CN117695966A - System and method for producing hydrogen from natural gas - Google Patents
System and method for producing hydrogen from natural gas Download PDFInfo
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- CN117695966A CN117695966A CN202311675181.3A CN202311675181A CN117695966A CN 117695966 A CN117695966 A CN 117695966A CN 202311675181 A CN202311675181 A CN 202311675181A CN 117695966 A CN117695966 A CN 117695966A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000003345 natural gas Substances 0.000 title claims abstract description 85
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- 239000001257 hydrogen Substances 0.000 title claims abstract description 75
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 156
- 239000007789 gas Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 31
- 238000002407 reforming Methods 0.000 claims abstract description 20
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006057 reforming reaction Methods 0.000 claims abstract description 12
- 238000001651 catalytic steam reforming of methanol Methods 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000006477 desulfuration reaction Methods 0.000 claims description 30
- 230000023556 desulfurization Effects 0.000 claims description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000009919 sequestration Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000002453 autothermal reforming Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- 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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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/042—Purification by adsorption on solids
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C01B2203/06—Integration with other chemical processes
- C01B2203/061—Methanol production
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- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
- C01B2203/1264—Catalytic pre-treatment of the feed
- C01B2203/127—Catalytic desulfurisation
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Abstract
The invention relates to a system for producing hydrogen from natural gas and a method thereof, wherein the system comprises a feeding unit, a feeding control unit and a methane reforming unit which are connected in sequenceReaction unit, methanol synthesis unit and method for producing high purity H 2 And high purity CO 2 Is a methanol steam reforming hydrogen production unit. The natural gas and the medium-pressure steam output by the feeding unit generate synthesis gas in the methane reforming reaction unit, the synthesis gas enters the methanol synthesis unit to synthesize liquid methanol, and the liquid methanol generates H through the methanol reforming hydrogen production device 2 And CO 2 Separating by a PSA purifying and separating device to obtain high-purity H 2 And high purity CO 2 . High purity H 2 Can be directly used for filling fuel cell automobiles or other purposes, and high-purity CO 2 After collection, the natural gas hydrate is used for displacement exploitation, and meanwhile, CO is recovered 2 Sealing and storing to realize CO 2 Zero emission. The liquid methanol is used as a hydrogen carrier for transportation and distribution, so that the transportation efficiency is greatly improved, and the transportation cost is saved.
Description
Technical Field
The invention relates to the technical field of hydrogen production, in particular to a system and a method for producing hydrogen by natural gas.
Background
In recent years, with the continuous development of social economy, fossil energy is continuously consumed, and environmental pollution problems such as global warming, acid rain, haze, solid waste and the like are brought about at the same time of causing energy crisis. Thus, a kind of search is made
Environmentally friendly renewable energy sources are urgent. Hydrogen is a novel energy source with rich reserves, high heat generation and cleanness and high efficiency, gradually reflects on the eye curtains of people, and becomes an alternative energy source for fossil fuels such as coal, petroleum and the like.
The hydrogen production method is numerous, the yield is the highest, the natural gas hydrogen production accounts for 61%, the coal gasification hydrogen production accounts for 23%, and the water electrolysis hydrogen production accounts for 6%. Among them, methane reforming hydrogen production has the unique advantage: natural gas reserves are large, and reactant sources are rich; the methane-carbon-hydrogen ratio in hydrocarbon substances is minimum, and the theoretical hydrogen yield is highest; the carbon chain of methane is shortest, carbon is not easy to accumulate, the raw materials are cheap, the economy is good, and the process is relatively mature after century development. The methane reforming hydrogen production mainly comprises methane steam reforming hydrogen production (SMR), methane partial oxidation reforming hydrogen Production (POM), methane carbon dioxide reforming hydrogen production (CDRM), methane triple reforming hydrogen production (TRM) and methane autothermal reforming hydrogen production (ATR).
The hydrogen transportation mode is usually long-tube trailer transportation, at present, the domestic common transportation pressure is 20Mpa tube bundle, each long-tube trailer can be filled with about 400kg of high-pressure hydrogen, however, the residual pressure in the tube bundle is required to be not lower than 2Mpa in the unloading process, so that the single transportation hydrogen quantity is only about 300kg in practice, and the transportation efficiency is low and the cost is high. The liquid hydrogen transportation is to convert hydrogen into liquid at a low temperature of minus 253 ℃ and then transport the liquid by a tank truck. Unlike high pressure gas transport, the volumetric energy density of liquid hydrogen is higher, and the transport efficiency is greatly improved. The tank truck can be used for delivering the liquid hydrogen by about 4300kg of liquid hydrogen in a single time, and the transportation capacity of the tank truck is more than 10 times of that of the cluster bottle group trailer. However, the energy consumption of hydrogen liquefaction is high, and meanwhile, the heat preservation requirement in the transportation of liquid hydrogen is extremely high so as to prevent the danger of boiling of the liquid hydrogen.
