CN116654870B - Self-heating type method for preparing hydrogen by reforming green alcohol and alcohol water solution - Google Patents
Self-heating type method for preparing hydrogen by reforming green alcohol and alcohol water solution Download PDFInfo
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- CN116654870B CN116654870B CN202310716603.0A CN202310716603A CN116654870B CN 116654870 B CN116654870 B CN 116654870B CN 202310716603 A CN202310716603 A CN 202310716603A CN 116654870 B CN116654870 B CN 116654870B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002407 reforming Methods 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 58
- 238000003860 storage Methods 0.000 claims abstract description 52
- 238000002485 combustion reaction Methods 0.000 claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 238000002309 gasification Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000005265 energy consumption Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
Classifications
-
- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
- F28D21/0001—Recuperative heat exchangers
- F28D21/0014—Recuperative heat exchangers the heat being recuperated from waste air or from vapors
-
- 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
-
- 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
Abstract
The invention provides a method for preparing hydrogen by reforming self-heating type green alcohol and alcohol water solution, which comprises the steps of preprocessing water, green alcohol or alcohol water solution, inputting the preprocessed water, green alcohol or alcohol water solution into a storage tank, and mixing the pretreated water, green alcohol or alcohol water solution with the storage tank to obtain raw gas; the raw material gas is input into a reactor for reforming hydrogen production reaction to obtain mixed gas; the mixed gas is input into a cooler after passing through a seventh heat exchanger and an eighth heat exchanger, then is input into a flash tank for gas-liquid separation, and the liquid is input into a storage tank; the gas is input into a membrane separator to separate and store hydrogen, and the residual gas is input into a combustion furnace to burn and release heat; the combustion furnace is internally provided with a first heat exchange tube for supplying heat to the sixth heat exchanger, a second heat exchange tube for supplying heat to the heat conduction oil, a third heat exchange tube for supplying heat to the third heat exchanger and a fourth heat exchange tube for supplying heat to the first heat exchanger, and the heat conduction oil supplies heat to the reactor. According to the invention, the heat exchange pipe and the heat exchanger realize gradient utilization of heat, so that efficient utilization of energy is realized; the liquid after gas-liquid separation is input into the storage tank for recycling, so that the utilization rate of raw materials is improved.
Description
Technical Field
The invention relates to a method for preparing hydrogen by reforming self-heating type green alcohol and an alcohol water solution, belonging to the technical field of hydrogen preparation.
Background
Hydrogen is one of the most ideal energy sources in the 21 st century, and in the case of burning the same weight of coal, gasoline and hydrogen, the energy generated by hydrogen is the most, and the product of its combustion is water, without ash and exhaust gas, and without polluting the environment.
Methanol is liquid at normal temperature and normal pressure, is convenient to store and transport, is suitable for low-cost long-distance transportation, is an optimal hydrogen energy carrier for water electrolysis and hydrogen production in green electricity sufficient areas, and is honored as liquid sunlight by scientists in China. In addition, china is the largest global methanol producer, and has 60% of global methanol productivity. The methanol has rich sources and low cost, and is convenient to store and transport as liquid at normal temperature and normal pressure. Compared with other hydrogen production modes such as industrial hydrogen production, the energy consumption and the cost of the methanol hydrogen production are lower. However, the existing equipment and method for producing hydrogen from methanol have the problems of high operation energy consumption, large occupied area, inconvenient transportation and the like, so that the existing hydrogen production method cannot be widely popularized.
In view of the foregoing, there is a need for a method for producing hydrogen by reforming autothermal green alcohol and aqueous alcohol solutions.
Disclosure of Invention
The invention aims to provide a method for preparing hydrogen by reforming self-heating type green alcohol and an alcohol aqueous solution, which aims to solve the problems of high operation energy consumption, large occupied area and inconvenient transportation of the existing equipment and method for preparing hydrogen by methanol.
