CN109761192A - A kind of producing hydrogen by using chemical chain - Google Patents
A kind of producing hydrogen by using chemical chain Download PDFInfo
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- CN109761192A CN109761192A CN201910173435.9A CN201910173435A CN109761192A CN 109761192 A CN109761192 A CN 109761192A CN 201910173435 A CN201910173435 A CN 201910173435A CN 109761192 A CN109761192 A CN 109761192A
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- gas
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- oxygen carrier
- carrier body
- light hydrocarbon
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 131
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 131
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000000126 substance Substances 0.000 title claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 72
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 68
- 239000001301 oxygen Substances 0.000 claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 31
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 25
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 9
- 239000003546 flue gas Substances 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 238000002347 injection Methods 0.000 claims abstract description 8
- 239000007924 injection Substances 0.000 claims abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000007423 decrease Effects 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 4
- 230000003247 decreasing effect Effects 0.000 claims abstract description 3
- 239000003245 coal Substances 0.000 claims description 26
- 239000003345 natural gas Substances 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000006298 dechlorination reaction Methods 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 44
- 230000008569 process Effects 0.000 abstract description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- 239000000446 fuel Substances 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 13
- 238000002309 gasification Methods 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000000629 steam reforming Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
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- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- -1 nickel Hydrocarbons Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
A kind of producing hydrogen by using chemical chain, the following steps are included: (1) is to being filled with Fe2O3It is passed through the light hydrocarbon feedstocks gas rich in methane in the reactor of oxygen carrier body catalyst, under the action of 0.01-0.35MPa, 600-900 DEG C and oxygen carrier body catalyst, is oxidized light hydrocarbon feedstocks gas and generates CO2And H2O；(2) when the conversion ratio of light hydrocarbon feedstocks gas is decreased obviously, the charging of light hydrocarbon feedstocks gas is cut off, reactor is injected water into, under the conditions of 0.01-0.35MPa, 600-900 DEG C, it decomposes water under the action of oxygen carrier body catalyst and generates hydrogen, while oxygen carrier body catalyst being made gradually to be oxidized to Fe3O4；(3) when the decline of the gas production of above-mentioned steps (2) and basic no hydrogen output, stop water filling, air is injected into reactor, by adjusting air capacity, it controls the temperature of oxygen carrier catalyst bed in 600-900 DEG C, oxygen carrier body catalyst is further aoxidized；After the oxygen content in reactor outlet flue gas is basically unchanged, stop air injection.Process simplification small investment, takes up little area, facilitates implementation.
Description
Technical field
The present invention relates to light hydrocarbon feedstocks hydrogen producing technology fields, are a kind of to prepare hydrogen using chemical chain technology more specifically
The process of gas.
Background technique
Hydrogen is widely used in the industrial production.Hydrogen is used to manufacture ammonium hydroxide and chemical fertilizer together with other materials, while
It is applied in gasoline refinery practice, glass polishing, gold welding, meteorological balloon detection and food industry.And liquified hydrogen can be made
For rocket fuel.
Hydrogen utilization form is more, both can generate thermal energy by burning, generate mechanical work in Thermal Motor, and can be with
It is used for fuel cell as energy and material, or is converted into solid state hydrogen as structural material.Coal and petroleum is replaced to make internal combustion engine with hydrogen
Fuel is not required to make existing technical equipment great transformation, and present internal combustion engine certain modification can be used.
The major advantage of Hydrogen Energy has: combustion heat value is high, and the calorific capacity of hydrogen is all fossil fuels, chemical industry combustion in addition to nuclear fuel
It is highest in material and bio-fuel, it is 142,351kJ/kg, the heat that the hydrogen for the equal quality that burns generates, about the 3 of gasoline times,
3.9 times of alcohol, 4.5 times of coke.Hydrogen burning performance is good, lights fastly, there is extensive flammable range when mixing with air, and
Burning point is high, and burning velocity is fast.Hydrogen itself is nontoxic, and the product of burning is water, is the energy most clean in the world.With other fuel phases
It is most cleaned when than hydrogen burning, such as carbon monoxide, carbon dioxide, nytron will not be generated in addition to generating water and a small amount of ammonia
The environmentally harmful polluters such as object, leaded object and dust particles, a small amount of ammonia will not pollute ring by proper treatment
Border, and the water generated that burns can also continue to hydrogen manufacturing, be repeatedly circulated.
Application of the Hydrogen Energy on car, truck, bus, taxi, motorcycle and business ship has become focus.
