CN111137856A - Skid-mounted mobile on-site hydrogen production all-in-one machine - Google Patents
Skid-mounted mobile on-site hydrogen production all-in-one machine Download PDFInfo
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- CN111137856A CN111137856A CN202010145433.1A CN202010145433A CN111137856A CN 111137856 A CN111137856 A CN 111137856A CN 202010145433 A CN202010145433 A CN 202010145433A CN 111137856 A CN111137856 A CN 111137856A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 216
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 216
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 81
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 164
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 43
- 238000000746 purification Methods 0.000 claims abstract description 41
- 238000011084 recovery Methods 0.000 claims abstract description 33
- 239000002918 waste heat Substances 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009413 insulation Methods 0.000 claims abstract description 9
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- 238000000197 pyrolysis Methods 0.000 claims abstract description 7
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- 238000005336 cracking Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
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- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
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- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 25
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 238000004523 catalytic cracking Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
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- 239000003345 natural gas Substances 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 238000002407 reforming Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- 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
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/08—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being otherwise bent, e.g. in a serpentine or zig-zag
- F28D7/082—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being otherwise bent, e.g. in a serpentine or zig-zag with serpentine or zig-zag configuration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention provides a skid-mounted mobile on-site hydrogen production integrated machine, which comprises a gasifier, a drying filter, a preheating heater and an ammonia pyrolysis hydrogen separation and purification unit which are sequentially communicated; the preheating heater comprises a waste heat recovery part and a heating branch part, wherein the heating branch part is provided with a branch manifold, and the outer side of the branch manifold is wound with a dry-burning heating wire; the ammonia pyrolysis hydrogen separation and purification unit comprises a hydrogen production part and a purification part; the hydrogen production part comprises an ammonia gas inlet manifold and a hydrogen gas outlet manifold; the hydrogen production part is also provided with a nitrogen outlet communicated with the waste heat recovery part; the purification section is filled with a molecular sieve adsorbent; the all-in-one machine is of an up-down structure; the outside of the all-in-one machine is separated from the outside by arranging a heat insulation plate, and the upper layer and the lower layer of the all-in-one machine are separated from each other by the heat insulation plate. Solves the problems of high energy consumption and high emission in the prior field hydrogen production technology.
Description
Technical Field
The invention relates to the field of ammonia gas cracking and converting hydrogen production equipment, in particular to a skid-mounted mobile on-site hydrogen production all-in-one machine.
Background
Among various renewable energy sources, hydrogen energy is known as 'Mingzhu on the energy crown' and is a completely clean and renewable ultimate energy source. Although hydrogen is widely distributed, the existing amount of free hydrogen in the natural state is very small, and how to produce hydrogen by enrichment and purification with low carbon and environmental protection is a big problem of popularization of hydrogen energy at present. The storage and transportation after hydrogen production are complex and extremely expensive, the hydrogen storage tank with the design pressure of 98MPa needs to be produced to meet the requirements for gaseous pressure hydrogen storage, the hydrogen storage and transportation of liquid hydrogen needs to be liquefied by reducing the temperature of the hydrogen to-253 ℃ under normal pressure, and the requirements for storage tank technology difficulty and materials are extremely high. In the case of the above-mentioned technical immaturity, it is urgently necessary to find an alternative hydrogen production method with economical hydrogen storage. Therefore, the on-site hydrogen production technology is produced at the beginning, the problems of economy and safety of hydrogen energy storage and transportation after large-scale hydrogen production are eliminated, and technologies such as hydrogen station and the like which are used for on-site hydrogen production need to be used for on-site hydrogen production are more and more concerned by people.