In order to achieve the above object, the present invention provides a method for producing hydrogen by reforming self-heating type green alcohol and an alcohol aqueous solution, comprising:
s1, pressurizing a green alcohol or alcohol water solution, sequentially heating the green alcohol or alcohol water solution through a first heat exchanger, a second heat exchanger and a third heat exchanger, and then inputting the green alcohol or alcohol water solution into a storage tank for standby;
s2, pressurizing water, sequentially inputting the water into a fourth heat exchanger, a fifth heat exchanger and a sixth heat exchanger for heating, and inputting the water into a storage tank for mixing with green alcohol or alcohol water solution to obtain raw gas;
s3, inputting raw material gas into a reactor for carrying out a hydrogen production reaction by reforming the green alcohol and the alcohol aqueous solution so as to obtain mixed gas;
s4, the mixed gas is input into a cooler for cooling after passing through a seventh heat exchanger and an eighth heat exchanger, and is input into a flash tank for gas-liquid separation after cooling, and the separated liquid is input into a storage tank for mixing with the raw gas;
s5, the separated gas is input into a membrane separator to separate and store hydrogen, and the rest gas is input into a combustion furnace to burn and release heat;
the combustion furnace can transfer energy with the fourth heat exchanger, the first heat exchange tube for supplying heat to the sixth heat exchanger, the second heat exchange tube for supplying heat to the heat conduction oil, the third heat exchange tube for supplying heat to the third heat exchanger and the fourth heat exchange tube for supplying heat to the first heat exchanger are sequentially arranged in the combustion furnace along the smoke discharge direction, and the heat conduction oil supplies heat to the reactor.
As a further improvement of the invention, the seventh heat exchanger is capable of heat transfer with the second heat exchanger to supply heat to the second heat exchanger, and the eighth heat exchanger is capable of heat transfer with the fourth heat exchanger to supply heat to the fourth heat exchanger.
As a further improvement of the present invention, in S1: the green alcohol or alcohol water solution is pressurized to 5atm by a pump, then is input into the first heat exchanger and the second heat exchanger to be heated to gasification, and then is input into the third heat exchanger to be heated to 250-300 ℃.
As a further improvement of the present invention, in S2: the water is pressurized to 5atm by a pump, then is fed into the fourth heat exchanger and the fifth heat exchanger to be heated to gasification, and then is fed into the sixth heat exchanger to be heated to 250-300 ℃.
As a further improvement of the present invention, in S3: the raw material gas enters the reactor through a ninth heat exchanger, the ninth heat exchanger heats the raw material gas to 250-300 ℃, and the ninth heat exchanger is electrically heated.
As a further improvement of the present invention, in S3: the reactor is a coil pipe type reactor, the reaction temperature of the reactor is 250-300 ℃, and the catalyst is Cu/ZnO/Al 2 O 3 、Pt/SiO 2 、Pt/Al 2 O 3 、Pd/SiO 2 、Pd/Al 2 O 3 Any one of the following.
As a further improvement of the present invention, in S4: the temperature of the mixed gas is reduced to 180 ℃ in the seventh heat exchanger, then reduced to 61 ℃ in the eighth heat exchanger, and the cooler is reduced by condensed water so as to reduce the temperature of the mixed gas to 35 ℃.
As a further improvement of the invention, the condensed water flows through the cooler and is then input into the cooling device for cooling, and is then input into the water storage tank for storage after cooling, and the water storage tank is communicated with the cooler so as to realize the recycling of the condensed water.
As a further improvement of the present invention, in S5: when the temperature in the combustion furnace is lower, the green alcohol or the alcohol water solution is directly input for combustion so as to improve the temperature of the combustion furnace.
As a further improvement of the invention, the second heat exchange tube supplies heat to the tenth heat exchanger to heat the heat conduction oil, the heat conduction oil flows through the reactor and then is input into the oil storage tank, and the oil storage tank is communicated with the tenth heat exchanger to realize the recycling of the heat conduction oil.
The beneficial effects of the invention are as follows: the energy in the combustion furnace is used for reforming reaction, so that the device has weak dependence on the matched public facilities; the heat exchanger is used for cascade utilization of heat, so that efficient utilization of energy is realized; the liquid after gas-liquid separation is input into the storage tank for recycling, so that the utilization rate of raw materials is improved.