The application CN115849304a synthesizes ammonia gas from hydrogen and nitrogen gas obtained by reforming methane to prepare hydrogen, and then liquefies the ammonia gas to form liquid ammonia as a hydrogen storage medium, and although the high efficiency of the hydrogen transportation process is realized, the reaction condition of the synthesized ammonia requires high temperature and high pressure, the requirement on production equipment is high, the equipment investment is large, the ammonia itself is also large in danger and toxic and corrosive, a large amount of heat is consumed in the gasification and decomposition hydrogen preparation process of the liquid ammonia, and the economical efficiency is poor.
Disclosure of Invention
The invention aims to overcome the defects of low conveying efficiency, high cost and the like in the prior art and provides a system and a method for producing hydrogen by natural gas, which are safe and have low transportation cost.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a system for producing hydrogen from natural gas, which comprises a feeding unit, a feeding control unit, a methane reforming reaction unit, a methanol synthesis unit and a device for producing high-purity H, which are connected in sequence 2 And high purity CO 2 Is a methanol steam reforming hydrogen production unit.
Further, the feeding unit comprises a natural gas desulfurization unit and a steam generation unit.
Furthermore, the natural gas desulfurization unit is used for removing sulfur-containing compounds in the raw natural gas to obtain the desulfurized natural gas.
Further, the natural gas desulfurization unit is a natural gas desulfurization tower, and the natural gas desulfurization tower is divided into a convection section and a zinc oxide desulfurization tank.
Further, the steam generating unit is used for vaporizing desalted water to obtain medium-pressure steam.
Still further, the steam generating unit comprises a desalted water preheater, a steam drum and a water separator, wherein desalted water enters the steam drum to generate steam after being heated by the desalted water preheater, and medium-pressure steam is generated by the water separator.
Further, the feed control unit is used for receiving the desulfurized natural gas and the medium-pressure steam and controlling the proportion of the desulfurized natural gas and the medium-pressure steam entering the methane reforming reaction unit.
Further, the feeding control unit is provided with a flowmeter and a regulating valve, and is used for controlling the proportion of the output desulfurized natural gas and the medium-pressure steam.
Further, the methane reforming reaction unit comprises a reformer and a gas-liquid separator, wherein the inlet of the reformer is communicated with the outlet of a gas pipeline controlled by the regulating valve, and the desulfurized natural gas and the medium-pressure steam react in the reformer to generate reformed gas; the outlet of the reformer is connected with the inlet of the gas-liquid separator.
Further, the outlet end of the gas-liquid separator is connected with the methanol synthesis unit, and the methanol synthesis unit synthesizes liquid methanol.
Further, the methanol synthesis unit comprises a synthesis reactor and a methanol product separation cooling device which are connected in sequence.
Further, the methanol steam reforming hydrogen production unit comprises a methanol reforming reactor device and a PSA purifying and separating device, wherein the methanol reforming reactor device outputs H 2 And CO 2 The method comprises the steps of carrying out a first treatment on the surface of the Said H 2 High purity H produced by PSA purification separation device 2 。
Further, the methanol steam reforming hydrogen production unit also comprises CO 2 Enrichment utilization device, the methanol reforming deviceCO output from the reactor unit 2 By the CO 2 High-purity CO generated by enrichment utilization device 2 The high purity CO 2 And collecting the natural gas hydrate used as a replacement for exploiting the natural gas hydrate.
The invention also provides a method for producing hydrogen by using the natural gas of the system, which comprises the following steps:
s1: the raw natural gas enters a natural gas desulfurization tower, and organic sulfur contained in the raw natural gas is converted into inorganic sulfur H through a desulfurization catalyst of the convection section 2 S, inorganic sulfur H is separated by the desulfurization tank 2 S, removing to obtain desulfurized natural gas; the desalted water is heated by a desalted water preheater of the steam generating unit and then enters a steam packet to generate steam, and medium-pressure steam is generated by a water separator;
s2: the medium-pressure water vapor and the desulfurized natural gas are mixed and then enter a reformer;
s3: the mixed desulfurized natural gas reacts with medium-pressure steam in a reformer to convert alkane in the natural gas into a mixture containing CO and H 2 Is converted into gas at high temperature;
s4: s3, separating condensate from the high-temperature converted gas in a gas-liquid separator of the methane reforming reaction unit after heat exchange and cooling to obtain synthesis gas;
s5: the synthesis gas in the step S4 enters a synthesis reactor of a methanol synthesis unit to synthesize methanol, the methanol is cooled, separated and purified by a methanol product separation cooling device to obtain liquid methanol, and unreacted synthesis gas is recycled;
s6: the liquid methanol in step S5 is passed through a methanol reforming reactor device to produce H 2 And CO 2 Separating to obtain high-purity H by a PSA purifying device 2 And high purity CO 2 。
Further, the desulfurization catalyst in step S1 is Fe 2 O 3 ZnO, mgO, caO or Na 2 One or more of O.
