CN111056533A - Quickly-started methanol-water reforming hydrogen production system and method - Google Patents
Quickly-started methanol-water reforming hydrogen production system and method Download PDFInfo
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- CN111056533A CN111056533A CN201911295107.2A CN201911295107A CN111056533A CN 111056533 A CN111056533 A CN 111056533A CN 201911295107 A CN201911295107 A CN 201911295107A CN 111056533 A CN111056533 A CN 111056533A
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- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 title claims abstract description 240
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 148
- 239000001257 hydrogen Substances 0.000 title claims abstract description 148
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 238000002407 reforming Methods 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 83
- 239000006200 vaporizer Substances 0.000 claims abstract description 54
- 230000008016 vaporization Effects 0.000 claims abstract description 50
- 239000007858 starting material Substances 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000005086 pumping Methods 0.000 claims abstract description 19
- 238000003860 storage Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims description 66
- 238000002485 combustion reaction Methods 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000009834 vaporization Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 9
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000742 Cotton Polymers 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000002309 gasification Methods 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0816—Heating by flames
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- 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
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1604—Starting up the process
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- C01B2203/1614—Controlling the temperature
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Abstract
The invention discloses a quickly started methanol-water reforming hydrogen production system and a method, wherein the reforming hydrogen production system comprises a methanol-water storage container, a delivery pump, a heat exchanger, a reformer, an electromagnetic valve, a starter, a check valve and a control system, wherein: the discharge end of the delivery pump is connected with a reforming delivery pipeline and a starting delivery pipeline, and the starting delivery pipeline is used for delivering a methanol water raw material to a methanol water quantitative vaporizer of the starter under the pumping action of the delivery pump; the electromagnetic valve is arranged on the starting conveying pipeline; the starter comprises a methanol-water quantitative vaporizer and an electric heater, wherein the methanol-water quantitative vaporizer is used for storing and vaporizing quantitative methanol-water raw materials, and the electric heater is used for vaporizing the quantitative methanol-water raw materials stored in the methanol-water quantitative vaporizer; the discharge end of the methanol-water quantitative vaporizer is provided with a steam pipeline, and the methanol-water quantitative vaporizer is communicated with the reformer through the steam pipeline. The invention has short start-up time and high heating efficiency, and does not need to arrange a starter in the reformer.
Description
Technical Field
The invention relates to the technical field of methanol-water hydrogen preparation equipment, in particular to a quickly started methanol-water reforming hydrogen production system and a method.
Background
Currently, methanol steam reforming technology is used to produce H2With CO2The mixed gas is separated by a palladium membrane separator to respectively obtain H2And CO2. Referring to the Chinese patent application 201310340475.0 (applicant: Shanghai synthetic Hydrogen machine Co., Ltd.), the patent discloses a methanol water preparation methodThe hydrogen system, the reforming chamber of the methanol and steam reformer, under the pressure condition of 1-5M Pa at the temperature of 350-409 ℃ and the action of the catalyst, generates the methanol cracking reaction and the shift reaction of carbon monoxide to generate hydrogen and carbon dioxide, and is a multi-component and multi-reaction gas-solid catalytic reaction system. The reaction equation is as follows: (1) CH (CH)3OH→CO+2H2；(2)H2O+CO→CO2+H2；(3)CH3OH+H2O→CO2+3H2H formed by reforming reaction2And CO2And then the H is separated by a palladium membrane separator of the separation chamber2And CO2Separating to obtain high-purity hydrogen.
The catalytic reaction of the methanol water is completed in a reformer of the methanol water hydrogen production equipment, the reformer comprises a reformer shell, and a combustion chamber and a reforming chamber which are positioned in the reforming hydrogen production device shell, generally, the temperature of 350-409 ℃ is needed in the reforming chamber, and the temperature of 405-570 ℃ is needed in the combustion chamber, so that the reformer can normally work. The start-up of the reformer is accomplished by a start-up device, which in the conventional art takes about 10-15 minutes and is very slow.
