CN114774165B - Oxygen decoupling oxygen carrier, preparation method and application - Google Patents
Oxygen decoupling oxygen carrier, preparation method and application Download PDFInfo
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- CN114774165B CN114774165B CN202210229871.5A CN202210229871A CN114774165B CN 114774165 B CN114774165 B CN 114774165B CN 202210229871 A CN202210229871 A CN 202210229871A CN 114774165 B CN114774165 B CN 114774165B
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 286
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 239000001301 oxygen Substances 0.000 title claims abstract description 282
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 85
- 239000011572 manganese Substances 0.000 claims abstract description 68
- 238000002309 gasification Methods 0.000 claims abstract description 67
- 239000000126 substance Substances 0.000 claims abstract description 52
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 34
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 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 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 96
- 238000006243 chemical reaction Methods 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- -1 iron ions Chemical class 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000499 gel Substances 0.000 description 14
- 239000000446 fuel Substances 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910014460 Ca-Fe Inorganic materials 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011240 wet gel Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000010806 kitchen waste Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
-
- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The present disclosure provides an oxygen decoupling oxygen carrier, a method of making and a method of using the sameWith the oxygen decoupling oxygen carrier in this disclosure comprising: ca (Ca) 2 Fe 2 O 5 A substrate; doped to Ca 2 Fe 2 O 5 Mn element on the matrix, and the molecular formula of the oxygen-decoupling oxygen carrier is as follows: mn/Ca 2 Fe 2 O 5 Wherein, the mole ratio of Mn, ca and Fe is 1:1: 1-2: 1:1. the preparation method of the oxygen decoupling oxygen carrier provided by the disclosure comprises the following steps: s1, mixing ferric nitrate, calcium nitrate and manganese nitrate and preparing nitrate solution; s2, adding a complexing agent into the nitrate solution, adding the complexing agent into the nitrate solution, adjusting the pH value of the solution, and heating to form gel; s3, calcining the dried gel at a first preset temperature to decompose nitrate, and heating to a second preset temperature to calcine to obtain Mn/Ca 2 Fe 2 O 5 An oxygen carrier. The present disclosure also provides the use of an oxygen-decoupled oxygen carrier for biogas residue chemical chain gasification.
Description
Technical Field
The disclosure belongs to the technical field of energy chemical industry and materials, and particularly relates to an oxygen decoupling oxygen carrier, a preparation method and application.
Background
Due to the massive consumption of fossil energy sources mainly comprising coal resources, serious environmental pollution and resource shortage problems are caused. The anaerobic fermentation technology is a biomass utilization technology with great application prospect, and can treat solid waste to solve the problem of environmental pollution and obtain clean biogas energy. However, biogas residues are used as byproducts of anaerobic fermentation, and the development of the anaerobic fermentation industry is severely limited due to the problems of large quantity and difficult treatment. Although biogas residue is considered to be useful as an organic fertilizer, it is generally unsuitable for large-scale applications due to its disadvantages of high transportation costs, poor dosage controllability, and the like.
The gasification technology can realize the high-efficiency treatment of the solid waste while well utilizing the organic matters in the solid waste in a mode of producing the synthesis gas, so that the gasification technology is widely applied to the fields of petroleum, chemical industry and the like. Meanwhile, trace elements such as potassium in the biogas residue have a certain catalytic effect on gasification, so that the reaction can be quickened, and the biogas residue is treated by utilizing the gasification technology, so that the method has great practical significance. However, conventional gasification methods have significant limitations, such as: the air is taken as gasification medium to bring a large amount of N 2 Resulting in a reduction in the calorific value of the synthesis gas; the use of pure oxygen or steam as gasification medium complicates the process and the need for equipment such as air separators can greatly increase the cost of syngas production. Therefore, there is an urgent need to develop a novel method for treating and utilizing biogas residues to promote the development of biogas engineering.
Chemical looping gasification (chemical looping gasification, CLG) is an emerging gasification scheme that utilizes lattice oxygen in an oxygen carrier as a gasification medium in place of conventional gasifying agents to provide oxygen required for gasification reactions to fuels. Chemical chain gasification overcomes the limitation of traditional gasification, and simultaneously provides energy for gasification of biogas residues by carrying heat released during regeneration of the oxygen carrier, thereby realizing cascade utilization of heat energy. And the oxygen carrier is used as metal oxide, has certain catalytic action while providing lattice oxygen, and can realize catalytic gasification and tar cracking in the furnace. In view of the advantages, the biogas residue chemical chain gasification technology has wide application prospect as an effective way for efficiently treating and recycling biogas residues.
