CN114716300A - Method for co-production of alcohol and hydrogen by chemical chain conversion of natural gas hydrate - Google Patents
Method for co-production of alcohol and hydrogen by chemical chain conversion of natural gas hydrate Download PDFInfo
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- CN114716300A CN114716300A CN202210368923.7A CN202210368923A CN114716300A CN 114716300 A CN114716300 A CN 114716300A CN 202210368923 A CN202210368923 A CN 202210368923A CN 114716300 A CN114716300 A CN 114716300A
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- Prior art keywords
- natural gas
- gas hydrate
- oxygen carrier
- hydrogen
- chemical
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- 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 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- 239000000126 substance Substances 0.000 title claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000002407 reforming Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 230000008929 regeneration Effects 0.000 claims abstract description 4
- 238000011069 regeneration method Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 239000003345 natural gas Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 5
- -1 natural gas hydrates Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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- C—CHEMISTRY; METALLURGY
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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
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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Abstract
The invention discloses a method for co-producing alcohol hydrogen by natural gas hydrate chemical chain conversion. The method converts gas-liquid two-phase composition of the natural gas hydrate into methanol and high-purity hydrogen through the steps of oxygen carrier preparation, chemical chain reforming, methanol synthesis, chemical chain hydrogen production, oxygen carrier regeneration and the like, thereby realizing high-value utilization of the natural gas hydrate and high comprehensive utilization efficiency of resources. The technology does not need the process of preparing an oxidation medium in the traditional methanol synthesis process, has the advantages of simple process, low cost, cleanness, environmental protection and good economic benefit of the product, partially solves the problem of difficult storage and transportation of the traditional natural gas hydrate, and has wide application prospect.
Description
Technical Field
The invention relates to the fields of clean fuel conversion, functional materials and environmental protection, in particular to a method for co-producing alcohol hydrogen by chemical chain conversion of natural gas hydrate.
Background
The natural gas hydrate is an ice-like crystalline compound with a cage-like structure formed under the conditions of low temperature and high pressure, is mainly produced in submarine sediments and land permafrost zones, and has the properties of non-stoichiometry, phase equilibrium property, self-protection property and the like. The natural gas hydrate contains huge natural gas resources of 1m3The natural gas hydrate is equivalent to 160-180 m3(Standard) natural gas, from which estimated about 1.8X 10 gas hydrate deposits are stored in global natural gas hydrate deposits16～2.1×1016m3Natural gas resources, the total amount of which is 2 times of the total amount of coal, oil and natural gas resources which have been ascertained worldwide. Research shows that the total resource amount of natural gas hydrate in south China sea is equal to 643.5-772.2 million tons of oil equivalent, and is equal to more than half of the total resource amount of onshore oil and gas in China. The great development of the development and utilization technology of the natural gas hydrate has great significance for relieving the energy supply crisis of China, protecting the ecological environment and reducing the carbon emission.
Currently, the research aiming at the natural gas hydrate mainly focuses on the exploration and exploitation stages. The Chinese invention patent CN202111352922.5 discloses an active excitation type precise evaluation device for vertical content distribution of a submarine hydrate reservoir, which realizes precise evaluation of the vertical content distribution of the submarine hydrate reservoir through a gas collection mechanism, a screw-in long sleeve and a plurality of groups of thermal excitation mechanisms. The invention patent CN201510325300.1 discloses a method and a device for exploiting seabed surface layer natural gas hydrate by using ultrasonic waves, wherein ultrasonic waves emitted by an ultrasonic generator drive a crushing head to vibrate and react with the natural gas hydrate to crush the natural gas hydrate into particle slurry, and then natural gas is collected and decomposed to realize continuous exploitation. The Chinese invention patent CN201810226738.8 discloses a method for exploiting marine natural gas hydrate by utilizing a coupling freezing wall to reduce pressure, which realizes the exploitation of natural gas hydrate by leading natural gas hydrate into a refrigeration pipe network to form the freezing wall. The invention of China patent CN201810346002.4 discloses a method for exploiting natural gas hydrate by using an electromagnetic heating mode, which adopts a jet flow mode to inject drilling fluid containing iron powder into a natural gas hydrate reservoir, converts alternating current into high-frequency current by using a high-frequency electric heating principle to generate a high-frequency magnetic field, and when magnetic lines in the magnetic field act on the iron powder through an insulated natural gas hydrate reservoir, the magnetic lines are cut to generate eddy current to heat the iron powder, thereby achieving the purpose of heating the natural gas hydrate reservoir and realizing the thermal excitation exploitation of the natural gas hydrate reservoir. In addition, the current natural gas hydrate exploitation methods also include a depressurization method, a chemical reagent injection method, a gas replacement method and the like.