In view of this, the inventor applies for an invention patent cn201410621689.x on 11/7/2014, which discloses a reformer of a methanol-water hydrogen production system, wherein one end of the reformer is provided with a starting device, the starting device comprises a cup seat, and a raw material input pipeline, a heating gasification pipeline, an ignition device and a temperature detection device are arranged on the cup seat; the raw material input pipeline is communicated with the heating gasification pipeline, and the raw material enters the heating gasification pipeline through the raw material input pipeline and is output from the tail end of the heating gasification pipeline; the ignition device is arranged at the position corresponding to the tail end of the heating gasification pipeline and used for igniting the raw material output from the heating gasification pipeline, the raw material is ignited by the ignition device and then combusted, the heating gasification pipeline can be heated, the raw material in the heating gasification pipeline is gasified, the combustion intensity is rapidly increased, and the heating degree of the reformer is further increased. The start-up device can start up the reformer (i.e., reforming hydrogen production device) within typically 5 minutes without the use of an electrical heating device. However, the starting device also has the following drawbacks: firstly, the ignition success rate of an ignition device is difficult to guarantee, because the methanol water raw material is output from the tail end of a heating gasification pipeline and is generally output in a dripping mode, the methanol water can not contact the ignition device frequently and is not ignited frequently in the dripping process, and the ignition is required to be re-ignited; secondly, because the diameter of the cup seat is smaller and the cup seat cannot be provided with a vent hole, the methanol water combustion area of the starting device is small and the flame is not large enough; thirdly, the methanol-water raw material in the heating gasification pipeline is still difficult to vaporize under the condition of high flow velocity, so that the methanol-water raw material with low flow velocity can be only conveyed to a starting device, the combustion intensity of the methanol-water raw material is further influenced, and the starting time of the reformer is prolonged; fourthly, the starting device is arranged at the lower end of the combustion chamber in the reformer, after the reformer is started, although the starting device stops working, the combustion chamber needs to work continuously, so that the starting device is always in a high-temperature environment, and the service life is greatly influenced; and fifthly, the starting device is arranged in the reformer, occupies the internal space of the reformer and has adverse effect on the structural layout in the reformer.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a quickly started methanol-water reforming hydrogen production system aiming at the defects in the prior art, wherein the methanol-water reforming hydrogen production system has the advantages of short starting time, high heating efficiency and no need of arranging a starter in a reformer. The invention also provides a method for quickly starting the methanol-water reforming hydrogen production system.
In order to solve the first technical problem, the technical scheme of the invention is as follows: the utility model provides a quick start's methanol-water reforming hydrogen manufacturing system, includes methanol-water storage container, delivery pump, heat exchanger, reformer, solenoid valve, starter, check valve and control system, wherein:
the methanol-water storage container is used for storing liquid methanol-water raw materials;
the feed end of the delivery pump is communicated with the methanol water storage container, and the discharge end of the delivery pump is connected with a reforming delivery pipeline and a starting delivery pipeline; the reforming conveying pipeline is used for conveying the methanol-water raw material to the reformer under the pumping action of the conveying pump; the starting conveying pipeline is used for conveying the methanol water raw material to a methanol water quantitative vaporizer of the starter under the pumping action of the conveying pump;
the heat exchanger is arranged on a reforming conveying pipeline between the conveying pump and the reformer, the methanol-water raw material exchanges heat with high-temperature hydrogen output by the reformer in the heat exchanger, the temperature of the methanol-water raw material is increased, and the temperature of the hydrogen is reduced;
the reformer is used for reforming hydrogen production reaction of methanol and water generated from the methanol-water raw material to obtain hydrogen and output the hydrogen;
the electromagnetic valve is arranged on a starting conveying pipeline between the conveying pump and the starter;
the starter comprises a methanol-water quantitative vaporizer and an electric heater, wherein the methanol-water quantitative vaporizer is used for storing and vaporizing quantitative methanol-water raw materials, and the electric heater is used for supplying heat to the methanol-water quantitative vaporizer to vaporize the quantitative methanol-water raw materials stored in the methanol-water quantitative vaporizer; the discharging end of the methanol-water quantitative vaporizer is provided with a steam pipeline, and the methanol-water quantitative vaporizer is communicated with the reformer through the steam pipeline;
the check valve is arranged on a steam pipeline between the methanol-water quantitative vaporizer and the reformer;
and the control system is electrically connected with the delivery pump, the reformer, the electromagnetic valve and the starter and controls the operation of the delivery pump, the reformer, the electromagnetic valve and the starter.
Preferably, the capacity of the methanol water quantitative vaporizer of the starter is 80ml-160ml, and the electric heater comprises an electric heating wire wound outside the methanol water quantitative vaporizer.
