustion chamber provides a heat source for the evaporator and the reactor;
the liquid outlet of the raw material liquid storage tank is connected with the raw material liquid inlet of the solution preparation tank through a third valve; a second water outlet of the water collecting tank is connected with a water inlet of the solution preparation tank through a fourth valve;
the liquid outlet of the solution preparation tank is connected with the inlet of the static mixer through a fifth valve;
the outlet of the static mixer is connected with the second raw material liquid storage tank through a sixth valve;
the raw material liquid storage tank II is connected with the electrolytic cell through a discharge pipe, and an electrolytic power supply supplies power to the electrolytic cell;
the hydrogen outlet of the electrolytic cell is connected with the electrolytic hydrogen inlet of the hydrogen buffer tank;
and the second outlet of the hydrogen buffer tank is connected with the power generation system.
The invention provides a power generation system using methanol as a raw material, which comprises a methanol solution storage tank. The methanol solution storage tank stores methanol, and the methanol solution can be mixed with water in the water collecting tank to prepare methanol solutions with different proportions.
And a liquid outlet of the methanol solution storage tank is connected with a methanol inlet of the raw material liquid storage tank through a first valve.
The invention provides a power generation system using methanol as a raw material, which comprises a water collection tank. The water collecting tank is used for bearing water, the specification of the water collecting tank is not limited, and the water collecting tank can meet the practicability of the water collecting tank as is well known by the technical personnel in the field.
And the water outlet of the water collecting tank is connected with the water inlet of the raw material liquid storage tank through a second valve.
The invention provides a power generation system using methanol as a raw material. The raw material liquid storage tank is used for storing raw materials for methanol reforming hydrogen production reaction; the molar ratio of methanol to water in the raw material liquid storage tank is preferably (1-5): 1, and specifically can be 1, 2.5 or 3.5.
The invention provides a power generation system using methanol as a raw material, which comprises an evaporator. And the raw material liquid storage tank is connected with the inlet of the evaporator through a discharge pipe. The evaporator water outlet is connected with the second water inlet of the water collecting tank.
The evaporator of the present invention is not limited thereto, and those skilled in the art will appreciate that the evaporator is not limited thereto.
The invention provides a power generation system using methanol as a raw material, which comprises a reactor.
The gas outlet of the evaporator is connected with the inlet of the reactor. A methanol reforming catalyst is arranged in the reactor. The present invention is not limited to the specific types thereof, and those skilled in the art will be familiar with the present invention.
The methanol solution is stored in a methanol solution storage tank 1, wherein the methanol solution with the molar ratio of methanol to water of 1: 1 to 1:0 is pure methanol solution when the molar ratio of methanol to water is 1: 0. The water collection tank 12 stores therein water collected from the combustion chamber 11, the power generation system 24), and the like. When the valve 2 and the valve 3 are opened, the methanol solution in the methanol solution storage tank 1 is mixed with the water in the water collection tank 12, and when the opening degree of the valve is changed, the solution concentration in the raw material solution storage tank 4 is also changed. The raw material stored in the raw material liquid storage tank 4 is used for the methanol reforming hydrogen production reaction based on the thermocatalytic conversion.
The invention provides a power generation system using methanol as a raw material, which comprises a purification chamber, a hydrogen buffer tank and a combustion chamber. The outlet of the reactor is connected with the inlet of the purification chamber.
Wherein the hydrogen outlet of the purification chamber is connected with the reformed hydrogen inlet of the hydrogen buffer tank. The pressure relief outlet of the hydrogen buffer tank is connected with the inlet of the combustion chamber, and the combustion chamber provides a heat source for the evaporator and the reactor. The pressure of hydrogen in the buffer tank is 3.5 atm-6 atm. Excess gas is delivered through the canister valve into the combustion chamber to supply heat to the system.