Still further, the desulfurization catalyst preferably employs ZnO.
Further, the total sulfur content of the desulfurized natural gas in the step S1 is less than 0.1ppm.
Further, the medium-pressure water vapor and the desulfurized natural gas in the step S2 are mixed according to the volume ratio of 1.2-2.
Further, the heat exchange process in step S4 specifically includes: the high-temperature converted gas at 820-840 ℃ after reaction enters a steam generating unit to generate medium-pressure steam, the temperature of the converted gas is reduced to 305-315 ℃, then the temperature of the converted gas is reduced to 200-220 ℃ after entering a convection section of a converting furnace to exchange heat with raw material natural gas, and the temperature of the converted gas after heat exchange is reduced to 90-110 ℃ after exchanging heat with a desalted water preheater of the steam generating unit.
Further, the hydrogen quality described in step S6 satisfies the following requirements: the purity of the hydrogen is more than 99.999, the content of CO is less than 0.2ppm, the content of sulfur is less than 1ppb, the dew point is less than-50 ℃, and the quality meets the hydrogen standard for proton exchange membrane fuel cells; said high purity H 2 The fuel cell can be directly used for filling a fuel cell automobile; said high purity CO 2 And collecting the natural gas hydrate used as a replacement for exploiting the natural gas hydrate.
Compared with the prior art, the invention has the following advantages:
(1) Methanol is used as a hydrogen carrier for transportation and distribution, so that the transportation efficiency is greatly improved, and the transportation cost is saved.
(2) The CO medium temperature conversion process of the traditional methane reforming hydrogen production reformer is reduced, and the equipment manufacturing cost and the catalyst cost are saved;
(3) And the heat is fully recycled in the hydrogen production process, so that the energy utilization efficiency is improved.
(4) CO produced by the end product 2 The natural gas hydrate is recycled and replaced to produce CH 4 At the same time as CO 2 Sealing and storing are carried out, and CO is realized 2 Zero emission.
Drawings
FIG. 1 is a process flow diagram of a natural gas hydrogen production system in accordance with an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is described in detail below with reference to the accompanying drawings and specific embodiments. The following examples are only some of the embodiments of the technical solution of the present invention, but not limiting the scope of the claims of the present invention, and any other embodiments obtained without inventive work are within the scope of the claims of the present invention.
A system for producing hydrogen from natural gas as shown in fig. 1, the system comprising:
the device comprises a natural gas desulfurization unit, a steam generation unit, a feed control unit, a methane reforming reaction unit, a methanol synthesis unit and a methanol steam reforming hydrogen production unit.
Natural gas enters a natural gas desulfurization tower of a desulfurization unit through a pipeline, and sulfur-containing compounds in the natural gas are removed to obtain desulfurized natural gas; the steam generating unit is used for vaporizing desalted water to obtain medium-pressure steam. The feeding control unit is used for receiving the desulfurized natural gas and the medium-pressure steam, and comprises a flowmeter and a regulating valve, and the mixing ratio of the desulfurized natural gas and the medium-pressure steam can be controlled. The mixed desulfurized natural gas and medium-pressure steam enter a reformer of a methane reforming reaction unit, and after the mixed desulfurized natural gas and medium-pressure steam react in the reformer, the mixed desulfurized natural gas and medium-pressure steam enter a gas-liquid separator for gas-liquid separation through heat exchange and cooling, so that synthesis gas is obtained. The synthesis gas enters a methanol synthesis reactor through a gas pipeline to synthesize methanol, and the liquid methanol is obtained through cooling, separating and purifying by a methanol product separating and cooling device. Liquid methanol is passed through a methanol reforming reactor apparatus to produce H 2 And CO 2 Separating by a PSA purifying and separating device to obtain high-purity H 2 And high purity CO 2 . High purity H after separation 2 Delivering the high-purity CO to a hydrogen using device through a pipeline, and separating the high-purity CO 2 Collected by the collecting device and sent to a methane hydrate exploitation well for methane replacement.