Preferably, the reformer comprises a vaporization coil, a reforming chamber, a purifier, and a combustion chamber; the vaporizing coil is used for heating and vaporizing the methanol water raw material, and the vaporized methanol water gas enters the reforming chamber; the reforming chamber is internally provided with a catalyst, methanol water gas generates reforming hydrogen production reaction of methanol and water in the reforming chamber, and high-temperature hydrogen-rich mixed gas is prepared and is transmitted to the purifier; the purifier is provided with an air inlet pipe, a purifier main body, a pure hydrogen discharge pipe and a hydrogen-containing residual gas discharge pipe, the air inlet pipe is communicated with the reforming chamber, the high-temperature hydrogen-rich mixed gas conveyed from the reforming chamber enters the purifier main body through the air inlet pipe, and is separated into pure hydrogen and hydrogen-containing residual gas in the purifier main body, wherein the pure hydrogen is output outwards through the pure hydrogen discharge pipe, and the hydrogen-containing residual gas is conveyed to the combustion chamber through the hydrogen-containing residual gas discharge pipe; the combustion chamber is provided with an air feeding channel for inputting outside air, the combustion chamber is used for combustion heat release of hydrogen-containing residual gas and the outside air, heat is provided for the vaporization coil, the reforming chamber and the purifier, and tail gas after combustion is output outwards.
Preferably, the quickly started methanol-water reforming hydrogen production system further comprises a reformer shell, a reforming cavity is mounted in the reformer shell, the reforming cavity comprises a cylindrical outer cavity wall and a cylindrical inner cavity wall, the cylindrical inner cavity wall is mounted in the cylindrical outer cavity wall, and a cavity between the cylindrical outer cavity wall and the cylindrical inner cavity wall forms the reforming chamber for methanol-water reforming hydrogen production; a cylindrical through hole which is communicated up and down is arranged in the wall of the cylindrical inner cavity, and the vaporizing coil is arranged in the cylindrical through hole; the vaporizing coil is provided with a middle hole which is communicated up and down, and the purifier is arranged in the middle hole of the vaporizing coil; a space is provided between the purifier and the vaporizing coil, and the space forms the combustion chamber.
Preferably, the reformer shell comprises an outer shell, an inner shell, a chimney and heat insulation cotton, the upper ends of the outer shell and the inner shell are closed, the lower ends of the outer shell and the inner shell are hollow, the inner shell is arranged in the outer shell, and the heat insulation cotton is filled between the outer shell and the inner shell; one side of the upper ends of the outer shell and the inner shell is provided with a smoke hole, and the chimney is arranged in the smoke hole.
Preferably, the vaporizing coil pipe sequentially comprises a methanol water feed end, a spiral coil pipe part and a methanol water discharge pipe along the conveying direction of the methanol water raw material, wherein the methanol water feed end is positioned at the lower end of the vaporizing coil pipe and is used for inputting the methanol water raw material to the spiral coil pipe part; the spiral coil pipe part is spirally coiled from bottom to top and is used for vaporizing the methanol-water raw material into methanol-water gas; the upper end of spiral coil portion communicates the upper end of methanol-water discharging pipe, and the methanol-water discharging pipe is vertical to be set up in one side of spiral coil portion, and the lower extreme intercommunication of methanol-water discharging pipe the lower extreme of reforming chamber.
Preferably, the purifier is a membrane separation device for vacuum plating of palladium-silver alloy on the surface of porous ceramic, the plating layer is the palladium-silver alloy, the mass percent of palladium-silver alloy is 75-78%, and the mass percent of silver is 22-25%.
In order to solve the second technical problem, the technical solution of the present invention is: the method for quickly starting the methanol-water reforming hydrogen production system comprises the following steps:
step I, the starter prepares quantitative methanol water raw materials constantly, including:
a. the control system controls the electromagnetic valve on the starting conveying pipeline to be opened;
b. pumping the methanol-water raw material in the methanol-water storage container to a methanol-water quantitative vaporizer of a starter through a starting conveying pipeline under the pumping action force of a conveying pump until the methanol-water quantitative vaporizer is filled with the set volume of the methanol-water raw material;
c. the control system controls the electromagnetic valve on the starting conveying pipeline to be closed;
II, quickly starting a methanol-water reforming hydrogen production system, comprising the following steps:
a. the control system controls an electric heater of the starter to work and supplies heat to the methanol water quantitative vaporizer;
b. the quantitative methanol-water raw material stored in the methanol-water quantitative vaporizer is vaporized to form high-temperature methanol-water gas;
c. the vaporized high-temperature methanol water gas is conveyed to a reformer along a steam pipeline, and the reformer is started to work;
d. after the reformer is started, the step I is executed, so that the starter always prepares quantitative methanol water raw materials.