The patent relates to the processes of detection, exploitation and the like of the natural gas hydrate, but does not relate to the subsequent resource utilization process of the natural gas hydrate. In 2017, China continuously tries to produce natural gas hydrates in the sea area of Shenhu in south China sea for 60 days, and multiple major breakthrough achievements of longest continuous gas production time, largest total gas production amount and the like are obtained, which represent the highest level in the world at present. Therefore, the development of the clean and high-value utilization of the natural gas hydrate is significant to China. On the basis, the invention provides a method for co-producing alcohol and hydrogen by natural gas hydrate chemical chain conversion, which can solve the problem of subsequent clean high-value utilization of natural gas hydrate.
Disclosure of Invention
The invention aims to provide a method for co-producing alcohol hydrogen by chemical chain conversion of natural gas hydrate.
The technical scheme adopted by the invention is as follows:
a method for co-producing alcohol hydrogen by natural gas hydrate chemical chain conversion comprises the following steps:
(1) the natural gas hydrate is released by stage decompression to obtain a gas phase product and a liquid phase product;
(2) preparing synthesis gas from the gas-phase product, an oxygen carrier and an auxiliary agent in a reactor through chemical chain reforming, wherein the reaction temperature is 750-1000 ℃, and the reaction time is 25-35 min;
(3) reacting the synthesis gas with a synthetic methanol catalyst to prepare methanol, wherein the reaction temperature is 200-290 ℃, the pressure is 3-8 Mpa, and the reaction time is 0.5-3 s;
(4) reacting the liquid-phase product with the oxygen carrier subjected to chemical chain reforming to prepare hydrogen, wherein the reaction temperature is 750-1000 ℃, and the reaction time is 20-35 min;
(5) the oxygen carrier after hydrogen production reaction is regenerated by air to recover lattice oxygen in the oxygen carrier.
In the step (1), the step-by-step pressure reduction is carried out at 6-1 MPa, and the temperature range is-160-normal temperature.
In the step (2), the oxygen carrier is selected from at least one of iron-based, manganese-based, copper-based, cobalt-based, zinc-based and nickel-based. The oxygen carrier also contains Al2O3CaO or SiO2As a support. The oxygen carrierThe preparation method comprises the following steps: preparing a precursor by adopting wet chemical synthesis, chemical coprecipitation, sol-gel or chemical self-assembly, reacting at the high temperature of 850-1000 ℃ for 3-5 h, crushing and screening to obtain the nano-composite material with the particle size of 60-80 meshes.
In the step (2), the auxiliary agent is at least one selected from Ce, Rb, Li and Na.
And (2) introducing a small amount of water vapor to inhibit carbon deposition on the surface of the oxygen carrier.
In the step (2), the gas phase product of the natural gas hydrate and oxygen carrier lattice oxygen are subjected to partial oxidation reaction to generate H2CO-based synthesis gas, by introducing steam to suppress surface carbon deposition while regulating product gas H2the/CO ratio is increased by introducing part of Ce, Rb, Li, Na and the like to strengthen the oxygen transfer of reaction lattices and improve the reaction rate. Gaseous product H2The ratio/CO ranges between 1.86 and 2.15.
In the step (3), the methanol synthesis catalyst consists of two parts, namely an active component and an auxiliary agent, wherein the active component is selected from at least one of copper base, manganese base, zinc base, aluminum base, molybdenum base and palladium base, and the auxiliary agent is selected from at least one of K, Ca, Na, Mg and Si. The preparation method of the methanol catalyst comprises the steps of respectively preparing active components and an auxiliary agent into a solution, carrying out chemical synthesis and crystallization drying under the conditions of constant temperature, stirring and constant pH value to obtain a catalyst precursor, and then calcining to obtain the required catalyst.