The raw material in the raw material liquid storage tank 4 enters the evaporator 6 through the raw material liquid discharge pipe 5, and the liquid raw material is converted into a steam state after heat is absorbed. Enters the reactor 7 and absorbs heat from the combustion chamber 11, and undergoes catalytic reforming reaction to obtain reformed gas. The reformed gas, whose main constituents are hydrogen, carbon dioxide, water, enters the purification chamber 8 where water, carbon dioxide and most of the carbon monoxide are removed by conventional methods. In the purification chamber 8, the existing technical means are utilized, such as the method of condensation and adsorption is adopted to remove moisture, the method of adsorption or absorption is adopted to remove carbon dioxide by substances such as calcium lime, mixed organic amine, calcium hydroxide and the like, and the carbon monoxide adsorbent such as hopcalite agent, copper-loaded activated carbon and the like is adopted to remove most of carbon monoxide; or the concentration of carbon dioxide and carbon monoxide can be reduced by selective oxidation, methanation and other reactions by adopting a chemical method. However, the method can only reduce the carbon monoxide content in the hydrogen to 1ppm at most, and is far from meeting the requirement of the fuel cell for 0.2ppm, and generally needs to adopt technologies such as membrane separation, Pressure Swing Adsorption (PSA) and the like to further purify the hydrogen. The hydrogen gas from the purification chamber 8 enters a hydrogen buffer tank 9.
The invention provides a power generation system using methanol as a raw material, which comprises a solution preparation tank.
The liquid outlet of the raw material liquid storage tank is connected with the raw material liquid inlet of the solution preparation tank through a third valve; and a second water outlet of the water collecting tank is connected with a water inlet of the solution preparation tank through a fourth valve.
The invention provides a power generation system using methanol as a raw material, which comprises a static mixer and a raw material liquid storage tank. The liquid outlet of the solution preparation tank is connected with the inlet of the static mixer through a fifth valve; and the outlet of the static mixer is connected with the second raw material liquid storage tank through a sixth valve.
The invention is not limited to the specific type and specification of the static mixer, and the solution can be mixed as is well known to those skilled in the art.
The raw material liquid two storage tank is used for storing a raw material for hydrogen production reaction by hydrolyzing methanol; the concentration of the methanol aqueous solution in the raw material liquid two storage tank is preferably 4 mol/L.
Specifically, when the valves 13 and 14 are opened, the solution in the raw material liquid-one tank 4 is further diluted and a methanol solution having a lower concentration than that in the raw material liquid-one tank 4 is obtained in the solvent-fixing solution preparation tank 15. When preparing the solution, the valve 13 and the valve 16 are closed, the valve 14 is opened, 1/10 solution is filled in the solution preparation tank 15, the valve 14 is closed and the weight of the solution is measured to determine the methanol concentration, then the valve 13 is opened, and a certain amount of pure water is injected into the solution preparation tank 15 under the control of the flow meter until the required concentration is reached. Valve 13 is then closed, valve 16 and valve 18 are opened, and the prepared solution is passed through static mixer 17 and into feed solution two reservoir 19. And the raw material stored in the raw material liquid second storage tank 19 is used for the hydrogen production reaction of the electrolytic methanol based on the electrocatalytic conversion.
The invention provides a power generation system using methanol as a raw material, which comprises an electrolytic cell, a hydrogen buffer tank and a power generation system.
The raw material liquid storage tank II is connected with the electrolytic cell through a discharge pipe, and an electrolytic power supply supplies power to the electrolytic cell; the hydrogen outlet of the electrolytic cell is connected with the electrolytic hydrogen inlet of the hydrogen buffer tank; and the second outlet of the hydrogen buffer tank is connected with the power generation system.
A tail gas drain pipe in the power generation system is connected with a first water inlet of the water collecting tank; and a tail gas outlet in the power generation system is connected with an inlet of the combustion chamber.
The combustion chamber can be an independent fuel combustion device which heats the evaporator through heat transfer oil heat exchange, and can also be a shell sleeved outside the evaporator and form a whole with the evaporator;
the combustion chamber can be an independent fuel combustion device for heating the reactor through heat transfer oil heat exchange, and can also be a shell sleeved outside the reactor to form a whole with the reactor;
the combustion chamber can be an independent fuel combustion device, the heat conduction oil heat exchange reactor and the evaporator are used for heating, and the heat conduction oil firstly provides heat for the reactor and then provides heat for the evaporator.