A method for producing hydrogen from natural gas, comprising the steps of:
step 1: the raw material natural gas enters a convection section of a natural gas desulfurization tower and is heated to 200 ℃, and then catalytic reaction is carried out through a desulfurization catalyst, so that organic sulfur such as thiophene, pyridine and the like in the raw material natural gas is converted into inorganic sulfur H 2 S, then H is separated by a zinc oxide desulfurization tank 2 S is removed, and desulfurized natural gas is obtained, wherein the total sulfur content in the desulfurized natural gas is less than 0.1ppm; desalted water is preheated to 95 ℃ by heat exchange of the conversion gas of the preheater, and then enters a steam drum of a steam generating unit to generate steam, and the steam is generated by a water separatorGenerating 3Mpa medium-pressure water vapor.
Step 2: and (2) regulating the flow of the medium-pressure steam and the desulfurized natural gas obtained in the step (1) in a feeding control unit through a regulating valve, mixing the medium-pressure steam and the desulfurized natural gas according to the volume ratio of 1.5, further preheating, and introducing the mixed medium-pressure steam and desulfurized natural gas into a reformer after the temperature reaches 560 ℃.
Step 3: the mixed desulfurization natural gas and water vapor in the step 2 react in a nickel-based catalyst bed layer of the reformer to generate high-temperature reformed gas CO and H 2 。
Step 4: the high-temperature converted gas at 830 ℃ after reaction enters a steam generating unit to generate 3.0Mpa medium-pressure steam, the temperature of the high-temperature converted gas is reduced to about 310 ℃ and then enters a convection section of a reformer to exchange heat with raw material natural gas, the temperature is reduced to 210 ℃, the temperature of the converted gas after heat exchange is reduced to 100 ℃ after heat exchange with a desalted water preheater of the steam generating unit, and condensate is separated from the cooled high-temperature converted gas in a gas-liquid separator of a reforming reaction unit to obtain synthesis gas.
Step 5: the synthesis gas enters a reactor of a methanol synthesis unit to synthesize methanol, methanol and unreacted synthesis gas components are cooled, separated and purified to obtain liquid methanol after reaction, and the unreacted synthesis gas components are recycled through a compressor.
Step 6: the liquid methanol is used as a carrier for storing hydrogen to be transported and distributed by a dangerous chemical tank car, and is transported to a hydrogen using place to generate H by a methanol reforming reactor device 2 And CO 2 H produced 2 And CO 2 Further separating by a PSA purifying device to obtain high-purity H 2 And CO 2 The adsorbent of the PSA purifying device is assembled by adopting alumina and molecular sieve layers with different specifications, the purity of the purified hydrogen is more than 99.999, the CO content is less than 0.2ppm, the sulfur content is less than 1ppb, the dew point is less than-50 ℃, the quality of the adsorbent meets the hydrogen standard for proton exchange membrane fuel cells, and the high-purity hydrogen can be directly used for filling fuel cell automobiles or other purposes; separating and purifying the CO 2 After being collected, the gas hydrate is conveyed to a natural gas hydrate exploitation well, and CO 2 CH used in replacement exploitation of natural gas hydrate 4 In the process of extracting CH 4 Is stable to CO sequestration at the same time 2 Thereby realizing CO 2 Zero emission.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A system for producing hydrogen from natural gas is characterized by comprising a feeding unit, a feeding control unit, a methane reforming reaction unit, a methanol synthesis unit and a device for producing high-purity H, which are sequentially connected 2 And high purity CO 2 Is a methanol steam reforming hydrogen production unit;
the feeding unit comprises a natural gas desulfurization unit and a steam generation unit;
the natural gas desulfurization unit is used for removing sulfur-containing compounds in the raw natural gas to obtain desulfurized natural gas;
the steam generating unit is used for purifying desalted water to obtain medium-pressure water steam;
the feeding control unit is used for receiving the desulfurized natural gas and the medium-pressure steam and controlling the proportion of the desulfurized natural gas and the medium-pressure steam entering the methane reforming reaction unit;
the feeding control unit is provided with a flowmeter and a regulating valve and is used for controlling the proportion of the output desulfurization natural gas and the medium-pressure steam;
the methane reforming reaction unit comprises a reformer and a gas-liquid separator; the inlet of the reformer is communicated with the outlet of the gas pipeline controlled by the regulating valve, and the desulfurized natural gas and the medium-pressure steam in the reformer react to generate reformed gas; the outlet of the reformer is connected with the inlet of the gas-liquid separator;
the outlet end of the gas-liquid separator is connected with the methanol synthesis unit, and the methanol synthesis unit synthesizes liquid methanol;
the methanol steam reforming hydrogen production unit comprises a methanol reforming reactor device and a PSA purifying and separating device, and the methanol reforming reactor device outputs H 2 And CO 2 The method comprises the steps of carrying out a first treatment on the surface of the Said H 2 High purity H produced by PSA purification separation device 2 。
2. The system for producing hydrogen from natural gas according to claim 1, wherein the natural gas desulfurization unit is a natural gas desulfurization tower, and the natural gas desulfurization tower is divided into a convection section and a zinc oxide desulfurization tank.