Drawings
FIG. 1 is a process flow diagram of a method for producing hydrogen from autothermal green alcohol and aqueous alcohol reforming in accordance with a preferred embodiment of the present invention.
Reference numerals illustrate: the heat exchanger comprises a first pump 1, a first heat exchanger 2, a second heat exchanger 3, a third heat exchanger 4, a second pump 5, a fourth heat exchanger 6, a fifth heat exchanger 7, a sixth heat exchanger 8, a storage tank 9, a ninth heat exchanger 10, a reactor 11, a seventh heat exchanger 12, an eighth heat exchanger 13, a cooler 14, a flash tank 15, a membrane separator 16, a combustion furnace 17, a first heat exchange tube 18, a second heat exchange tube 19, a third heat exchange tube 20, a fourth heat exchange tube 21, a cooling device 22, a water storage tank 23, a third pump 24, an oil storage tank 25, a fourth pump 26, a tenth heat exchanger 27, an eleventh heat exchanger 28, and a pressurizer 29.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Referring to FIG. 1, the invention discloses a method for preparing hydrogen by reforming self-heating type green alcohol and alcohol aqueous solution, which realizes efficient energy utilization by cascade utilization of energy through a heat exchanger, so that the method can be used in sites with remote positions and low redundancy degree matched with public works.
The device of the method for preparing hydrogen by reforming the green alcohol and the aqueous alcohol solution in the technical scheme is skid-mounted, namely the device is of a movable container type, so that the device is convenient to transport, hydrogen is prepared by utilizing methanol at a remote position, and the practicability of the method is improved; furthermore, autothermal interpretation is that the process does not rely on external energy or substance supplementation.
A method for producing hydrogen by reforming self-heating green alcohol and an aqueous alcohol solution, comprising the following steps:
s1, pressurizing the green alcohol or alcohol water solution, sequentially heating the green alcohol or alcohol water solution through the first heat exchanger 2, the second heat exchanger 3 and the third heat exchanger 4, and then inputting the green alcohol or alcohol water solution into a storage tank 9 for standby.
The green alcohol or the alcohol aqueous solution is pressurized to 5atm by a pump, then is fed into the first heat exchanger 2 and the second heat exchanger 3 to be heated to gasification, and then is fed into the third heat exchanger 4 to be heated to 250-300 ℃.
S2, pressurizing water, sequentially inputting the water into the fourth heat exchanger 6, the fifth heat exchanger 7 and the sixth heat exchanger 8 for heating, and inputting the water into the storage tank 9 for mixing with the green alcohol or the alcohol water solution to obtain raw gas.
The water is pressurized to 5atm by a pump, then is introduced into the fourth heat exchanger 6 and the fifth heat exchanger 7 to be heated to gasification, and then introduced into the sixth heat exchanger 8 to be heated to 250-300 deg.c.
In this embodiment, for convenience of description, steps of processing the aqueous solution of the green alcohol or the alcohol and processing the water will be distinguished, however, in other embodiments, the pretreatment of the water may be performed first, or the pretreatment of the aqueous solution of the green alcohol or the alcohol may be performed simultaneously, so long as the purpose of storing the water and the aqueous solution of the green alcohol or the alcohol in the tank 9 after gasification can be achieved, and the present invention is not limited thereto.
S3, inputting the raw material gas into a reactor 11 for carrying out a hydrogen production reaction by reforming the green alcohol and the alcohol water solution so as to obtain mixed gas.
The raw material gas enters the reactor 11 through the ninth heat exchanger 10, the ninth heat exchanger 10 heats the raw material gas to 250-300 ℃, the ninth heat exchanger 10 is electrically heated, and the raw material gas is heated through the mixed gas, so that the temperature of the raw material gas is increased to synthesize more products. In this embodiment, the ninth heat exchanger 10 is electrically heated, and the electric energy source may be external electric energy directly input, or may be solar energy, wind energy or other power generation input, and the ninth heat exchanger 10 may also supply heat to the combustion furnace 17, which is not limited herein.