It replaces gasoline to make the fuel of automobile engine with hydrogen, has been subjected to the examination of many motor corporations such as Japan, the U.S., Germany, China
It tests, it was demonstrated that hydrogen is feasible as the technology of motor vehicle fuel.
The hydrogen producing technology of existing maturation mainly has water electrolysis hydrogen producing, coal hydrogen manufacturing, lighter hydrocarbons (natural gas) vapor reforming hydrogen production
Etc. technologies.
Water electrolysis hydrogen producing is a kind of conveniently method.It is passed through in the electrolytic cell full of potassium hydroxide or sodium hydroxide
Electrochemical reaction occurs on the electrode for direct current, hydrone, resolves into hydrogen and oxygen.Water electrolysis hydrogen production technology has obtained work
Industry application, there are about 4% hydrogen sources in electrolysis water in the whole world.Traditional alkaline aqueous solution electrolytic hydrogen production because hydrogen production efficiency is low,
Electric energy loss is big and limits its scope of application.The technology of various countries slightly has difference, and power consumption is in 4.3-4.9kWh/Nm3H2Range.
Researcher has carried out a large amount of research work to improve hydrogen production efficiency, research contents mainly include low overpotential electrode material,
Proton exchange membrane water electrolyzer and high temperature electrolysis of steam.In addition, present new technology research and development concentrate on light for water hydrogen manufacturing path
Water hydrogen manufacturing is catalytically decomposed, directly thermally decomposes water hydrogen manufacturing, the several approach of thermochemical cycles water-splitting hydrogen production.
Due to water electrolysis hydrogen production higher cost, so hydrogen gas production, which has 90% or more, to be produced by fossil fuel.In mine
In object fuel, coal resources relative abundance, hydrogen production from coal gasification was once main hydrogen production process.It is special with the rise of petroleum industry
It is not the appearance of natural gas steam reforming hydrogen production process, the developing state gradually slowed down is presented in hydrogen production from coal gasification technology.Coal gasification
Hydrogen manufacturing mainly includes three processes: gas making reaction, the purifying and compression of water gas shift reaction, hydrogen.
Coal gasification is an endothermic reaction, reacts institute's calorific requirement by oxygen and reacts offer with oxidation of coal.Coal gasifying process has
It is a variety of, such as Koppers-Totzek method, Texco method, Lurgi method, vapour iron processes, fluidized bed process.It has also researched and developed in recent years more
The new process of kind coal gasification, the hydrogen manufacturing such as combined using the conducting coating hydrogen manufacturing new process of coal gasification, coal gasification with high-temperature electrolysis
Technique, thermal cracking process for making hydrogen of coal etc..During Koppers-Totzek method hydrogen manufacturing, coal slirne under normal pressure rapidly by
Oxygen and steam oxidation, gained synthesis gas typical case group become 29%H2, 60%CO, 10%CO2, 1%N2+Ar.It is come out from vaporizer
High-temperature synthesis gas be washed with water after Waste Heat Recovery except deashing, while obtaining steam needed for conversion reaction.Then pass through
Compression, transformation and purification for gas, obtaining pressure is the hydrogen of 2.8MPa, purity greater than 97.5%.Hydrogen compression and synthesis air pressure
Contracting is the same, requires consumption energy.And the hydrogen that hydrogen users need has certain pressure, therefore carries out coal under a certain pressure
Gasification can be more effective.Since the material of coal gasification processing is solid, a large amount of ash contents are removed, therefore process is complicated.Handle solid
Waste material has larger impact to producing cost.The expenditure pattern of Texco hydrogen production process substantially cost of raw and processed materials accounts for 25.8%, equipment
Investment cost accounts for 54.6%, and operation is added with administration fee accounts for 19.6%.The producing cost of hydrogen production from coal gasification, which depends primarily on, to be set
Standby investment cost, the followed by price of coal.In general, coal generating gas equipment component investment cost accounts for entire hydrogen production from coal gasification factory
The major part of equipment investment expense.Since the equipment investment of hydrogen production from coal gasification technology is high, needs to handle solid material, produce
Higher cost, so hydrogen production from coal gasification development trend is slow.