Ammonia is used as an organic substance containing 17.6% of hydrogen by mass, a conventional catalyst is added at about 600-800 ℃ and normal pressure to be completely cracked into hydrogen and nitrogen, the conversion efficiency can reach 99.9%, and the method has very large on-site hydrogen production potential. 2.64 cubic meters of mixed gas can be prepared by each kilogram of liquid ammonia, wherein 1.98 cubic meters of hydrogen and 0.66 cubic meter of nitrogen are contained, and other nitrogen, oxygen and carbon pollutants are not contained. And the volume energy density of the liquid ammonia is 1.53 times of that of the liquid hydrogen, and the energy storage and transportation rate is higher under the same volume condition. At present, the price of hydrogen in domestic hydrogen stations is about 70 yuan per kilogram, while the price of liquid ammonia is about 3000 yuan per ton, and the hydrogen obtained by decomposition is about 16.7 yuan per kilogram, wherein the price difference of the costs of hydrogen and ammonia in storage, transportation, decomposition and the like does not exist. Therefore, ammonia is used as a raw material gas source for hydrogen storage-hydrogen production and a promising and new attractive technical form.
However, the most common methods for producing hydrogen on site currently include water electrolysis hydrogen production, natural gas reforming hydrogen production, methane and ammonia cracking hydrogen production, and the like. A considerable proportion of the foreign hydrogen stations use the electrolytic water to produce hydrogen, although the raw materials are most easily obtained, the main cost is the electricity and the current density of an electrolytic cell to determine the hydrogen production rate, at present, each cubic hydrogen (0.089kg) needs to consume 5 kilowatts of electricity, the unit mass hydrogen storage amount of water is only 11.1 percent, and the hydrogen production purity is high, but the economy and the rationality need to be comprehensively considered. The natural gas reforming and methane cracking hydrogen production are not suitable for on-site operation due to the fact that the byproducts can generate CO and CO2, and the related processes have more capture processes, and the hydrogen carrying content of the natural gas and the methane is not higher than 17.6% and not higher than 12.4% of ammonia. In view of the fact that the existing on-site hydrogen production technology focuses on the aspects of high energy consumption, high emission and the like, and the energy consumption and emission during hydrogen production-hydrogen storage are not offset by the energy efficiency during hydrogen utilization, a novel, compact and efficient on-site hydrogen production method and equipment are urgently needed.
Disclosure of Invention
According to the technical problems that the existing on-site hydrogen production technology has high energy consumption and high emission and the energy efficiency during hydrogen production-hydrogen storage does not offset the energy consumption emission during hydrogen production-hydrogen storage, the skid-mounted mobile on-site hydrogen production all-in-one machine is provided. The invention takes the hydrogen-rich liquid ammonia (the hydrogen storage capacity per unit mass is 17.6%) as a hydrogen storage carrier, gasifies the received liquid ammonia, preheats and heats ammonia, catalyzes and decomposes ammonia, purifies hydrogen finally and the like, and integrates a series of energy conversion processes, thereby not only effectively and economically manufacturing hydrogen with the purification rate of more than 99.9% on a mobile site, but also reducing the energy consumption of hydrogen production by utilizing the waste heat recovery of integrated heat exchange equipment, simultaneously considering no pollution of waste gas, having compact and efficient structure and meeting the requirements of hydrogen production on the mobile site of a hydrogen station and related occasions needing hydrogen energy.