In the step (4), the reaction temperature zone for oxygen carrier regeneration is 850-1000 ℃, and the reaction time is 70-90 min. The reaction heat generated in the regeneration process provides heat for the chemical-looping reforming and chemical-looping hydrogen production processes through oxygen carrier circulation, and the part with insufficient heat of the whole system supplies heat by burning the tail gas of the methanol synthesis unit in the step (3).
The invention has the following beneficial effects:
1. the technology for co-producing alcohol and hydrogen through natural gas hydrate chemical chain conversion provided by the invention solves the problem of high-value utilization of natural gas hydrate, and the method for preparing the natural gas hydrate into the liquid methanol breaks through the bottleneck that the traditional natural gas hydrate is difficult to store and transport, and has the advantages of simplicity and convenience in operation, low cost, cleanness, high efficiency and good economic benefit.
2. The method simultaneously utilizes gas-liquid two-phase substances in the natural gas hydrate to prepare the methanol and the high-purity hydrogen, has high comprehensive utilization efficiency of resources, does not need the process of preparing an oxidation medium in the traditional methanol synthesis process, has simple process, and has wide application scenes of the prepared methanol and high-purity hydrogen products
Drawings
FIG. 1 is a flow diagram of chemical chain conversion and alcohol hydrogen co-production of natural gas hydrates.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
The methods for preparing the composite oxygen carrier and the synthetic methanol catalyst in the following examples are all conventional technical methods in the field.
Example 1
The embodiment discloses a method for co-producing alcohol and hydrogen by natural gas hydrate chemical chain conversion, which comprises the following steps:
(1) the natural gas hydrate is released into a gas phase product and a liquid phase product through 6MPa, 2MPa and 1MPa three-stage grading decompression (the temperature range is minus 160 ℃ to normal temperature), so that the heat loss is reduced, and the gas-liquid separation is realized.
(2) A Fe/Ni/Al-based composite oxygen carrier precursor is constructed by a chemical precipitation method, calcined at 1000 ℃ for 3 hours, and then crushed and sieved to prepare oxygen carrier particles with the particle size range of 60-80 meshes.
(3) And (3) carrying out a chemical chain reforming process on the gas-phase product obtained in the step (1) and the Fe/Ni/Al (the atomic ratio is 0.6/0.2/0.2) based composite oxygen carrier obtained in the step (2) to prepare the synthesis gas, wherein the reaction temperature is 850 ℃, and the reaction retention time is 25 minutes. The gas phase product of the natural gas hydrate and oxygen carrier lattice oxygen are subjected to partial oxidation reaction to generate H2And synthetic gas mainly containing CO, introducing proper amount of water vapor in the reaction process to inhibit carbon deposition on the surface of the oxygen carrier and simultaneously regulating product gas H2The ratio of/CO.
(4) Preparing Cu/Zn/Al-Na methanol synthesizing catalyst by using Cu (NO)3)2、ZnNO3、Al(NO3)3Preparing mixed liquor according to Cu/Zn/Al as 0.8/1/0.2 atomic ratio, adopting Na2CO3Preparing a solution by taking the Na-containing catalyst as an auxiliary agent, dropwise adding the solution into a Cu/Zn/Al mixed solution under the stirring condition, keeping the pH value between 7.8 and 8.2, aging at 70 ℃ for 3 hours, filtering the obtained precipitate, washing for 3 times, drying at 105 ℃ for 12 hours, calcining at 300 ℃ for 5 hours, and forming to obtain the required catalyst, wherein the molar content of Na atoms in the catalyst is 0.5 to 10 percent, and the catalytic particle size is 2 to 4 mm.
(5) And (4) reacting the synthesis gas obtained in the step (3) with the Cu/Zn/Al-Na methanol synthesis catalyst prepared in the step (4) to prepare methanol, wherein the reaction temperature is 280 ℃, the pressure is 5Mpa, and the reaction time is 1 s.
(6) And (2) reacting the liquid-phase product obtained in the step (1) with the oxygen carrier subjected to chemical chain reforming to prepare hydrogen, wherein the reaction temperature is 800 ℃, and the reaction time is 25 minutes.