For a long time, natural gas steam reforming is always most economical hydrogen production process.The day obtained through underground mining
Right gas contains multicomponent, and main component is methane, and other ingredients have water, other hydrocarbons, hydrogen sulfide, nitrogen and carbon oxygen
Compound.Therefore, before natural gas enters pipe network, the impurity such as sulfide to be removed.Natural gas into pipe network generally contains methane
75%~85% and some low-carbon saturated hydrocarbons, carbon dioxide etc..The reaction of methane on nickel catalysts is as follows:
The carbon monoxide and steam reaction generated is reacted, realizes the further preparation of hydrogen, is reacted as follows:
Industrial methane steam reforming process uses Raney nickel, and 750~920 DEG C of operation temperature, operating pressure 2.17-
2.86MPa.The methane steam reforming process of early stage operates under normal pressure, but higher pressure can improve process efficiency.
Reaction is heat absorption, and heat is supplied by combustion chambers burn methane.Methane steam reforming synthesis gas obtained becomes by high/low temperature
Reaction general-carbon oxide conversion is changed into carbon dioxide and additional hydrogen.Methane steam reforming process analyses carbon, reaction in order to prevent
Excessive water vapour is used in charging, industrial process steam/hydrocarbons ratio is 3~5.
Natural gas hydrogen preparation technique is made of four big units, and mainly raw material gas disposal, steam conversion, CO transformation and hydrogen mention
Pure four units, these units play the role of in the hydrogen production process respectively it is different, constitute natural gas hydrogen preparation technology.
Unstripped gas processing unit: raw material gas disposal is first stage and initial stage for natural gas hydrogen preparation,
The quality of this phase process directly decides the quality of natural gas hydrogen preparation, this stage is mainly desulfurization, using some desulfurization
Agent carries out the desulfurization of Primordial Qi, because material gas quantity is bigger, this just needs to compress it, selects bigger centrifugal pressure
Contracting machine is proper, after distilling natural gas, needs to carry out sulfur removal technology before melting down.
Steam conversion unit: it is a more complicated stage that steam, which converts this unit, and vapor is oxidant, in nickel
Hydrocarbons are converted under the action of catalyst, obtain the conversion gas of hydrogen making.It is substantially in this stage using high temperature
The technological parameter of conversion and relatively low water charcoal ratio is arranged, and can preferably economize on resources, improve the economic benefit of enterprise.
CO converter unit: contain a certain amount of CO in the unstripped gas that second unit is sent, in the transformed of this unit
In journey under the effect of the catalyst, make CO and steam reaction and generate CO2And H2.In this unit mainly with high temperature (350
~400 DEG C) and middle low temperature (being lower than 300~350 DEG C) progress.With the development of science and technology, besides to the saving consideration side of resource
Face mainly takes two stages of pyrolytic conversion and low temperature conversion, can preferably economize on resources in this way, reduce cost.
Hydrogen purification unit: this is a critical stage of the last stage and natural gas hydrogen preparation.Current many systems
Hydrogen company all takes the pressure swing adsorption purge system of low power consuming, and the decarburization purification system and methane of highly energy-consuming are compared in this hydrogen manufacturing
Energy conservation and the simplification of process can be better achieved in more low consumption saving for change system.
Existing natural gas steam reforming hydrogen producing process there is also some problems that these problems are mainly manifested in following several at present
A aspect:
(1) process flow is long, and equipment number is more, and hydrogen manufacturing needs pyroreaction, this just needs more expensive material,
Otherwise it is not able to satisfy hydrogen manufacturing demand, causes equipment investment height；
(2) on the one hand hydrogen production process needs a large amount of fuel gas, and fuel cost is excessively high, and another aspect residual heat collection is sharp again
With not high, stack outlet temperature is excessively high in the hydrogen production process, leads to many heat wastes, this just allows enterprise's hydrogen manufacturing cost to increase；
(3) whole process needs the catalyst of multiple types, such as selexol process catalyst, steam conversion unit Ni catalysis
Agent, synthesis gas high conversion catalyst, low change catalyzer, a variety of adsorbents of hydrogen purification unit.These catalyst are expensive, consume
Dosage is big, and technical management is complicated, increases administration fee；
(4) methane conversion is about 82%, and for CO conversion ratio less than 45%, process condition is harsh, right in conversion reaction
Equipment manufactures and designs more demanding with the technical ability of operator and theoretical level.
Summary of the invention
It is an object of the invention to: provide a kind of process flow significantly simplify, build and operating cost is substantially reduced by
The method that light hydrocarbon feedstocks prepare hydrogen.