Preferably, the method for rapidly starting the methanol-water reforming hydrogen production system further comprises the following steps:
and III, after the methanol-water reforming hydrogen production system is started, the methanol-water reforming hydrogen production working step comprises the following steps:
a. pumping the methanol-water raw material in the methanol-water storage container to a reformer through a heat exchanger under the pumping action force of a delivery pump; the methanol-water raw material exchanges heat with high-temperature pure hydrogen in the process of passing through the heat exchanger, and the temperature of the methanol-water raw material is raised;
b. in the reformer, a methanol-water raw material is heated and vaporized through a vaporization coil, the vaporized methanol-water gas enters a reforming chamber, reforming hydrogen production reaction of methanol and water is carried out in the reforming chamber, and a high-temperature hydrogen-rich mixed gas is prepared and is transmitted to a purifier; separating the hydrogen into high-temperature pure hydrogen and hydrogen-containing residual gas in a purifier, wherein the high-temperature pure hydrogen is output outwards, and the hydrogen-containing residual gas is conveyed to a combustion chamber; in the combustion chamber, the hydrogen-containing residual gas and the outside air are combusted to release heat, heat is provided for the vaporization coil, the reforming chamber and the purifier, and the combusted tail gas is output outwards;
c. the prepared high-temperature pure hydrogen is conveyed to the heat exchanger, the high-temperature pure hydrogen exchanges heat with the methanol water raw material in the process of passing through the heat exchanger, the temperature of the high-temperature pure hydrogen is reduced, and the high-temperature pure hydrogen is converted into low-temperature pure hydrogen and then is output outwards.
Preferably, in the step of quickly starting the methanol-water reforming hydrogen production system, the high-temperature methanol-water gas output from the methanol-water quantitative vaporizer firstly enters the vaporizing coil of the reformer and then enters the reforming chamber, and the temperature of the high-temperature methanol-water gas is 350-570 ℃; in the working step of hydrogen production by methanol-water reforming, the temperature in the reforming chamber and the purifier is 350-570 ℃.
The invention has the beneficial effects that: firstly, because the invention is separately provided with a starter which comprises a methanol water quantitative vaporizer and an electric heater, and simultaneously, a starting conveying pipeline for conveying a methanol water raw material to the methanol water quantitative vaporizer is additionally arranged at the output end of a conveying pump, and an electromagnetic valve and a check valve are arranged, when the reformer is started, a control system can directly control the electric heater of the starter to work, so that the quantitative methanol water raw material stored in the methanol water quantitative vaporizer is quickly vaporized to form high-temperature methanol water gas, and is conveyed to the reformer along a steam pipeline to start the reformer to work, the starting process is very quick, the heating efficiency is high, and the reformer can be started only by 30 seconds to one minute; secondly, the starter is arranged independently and separated from the reformer, so that the problem that the starter is in a high-temperature combustion environment for a long time is solved, the internal space of the reformer is not occupied, the service life of the starter is long, and the internal structure layout of the reformer is not influenced.
Drawings
Fig. 1 is a block diagram showing the overall structure of the present invention.
Fig. 2 is a schematic view of an external structure of the reformer.
Fig. 3 is a schematic view of a dispersion structure of the reformer.
Fig. 4 is a schematic structural diagram of a vaporizing coil, a reforming cavity, a purifier and a combustion chamber of the reformer.
Detailed Description
The structural and operational principles of the present invention are explained in further detail below with reference to the accompanying drawings.
As shown in figure 1, the invention relates to a quick-start methanol-water reforming hydrogen production system, which comprises a methanol-water storage container 1, a delivery pump 2, a heat exchanger 3, a reformer 4, an electromagnetic valve 5, a starter 6, a check valve 7 and a control system 8, wherein:
a methanol-water storage container 1 in which a liquid methanol-water raw material is stored;
the feed end of the transfer pump 2 is communicated with the methanol water storage container 1, and the discharge end of the transfer pump is connected with a reforming transfer pipeline 21 and a starting transfer pipeline 22; the reforming conveying pipeline 21 is used for conveying the methanol water raw material to the reformer 4 under the pumping action of the conveying pump 2; the starting conveying pipeline 22 is used for conveying the methanol water raw material to the methanol water quantitative vaporizer 61 of the starter 6 under the pumping action of the conveying pump 2;
the heat exchanger 3 is arranged on a reforming conveying pipeline 21 between the conveying pump 2 and the reformer 4, the methanol water raw material exchanges heat with high-temperature hydrogen output by the reformer 4 in the heat exchanger 3, the temperature of the methanol water raw material is increased, and the temperature of the hydrogen is reduced;
the reformer 4 is used for reforming the methanol water raw material to produce hydrogen reaction with methanol and water to produce hydrogen and outputting the hydrogen;
the electromagnetic valve 5 is arranged on a starting conveying pipeline 21 between the conveying pump 2 and the starter 6;
the starter 6 comprises a methanol-water quantitative vaporizer 61 and an electric heater 62, wherein the methanol-water quantitative vaporizer 61 is used for storing and vaporizing quantitative methanol-water raw materials, and the electric heater 62 is used for supplying heat to the methanol-water quantitative vaporizer 61 to vaporize the quantitative methanol-water raw materials stored in the methanol-water quantitative vaporizer 61; a steam pipeline 63 is arranged at the discharge end of the methanol-water quantitative vaporizer 61, and the methanol-water quantitative vaporizer 61 is communicated with the reformer 4 through the steam pipeline 63;
a check valve 7 installed on a steam pipe 63 between the methanol-water quantitative vaporizer 61 and the reformer 4;
and the control system 8 is electrically connected with the delivery pump 2, the reformer 4, the electromagnetic valve 5 and the starter 6 and controls the operation of the electromagnetic valve.