The raw material in the raw material liquid two-storage tank 19 enters the electrolytic cell 21 through the raw material liquid two-discharge pipe 20, and the liquid raw material is converted into hydrogen and carbon dioxide products by the electric energy of the electrolytic power supply 22. The hydrogen product 23 is pure hydrogen and directly enters the hydrogen buffer tank 9 without purification.
The hydrogen gas obtained from the reforming of methanol and the hydrogen gas obtained from the electrolysis of a methanol solution are received in the hydrogen buffer tank 9, and these two streams are mixed in the hydrogen buffer tank. Because the two hydrogen streams have different purities, hydrogen products with different purities can be obtained by adjusting the proportion of the two hydrogen streams. The hydrogen buffer tank 9 is provided with two outlets, the first outlet leads out a stream 10 for adjusting the pressure, and the stream enters the combustion chamber 1 for combustion and provides a part of heat source for reforming reaction; the second outlet is a product gas outlet, which is the product hydrogen meeting the requirements of the fuel cell and is directly supplied to the power generation system (4).
In the system, some valves, pumps, etc. are not shown in the figure. The combustion feed to the combustion chamber 11 also contains a methanol solution, which is not shown in this figure. Hydrogen stream 23 is in this case hydrogen produced by electrolysis of methanol, it should be noted that the present scheme provides a concept that any high purity hydrogen can be introduced into the system via stream 23, such as hydrogen cylinders for hydrogen, solid hydride for hydrogen, reaction products of metals and sulfuric acid, etc.
The electrolytic power supply is selected from solar energy, wind energy or other external electric energy.
FIG. 1 is a schematic diagram of a power generation system using methanol as a raw material according to the present invention. Reference numbers in the figures:
the device class is as follows:
1-methanol solution storage tank; 4-a storage tank for the raw material liquid. Is used for the hydrogen production reaction by methanol reforming. 6-an evaporator; 7-a reactor; 8-a purification chamber; 9-hydrogen buffer tank; 11-a combustion chamber; 12-a water collecting tank; 15-solution preparation tank; 17-a static mixer; 19-a raw material liquid storage tank II; is used for the hydrogen production reaction by electrolyzing methanol. 21-an electrolytic cell; 22-an electrolytic power supply; 24-power generation systems, such as fuel cells;
2. 3, 13, 14, 16, 18-valves; where 2 is the first valve, 3 is the second valve, 14 is the third valve, 13 is the fourth valve, 16 is the fifth valve, 18 is the sixth valve.
Pipeline type:
5-a raw material liquid discharge pipe; 20-a raw material liquid II discharge pipe; 23-electrolyzing hydrogen into a buffer tank pipe; 10-a buffer tank pressure relief outlet; 25-a power generation system tail gas outlet; and 26-tail gas drainage pipe of the power generation system.
The invention provides a power generation system using methanol as a raw material, which comprises: a liquid outlet of the methanol solution storage tank is connected with the raw material liquid storage tank through a first valve; a water outlet of the water collecting tank is connected with the raw material liquid storage tank through a second valve; the raw material liquid storage tank is connected with an inlet of the evaporator through a discharge pipe; the gas outlet of the evaporator is connected with the inlet of the reactor; the outlet of the reactor is connected with the inlet of the purification chamber; a hydrogen outlet of the purification chamber is connected with a reformed hydrogen inlet of the hydrogen buffer tank; the pressure relief outlet of the hydrogen buffer tank is connected with the inlet of the combustion chamber, and the combustion chamber provides a heat source for the evaporator and the reactor; a liquid outlet of the raw material liquid storage tank is connected with a raw material liquid inlet of the solution preparation tank through a third valve; a second water outlet of the water collecting tank is connected with a water inlet of the solution preparation tank through a fourth valve; the liquid outlet of the solution preparation tank is connected with the inlet of the static mixer through a fifth valve; the outlet of the static mixer is connected with the second raw material liquid storage tank through a sixth valve; the raw material liquid storage tank II is connected with the electrolytic cell through a discharge pipe, and an electrolytic power supply supplies power to the electrolytic cell; the hydrogen outlet of the electrolytic cell is connected with the electrolytic hydrogen inlet of the hydrogen buffer tank; and a second outlet of the hydrogen buffer tank is connected with the power generation system. The invention can adjust the composition of raw materials, can provide the raw material concentration meeting the catalytic reforming reaction and adjust the water-carbon ratio according to the process requirement, and can also provide the raw material concentration required by the electrolytic methanol; the source of the desired hydrogen can be selected. If a catalytic conversion route is adopted, only heat energy needs to be input, and the heat in the tail gas can be fully recovered through the method; if electrochemical conversion is adopted, the electric energy is input, and renewable electric energy can be introduced from the electric energy input route; the hydrogen purification device can have two different hydrogen sources, and can realize the purification of hydrogen without technologies such as membrane separation, pressure swing adsorption and the like under a proper proportion so as to meet the requirement of a fuel cell; water generated in the hydrogen power generation process is further recovered in the water collecting tank and is partially pumped back to the raw material water tank for reuse, so that the utilization rate of system materials is effectively improved. On the other hand, incompletely combusted methanol possibly existing in the tail gas and part of impurities such as formaldehyde generated by methanol oxidation can be recovered along with moisture in the tail gas, so that the emission is reduced.