It is proposed by the invention using rich in methane class lighter hydrocarbons as raw material, using Simulation moving bed or similar devices chemical chain system
The method of hydrogen is based on following inventive concept:
The principle of the technology of the present invention is from burning chemistry chains.Chemical chain burning technology (chemical looping
Combustion, CLC) be a kind of novel energy utilization type, concept by Germany scientist Richter nineteen eighty-three for the first time
It proposes.The oxygen in air is absorbed by oxygen carrier and is converted into the Lattice Oxygen inside oxygen carrier, under the high temperature conditions, fuel and load
The reaction of the oxygen of the intracorporal Lattice Oxygen of oxygen or oxygen carrier pyrolytic is burnt, and heat, metal oxide in combustion process are released
(Me/MeO) oxygen carrier is reduced into Me by fuel (synthesis gas or natural gas) in fuel reactor, and Me is again in air reactor
It is oxidised with air to MeO, reduction and oxidation alternately, avoid the direct contact of fuel and air in combustion process.Burning
Process is because of N in no air2It participates in, reduces the generation of fuel type NOx；The CO that combustion process generates2It is not necessarily to and N2Separation, and it is logical
The step reduction for crossing oxygen carrier realizes the cascade utilization of fuel.Therefore CLC has CO2Interior separation, capacity usage ratio height, energy
Consume the advantages such as low with NOx emission.
For using iron oxide as oxygen carrier, the process of hydrocarbon compound hydrogen manufacturing under oxygen carrier effect is mainly anti-by 3
It should form, respectively the reduction reaction, oxidation reaction and combustion reaction of metal oxygen carrier.Using methane as raw material, iron oxide is to carry
The hydrogen production of chemical chain process chemistry reaction equation of oxysome catalyst is expressed as follows:
Reduction reaction:
CH4+Fe2O3→CO2+H2O+Fe/FeO (1)
Oxidation reaction:
Fe/FeO+H2O→Fe3O4+H2 (2)
Combustion reaction:
Fe3O4+O2 → Fe2O3+ thermal energy (3)
Overall reaction:
CH4+O2 → CO2+H2+ thermal energy (4)
Metal oxygen carrier recycles between 3 reactions, completes oxidation-reduction reaction process, is regenerated, cyclic process is shown
Meaning such as Fig. 1.In order to by the principles of chemistry realize engineering application, natural gas chemistry chain hydrogen production process use three reactors, one
For reduction reactor, one is oxidation reactor, and one is air burning reactor, in which:
Reduction reactor: it feeds as hydrocarbon, iron oxide, discharges as CO2、H2O and ferrous oxide and/or reduced iron；
Oxidation reactor: it feeds as H2O, ferrous oxide and/or reduced iron discharge as H2, ferroso-ferric oxide；
Combustion reactor: it feeds as air, ferroso-ferric oxide, discharges as oxygen deprivation flue gas, iron oxide.
The advantages of above-mentioned hydrogen production of chemical chain reaction process (hereinafter referred to as CLH), is: 1. due to without water-gas shift device and
H2And CO2Purification & isolation device, therefore system is relatively easy；2. only needing a kind of solid particle of oxygen carrier；3. by oxidation reactor
The gas of outlet, which directly condenses, can be obtained pure H2, do not need complicated H2Purification process；4. reduction reactor and burning are anti-
Answer device internal reaction temperature relatively low, and fuel does not contact directly with oxygen, it is raw almost without thermal NO x and Quick-type NOx
At polluted gas discharge is few；5. fuel combustion products are mainly CO in reduction reactor2And vapor, by simple condensation
Pure CO can be obtained2, complicated separator is not needed, small investment, low energy consumption.
But CLH process uses three reactors, oxygen carrier flows between three reactors, needs a large amount of height
The investment such as warm reactor, container, hopper, valve, sensing and measuring instrument and meter.Moreover, oxygen carrier is after repeatedly recycling
There are wear phenomenon, the catalyst fines generated are also required to separate, have both affected the service life of oxygen carrier, also resulted in
The problems such as journey pressure drop, equipment attrition.
Based on the above understanding, the present inventor, which audaciously proposes, uses three reactors of hydrogen production of chemical chain process
The main inventive concept that one reactor replaces, and carried out a series of experimental study.