As shown in FIG. 1, the methanol water quantitative vaporizer 61 of the starter 6 has a capacity of 80ml to 160ml, preferably 120ml, and the electric heater 62 comprises an electric heating wire wound outside the methanol water quantitative vaporizer 61 for rapid heating. Of course, the electric heater 62 may also be an electromagnetic heating method or other heating methods.
As shown in fig. 1 to 4, the reformer 4 includes a vaporization coil 41, a reforming chamber 42, a purifier 43, and a combustion chamber 44; the vaporizing coil 41 is used for heating and vaporizing the methanol water raw material, and the vaporized methanol water gas enters the reforming chamber 42; the reforming chamber 42 is internally provided with a catalyst, methanol water gas generates reforming hydrogen production reaction of methanol and water in the reforming chamber 42, and the reaction equation is as follows: (1) CH (CH)3OH→CO+2H2；(2)H2O+CO→CO2+H2；(3)CH3OH+H2O→CO2+3H2(ii) a The produced high-temperature hydrogen-rich mixed gas is transmitted to the purifier 43; the purifier 43 is provided with an air inlet pipe 431, a purifier main body 432, a pure hydrogen outlet pipe 433 and a hydrogen-containing residual gas outlet pipe 434, the air inlet pipe 431 is communicated with the reforming chamber 42, the high-temperature hydrogen-rich mixed gas conveyed from the reforming chamber 42 enters the purifier main body 432 through the air inlet pipe 431, and is separated into pure hydrogen and hydrogen-containing residual gas in the purifier main body 432, wherein the pure hydrogen is output outwards through the pure hydrogen outlet pipe 433, and the hydrogen-containing residual gas is conveyed to the combustion chamber 44 through the hydrogen-containing residual gas outlet pipe 434; the combustion chamber 44 is provided with an air feeding channel for inputting outside air, and the combustion chamber 44 is used for combustion heat release of hydrogen-containing residual gas and the outside air, and is used for vaporizing the coil 41 and reformingThe chamber 42 and the purifier 43 provide heat, and the tail gas after combustion is output to the outside. The purifier 43 is a membrane separation device for vacuum plating of palladium-silver alloy on the surface of porous ceramic, and the plating layer is palladium-silver alloy, wherein the mass percent of palladium-silver alloy is 75-78%, and the mass percent of silver is 22-25%.
As shown in fig. 2-4, the quick-start methanol-water reforming hydrogen production system further includes a reformer housing 45, a reforming cavity 46 is installed inside the reformer housing 45, the reforming cavity 46 includes a cylindrical outer cavity wall 461 and a cylindrical inner cavity wall 462, the cylindrical inner cavity wall 462 is installed inside the cylindrical outer cavity wall 461, and a cavity between the cylindrical outer cavity wall 461 and the cylindrical inner cavity wall 462 forms the reforming chamber 42 for methanol-water reforming hydrogen production; a cylindrical through hole 463 penetrating vertically is formed in the cylindrical inner chamber wall 462, and the vaporizing coil 41 is installed in the cylindrical through hole 463; the vaporizing coil 41 is provided with a middle hole 411 which is vertically penetrated, and the purifier 43 is arranged in the middle hole 411 of the vaporizing coil; between the purifier 43 and the vaporizing coil 41 there is a space which constitutes the combustion chamber 44. By adopting the reformer with the structure, on one hand, under the combustion heat release action of the combustion chamber, combustion flame can penetrate through the cylindrical through hole, so that the reforming cavity, the vaporization coil and the purifier are heated simultaneously, and the combustion efficiency is very high; on the other hand, the methanol-water liquid is vaporized in the vaporization coil, then enters the reforming chamber for reforming to produce hydrogen, and then enters the purifier for purification, and the residual hydrogen in the impurity gas is combusted in the combustion chamber to release heat, so that the methanol-water raw material is utilized to the maximum, the methanol-water reforming hydrogen production efficiency is high, and the energy utilization rate is high.