The invention provides a method for generating power by adopting the system in any one of the technical schemes, which comprises the following steps:
a catalytic conversion mode and/or an electrochemical conversion mode;
the catalytic conversion mode is specifically as follows: mixing methanol in the methanol solution storage tank with water in the water collection tank, heating and evaporating the mixture, then feeding the mixture into a reactor for methanol reforming hydrogen production reaction, feeding the obtained hydrogen into a purification chamber for preliminary purification and purification, feeding the purified hydrogen into a hydrogen buffer tank, and feeding the hydrogen into a power generation system for power generation;
the electrochemical conversion mode is specifically as follows: diluting and preparing the solution in the raw material solution I storage tank to obtain a diluted methanol solution; and electrolyzing the diluted methanol solution by an electrolytic cell to obtain hydrogen, and delivering the hydrogen to a hydrogen buffer tank to enter a power generation system for power generation.
The power generation method of the present invention includes a catalytic conversion mode.
The catalytic conversion mode is specifically as follows: methanol in the methanol solution storage tank is mixed with water in the water collection tank, the mixture is heated and evaporated and then enters a reactor to carry out methanol reforming hydrogen production reaction, and the obtained hydrogen is purified and reaches a hydrogen buffer tank to enter a power generation system to generate power.
The reaction conditions and specific parameters are not limited in the present invention and are well known to those skilled in the art.
When the power generation power is 1kW, the flow of the raw materials in the catalytic conversion mode is preferably 18-25 g/min.
The hydrogen produced by the catalytic conversion mode has a minimum concentration of 1ppm of carbon monoxide. In this mode, the molar ratio of water to methanol is preferably 3.5.
The power generation method of the invention comprises an electrochemical conversion mode. The electrochemical conversion mode is specifically as follows: diluting and preparing the solution in the raw material solution I storage tank to obtain a diluted methanol solution; and electrolyzing the diluted methanol solution by an electrolytic bath to obtain hydrogen, and feeding the hydrogen into a power generation system to generate power.
When the power generation power is 1kW, the flow of the raw materials in the electrochemical conversion mode is 30-50 g/min. In this mode, the molar concentration of the methanol solution is preferably 4 mol/L.
According to the invention, the ratio of the flow rate of the raw material in the catalytic conversion mode to the flow rate of the raw material in the electrochemical conversion mode is preferably 0.35-0.8; more preferably 0.35 to 0.75; most preferably 0.7 to 0.8.
The hydrogen production system can generate hydrogen through a single catalytic conversion route, can also generate hydrogen through single electrochemical conversion, can also simultaneously have the two conversion routes, collects the generated hydrogen into the buffer tank, and meets the requirements of a power generation system through proper process optimization.
When the two hydrogen production routes are used simultaneously, the concentration of carbon monoxide in the hydrogen buffer tank can be reduced to be less than 0.2 ppm.