Producing hydrogen by using chemical chain provided by the present invention the following steps are included:
(1) to being filled with Fe2O3The light hydrocarbon feedstocks gas rich in methane is passed through in the reactor of oxygen carrier body catalyst, in 0.01-
Under the action of 0.35MPa, 600-900 DEG C and the oxygen carrier body catalyst, it is oxidized the light hydrocarbon feedstocks gas and generates CO2With
H2O；
(2) when the conversion ratio of the light hydrocarbon feedstocks gas is decreased obviously, the light hydrocarbon feedstocks gas charging is cut off, is injected water into
The reactor, in 0.01-0.35MPa, 600-900 DEG C, the weight space velocity 0.1-2h of water-1Under the conditions of, make water in the oxygen carrier
It is decomposed under the action of body catalyst and generates hydrogen, while the oxygen carrier body catalyst being made gradually to be oxidized to Fe3O4；
(3) when the decline of the gas production of above-mentioned steps (2) and basic no hydrogen output, stop water filling, Xiang Suoshu reactor
Middle injection air, and by adjusting air capacity, control the temperature of the oxygen carrier catalyst bed in 600-1200 DEG C of range
It is interior, further oxidation reaction is carried out to the oxygen carrier body catalyst；When the oxygen content in the reactor outlet flue gas substantially not
After change, stop air injection.
Compared with the immediate prior art, method provided by the present invention is had the beneficial effect that:
1. hydrogen production process provided by the present invention uses only a reactor, process flow is greatly simplified, thus substantially
Reduce the investment of equipment construction or transformation；
2. plant area used by hydrogen production process of the present invention is small, can skid-mounted design, be suitable for distributed hydrogen production
System；
3. the obtained hydrogen of the present invention is pure, free from admixture；
4. oxygen carrier body catalyst of the present invention is fixed in reactor, without flowing, small, service life is worn
It is long, thus also reduce operating cost.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes a part of the invention, this hair
Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted to any restriction of the invention.In the accompanying drawings:
Fig. 1 is hydrogen production of chemical chain reaction principle schematic diagram；
Fig. 2 is a kind of flow diagram of embodiment of producing hydrogen by using chemical chain provided by the present invention.
It should be noted that not providing heating, temperature measure and control, flow measurement and control in Fig. 2, cooling, changing
Heat, level gauging and control, pressure measurement and control, compressor, inert gas (such as nitrogen) blow line ancillary equipment, instrument
The gas-chromatography of table, electrical and control loop and necessary online analytical instrument such as gas composition analysis, but art technology
Personnel are appreciated that the normal operation in order to maintain device, need to be equipped with above-mentioned ancillary equipment and correlation according to related common sense
Control, analysis means.
Specific embodiment
To further illustrate the purpose of the present invention, technical scheme and beneficial effects, below in conjunction with related attached drawing to this hair
Bright technical solution is illustrated, and the present invention is not therefore subject to any restriction.In addition, the common sense of this field, such as various auxiliary
Equipment and complementary operation (such as equipment purging, liquid level/Level control), details are not described herein.
In the present invention, the light hydrocarbon feedstocks gas rich in methane can be selected from: biogas, natural gas, shale gas, coal seam
One of lighter hydrocarbons resource rich in methane such as gas, oil refinery dry gas, oven gas, casing-head gas and coal mine gallery gas is a variety of.It is preferred that
Ground, unstripped gas should carry out desulfurization, dechlorination, dearsenification, the de- refinement treatments such as again before entering chemical chain reaction device, usually require that S <
50ppb, Cl<0.5ppm, As<20ppb, Hg<0.5ppb, methane content>95% (percentage by volume).
The present invention passes through program-controlled feed switched mode Simulation moving bed using fixed bed reactors using chemical chain technology
Equipment produces high-purity hydrogen (H2), while exporting thermal energy.
In the present invention, used oxygen carrier body catalyst is iron series oxygen carrier.For example, the preparation process that can be used is such as
Under: according to Fe in catalyst2O3It is 1%- that content, which goes out concentration in 5-30% (mass percent, similarly hereinafter) stoichiometric arrangement,
20% iron nitrate solution, be poured at room temperature in advance by 900-1000 DEG C of roasting temperature 2-6h oxidation aluminum strip into
Row dipping, impregnates 0.5-3h at room temperature, and then rotation is evaporated to no liquid water under 80 DEG C of water-baths, then in 120 DEG C in baking oven
It is lower to dry moisture, then be warming up at 900-1200 DEG C with 10-100 DEG C/h speed and roast 2-6h, obtain the oxygen carrier catalysis
Agent.
Not therefore with reference to the accompanying drawing, producing hydrogen by using chemical chain provided by the present invention is further illustrated, but the present invention
And it is any way limited.