The reactor 11 is a coil reactor 11, the reaction temperature of the reactor 11 is 250-300 ℃, and the catalyst is Cu/ZnO/Al 2 O 3 、Pt/SiO 2 、Pt/Al 2 O 3 、Pd/SiO 2 、Pd/Al 2 O 3 Any one of the following. Of course, in other embodiments, the catalyst may be any one of a Pb-based catalyst, a Pt-based catalyst, and an Au-based catalyst, without limitation.
S4, the mixed gas is input into a cooler 14 for cooling after passing through a seventh heat exchanger 12 and an eighth heat exchanger 13, is input into a flash tank 15 for gas-liquid separation after cooling, and is input into a storage tank 9 for mixing with the raw gas.
The temperature of the mixture is lowered to 180 deg.c in the seventh heat exchanger 12 and then to 61 deg.c in the eighth heat exchanger 13, and the cooler 14 is cooled by condensed water to lower the temperature of the mixture to 35 deg.c.
The condensed water flows through the cooler 14 and is then input into the cooling device 22 for cooling, the cooled condensed water is input into the water storage tank 23 for storage, and the water storage tank 23 is communicated with the cooler 14 so as to realize the recycling of the condensed water.
S5, the separated gas is input into a membrane separator 16 to separate and store hydrogen, and the rest gas is input into a combustion furnace 17 to burn and release heat.
When the temperature in the combustion furnace 17 is low, the green alcohol or the alcohol water solution is directly input for combustion so as to increase the temperature of the combustion furnace 17.
In this embodiment, the combustion furnace 17 heats other devices in the apparatus by combusting the residual gas or the green alcohol raw material to increase the temperature, and of course, in other embodiments, the heat generated after combustion in the combustion furnace 17 may be used to generate electricity, and then the electricity is transferred to each apparatus and the apparatuses are electrically heated; when the heat of combustion is insufficient, the combustion furnace 17 can be heated electrically, and the electricity can be generated by solar energy, wind energy, tidal energy, biomass energy and the like, and the method is not limited.
The combustion furnace 17 can transfer energy with the fourth heat exchanger 6, and a first heat exchange tube 18 for supplying heat to the sixth heat exchanger 8, a second heat exchange tube 19 for supplying heat to the heat conduction oil, a third heat exchange tube 20 for supplying heat to the third heat exchanger 4, and a fourth heat exchange tube 21 for supplying heat to the first heat exchanger 2 are sequentially arranged in the combustion furnace 17 along the exhaust direction of flue gas, and the heat conduction oil supplies heat to the reactor 11.
Specifically, the distribution of heat in the combustion furnace 17 is controlled by controlling the split ratio in the combustion furnace 17, so that the heat provided by the combustion furnace 17 to the fifth heat exchanger 7 is smaller than the heat provided by the first heat exchange tube 18 to the sixth heat exchanger 8, and the gradient utilization of the heat in the combustion furnace 17 is realized. Of course, in other embodiments, a heat exchanger may be provided in the flue pipe of the burner 17 to supply heat to the fourth heat exchanger 6, without limitation.
Specifically, the second heat exchange tube 19 supplies heat to the tenth heat exchanger 27 to heat the heat transfer oil, the heat transfer oil flows through the reactor 11 and then is input into the oil storage tank 25, and the oil storage tank 25 is communicated with the tenth heat exchanger 27 to realize recycling of the heat transfer oil.
The seventh heat exchanger 12 is capable of heat transfer with the second heat exchanger 3 to supply heat to the second heat exchanger 3, and the eighth heat exchanger 13 is capable of heat transfer with the fourth heat exchanger 6 to supply heat to the fourth heat exchanger 6. By the arrangement, heat in the combustion furnace 17 can be utilized in a gradient manner, self-sufficiency of heat in the method for preparing hydrogen by reforming the self-heating type green alcohol and alcohol water solution is realized, external energy is avoided, and the method and the device using the method can be used in remote areas, so that the practicability is improved.