(7) Oxidation of oxygen carrier: and regenerating the oxygen carrier after hydrogen production reaction by air, wherein the reaction temperature is 900 ℃, and the reaction time is 80 minutes. The generated reaction heat provides heat for the chemical-looping reforming and chemical-looping hydrogen production processes through oxygen carrier circulation, and the part with insufficient heat of the whole system supplies heat through the tail gas of the methanol synthesis unit in the combustion step (5).
The flow chart of the chemical chain conversion and alcohol hydrogen co-production of the natural gas hydrate is shown in figure 1.
As a result, the gas phase product of the chemical-looping reforming process has a relative composition H2 54.39％，CO 27.11％,CO28.96％,CH4 6.38％，H2The ratio of/CO was 2.01 and the methane conversion was 93.62%. In the process of synthesizing the methanol, the space-time yield (initial activity) of the methanol is over 1.15g/mL.h, and the selectivity of the methanol is 91.17%. Chemical looping hydrogen production process H2Yield 1.08L/g, H2The concentration was 99.26%.
Example 2
Since the method for co-producing alcohol and hydrogen by natural gas hydrate chemical chain transformation is the same as that in example 1, the detailed description is omitted, only the implementation conditions are listed in table 1, and the implementation results are shown in table 1.
Table 1 example of chemical chain conversion of natural gas hydrates to co-produce alcohol and hydrogen
In the embodiment, a chemical chain self-assembly method is adopted to construct the Fe/Cu/Si-based composite oxygen carrier, and the Fe/Cu/Si-based composite oxygen carrier is calcined at 950 ℃ for 4 hours, and then is crushed and sieved to prepare oxygen carrier particles with the particle size range of 60-80 meshes. The preparation method of the methanol synthesis catalyst is the same as that of the example (1), and the active components and the auxiliary agents used are indicated in the table.
Example 3
Since the method for co-producing high-purity hydrogen by using olefin prepared by natural gas hydrate chemical looping is the same as that in example 1, the detailed description is omitted, and only the implementation conditions and the implementation results are listed in table 2, as shown in table 2.
Table 2 example of chemical chain conversion of natural gas hydrates to co-produce alcohol and hydrogen
The difference between the embodiment 1 and the embodiment 2 lies in that the oxygen carrier, the reaction temperature, the methanol synthesis catalyst and the reaction auxiliary agent are different, the methane conversion efficiency in the chemical chain reforming stage in the embodiment 2 is improved, the methanol selectivity in the methanol synthesis stage is good, and the hydrogen product concentration in the hydrogen production stage is reduced. In the embodiment 3, the Fe/Mn/Ca oxygen carrier and the Ce auxiliary agent have better carbon deposition resistance, the reaction effect in the hydrogen production stage is better, and the yield and the selectivity of the methanol synthesized by the corresponding Cu/Mo/Al/Pd-K/Mg/Si catalyst are higher.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. A method for co-producing alcohol hydrogen by natural gas hydrate chemical chain conversion is characterized by comprising the following steps:
(1) the natural gas hydrate is released by stage decompression to obtain a gas phase product and a liquid phase product;
(2) preparing synthesis gas from the gas-phase product, an oxygen carrier and an auxiliary agent in a reactor through chemical chain reforming, wherein the reaction temperature is 750-1000 ℃, and the reaction time is 25-35 min;
(3) the synthesis gas reacts with a synthetic methanol catalyst to prepare methanol, the reaction temperature is 200-290 ℃, the pressure is 3-8 Mpa, and the reaction time is 0.5-3 s;
(4) reacting the liquid-phase product with the oxygen carrier subjected to chemical chain reforming to prepare hydrogen, wherein the reaction temperature is 750-1000 ℃, and the reaction time is 20-35 min;
(5) the oxygen carrier after hydrogen production reaction is regenerated by air to recover lattice oxygen in the oxygen carrier.
2. The method for preparing olefin and co-producing high-purity hydrogen by using the natural gas hydrate chemical chain as claimed in claim 1, wherein in the step (1), the step-by-step pressure reduction is carried out at 6-1 MPa, and the temperature range is-160 ℃ to normal temperature.