The technical means adopted by the invention are as follows:
a skid-mounted mobile on-site hydrogen production integrated machine comprises a gasifier, a drying filter, a preheating heater and an ammonia cracking hydrogen separation and purification unit which are sequentially communicated; a pressure regulating valve group is arranged between the gasifier and the drying filter; a liquid ammonia flow regulating valve bank is arranged at an ammonia gas inlet of the gasifier, and a hydrogen pressure regulating valve bank is arranged at a hydrogen gas outlet;
the preheating heater comprises a waste heat recovery part and a heating branch part, an ammonia gas inlet of the waste heat recovery part is communicated with the drying filter, the heating branch part is provided with a branch manifold, and a dry-burning heating wire is wound on the outer side of the branch manifold;
the ammonia pyrolysis hydrogen separation and purification unit comprises a hydrogen production part and a purification part; the hydrogen production part comprises an ammonia gas inlet manifold and a hydrogen gas outlet manifold, a catalyst is filled in the hydrogen production part, the ammonia gas inlet manifold is communicated with the flow dividing manifold, the hydrogen gas outlet manifold is communicated with the purification part, and a hydrogen permeable membrane is attached to the inner wall of the hydrogen gas outlet manifold; the hydrogen production part is also provided with a nitrogen outlet communicated with the waste heat recovery part; high-temperature nitrogen generated after the cracking reaction in the hydrogen production part is introduced into the waste heat recovery part through the nitrogen outlet to carry out waste heat recovery; the purification part is communicated with the gasifier, and is filled with a molecular sieve adsorbent for removing miscellaneous gas; the gasifier is used for recovering heat of the high-temperature hydrogen generated by the purified hydrogen production part, cooling the hydrogen and using the recovered heat for gasifying liquid ammonia;
the integrated machine is of an up-down structure, the ammonia flow regulating valve group, the gasifier, the pressure regulating valve group, the drying filter and the hydrogen pressure regulating valve group are positioned at the lower layer of the integrated machine, and the preheating heater and the ammonia cracking hydrogen separation and purification unit are positioned at the upper layer of the integrated machine; the outside of the all-in-one machine is separated from the outside by arranging a heat insulation plate, and the upper layer and the lower layer of the all-in-one machine are separated from each other by the heat insulation plate.
Further, the waste heat recovery part is a dividing wall type heat exchanger; the heating shunt part is made of heat-resistant steel.
Further, liquid ammonia flow control valves is low temperature corrosion-resistant valves, pressure regulating valves is the explosion-proof group of normal atmospheric temperature corrosion-resistant valve, hydrogen pressure regulating valves is explosion-proof valves, the reposition of redundant personnel manifold the ammonia entry manifold with hydrogen outlet manifold is high temperature heat-resisting steel.
Further, the gasifier is a plate-fin type, plate type, wound tube type or shell-and-tube type heat exchanger and is made of corrosion-resistant and explosion-proof materials.
Further, the catalyst is a metal-based ammonia decomposition catalyst; the hydrogen-hydrogen permeable membrane is a palladium-based alloy membrane; the molecular sieve adsorbent is crystalline aluminosilicate.
Compared with the prior art, the invention has the following advantages:
1. the skid-mounted mobile field hydrogen production integrated machine overcomes the defects of high storage and transportation cost, flammability, explosiveness and the like of the existing hydrogen and liquid hydrogen, and the skid-mounted integrated equipment for reproducing field hydrogen production by utilizing the hydrogen-carrying raw material liquid ammonia is widely used for obtaining the liquid ammonia, has low cost (<3000 ￥/ton), contains 16.7 ￥/kg of hydrogen, has the hydrogen price of about 70 ￥/kg in the existing hydrogen station, has the hydrogen storage capacity per unit mass (17.6%) higher than that of other hydrogen-carrying systems, and has the volume energy density 1.53 times that of the liquid hydrogen.
2. The skid-mounted mobile field hydrogen production integrated machine provided by the invention has the advantages that the power consumption in the whole process is only that ammonia gas is heated to 650-700 ℃, and only ammonia decomposition catalysts and electric heating devices are added compared with the equipment consumables for producing hydrogen by water electrolysis, the skid-mounted mobile field hydrogen production integrated machine has the advantages of less investment, no complex devices such as an electrolysis tank and oxygen collection, small volume, low energy consumption, high efficiency, good economy and the like.
3. The skid-mounted mobile on-site hydrogen production integrated machine provided by the invention has the advantages of compact structure, small floor area, integral skid mounting, high safety, oxygen-free and carbon-free environment in the whole process, and the equipment works under normal pressure, so that the mobile on-site rapid hydrogen production can be realized, and the produced products are only hydrogen and nitrogen (the normal-temperature nitrogen can be directly discharged into the atmosphere), are safer, completely environment-friendly and non-flammable and explosive compared with the hydrogen production (oxygen production) natural gas by water electrolysis, and hydrogen production by reforming of methanol and the like (CO2 and other pollutants).