Example 1
The temperature of the green alcohol or the alcohol aqueous solution is increased to 112 ℃ for heating and gasification after the green alcohol or the alcohol aqueous solution is pressurized to 5atm by a first pump 1at 25 ℃ and then is sequentially input into a first heat exchanger 2 and a second heat exchanger 3, and then is input into a third heat exchanger 4 for heating to 250-300 ℃. Preferably 300 ℃. After reaching the reaction temperature, the mixture is fed into a storage tank 9. Wherein, the heat of the first heat exchanger 2 is sourced from a fourth heat exchange tube 21 in the combustion furnace 17, the heat of the second heat exchanger 3 is sourced from a seventh heat exchanger 12, and the heat of the third heat exchanger 4 is sourced from a third heat exchange tube 20.
Specifically, the first heat exchange tube 18, the second heat exchange tube 19, the third heat exchange tube 20 and the fourth heat exchange tube 21 are disposed in the combustion furnace 17, wherein the first heat exchange tube 18, the second heat exchange tube 19, the third heat exchange tube 20 and the fourth heat exchange tube 21 are sequentially disposed along the exhaust direction of the flue gas of the combustion furnace 17, that is, the heat exchange medium is the flue gas, and the flue gas sequentially flows through the first heat exchange tube 18, the second heat exchange tube 19, the third heat exchange tube 20 and the fourth heat exchange tube 21 and is exhausted.
The process water with the temperature of 25 ℃, 1atm and 1.75kmol/h is pressurized to 5atm by the second pump 5, then is sequentially input into the fourth heat exchanger 6 and the fifth heat exchanger 7 to be heated to 152 ℃ for heating gasification, and then is input into the sixth heat exchanger 8 to be heated to 250-300 ℃. Preferably, the temperature is raised to 300 ℃. Is sent into a storage tank 9 to be mixed with green alcohol or alcohol water solution as raw material gas for standby. The heat source of the fourth heat exchanger 6 is an eighth heat exchanger 13, the heat source of the fifth heat exchanger 7 is a combustion furnace 17, and the heat source of the sixth heat exchanger 8 is a first heat exchange tube 18.
The temperature of the raw material gas of 2.75kmol/h in the storage tank 9 is raised to 250-300 ℃, preferably 300 ℃ by a ninth heat exchanger 10, and then the raw material gas enters a reactor 11 to carry out the reforming hydrogen production reaction of the green alcohol and the alcohol water solution so as to obtain mixed gas and water, wherein the water can be directly discharged outwards or recycled to a second pump 5 to be used as process water, and the reforming hydrogen production reaction comprises the following steps:
the main reaction: CH (CH) 4 O+H 2 O＝CO 2 +3H 2
Side reaction: CO 2 +H 2 ＝CO+H 2 O
It should be noted that, in the present application, the ninth heat exchanger 10 is disposed between the storage tank 9 and the reactor 11, so as to avoid cooling the raw material gas in the storage tank 9, and maintain the temperature of the raw material gas between 250 ℃ and 300 ℃ to improve the raw material utilization rate in the reactor 11, however, in other embodiments, no heat exchanger may be disposed between the storage tank 9 and the reactor 11, and the raw material gas in the storage tank 9 is directly input into the reactor 11 to react, which is not limited herein.
4.73185kmol/H mixture (wherein the mixture includes H) 2 、CO 2 、CO、H 2 O、CH 4 O), the heat exchange temperature of the mixed gas is reduced to 180 ℃ through a seventh heat exchanger 12, the reduced heat is used for heating the second heat exchanger 3, the temperature of the mixed gas is subsequently reduced to 61 ℃ through an eighth heat exchanger 13, the reduced heat is used for heating the fourth heat exchanger 6, the mixed gas is then input into a cooler 14 for cooling, and the cooled mixed gas is input into a flash tank 15 for gas-liquid separation operation after being cooled to 35 ℃.