As shown in fig. 2 to 4, the reformer housing includes an outer housing, an inner housing, a chimney 451, and heat-insulating cotton, the upper ends of the outer housing and the inner housing are closed, the lower ends of the outer housing and the inner housing are open, the inner housing is installed inside the outer housing, and the heat-insulating cotton is filled between the outer housing and the inner housing; the upper end of the outer shell and the inner shell is provided with a smoke hole, and the chimney 451 is arranged in the smoke hole.
As shown in fig. 2-4, the vaporizing coil 41 sequentially includes a methanol water feed end 412, a spiral coil part 413, and a methanol water discharge pipe 414 along the conveying direction of the methanol water raw material, wherein the methanol water feed end 412 is located at the lower end of the vaporizing coil 41 and is used for inputting the methanol water raw material to the spiral coil part 413; the spiral coil pipe part 413 is spirally coiled from bottom to top, and the spiral coil pipe part 413 is used for vaporizing a methanol water raw material into methanol water gas; the upper end of spiral coil portion 413 communicates the upper end of methanol-water discharging pipe 414, and methanol-water discharging pipe 414 vertically sets up in one side of spiral coil portion 413, and the lower extreme intercommunication of methanol-water discharging pipe 414 the lower extreme of reforming chamber 42.
The invention relates to a method for quickly starting a methanol-water reforming hydrogen production system, which comprises the following steps:
step I, the starter prepares quantitative methanol water raw materials constantly, including:
a. the control system controls the electromagnetic valve on the starting conveying pipeline to be opened;
b. pumping the methanol-water raw material in the methanol-water storage container to a methanol-water quantitative vaporizer of a starter through a starting conveying pipeline under the pumping action force of a conveying pump until the methanol-water quantitative vaporizer is filled with the set volume of the methanol-water raw material;
c. the control system controls the electromagnetic valve on the starting conveying pipeline to be closed;
II, quickly starting a methanol-water reforming hydrogen production system, comprising the following steps:
a. the control system controls an electric heater of the starter to work and supplies heat to the methanol water quantitative vaporizer;
b. the quantitative methanol-water raw material stored in the methanol-water quantitative vaporizer is vaporized to form high-temperature methanol-water gas;
c. the vaporized high-temperature methanol water gas is conveyed to a reformer along a steam pipeline, and the reformer is started to work;
d. after the reformer is started, the step I is executed, so that the starter always prepares quantitative methanol water raw materials.
The method for quickly starting the methanol-water reforming hydrogen production system further comprises the following steps:
and III, after the methanol-water reforming hydrogen production system is started, the methanol-water reforming hydrogen production working step comprises the following steps:
a. pumping the methanol-water raw material in the methanol-water storage container to a reformer through a heat exchanger under the pumping action force of a delivery pump; the methanol-water raw material exchanges heat with high-temperature pure hydrogen in the process of passing through the heat exchanger, and the temperature of the methanol-water raw material is raised;
b. in the reformer, a methanol-water raw material is heated and vaporized through a vaporization coil, the vaporized methanol-water gas enters a reforming chamber, reforming hydrogen production reaction of methanol and water is carried out in the reforming chamber, and a high-temperature hydrogen-rich mixed gas is prepared and is transmitted to a purifier; separating the hydrogen into high-temperature pure hydrogen and hydrogen-containing residual gas in a purifier, wherein the high-temperature pure hydrogen is output outwards, and the hydrogen-containing residual gas is conveyed to a combustion chamber; in the combustion chamber, the hydrogen-containing residual gas and the outside air are combusted to release heat, heat is provided for the vaporization coil, the reforming chamber and the purifier, and the combusted tail gas is output outwards;
c. the prepared high-temperature pure hydrogen is conveyed to the heat exchanger, the high-temperature pure hydrogen exchanges heat with the methanol water raw material in the process of passing through the heat exchanger, the temperature of the high-temperature pure hydrogen is reduced, and the high-temperature pure hydrogen is converted into low-temperature pure hydrogen and then is output outwards.
Preferably, in the step of quickly starting the methanol-water reforming hydrogen production system, the high-temperature methanol-water gas output from the methanol-water quantitative vaporizer firstly enters the vaporizing coil of the reformer and then enters the reforming chamber, and the temperature of the high-temperature methanol-water gas is 350-570 ℃; in the working step of hydrogen production by methanol-water reforming, the temperature in the reforming chamber and the purifier is 350-570 ℃.
The above description is only a preferred embodiment of the present invention, and all the minor modifications, equivalent changes and modifications made to the above embodiment according to the technical solution of the present invention are within the scope of the technical solution of the present invention.