In conclusion, the invention has the advantages of compact structure, safety, environmental protection, high efficiency and good economic performance. The method is suitable for rapidly moving on-site hydrogen production through skillfully designed waste heat recovery and upper and lower structural equipment layering and modular design. Therefore, the technical scheme of the invention solves the problems of high energy consumption and high emission in the existing field hydrogen production technology and energy consumption emission during hydrogen production-hydrogen storage is not offset by energy efficiency during hydrogen production.
Based on the reasons, the invention can be widely popularized in the fields of relevant hydrogen stations, chemical hydrogen system starting, electronic monocrystalline silicon nonferrous metal production, hydrogen energy automobiles, ships and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of the structure and principle of the skid-mounted mobile on-site hydrogen production all-in-one machine.
FIG. 2 is a flow chart of energy recovery and utilization in the skid-mounted mobile on-site hydrogen production all-in-one machine.
FIG. 3 is a schematic diagram of a preheat heater according to the present invention.
FIG. 4 is a schematic structural diagram of the separation and purification unit for hydrogen from ammonia cracking.
In the figure: 1. an ammonia flow regulating valve group; 2. a gasifier; 3. a pressure regulating valve group; 4. drying the filter; 5. preheating a heater; 51. a waste heat recovery section; 52. a heating shunt part; 53. a manifold; 6. an ammonia cracking hydrogen separation and purification unit; 61. a hydrogen production section; 611. an ammonia gas inlet manifold; 612. a hydrogen gas outlet manifold; 613. a nitrogen outlet; 62. a purification section; 7. a hydrogen pressure regulating valve group.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise. Meanwhile, it should be understood that the sizes of the respective portions shown in the drawings are not drawn in an actual proportional relationship for the convenience of description. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. Any specific values in all examples shown and discussed herein are to be construed as exemplary only and not as limiting. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
In the description of the present invention, it is to be understood that the orientation or positional relationship indicated by the directional terms such as "front, rear, upper, lower, left, right", "lateral, vertical, horizontal" and "top, bottom", etc., are generally based on the orientation or positional relationship shown in the drawings, and are used for convenience of description and simplicity of description only, and in the absence of any contrary indication, these directional terms are not intended to indicate and imply that the device or element so referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore should not be considered as limiting the scope of the present invention: the terms "inner and outer" refer to the inner and outer relative to the profile of the respective component itself.
Spatially relative terms, such as "above … …," "above … …," "above … …," "above," and the like, may be used herein for ease of description to describe one device or feature's spatial relationship to another device or feature as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if a device in the figures is turned over, devices described as "above" or "on" other devices or configurations would then be oriented "below" or "under" the other devices or configurations. Thus, the exemplary term "above … …" can include both an orientation of "above … …" and "below … …". The device may be otherwise variously oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
It should be noted that the terms "first", "second", and the like are used to define the components, and are only used for convenience of distinguishing the corresponding components, and the terms have no special meanings unless otherwise stated, and therefore, the scope of the present invention should not be construed as being limited.