The cooler 14 is filled with condensed water, the condensed water flows through the cooler 14 and then flows into the cooling device 22 for cooling, and the cooled condensed water is input into the water storage tank 23 for storage, wherein the water storage tank 23 is connected with the cooler 14 through the third pump 24, and the condensed water in the water storage tank 23 is conveyed to the cooler 14 through the third pump 24, so that the circulation cooling of the condensed water is realized.
0.867289kmol/H liquid H in flash tank 15 2 O、CH 4 O and the like can be input into the storage tank 9 for recycling, can be directly discharged or input into the combustion furnace 17 for combustion,3.86457kmol/H gas H 2 、CO 2 CO, a small amount of CH 4 O is sent into a membrane separator 16 for separation, 2.37503kmol/H of product H 2 And outputting and storing, and delivering 1.48944kmol/h noncondensable steam and a small amount of methanol into the combustion furnace 17 for burning to recover heat, wherein the recovered heat is used for heating heat conduction oil or each preheater.
The 300 c, 1atm, 10kmol/h heat transfer oil in the oil storage tank 25 is inputted into the tenth heat exchanger 27 through the fourth pump 26 to raise the temperature to 312 c and then inputted into the reactor 11 to heat the reactor 11, and then the temperature is lowered to 300 c and then inputted into the oil storage tank 25 to be stored. The tenth heat exchanger 27 heats the reactor 11 through the second heat exchange tube 19 in the combustion furnace 17, and the heated heat transfer oil heats the reactor 11, and an eleventh heat exchanger 28 is further disposed between the tenth heat exchanger 27 and the reactor 11, and is configured to exchange heat between the heat transfer oil input into the reactor 11 and the heat transfer oil output from the reactor 11, and then input into the oil storage tank 25 for storage. Of course, in other embodiments, the eleventh heat exchanger 28 may not be provided, and the heat transfer oil may directly flow back to the oil storage tank 25 after being fed into the reactor 11 from the tenth heat exchanger 27, which is not limited herein.
The condensed water of 25 ℃, 1atm and 5kmol/h is used for cooling the mixed gas by the cooler 14, the condensed water passing through the cooler 14 flows back to the cooling device 22 for cooling, and after the temperature is reduced to 20-30 ℃, the condensed water is sent into the water storage tank 23 for recycling.
When the device is started, as the combustion furnace 17 is in a normal temperature state and can not heat each heat exchanger, heat can be provided by combusting green alcohol and an alcohol water solution, and the heat is provided by combusting non-condensing water after the whole process flow normally runs. Specifically, the method further comprises a pressurizer 29 connected with the combustion furnace 17, wherein the pressurizer 29 pressurizes air and inputs the air into the combustion furnace 17, and the air is mixed with noncondensable gas and then inputs the air into the combustion furnace 17 for combustion.
In the embodiment, the reactor 11 for preparing hydrogen by reforming the aqueous solution of the green alcohol and the alcohol adopts a coil reactor 11, the reaction temperature ranges from 250 ℃ to 300 ℃, and the catalyst is Cu/ZnO/Al 2 O 3 . The heat transfer rate of the whole reaction can be effectively improved, and the consumption and energy are reduced; and the wall thickness of the coil reactor 11The bearing capacity of the whole reactor 11 body can be effectively improved; in addition, the coil pipe type reactor 11 is heated by heat conduction oil, so that the energy consumption is low.
The high-temperature flue gas in the combustion furnace 17 is subjected to four-stage heat recovery through a first heat exchange tube 18, a second heat exchange tube 19, a third heat exchange tube 20 and a fourth heat exchange tube 21 which are sequentially arranged, so that the high-efficiency utilization of heat is realized, and an oil storage tank 25 is a low-temperature heat storage power supply.