3. The method for preparing olefin and co-producing high-purity hydrogen by using the natural gas hydrate chemical chain as claimed in claim 1, wherein in the step (2), the oxygen carrier is selected from at least one of iron-based, manganese-based, copper-based, cobalt-based, zinc-based and nickel-based.
4. The method of claim 3, wherein the oxygen carrier further comprises Al2O3CaO or SiO2As a support.
5. The method for preparing olefin and co-producing high-purity hydrogen by using the natural gas hydrate chemical chain as claimed in claim 4, wherein the preparation method of the oxygen carrier is as follows: preparing a precursor by adopting a wet chemical synthesis method, a chemical coprecipitation method, a sol-gel method or a chemical self-assembly method, reacting at the high temperature of 850-1000 ℃ for 3-5 h, crushing and screening to obtain the nano-composite material with the particle size of 60-80 meshes.
6. The method for preparing olefin and co-producing high-purity hydrogen by using natural gas hydrate chemical chains as claimed in claim 1, wherein in the step (2), the auxiliary agent is at least one selected from Ce, Rb, Li and Na.
7. The method for co-production of olefins and high purity hydrogen by natural gas hydrate chemical looping according to claim 1,
and (2) introducing a small amount of water vapor to inhibit carbon deposition on the surface of the oxygen carrier.
8. The method for co-production of olefins and high purity hydrogen by natural gas hydrate chemical looping according to claim 1,
in the step (3), the methanol synthesis catalyst consists of an active component and an auxiliary agent, wherein the active component is selected from at least one of copper base, manganese base, zinc base, aluminum base, molybdenum base and palladium base, and the auxiliary agent is selected from at least one of K, Ca, Na, Mg and Si.
9. The method for co-production of olefins and high purity hydrogen by natural gas hydrate chemical looping according to claim 1,
in the step (4), the reaction temperature zone for oxygen carrier regeneration is 850-1000 ℃, and the reaction time is 70-90 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080043161A (en) * | 2006-11-13 | 2008-05-16 | 고려대학교 산학협력단 | Supported catalyst for producing hydrogen gas by steam reforming reaction of liquefied natural gas, method for preparing the supported catalyst and method for producing hydrogen gas using the supported catalyst |
| WO2009051353A2 (en) * | 2007-10-15 | 2009-04-23 | Korea Research Institute Of Chemical Technology | Method of direct synthesis of light hydrocarbons from natural gas |
| CN101679168A (en) * | 2007-06-21 | 2010-03-24 | 南加州大学 | Conversion of carbon dioxide to dimethyl ether using bi-reforming of methane or natural gas |
| CN110876938A (en) * | 2019-11-05 | 2020-03-13 | 天津大学 | Perovskite type composite metal oxide oxygen carrier and preparation method and application thereof |
-
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- 2022-04-08 CN CN202210368923.7A patent/CN114716300B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080043161A (en) * | 2006-11-13 | 2008-05-16 | 고려대학교 산학협력단 | Supported catalyst for producing hydrogen gas by steam reforming reaction of liquefied natural gas, method for preparing the supported catalyst and method for producing hydrogen gas using the supported catalyst |
| CN101679168A (en) * | 2007-06-21 | 2010-03-24 | 南加州大学 | Conversion of carbon dioxide to dimethyl ether using bi-reforming of methane or natural gas |
| CN101730657A (en) * | 2007-06-21 | 2010-06-09 | 南加州大学 | Use the conversion of two carbon dioxide to methanol that transform of methane or Sweet natural gas |
| WO2009051353A2 (en) * | 2007-10-15 | 2009-04-23 | Korea Research Institute Of Chemical Technology | Method of direct synthesis of light hydrocarbons from natural gas |
| CN110876938A (en) * | 2019-11-05 | 2020-03-13 | 天津大学 | Perovskite type composite metal oxide oxygen carrier and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 唐翠萍 等: "天然气水合物新型动力学抑制剂抑制性能研究", 《西安交通大学学报》, vol. 42, no. 3, 31 March 2008 (2008-03-31), pages 333 - 337 * |
| 黄振 等: "基于晶格氧的甲烷化学链重整制合成气", 《化学进展》, vol. 24, no. 8, 31 August 2012 (2012-08-31), pages 1599 - 1609 * |
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