3. A system for producing hydrogen from natural gas as claimed in claim 1 wherein said steam generating unit comprises a desalinated water preheater, a drum and a water separator; desalted water enters the steam drum to produce steam after being heated by the desalted water preheater, and medium-pressure steam is produced by the water separator.
4. A system for producing hydrogen from natural gas as in claim 1 wherein said methanol synthesis unit comprises a synthesis reactor and a methanol product separation cooling means connected in sequence.
5. A system for producing hydrogen from natural gas as in claim 1 wherein said methanol steam reforming hydrogen generation unit further comprises CO 2 Enrichment utilization device, CO output by the methanol reforming reactor device 2 By the CO 2 High-purity CO generated by enrichment utilization device 2 The high purity CO 2 And collecting the natural gas hydrate used as a replacement for exploiting the natural gas hydrate.
6. A method of producing hydrogen from natural gas using the system of any one of claims 1-5, comprising the steps of:
s1: the raw material natural gas enters the natural gas desulfurization tower, and desulfurized natural gas is obtained through the natural gas desulfurization tower; the desalted water is heated by a desalted water preheater of the steam generating unit and then enters a steam packet to generate steam, and medium-pressure steam is generated by a water separator;
s2: the medium-pressure water vapor and the desulfurized natural gas are mixed and then enter the reformer;
s3: the mixed desulfurized natural gas and the medium-pressure steam react in the reformer to convert alkane in the desulfurized natural gas into a mixture containing CO and H 2 Is converted into gas at high temperature;
s4: s3, cooling the high-temperature converted gas through heat exchange, and separating condensate in a gas-liquid separator of the methane reforming reaction unit to obtain synthesis gas;
s5: step S4, the synthesis gas enters a synthesis reactor to synthesize methanol, and the methanol is cooled, separated and purified by a methanol product separation cooling device to obtain liquid methanol;
s6: the liquid methanol is passed through a methanol reforming reactor device to produce H 2 And CO 2 Separating by a PSA purifying and separating device to obtain high-purity H 2 And high purity CO 2 。
7. A method for producing hydrogen from natural gas as claimed in claim 6, wherein the desulfurization catalyst in step S1 is Fe 2 O 3 ZnO, mgO, caO or Na 2 One or more of O; the desulfurization tank is a zinc oxide desulfurization tank; the total sulfur content of the desulfurized natural gas is less than 0.1ppm.
8. A method for producing hydrogen from natural gas as claimed in claim 6, wherein the medium pressure steam and the desulphurised natural gas of step S2 are mixed in a volume ratio of 1.2-2.
9. The method for producing hydrogen from natural gas according to claim 6, wherein the heat exchanging process in step S4 specifically comprises: the high-temperature converted gas at 820-840 ℃ after reaction enters a steam generating unit to generate medium-pressure steam, the temperature of the high-temperature converted gas is reduced by 305-315 ℃, then enters a convection section of a converter to exchange heat with natural gas, the temperature is reduced to 200-220 ℃, and the temperature of the high-temperature converted gas after heat exchange is reduced to 90-110 ℃ after heat exchange with a desalted water preheater of the steam generating unit.
10. A method for producing hydrogen from natural gas as claimed in claim 6, wherein the high purity H of step S6 2 The quality meets the following requirements: the purity of the hydrogen is more than 99.999, the content of CO is less than 0.2ppm, the content of sulfur is less than 1ppb, the dew point is less than-50 ℃, and the quality meets the hydrogen standard for proton exchange membrane fuel cells; high purity CO as described in step S6 2 After collection, the mixture is conveyed to a natural gas hydrate exploitation well, and CO is recycled in the methanol reforming reactor device 2 Displacing CH in natural gas hydrate 4 In the process of extracting CH 4 Is stable to CO sequestration at the same time 2 Realize CO 2 Zero emission.
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