Example 2
The method and apparatus for producing hydrogen from green alcohol in this example are the same as in example 1, except that: in this embodiment, the combustion furnace 17 does not adopt green alcohol for heating, but adopts an electric heating mode to provide heat for each device, so that energy is saved. Wherein the source of electrical energy may be solar energy, wind energy, tidal energy, biomass energy, etc., without limitation
In summary, the present invention makes the present device less dependent on the infrastructure of the mating utility by using the energy in the furnace 17 for the reforming reaction; the heat exchanger is used for cascade utilization of heat, so that efficient utilization of energy is realized, and efficient, green and continuous production of hydrogen can be realized; by setting the reforming hydrogen production reactor 11 as a coil pipe reactor 11, the heat transfer rate of the whole reaction is effectively improved, and the consumption and energy are reduced; simultaneously, the bearing capacity of the whole reactor 11 is effectively improved; furthermore, the coil reactor 11 is heated by heat conduction oil, so that the energy consumption is low; the liquid after gas-liquid separation is input into the storage tank 9 for recycling, so that the utilization rate of raw materials is improved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. A method for producing hydrogen by reforming self-heating green alcohol and an aqueous alcohol solution, which is characterized by comprising the following steps:
s1, pressurizing a green alcohol or alcohol water solution, sequentially heating the green alcohol or alcohol water solution through a first heat exchanger, a second heat exchanger and a third heat exchanger, and then inputting the green alcohol or alcohol water solution into a storage tank for standby;
s2, pressurizing water, sequentially inputting the water into a fourth heat exchanger, a fifth heat exchanger and a sixth heat exchanger for heating, and inputting the water into a storage tank for mixing with green alcohol or alcohol water solution to obtain raw gas;
s3, inputting raw material gas into a reactor for carrying out a hydrogen production reaction by reforming the green alcohol and the alcohol aqueous solution so as to obtain mixed gas;
s4, cooling the mixed gas through a seventh heat exchanger and an eighth heat exchanger, inputting the cooled mixed gas into a flash tank for gas-liquid separation, inputting the separated liquid into a storage tank for mixing with raw gas, cooling the mixed gas to 180 ℃ in the seventh heat exchanger, then cooling the mixed gas to 61 ℃ in the eighth heat exchanger, cooling the mixed gas to 35 ℃ through condensed water, inputting the cooled condensed water into a cooling device for cooling after flowing through the cooler, inputting the cooled condensed water into a water storage tank for storage after cooling, and communicating the water storage tank with the cooler for recycling condensed water;
s5, the separated gas is input into a membrane separator to separate and store hydrogen, and the rest gas is input into a combustion furnace to burn and release heat;
the combustion furnace can carry out energy transfer with the fourth heat exchanger, be equipped with in proper order along the flue gas emission direction in the combustion furnace to first heat exchange tube, the second heat exchange tube of conduction oil heat supply, to the third heat exchange tube of third heat exchanger heat supply and to the fourth heat exchange tube of first heat exchanger heat supply, the conduction oil supplies heat to the reactor, seventh heat exchanger can carry out heat transfer with the second heat exchanger, in order to supply heat to the second heat exchanger, eighth heat exchanger can carry out heat transfer with the fourth heat exchanger, in order to supply heat to the fourth heat exchanger, the second heat exchange tube supplies heat to the tenth heat exchanger, in order to heat the conduction oil, the conduction oil inputs the oil storage tank after flowing through the reactor, the oil storage tank with the tenth heat exchanger intercommunication in order to realize the cyclic utilization of conduction oil.
2. The method for producing hydrogen from the reforming of autothermal green alcohol and aqueous alcohol solution in accordance with claim 1, wherein in S1: the green alcohol or alcohol water solution is pressurized to 5atm by a pump, then is input into the first heat exchanger and the second heat exchanger to be heated to gasification, and then is input into the third heat exchanger to be heated to 250-300 ℃.
3. The method for producing hydrogen from the reforming of autothermal green alcohol and aqueous alcohol solution in accordance with claim 1, wherein in S2: the water is pressurized to 5atm by a pump, then is fed into the fourth heat exchanger and the fifth heat exchanger to be heated to gasification, and then is fed into the sixth heat exchanger to be heated to 250-300 ℃.