As shown in Fig. 2, the step of producing hydrogen by using chemical chain provided by the present invention, is as follows:
Step (1):
The valve 6 on the valve 4 on waterflood-transmission line and injection air line is closed, the valve on hydrogen discharge pipe line is closed
5 and flue gas emission pipeline on valve 7.Open the CO at the top of the valve 2 and separator in reactor head gas discharge pipe line2
Valve 3 on discharge pipe.
The valve 1 on light hydrocarbon feedstocks gas CxHy injection pipeline is opened, to being already loaded with Fe2O3Oxygen carrier body catalyst it is anti-
Answer injection light hydrocarbon feedstocks gas in device 10, under the action of 0.01-0.35MPa, 600-900 DEG C and oxygen carrier body catalyst, unstripped gas
It is oxidized and generates CO2And H2O.Wherein, preferred reaction condition is 0.1-0.3MPa, 650-880 DEG C, air speed 50-1000Nml/
g.h.CO generated2And H2It is cooling through cooler 14 after being drawn in O high-temperature mixed gas autoreactor, it is then sent to separation
CO is carried out in device 122And H2The separation of O.CO2Subsequent cell is delivered to from separator overhead line.H generated2O can be through water pump
The recycling of reactor 10 is delivered to after 13 pressurizations.Heating furnace 11 shown in Fig. 2 can be used for maintaining catalyst reactor bed
Layer temperature.
In above-mentioned reaction process, reduction reaction occurs for oxygen carrier body catalyst itself, is gradually reduced into FeO/Fe.It is carrying
After oxysome catalyst restores, the conversion ratio of unstripped gas will decline, and will appear the raw material and CO of unreacted conversion in product gas
Equal impurity, close valve 1 at this time, stop the reduction reaction of oxygen carrier body catalyst.
Step (2):
Switch on the pump power supply, opens the valve 4 on waterflood-transmission line, reactor is injected water into, in 0.01-0.35MPa, 600-
900 DEG C, the weight space velocity 0.1-2h of water-1Under the conditions of reacted.Water decomposes under oxygen carrier catalyst action generates hydrogen, together
When oxygen carrier body catalyst be gradually oxidized to Fe3O4.Just start the hydrogen generated after filling the water into reactor, is entrained with first
The gas component to remain in a standstill in reactor and in the equipment of reactor outlet, pipeline after reaction terminating is walked, the purity of hydrogen is not high,
This stage reactors product leads to separator yet by valve 2, and goes out gas to system outlet by valve 3.When with displacement
Between extension, hydrogen purity quickly improves.When the purity for measuring hydrogen meets the requirements such as > 99.99%, valve 2 is closed, is opened
Valve 5, system generate high-purity hydrogen.
When product gas output decline, and almost without produce hydrogen when, switch off the pump power supply, close valve 4, valve 5, stop carry
The oxidation reaction of oxysome catalyst.
Step (3):
The valve 7 on flue gas emission pipeline is opened, valve 6 is opened and introduces air, air capacity is adjusted, by oxygen carrier body catalyst
Bed temperature is controlled in 600-1200 DEG C of range, it is preferable that reaction bed temperature is controlled in 650-1100 DEG C of range, further
Preferably, reaction bed temperature control carries out further oxidation reaction to oxygen carrier body catalyst in 650-1000 DEG C of range.It is excellent
Selection of land, the oxygen deprivation flue gas of reactor outlet is used for heat energy utilization at this time.
After measuring the oxygen content in reactor outlet flue gas and no longer changing, valve 7 and valve 6 are closed, it is anti-to stop burning
It answers.
In the present invention, the above process is a circulation.The process utilizes the cyclic switching of reactor feed, simulation movement
Flowing of the oxygen carrier between three reactors in bed reactor process.It loops back and forth like this, program-controlled switching stepwise reaction, thus real
Now by hydrocarbon raw material gas hydrogen making.
Not therefore producing hydrogen by using chemical chain provided by the present invention is further illustrated below by embodiment, but the present invention
And it is any way limited.
Embodiment 1
This example demonstrates that: the preparation of oxygen carrier body catalyst.
Weigh the cloverleaf pattern oxygen roasted at 980 DEG C of 16g Sinopec catalyst branch Chang Ling catalyst plant production
Change aluminium extruded item, is placed in 500ml round-bottomed flask stand-by.Separately weigh the industrial high-class product nine of the prosperous beautiful peaking plant produced in Taiyuan City
Water ferric nitrate 20.23g is placed in 200ml beaker, and 113g distilled water is added into beaker, and stirring and dissolving obtains iron nitrate solution.