Example 1
As shown in figure 1, the invention provides a skid-mounted mobile on-site hydrogen production integrated machine, which comprises a gasifier 2, a drying filter 4, a preheating heater 5 and an ammonia pyrolysis hydrogen separation and purification unit 6 which are sequentially communicated; a pressure regulating valve group 3 is arranged between the gasifier 2 and the drying filter 4; a liquid ammonia flow regulating valve group 1 is arranged at an ammonia gas inlet of the gasifier 2, and a hydrogen pressure regulating valve group 7 is arranged at a hydrogen gas outlet; all the devices of the all-in-one machine are communicated through pipelines;
as shown in fig. 3, the preheating heater 5 includes a waste heat recovery part 51 and a heating split part 52, an ammonia gas inlet of the waste heat recovery part 51 is communicated with the drying filter 4, the waste heat recovery part 51 is used for recovering waste heat of high-temperature nitrogen gas generated after hydrogen production, and the recovered waste heat is used for preheating raw ammonia gas, so as to reduce subsequent electric heating power consumption;
the heating flow-splitting part 52 is provided with a flow-splitting manifold 53, the outer side of the flow-splitting manifold 53 is wound with a dry-heating electric heating wire for heating the raw ammonia gas to the reaction temperature, the preheated ammonia gas enters the flow-splitting manifold 53 and is divided into a plurality of strands, and the preheated ammonia gas is heated to the preset temperature of 650-700 ℃ and then is introduced into the ammonia gas cracking hydrogen separation and purification unit 6;
as shown in fig. 4, the ammonia pyrolysis hydrogen separation and purification unit 6 includes a hydrogen production section 61 and a purification section 62; the hydrogen production part 61 comprises an ammonia gas inlet manifold 611 and a hydrogen gas outlet manifold 612, a catalyst is filled in the hydrogen production part 61, the ammonia gas inlet manifold 611 is communicated with the flow dividing manifold 53, the hydrogen gas outlet manifold 612 is communicated with the purification part 62, a hydrogen permeable membrane is attached to the inner wall of the hydrogen gas outlet manifold 612, only hydrogen gas can enter the hydrogen gas outlet manifold 612, and then each strand of hydrogen gas attacks the purification part 62;
the hydrogen production section 61 is further provided with a nitrogen outlet 613 communicated with the waste heat recovery section 51; high-temperature nitrogen generated after the cracking reaction in the hydrogen production part 61 is introduced into the waste heat recovery part 51 through the nitrogen outlet 613 to recover waste heat; the purification part 62 is communicated with the gasifier 2, and the purification part 62 is filled with a molecular sieve adsorbent for removing miscellaneous gas; the gasifier 2 is used for recovering heat of the high-temperature hydrogen generated by the purified hydrogen production part 61, cooling the hydrogen and using the recovered heat for gasifying liquid ammonia, and the cooled hydrogen is subjected to pressure regulation by the hydrogen regulating valve group 7 and then is transported to a user on site through a corresponding pipeline for use;
the integrated machine is of an up-down structure, the ammonia flow regulating valve group 1, the gasifier 2, the pressure regulating valve group 3, the drying filter 4 and the hydrogen pressure regulating valve group 7 are positioned at the lower layer of the integrated machine, and the preheating heater 5 and the ammonia cracking hydrogen separation and purification unit 6 are positioned at the upper layer of the integrated machine; the outside of the all-in-one machine is separated from the outside by arranging a heat insulation plate, and the upper layer and the lower layer of the all-in-one machine are separated from each other by the heat insulation plate.
The working process of the integrated machine mainly comprises the processes of receiving liquid ammonia, gasifying, removing impurities, preheating and heating ammonia gas, performing catalytic cracking conversion to prepare hydrogen, separating and purifying, finally cooling hydrogen and the like, wherein the processes of gasifying and preheating liquid ammonia, cooling catalytic cracking waste gas and cooling hydrogen are integrally connected to perform energy recovery and reuse; firstly, inflow is regulated through the liquid ammonia flow regulating valve group 1 to regulate the supply flow of liquid ammonia, the liquid ammonia is gasified through the gasifier 2, and the pressure of equipment and the flow rate of ammonia in the integrated machine are regulated by the pressure regulating valve group 3; secondly, removing moisture and impurities in the raw ammonia gas through the drying filter 4, preheating the raw ammonia gas through a heating shunt part 51 of the preheating heater 5, dividing the raw ammonia gas into a plurality of streams of fluid through a shunt manifold 53, winding and arranging a snakelike dry-burning heating wire on the outer side of the shunt manifold 53, introducing the raw ammonia gas into the ammonia gas hydrogen cracking separation and purification unit 6 after the raw ammonia gas is heated to the temperature of 650-700 ℃ under the specified process condition, carrying out catalytic cracking on the raw ammonia gas into hydrogen gas and nitrogen gas in a hydrogen production part 61, wherein the waste nitrogen gas is converged through a nitrogen gas outlet and introduced into a waste heat recovery part 52 of the preheating heater 5 for energy recovery, and preheating and heating the ammonia gas introduced into the preheating heater 5 to enable the ammonia; finally, the hydrogen that hydrogen manufacturing portion 61 made passes through hydrogen outlet manifold 612 lets in purification portion 62 carry out molecular sieve swing adsorption in purification portion 62 and detach the micro miscellaneous gas, and the hydrogen after the purification lets in vaporizer 2 cools off the back process hydrogen pressure regulating valve group 7 pressure regulating is carried for the user, simultaneously vaporizer 2 carries out waste heat recovery for the liquid ammonia that lets in gasifies.