The concentration of hydrogen in the hydrogen buffer tank of the present invention is not higher than the concentration of hydrogen in the purification chamber. Preferably, the concentration of carbon monoxide in the hydrogen in the purification chamber is 1ppm or less; the concentration of carbon monoxide in the buffer tank is below 0.2 ppm.
Correspondingly, the raw material system can realize the configuration of different raw material liquids through simple valve opening and closing operations. And preparing the required dilute solution from the high-concentration raw material solution and water according to different proportions on a production site according to requirements. The beneficial effects are that, only need high concentration's raw materials liquid and water, reduced the burden of commodity circulation in the transportation. When the device is used in the field, the fuel allocation car only needs to distribute the methanol liquid with high concentration to meet different process requirements. In addition, since a hydrogen fuel power generation system such as a fuel cell can generate excessive moisture by itself, it is possible to recover the water for use in preparing a methanol solution by the device.
The invention provides a hydrogen production and power generation system using methanol as a raw material. Mixing methanol and water according to a certain proportion to obtain a methanol water solution with a certain concentration. Methanol aqueous solutions with different concentrations, i.e., raw material solutions, are prepared according to different chemical reactions (e.g., catalytic conversion or electrochemical conversion). The feed solution is converted into a hydrogen-rich gas by a series of chemical transformations. And purifying the hydrogen-rich gas, injecting the purified hydrogen-rich gas into a hydrogen buffer tank, further adjusting the purity of the hydrogen-rich gas, and using the purified hydrogen-rich gas as fuel to generate electricity. In the power generation process, the hydrogen-containing tail gas is mixed with other heat supply gases (such as methanol and hydrogen) and then enters a combustor together to provide heat for a system. And water generated in the combustor is subjected to heat exchange and cooling and then collected to a raw material water storage tank.
In order to further illustrate the present invention, the following will describe a power generation system and method using methanol as a raw material in detail with reference to the following examples.
Example 1
The system is connected according to the invention: a methanol-fed power generation system comprising: a liquid outlet of the methanol solution storage tank is connected with the raw material liquid storage tank through a first valve; a water outlet of the water collecting tank is connected with the raw material liquid storage tank through a second valve; the raw material liquid storage tank is connected with an inlet of the evaporator through a discharge pipe; the gas outlet of the evaporator is connected with the inlet of the reactor; the outlet of the reactor is connected with the inlet of the purification chamber; a hydrogen outlet of the purification chamber is connected with a reformed hydrogen inlet of the hydrogen buffer tank; the pressure relief outlet of the hydrogen buffer tank is connected with the inlet of the combustion chamber, and the combustion chamber provides a heat source for the evaporator and the reactor; a liquid outlet of the raw material liquid storage tank is connected with a raw material liquid inlet of the solution preparation tank through a third valve; a second water outlet of the water collecting tank is connected with a water inlet of the solution preparation tank through a fourth valve; the liquid outlet of the solution preparation tank is connected with the inlet of the static mixer through a fifth valve; the outlet of the static mixer is connected with the second raw material liquid storage tank through a sixth valve; the raw material liquid storage tank II is connected with the electrolytic cell through a discharge pipe, and an electrolytic power supply supplies power to the electrolytic cell; the hydrogen outlet of the electrolytic cell is connected with the electrolytic hydrogen inlet of the hydrogen buffer tank; and a second outlet of the hydrogen buffer tank is connected with the power generation system. A tail gas drain pipe in the power generation system is connected with a first water inlet of the water collecting tank; the evaporator water outlet is connected with the second water inlet of the water collecting tank. And a tail gas outlet in the power generation system is connected with an inlet of the combustion chamber. A methanol reforming catalyst is disposed in the reactor. The pressure of hydrogen in the buffer tank is 3.5 atm-6 atm.
Example 2
The flow rate of the raw material of the catalytic conversion methanol-water mixed solution is 19.24g/min, and the molar ratio of water to methanol is adjusted to 2.5. The flow rate of the raw material of the electrochemical conversion methanol-water mixed solution is adjusted to be 32.19g/min, the concentration of the raw material is 4mol/L, and the rate of the electrochemical hydrogen generation is about 3.00 g/min. The system produced 4.50g/min of hydrogen in total and 0.28ppm of CO. This procedure consumed 9.80g/min of methanol.