Configured iron nitrate solution is slowly dropped in the round-bottomed flask equipped with 16g oxidation aluminum strip, rotary evaporation 2h, revolving speed
35rpm/min, 80 DEG C of water-bath.The aluminium oxide extrusion for being impregnated with ferric nitrate is moved in baking oven, 120 DEG C of drying overnight are carried
Oxysome catalyst precursor.Again by presoma in Muffle furnace, 950 DEG C of constant temperature calcining 4h are warming up to 2 DEG C/min speed, it is natural
Cooling obtains oxygen carrier body catalyst.
Embodiment 2
This example demonstrates that: the implementation result of hydrogen production process provided by the present invention.
The oxygen carrier body catalyst 10g that embodiment 1 is prepared is packed into fixed bed reactors.Use methane as raw material
Gas carries out hydrogen manufacturing with process conditions according to the following steps:
Step 1: setting methane gas flow as 50Nml/min, 850 DEG C of reaction temperature, normal pressure, the reaction time is about
2.38min.It is accumulative to use methane gas 119Nml, generate carbon dioxide gas about 119Nml, water about 0.19g.Carbon dioxide gas
Middle CO < 5ppm, CH4< 0.15%.
Step 2: injection flow 5ml/h, reaction temperature is 850 DEG C, when reaction starts rear timing to 0.35min, measures valve
Hydrogen purity > 99.99% (percentage by volume) before door 5 closes valve 2, opens valve 5, collects hydrogen.The reaction time about
Terminate second step when 1.67min.Second step total water consumption 0.14g.Collect the high-purity hydrogen tolerance about 130Nml generated.
Step 3: air mass flow 50Nml/h, 850 DEG C of reaction temperature, reaction time about 5min, reaction was completed.
By embodiment as it can be seen that using the method for the present invention, a fixed bed reactors Simulation moving bed mode can be used and realize
Light hydrocarbon feedstocks hydrogen production of chemical chain, gained hydrogen is pure, no longer needs to be purified, refinement treatment.Hydrogen production process by-product CO2Gas is pure
Degree is high, can be used for CCS without being concentrated, and lowers carbon emission.Process equipment is simple, invests low, production process environmental protection.
Claims (10)
1. a kind of producing hydrogen by using chemical chain, the following steps are included:
(1) to being filled with Fe2O3The light hydrocarbon feedstocks gas rich in methane is passed through in the reactor of oxygen carrier body catalyst, in 0.01-
Under the action of 0.35MPa, 600-900 DEG C, air speed 50-1000Nml/g.h and the oxygen carrier body catalyst, make the light hydrocarbon feedstocks
Gas, which is oxidized, generates CO2And H2O；
(2) when the conversion ratio of the light hydrocarbon feedstocks gas is decreased obviously, the light hydrocarbon feedstocks gas charging is cut off, is injected water into described
Reactor, in 0.01-0.35MPa, 600-900 DEG C, the weight space velocity 0.1-2h of water-1Under the conditions of, urge water in the oxygen carrier
It is decomposed under the action of agent and generates hydrogen, while the oxygen carrier body catalyst being made gradually to be oxidized to Fe3O4；
(3) when the decline of the gas production of above-mentioned steps (2) and basic no hydrogen output, stop water filling, infused in Xiang Suoshu reactor
Enter air, and by adjusting air capacity, controls the temperature of the oxygen carrier catalyst bed within the scope of 600-1200 DEG C, it is right
The oxygen carrier body catalyst carries out further oxidation reaction；After the oxygen content in the reactor outlet flue gas is basically unchanged,
Stop air injection.
2. producing hydrogen by using chemical chain according to claim 1, which is characterized in that the oxygen carrier body catalyst passes through step
(3) after oxidation reaction, repeat the operation of step (1) to step (3).
3. producing hydrogen by using chemical chain according to claim 2, which is characterized in that light hydrocarbon feedstocks gas described in step (1)
Reaction condition is 0.1-0.3MPa, 650-880 DEG C, air speed 50-1000Nml/g.h；Reaction bed temperature described in step (3)
Control is in 650-1100 DEG C of range, it is preferable that the reaction bed temperature control is in 650-1000 DEG C of range.
4. producing hydrogen by using chemical chain according to claim 1, which is characterized in that the light hydrocarbon feedstocks gas choosing rich in methane
From: one of biogas, natural gas, shale gas, coal bed gas, oil refinery dry gas, oven gas, casing-head gas and coal mine gallery gas are more
Kind.