Preferably, the hydrogen production part comprises a shell-and-tube cracking separation device, an ammonia gas inlet manifold 611, a nitrogen gas outlet 613 and a hydrogen gas outlet manifold 612, the shell-and-tube cracking separation device is filled with a catalyst, one end of the ammonia gas inlet manifold 611 is communicated with the inside of the shell-and-tube cracking separation device, and the other end of the ammonia gas inlet manifold 611 is communicated with the flow dividing manifold 53; one end of the hydrogen outlet manifold 612 extends into the shell-and-tube cracking and separating device, and the other end is communicated with the purifying part 62; a hydrogen permeable membrane is attached to the inner wall of the hydrogen outlet manifold 612.
According to the integrated machine, the liquid ammonia flow regulating valve group 1, the gasifier 2, the pressure regulating valve group 3, the drying filter 4, the preheating heater 5, the ammonia catalytic cracking hydrogen separation and purification unit 6 and the hydrogen pressure regulating valve group 7 are arranged in the integrated machine in a modularized manner, so that the integrated machine is more compact.
Further, the heat insulation board is made of high-strength heat insulation materials, so that energy dissipation and heating loss can be prevented.
Further, the exhaust heat recovery unit 51 is a dividing wall type heat exchanger; the heating branch portion 52 is made of heat-resistant steel.
Further, liquid ammonia flow control valves 1 is low temperature corrosion-resistant valves, pressure regulating valves 3 is the explosion-proof group of normal atmospheric temperature corrosion-resistant valve, hydrogen pressure regulating valves 7 is explosion-proof valves, flow distribution manifold 53 ammonia entry manifold 611 with hydrogen outlet manifold 612 is high temperature heat-resistant steel.
Further, the gasifier 2 is a plate-fin, plate, wound tube or shell-and-tube heat exchanger and is made of corrosion-resistant and explosion-proof materials.
Further, the catalyst is a metal-based ammonia decomposition catalyst such as Ru, Ni and Fe and other compound components; the hydrogen permeable membrane is a palladium-based alloy membrane and other related hydrogen permeable membranes; the molecular sieve pressure swing adsorbent is a crystalline aluminosilicate and other related materials.
Further, in the ammonia catalytic cracking hydrogen separation and purification unit 6, during the ammonia catalytic cracking separation, hydrogen purification, waste gas heat recovery and hydrogen cooling processes, the reaction process of catalytically cracking ammonia into hydrogen and nitrogen by using the catalyst filled inside is as follows:
the process is endothermic expansion reaction, i.e. unit mole of ammonia gas is cracked into 75% of hydrogen and 25% of ammonia gas under the catalysis of a certain temperature and absorbs 47.3kJ of heat, so that the temperature is increased and the pressure is reduced to facilitate the dynamic decomposition of ammonia, and thus the cracking conversion rate of ammonia gas under normal pressure and about 650 ℃ can reach 99.9% under the help of a catalyst.