4. The method for producing hydrogen from the reforming of autothermal green alcohol and aqueous alcohol solution in accordance with claim 1, wherein in S3: the raw material gas enters the reactor through a ninth heat exchanger, the ninth heat exchanger heats the raw material gas to 250-300 ℃, and the ninth heat exchanger is electrically heated.
5. The method for producing hydrogen from the reforming of autothermal green alcohol and aqueous alcohol solution in accordance with claim 1, wherein in S3: the reactor is a coil pipe type reactor, the reaction temperature of the reactor is 250-300 ℃, and the catalyst is Cu/ZnO/Al 2 O 3 、Pt/SiO 2 、Pt/Al 2 O 3 、Pd/SiO 2 、Pd/Al 2 O 3 Any one of the following.
6. The method for producing hydrogen from the reforming of autothermal green alcohol and aqueous alcohol solution in accordance with claim 1, wherein in S5: when the temperature in the combustion furnace is lower, the green alcohol or the alcohol water solution is directly input for combustion so as to improve the temperature of the combustion furnace.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03232701A (en) * | 1990-02-08 | 1991-10-16 | Mitsubishi Heavy Ind Ltd | Methanol reformer |
| US5232682A (en) * | 1990-05-09 | 1993-08-03 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and installation for producing a gas containing hydrogen from methanol |
| CN203486893U (en) * | 2013-08-06 | 2014-03-19 | 上海合既得动氢机器有限公司 | Equipment for preparing hydrogen by utilizing methyl alcohol and water |
| CN109956450A (en) * | 2019-04-30 | 2019-07-02 | 广西氢朝能源科技有限公司 | A kind of instant hydrogen generating system of methanol-water and its hydrogen production process |
| CN110068218A (en) * | 2018-01-24 | 2019-07-30 | 玉溪新天力农业装备制造有限公司 | A kind of methanol recapitalization hydrogen-rich combustion heat supplying device |
| CN110835094A (en) * | 2019-10-28 | 2020-02-25 | 中科液态阳光(苏州)氢能科技发展有限公司 | Methanol steam and hydrogen mixed gas integrated ultrahigh pressure hydrogen production system and method thereof |
| CN214031727U (en) * | 2020-11-05 | 2021-08-24 | 上海齐耀动力技术有限公司 | Methanol reforming hydrogen production system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1787951B1 (en) * | 2004-07-12 | 2015-04-08 | Sumitomo Seika Chemicals Co., Ltd. | Hydrogen production system and reforming apparatus |
-
2023
- 2023-06-16 CN CN202310716603.0A patent/CN116654870B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03232701A (en) * | 1990-02-08 | 1991-10-16 | Mitsubishi Heavy Ind Ltd | Methanol reformer |
| US5232682A (en) * | 1990-05-09 | 1993-08-03 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and installation for producing a gas containing hydrogen from methanol |
| CN203486893U (en) * | 2013-08-06 | 2014-03-19 | 上海合既得动氢机器有限公司 | Equipment for preparing hydrogen by utilizing methyl alcohol and water |
| CN110068218A (en) * | 2018-01-24 | 2019-07-30 | 玉溪新天力农业装备制造有限公司 | A kind of methanol recapitalization hydrogen-rich combustion heat supplying device |
| CN109956450A (en) * | 2019-04-30 | 2019-07-02 | 广西氢朝能源科技有限公司 | A kind of instant hydrogen generating system of methanol-water and its hydrogen production process |
| CN110835094A (en) * | 2019-10-28 | 2020-02-25 | 中科液态阳光(苏州)氢能科技发展有限公司 | Methanol steam and hydrogen mixed gas integrated ultrahigh pressure hydrogen production system and method thereof |
| CN214031727U (en) * | 2020-11-05 | 2021-08-24 | 上海齐耀动力技术有限公司 | Methanol reforming hydrogen production system |
Non-Patent Citations (1)
| Title |
|---|
| Apparatus design and experimental study of methanol steam catalytic reforming for H2 production using engine exhaust heat;JI, C.W.等;Journal of Beijing University of Technology;20090630;第35卷(第6期);第815-819页 * |
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