Claims (10)
1. The utility model provides a quick start's methanol-water reforming hydrogen manufacturing system which characterized in that: including methanol-water storage container, delivery pump, heat exchanger, reformer, solenoid valve, starter, check valve and control system, wherein:
the methanol-water storage container is used for storing liquid methanol-water raw materials;
the feed end of the delivery pump is communicated with the methanol water storage container, and the discharge end of the delivery pump is connected with a reforming delivery pipeline and a starting delivery pipeline; the reforming conveying pipeline is used for conveying the methanol-water raw material to the reformer under the pumping action of the conveying pump; the starting conveying pipeline is used for conveying the methanol water raw material to a methanol water quantitative vaporizer of the starter under the pumping action of the conveying pump;
the heat exchanger is arranged on a reforming conveying pipeline between the conveying pump and the reformer, the methanol-water raw material exchanges heat with high-temperature hydrogen output by the reformer in the heat exchanger, the temperature of the methanol-water raw material is increased, and the temperature of the hydrogen is reduced;
the reformer is used for reforming hydrogen production reaction of methanol and water generated from the methanol-water raw material to obtain hydrogen and output the hydrogen;
the electromagnetic valve is arranged on a starting conveying pipeline between the conveying pump and the starter;
the starter comprises a methanol-water quantitative vaporizer and an electric heater, wherein the methanol-water quantitative vaporizer is used for storing and vaporizing quantitative methanol-water raw materials, and the electric heater is used for supplying heat to the methanol-water quantitative vaporizer to vaporize the quantitative methanol-water raw materials stored in the methanol-water quantitative vaporizer; the discharging end of the methanol-water quantitative vaporizer is provided with a steam pipeline, and the methanol-water quantitative vaporizer is communicated with the reformer through the steam pipeline;
the check valve is arranged on a steam pipeline between the methanol-water quantitative vaporizer and the reformer;
and the control system is electrically connected with the delivery pump, the reformer, the electromagnetic valve and the starter and controls the operation of the delivery pump, the reformer, the electromagnetic valve and the starter.
2. The rapidly started methanol-water reforming hydrogen production system according to claim 1, characterized in that: the capacity of the methanol water quantitative vaporizer of the starter is 80ml-160ml, and the electric heater comprises an electric heating wire which is wound outside the methanol water quantitative vaporizer.
3. The rapidly started methanol-water reforming hydrogen production system according to claim 1, characterized in that: the reformer comprises a vaporization coil, a reforming chamber, a purifier and a combustion chamber; the vaporizing coil is used for heating and vaporizing the methanol water raw material, and the vaporized methanol water gas enters the reforming chamber; the reforming chamber is internally provided with a catalyst, methanol water gas generates reforming hydrogen production reaction of methanol and water in the reforming chamber, and high-temperature hydrogen-rich mixed gas is prepared and is transmitted to the purifier; the purifier is provided with an air inlet pipe, a purifier main body, a pure hydrogen discharge pipe and a hydrogen-containing residual gas discharge pipe, the air inlet pipe is communicated with the reforming chamber, the high-temperature hydrogen-rich mixed gas conveyed from the reforming chamber enters the purifier main body through the air inlet pipe, and is separated into pure hydrogen and hydrogen-containing residual gas in the purifier main body, wherein the pure hydrogen is output outwards through the pure hydrogen discharge pipe, and the hydrogen-containing residual gas is conveyed to the combustion chamber through the hydrogen-containing residual gas discharge pipe; the combustion chamber is provided with an air feeding channel for inputting outside air, the combustion chamber is used for combustion heat release of hydrogen-containing residual gas and the outside air, heat is provided for the vaporization coil, the reforming chamber and the purifier, and tail gas after combustion is output outwards.
4. The rapidly started methanol-water reforming hydrogen production system according to claim 3, characterized in that: the reforming cavity comprises a cylindrical outer cavity wall and a cylindrical inner cavity wall, the cylindrical inner cavity wall is arranged in the cylindrical outer cavity wall, and a cavity between the cylindrical outer cavity wall and the cylindrical inner cavity wall forms the reforming chamber for reforming methanol water to produce hydrogen; a cylindrical through hole which is communicated up and down is arranged in the wall of the cylindrical inner cavity, and the vaporizing coil is arranged in the cylindrical through hole; the vaporizing coil is provided with a middle hole which is communicated up and down, and the purifier is arranged in the middle hole of the vaporizing coil; a space is provided between the purifier and the vaporizing coil, and the space forms the combustion chamber.