The skid-mounted mobile on-site hydrogen production integrated machine specifically comprises the following working processes:
(1) liquid ammonia gasification preheating temperature rise process
Liquid ammonia is stored in the storage tank at about minus 33 ℃ under normal pressure, the liquid ammonia is communicated with the flow regulating valve group 1 through a low-temperature pipeline to regulate the flow of the liquid ammonia, and the consumption of the liquid ammonia is determined according to the hydrogen demand, namely the hydrogen storage amount per unit mass of 5.68kg of liquid ammonia required by 1kg of hydrogen generated by the integrated machine is 17.6%. Liquid ammonia with a certain flow regulated enters the gasifier 2 to absorb heat and gasify and then becomes ammonia, the pressure in the all-in-one machine system is regulated through the pressure regulating valve group 3, the general system operates under normal pressure, and the pressure does not exceed 5 bar. After removing trace moisture and impurities from the gasified ammonia gas through a drying filter 4, preheating the gasified ammonia gas sequentially through a preheating heater 5, heating the gasified ammonia gas by a dry-burning heating pipe, raising the temperature to the catalytic cracking temperature of 650-.
(2) Process for separating and purifying hydrogen from ammonia by catalytic cracking
The raw material gas ammonia gas under the reaction temperature enters a catalytic cracking hydrogen production separation unit 6 and is decomposed into hydrogen and nitrogen by a catalyst; in order to increase the reaction area and reduce the catalyst poisoning failure phenomenon, the ammonia cracking hydrogen separation unit 6 receives each strand of raw material gas at the temperature to be reacted and carries out catalytic cracking in different shells filled with catalysts to form hydrogen and nitrogen, the hydrogen passes through a collecting pipe with a hydrogen permeable membrane palladium metal-based hydrogen permeable membrane open hole, and the hydrogen collected by each strand is converged at a manifold and then introduced into a molecular sieve for pressure swing adsorption to remove trace impurity gas.
(3) Integrated machine energy recycling process
As shown in fig. 2, the integrated machine of the present invention includes two energy recycling processes, which are respectively: the decomposed high-temperature waste nitrogen gas is recycled to preheat the incoming flow of ammonia gas to be decomposed in the preheating heater 5, so that the power consumption of electric heating of subsequent equipment is saved; and the decomposed purified hydrogen with higher temperature is subjected to energy recovery to gasify the incoming liquid ammonia in the gasifier 2, and the purified hydrogen is recovered to the normal temperature state to prevent high temperature, flammability and explosiveness so as to be delivered to relevant field users.
Compared with the prior art, the skid-mounted mobile on-site hydrogen production integrated machine has the advantages that the unique ammonia gas heating, catalyst cracking hydrogen separation and purification units are designed, preheated raw material gas ammonia enters a manifold and then is divided into a plurality of strands, the outer side of each strand of fluid pipe is wound with a snake-shaped dry-burning heating wire, the raw material gas is introduced into an ammonia catalytic cracking hydrogen separation and purification device 6 when the reaction gas is heated to the temperature of specified process conditions, and each strand of fluid enters different decomposition units filled with catalysts and is used for catalytically cracking the ammonia gas in each strand of fluid into hydrogen and nitrogen. After entering a collecting conduit with hydrogen permeable membrane openings in a pipe layer in the ammonia catalytic cracking hydrogen separation and purification equipment 6, each split stream of hydrogen is converged by an outlet manifold and flows into a molecular sieve pressure swing adsorption pipe, and then flows out after trace impurity gas is removed and purified.
In order to overcome the problem of energy consumption waste of heat exchange equipment and a heater, compared with the prior art that the heater is used in the gasification process and cooling water circulation is used in the cooling process, the system has the unique design that the system comprises two energy recovery processes, namely, the energy recovery of the decomposed high-temperature waste gas nitrogen is respectively carried out to preheat the incoming flow of the ammonia gas to be decomposed in the preheating heater 5, so that the power consumption of the electric heating of subsequent equipment is saved; and (3) recovering energy of the decomposed purified hydrogen with higher temperature to enable the purified hydrogen to gasify the incoming liquid ammonia in the gasifier 2, and recovering the purified hydrogen to a normal temperature state to prevent high temperature, flammability and explosiveness so as to deliver the purified hydrogen to relevant field users.