5. producing hydrogen by using chemical chain according to claim 3 or 4, which is characterized in that the light hydrocarbon feedstocks gas is entering instead
It answers and carries out refinement treatment before device, the S < 50ppb, C l < 0.5ppm, As < 20ppb, Hg in the light hydrocarbon feedstocks gas that makes that treated <
0.5ppb, methane content > 95 volume %；The refinement treatment of the light hydrocarbon feedstocks gas includes desulfurization, dechlorination, dearsenification, de- heavy constituent.
6. producing hydrogen by using chemical chain according to claim 5, which is characterized in that the preparation step of the oxygen carrier body catalyst
It is as follows: according to Fe in the oxygen carrier body catalyst2O3It is 1 mass %- that content, which goes out concentration in 5-30 mass % stoichiometric arrangement,
The iron nitrate solution of 20 mass % at room temperature impregnates the oxidation aluminum strip that iron nitrate solution pours into advance by roasting,
0.5-3h is impregnated at room temperature, no liquid water is then evaporated under 80 DEG C of water-baths, then dry moisture in baking oven, then be warming up to
2-6h is roasted at 900-1200 DEG C, obtains the oxygen carrier body catalyst.
7. producing hydrogen by using chemical chain according to claim 6, which is characterized in that reactor outlet described in step (3)
Oxygen deprivation flue gas is used for heat energy utilization.
8. producing hydrogen by using chemical chain according to claim 7, which is characterized in that supervised in the initial stage of the step (3)
The purity of generated hydrogen is surveyed, hydrogen purity is delivered to subsequent hydrogen pipe network after meeting the requirements.
9. producing hydrogen by using chemical chain according to claim 1 or 8, which is characterized in that the reactor is fixed bed reaction
Device.
10. producing hydrogen by using chemical chain according to claim 9, which is characterized in that implement the step (1) to step (3)
Device use skid-mounted design.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110562913A (en) * | 2019-09-30 | 2019-12-13 | 内蒙古大学 | method for producing hydrogen by using methane and water as raw materials |
| CN111232920A (en) * | 2020-03-17 | 2020-06-05 | 昆明理工大学 | Method for preparing hydrogen by coke oven coal gasification chemical looping |
| CN111378507A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Process method for producing hydrogen by coal gasification |
| CN114057163A (en) * | 2021-12-17 | 2022-02-18 | 中国核动力研究设计院 | System and method for producing hydrogen and carbon monoxide in lead coolant device |
| CN115111629A (en) * | 2022-06-10 | 2022-09-27 | 北京市燃气集团有限责任公司 | Zero-carbon heat supply method |
| CN115571855A (en) * | 2022-11-07 | 2023-01-06 | 中冶南方工程技术有限公司 | Converter gas resource utilization method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858601A (en) * | 2016-04-07 | 2016-08-17 | 中国石油化工股份有限公司 | Switchover-type chemical-looping hydrogen production plant and hydrogen production method |
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2019
- 2019-03-07 CN CN201910173435.9A patent/CN109761192A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858601A (en) * | 2016-04-07 | 2016-08-17 | 中国石油化工股份有限公司 | Switchover-type chemical-looping hydrogen production plant and hydrogen production method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378507A (en) * | 2018-12-28 | 2020-07-07 | 中国石油化工股份有限公司 | Process method for producing hydrogen by coal gasification |
| CN110562913A (en) * | 2019-09-30 | 2019-12-13 | 内蒙古大学 | method for producing hydrogen by using methane and water as raw materials |
| CN111232920A (en) * | 2020-03-17 | 2020-06-05 | 昆明理工大学 | Method for preparing hydrogen by coke oven coal gasification chemical looping |
| CN111232920B (en) * | 2020-03-17 | 2023-03-14 | 昆明理工大学 | Method for producing hydrogen by coke oven coal chemical looping |
| CN114057163A (en) * | 2021-12-17 | 2022-02-18 | 中国核动力研究设计院 | System and method for producing hydrogen and carbon monoxide in lead coolant device |
| CN115111629A (en) * | 2022-06-10 | 2022-09-27 | 北京市燃气集团有限责任公司 | Zero-carbon heat supply method |
| CN115571855A (en) * | 2022-11-07 | 2023-01-06 | 中冶南方工程技术有限公司 | Converter gas resource utilization method |
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