5. The rapidly started methanol-water reforming hydrogen production system according to claim 4, characterized in that: the reformer shell comprises an outer shell, an inner shell, a chimney and heat insulation cotton, the upper ends of the outer shell and the inner shell are closed, the lower ends of the outer shell and the inner shell are hollow, the inner shell is arranged in the outer shell, and the heat insulation cotton is filled between the outer shell and the inner shell; one side of the upper ends of the outer shell and the inner shell is provided with a smoke hole, and the chimney is arranged in the smoke hole.
6. The rapidly started methanol-water reforming hydrogen production system according to claim 4, characterized in that: the vaporizing coil sequentially comprises a methanol water feeding end, a spiral coil pipe part and a methanol water discharging pipe along the conveying direction of the methanol water raw material, wherein the methanol water feeding end is positioned at the lower end of the vaporizing coil and is used for inputting the methanol water raw material to the spiral coil pipe part; the spiral coil pipe part is spirally coiled from bottom to top and is used for vaporizing the methanol-water raw material into methanol-water gas; the upper end of spiral coil portion communicates the upper end of methanol-water discharging pipe, and the methanol-water discharging pipe is vertical to be set up in one side of spiral coil portion, and the lower extreme intercommunication of methanol-water discharging pipe the lower extreme of reforming chamber.
7. The rapidly started methanol-water reforming hydrogen production system according to claim 3, characterized in that: the purifier is a membrane separation device for vacuum plating of palladium-silver alloy on the surface of porous ceramic, and the plating layer is the palladium-silver alloy, wherein the mass percent of palladium-silver alloy is 75-78%, and the mass percent of silver is 22-25%.
8. The method for rapidly starting the methanol-water reforming hydrogen production system according to any one of claims 1 to 7, which is characterized by comprising the following steps:
step I, the starter prepares quantitative methanol water raw materials constantly, including:
a. the control system controls the electromagnetic valve on the starting conveying pipeline to be opened;
b. pumping the methanol-water raw material in the methanol-water storage container to a methanol-water quantitative vaporizer of a starter through a starting conveying pipeline under the pumping action force of a conveying pump until the methanol-water quantitative vaporizer is filled with the set volume of the methanol-water raw material;
c. the control system controls the electromagnetic valve on the starting conveying pipeline to be closed;
II, quickly starting a methanol-water reforming hydrogen production system, comprising the following steps:
a. the control system controls an electric heater of the starter to work and supplies heat to the methanol water quantitative vaporizer;
b. the quantitative methanol-water raw material stored in the methanol-water quantitative vaporizer is vaporized to form high-temperature methanol-water gas;
c. the vaporized high-temperature methanol water gas is conveyed to a reformer along a steam pipeline, and the reformer is started to work;
d. after the reformer is started, the step I is executed, so that the starter always prepares quantitative methanol water raw materials.
9. The method for rapidly starting the methanol-water reforming hydrogen production system according to claim 8, further comprising:
and III, after the methanol-water reforming hydrogen production system is started, the methanol-water reforming hydrogen production working step comprises the following steps:
a. pumping the methanol-water raw material in the methanol-water storage container to a reformer through a heat exchanger under the pumping action force of a delivery pump; the methanol-water raw material exchanges heat with high-temperature pure hydrogen in the process of passing through the heat exchanger, and the temperature of the methanol-water raw material is raised;
b. in the reformer, a methanol-water raw material is heated and vaporized through a vaporization coil, the vaporized methanol-water gas enters a reforming chamber, reforming hydrogen production reaction of methanol and water is carried out in the reforming chamber, and a high-temperature hydrogen-rich mixed gas is prepared and is transmitted to a purifier; separating the hydrogen into high-temperature pure hydrogen and hydrogen-containing residual gas in a purifier, wherein the high-temperature pure hydrogen is output outwards, and the hydrogen-containing residual gas is conveyed to a combustion chamber; in the combustion chamber, the hydrogen-containing residual gas and the outside air are combusted to release heat, heat is provided for the vaporization coil, the reforming chamber and the purifier, and the combusted tail gas is output outwards;
c. the prepared high-temperature pure hydrogen is conveyed to the heat exchanger, the high-temperature pure hydrogen exchanges heat with the methanol water raw material in the process of passing through the heat exchanger, the temperature of the high-temperature pure hydrogen is reduced, and the high-temperature pure hydrogen is converted into low-temperature pure hydrogen and then is output outwards.
10. The method for rapidly starting the methanol-water reforming hydrogen production system according to claim 9, characterized by comprising the following steps: in the quick starting step of the methanol-water reforming hydrogen production system, the high-temperature methanol-water gas output from the methanol-water quantitative vaporizer firstly enters a vaporizing coil of a reformer and then enters a reforming chamber, and the temperature of the high-temperature methanol-water gas is 350-570 ℃.
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