Example 3
By adopting the system of the embodiment 1 of the invention, the flow rate of the raw material of the catalytic conversion methanol-water mixed solution is 19.24g/min, and the molar ratio of water to methanol is adjusted to 2.5. The flow rate of the raw material of the electrochemical conversion methanol-water mixed solution is adjusted to be 48.25g/min, the concentration of the raw material is 4mol/L, and the rate of the electrochemical hydrogen generation is about 4.5 g/min. The system produced 6.0g/min of hydrogen in total and 0.21ppm of CO. This process consumed 11.95g/min of methanol.
Example 4
By adopting the system of the embodiment 1 of the invention, the raw material flow of the catalytic conversion methanol-water mixed solution is 21.49g/min, and the molar ratio of water to methanol is adjusted to 3. The flow rate of the raw material of the electrochemical conversion methanol-water mixed solution is adjusted to be 32.19g/min, the concentration of the raw material is 4mol/L, and the rate of the electrochemical hydrogen generation is about 3.0 g/min. The system produced 4.5g/min of hydrogen in total and 0.21ppm of CO. This procedure consumed 9.67g/min of methanol.
Example 5
By adopting the system of the embodiment 1 of the invention, the flow rate of the raw material of the catalytic conversion methanol-water mixed solution is 23.75g/min, and the molar ratio of water to methanol is adjusted to be 3.5. The flow rate of the raw material of the electrochemical conversion methanol-water mixed solution is adjusted to be 32.19/min, the concentration of the raw material is 4mol/L, and the rate of the hydrogen generated by the electrochemistry is about 3.0 g/min. The system produced 4.5g/min of hydrogen in total and 0.17ppm of CO. This procedure consumed 9.58g/min of methanol.
The carbon monoxide content in the product obtained by the embodiments 2-4 is still high, and the demand of a fuel cell or other hydrogen fuel power generation equipment cannot be met. By adjusting the process parameters, the optimization of the carbon monoxide content can be realized. Example 3 the flow of electrochemical hydrogen production was adjusted and the carbon monoxide content in the final product was reduced to 0.21 ppm. Example 4 the same effect can be achieved by adjusting the concentration composition of the first raw material liquid. In example 5, it can be seen that the carbon monoxide content can be reduced to less than 0.2ppm by adjusting the ratio of the two raw material liquids and the composition thereof.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A power generation system using methanol as a raw material, comprising:
the system comprises a methanol solution storage tank, a raw material liquid first storage tank, a water collecting tank, an evaporator, a reactor, a purification chamber, a hydrogen buffer tank, a combustion chamber, a solution preparation tank, a static mixer, a raw material liquid second storage tank, an electrolytic bath, a hydrogen buffer tank and a power generation system; a liquid outlet of the methanol solution storage tank is connected with a methanol inlet of the raw material liquid first storage tank through a first valve;
the water outlet of the water collecting tank is connected with the water inlet of the raw material liquid storage tank through a second valve;
the raw material liquid storage tank is connected with the inlet of the evaporator through a discharge pipe;
the gas outlet of the evaporator is connected with the inlet of the reactor;
the outlet of the reactor is connected with the inlet of the purification chamber;
the hydrogen outlet of the purification chamber is connected with the reformed hydrogen inlet of the hydrogen buffer tank;
the pressure relief outlet of the hydrogen buffer tank is connected with the inlet of the combustion chamber, and the combustion chamber provides a heat source for the evaporator and the reactor;
the liquid outlet of the raw material liquid storage tank is connected with the raw material liquid inlet of the solution preparation tank through a third valve; a second water outlet of the water collecting tank is connected with a water inlet of the solution preparation tank through a fourth valve;
the liquid outlet of the solution preparation tank is connected with the inlet of the static mixer through a fifth valve;
the outlet of the static mixer is connected with the second raw material liquid storage tank through a sixth valve;
the raw material liquid storage tank II is connected with the electrolytic cell through a discharge pipe, and an electrolytic power supply supplies power to the electrolytic cell;
the hydrogen outlet of the electrolytic cell is connected with the electrolytic hydrogen inlet of the hydrogen buffer tank;
and the second outlet of the hydrogen buffer tank is connected with the power generation system.