Compared with other hydrogen production equipment, particularly hydrogen production by water electrolysis, the system is more energy-saving and environment-friendly, and the power consumption part of the equipment is only the ammonia gas preheating heater 5 and no other power consumption equipment is needed. And the heater works at full load only when the equipment is started, and the heater is changed into a low-load working mode or an intermittent working mode after the energy recovery process of the hydrogen production system starts to circulate.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A skid-mounted mobile on-site hydrogen production integrated machine is characterized by comprising a gasifier (2), a drying filter (4), a preheating heater (5) and an ammonia pyrolysis hydrogen separation and purification unit (6) which are communicated in sequence; a pressure regulating valve group (3) is arranged between the gasifier (2) and the drying filter (4); a liquid ammonia flow regulating valve group (1) is arranged at an ammonia gas inlet of the gasifier (2), and a hydrogen pressure regulating valve group (7) is arranged at a hydrogen gas outlet;
the preheating heater (5) comprises a waste heat recovery part (51) and a heating branch part (52), an ammonia gas inlet of the waste heat recovery part (51) is communicated with the drying filter (4), the heating branch part (51) is provided with a branch manifold (53), and dry-burning electric heating wires are wound and arranged on the outer side of the branch manifold (53);
the ammonia pyrolysis hydrogen separation and purification unit (6) comprises a hydrogen production part (61) and a purification part (62); the hydrogen production part (61) comprises an ammonia gas inlet manifold (611) and a hydrogen gas outlet manifold (612), the hydrogen production part (61) is filled with a catalyst, the ammonia gas inlet manifold (611) is communicated with the flow dividing manifold (53), the hydrogen gas outlet manifold (612) is communicated with the purification part (62), and a hydrogen permeable membrane is attached to the inner wall of the hydrogen gas outlet manifold (612); the hydrogen production part (61) is also provided with a nitrogen outlet (613) communicated with the waste heat recovery part (51); high-temperature nitrogen generated after the cracking reaction in the hydrogen production part (61) is introduced into the waste heat recovery part (51) through the nitrogen outlet (613) for waste heat recovery; the purification part (62) is communicated with the gasifier (2), and the purification part (62) is filled with a molecular sieve adsorbent and used for removing miscellaneous gas; the gasifier (2) is used for recovering heat of the high-temperature hydrogen generated by the purified hydrogen production part (61), cooling the hydrogen and using the recovered heat for gasifying liquid ammonia;
the integrated machine is of an up-down structure, the ammonia flow regulating valve group (1), the gasifier (2), the pressure regulating valve group (3), the drying filter (4) and the hydrogen pressure regulating valve group (7) are positioned at the lower layer of the integrated machine, and the preheating heater (5) and the ammonia cracking hydrogen separation and purification unit (6) are positioned at the upper layer of the integrated machine; the outside of the all-in-one machine is separated from the outside by arranging a heat insulation plate, and the upper layer and the lower layer of the all-in-one machine are separated from each other by the heat insulation plate.
2. The skid-mounted mobile integrated on-site hydrogen production machine according to claim 1, wherein the waste heat recovery part (51) is a dividing wall type heat exchanger; the heating shunt part (52) is made of heat-resistant steel.
3. The skid-mounted mobile on-site hydrogen production all-in-one machine according to claim 1, wherein the liquid ammonia flow regulating valve bank (1) is a low-temperature corrosion-resistant valve bank, the pressure regulating valve bank (3) is a normal-temperature corrosion-resistant valve explosion-proof bank, the hydrogen pressure regulating valve bank (7) is an explosion-proof valve bank, and the flow distribution manifold (53), the ammonia gas inlet manifold (611) and the hydrogen gas outlet manifold (612) are made of high-temperature heat-resistant steel.
4. The skid-mounted mobile integrated on-site hydrogen production machine according to claim 1, wherein the gasifier (2) is a plate-fin, plate, wound-tube or shell-and-tube heat exchanger and is made of a corrosion-resistant and explosion-proof material.
5. The skid-mounted mobile integrated on-site hydrogen production machine according to claim 1, wherein the catalyst is a metal-based ammonia decomposition catalyst; the hydrogen-hydrogen permeable membrane is a palladium-based alloy membrane; the molecular sieve adsorbent is crystalline aluminosilicate.
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