2. The power generation system of claim 1, wherein an exhaust gas drain line in the power generation system is connected to the water collection tank first water inlet;
the evaporator water outlet is connected with the second water inlet of the water collecting tank.
3. The power generation system of claim 1, wherein the exhaust gas outlet is connected to the combustor inlet;
the combustion chamber can be an independent fuel combustion device which heats the evaporator through heat transfer oil heat exchange, or can be a shell sleeved outside the evaporator and forms a whole with the evaporator;
the combustion chamber can be an independent fuel combustion device which heats the reactor through heat transfer oil heat exchange, or can be a shell sleeved outside the reactor and forms a whole with the reactor;
the combustion chamber can be an independent fuel combustion device, the heat conduction oil heat exchange reactor and the evaporator are used for heating, and the heat conduction oil firstly provides heat for the reactor and then provides heat for the evaporator.
4. The power generation system of claim 1, wherein the feed solution storage tank is used for storing a feed for the methanol reforming hydrogen production reaction; the molar ratio of water to methanol in the raw material liquid I storage tank is 1-5;
the raw material liquid two storage tank is used for storing a hydrolysis methanol hydrogen production reaction raw material; the molar concentration of the methanol water solution in the raw material liquid two storage tank is 4 mol/L.
5. The power generation system of claim 1, wherein the reactor has a methanol reforming catalyst disposed therein;
the electrolytic power source is selected from solar energy, wind energy or other external electric energy.
6. The power generation system according to claim 1, wherein the pressure of hydrogen gas in the buffer tank is 3.5atm to 6 atm.
7. A method of generating electricity using the system of any one of claims 1 to 6, comprising the steps of:
a catalytic conversion mode and/or an electrochemical conversion mode;
the catalytic conversion mode is specifically as follows: mixing methanol in the methanol solution storage tank with water in the water collection tank, heating and evaporating the mixture, then feeding the mixture into a reactor for methanol reforming hydrogen production reaction, feeding the obtained hydrogen into a purification chamber for preliminary purification, feeding the hydrogen into a hydrogen buffer tank, and feeding the hydrogen into a power generation system for power generation;
the electrochemical conversion mode is specifically as follows: diluting and preparing the solution in the raw material solution I storage tank to obtain a diluted methanol solution; and electrolyzing the diluted methanol solution by an electrolytic cell to obtain hydrogen, and delivering the hydrogen to a hydrogen buffer tank to enter a power generation system for power generation.
8. The method according to claim 7, wherein the concentration of hydrogen in the hydrogen buffer tank is not higher than the concentration of hydrogen in the purification chamber.
9. The method of claim 8, wherein the concentration of carbon monoxide in the hydrogen gas in the purification chamber is 1ppm or less; the concentration of carbon monoxide in the buffer tank is below 0.2 ppm.
10. The method of claim 7, wherein the ratio of the flow rate of the feedstock in the catalytic conversion mode to the flow rate of the feedstock in the electrochemical conversion mode is between 0.35 and 0.8; when the power generation power is 1kW, the flow of the raw materials in the catalytic conversion mode is 18-25 g/min; the flow rate of the raw materials in the electrochemical conversion mode is 30-50 g/min.
CN202011524719.7A 2020-12-22 2020-12-22 Power generation system and method using methanol as raw material Pending CN112531185A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113738581A (en) * 2021-10-18 2021-12-03 西安热工研究院有限公司 Wind energy storage system and method based on coal-to-methanol
CN115692785A (en) * 2023-01-03 2023-02-03 四川荣创新能动力***有限公司 Stable hydrogen supply device for fuel cell and pressure stability control method for buffer tank

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113738581A (en) * 2021-10-18 2021-12-03 西安热工研究院有限公司 Wind energy storage system and method based on coal-to-methanol
CN115692785A (en) * 2023-01-03 2023-02-03 四川荣创新能动力***有限公司 Stable hydrogen supply device for fuel cell and pressure stability control method for buffer tank

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