The chemical chain gasification system consists of a fuel reactor, an air reactor and an oxygen carrier. Wherein the oxygen carrier is circulated between the fuel reactor and the air reactor as a medium. The performance of the oxygen carrier directly influences the operation and gasification effects of the whole chemical chain gasification. The preparation and optimization of the oxygen carrier is therefore the core and key of chemical chain gasification technology. Ca-Fe-based oxygen carrier has stronger H 2 Selectivity and tar catalytic performance, become a hot oxygen carrier for chemical chain gasification technology,however, the product CO exists in chemical chain gasification in which Ca-Fe-based oxygen carriers participate 2 High concentration, low gasification efficiency, non-ideal gas yield and the like. In order to realize the rapid reduction of biogas residues serving as anaerobic fermentation byproducts and the utilization of high added values, the development of novel and efficient oxygen carriers is urgently needed to be researched and solved.
Disclosure of Invention
In view of the above-mentioned technical problems, the present disclosure provides an oxygen-decoupling oxygen carrier, a preparation method and an application, so as to at least partially solve the above-mentioned technical problems.
To solve the above technical problem, as one aspect of the present disclosure, the present disclosure provides an oxygen decoupling oxygen carrier, including:
Ca 2 Fe 2 O 5 a substrate;
doped into the Ca 2 Fe 2 O 5 The Mn element on the substrate is a compound of Mn,
the molecular formula of the oxygen decoupling oxygen carrier is as follows:
Mn/Ca 2 Fe 2 O 5 ，
wherein, the mole ratio of Mn, ca and Fe is 1:1: 1-2: 1:1.
in one embodiment, the Mn element is uniformly supported on the Ca 2 Fe 2 O 5 The surface and bulk phases of the matrix.
In one embodiment, the oxygen-decoupling oxygen carrier comprises active oxygen between lattice oxygen and adsorbed oxygen.
As another aspect of the present disclosure, there is also provided a method for preparing an oxygen-decoupled oxygen carrier, including:
s1, mixing ferric nitrate, calcium nitrate and manganese nitrate and preparing nitrate solution;
s2, adding a complexing agent into the nitrate solution, adding a pH regulator solution, and heating to form gel;
s3, calcining the dried gel at a first preset temperature to decompose nitrate, and heating to a second preset temperature to calcine to obtain Mn/Ca 2 Fe 2 O 5 An oxygen carrier.
In another embodiment, the molar ratio of manganese ions, calcium ions and iron ions in the nitrate solution is 1:1: 1-2: 1:1, a step of;
the complexing agent is citric acid, and the molar ratio of the citric acid to metal ions in nitrate is 1:1-1: 2.
in another embodiment, S2 the adjusting the pH range of the solution includes: the pH value is adjusted to 1-2.
In one of the other embodiments of the present invention,
the first preset temperature range includes: 500-600 ℃;
the first preset temperature calcination time range includes: 0.5 to 1.5 hours;
the second preset temperature range includes: 850-950 ℃;
the calcination time range of the second preset temperature includes: and 1-3 h.
In another embodiment, the method further comprises grinding the calcined oxygen carrier to a powder to a particle size of less than 0.2nm.
As yet another aspect of the present disclosure, there is also provided an application of an oxygen-decoupled oxygen carrier for biogas residue chemical chain gasification.
In another embodiment, the biogas residue is mixed with the oxygen-decoupling oxygen carrier, and the biogas residue chemical chain gasification reaction is carried out at the temperature of 600-1000 ℃ to prepare H 2 And synthesis gas with CO as the main component.
Based on the above embodiments, the oxygen decoupling oxygen carrier, the preparation method and the application provided by the present disclosure at least include one of the following beneficial effects:
(1) In embodiments of the present disclosure, mn element is doped to oxygen carrier Ca 2 Fe 2 O 5 In the matrix, oxygen carrier Ca can be used 2 Fe 2 O 5 Is converted into an active oxygen between the lattice oxygen and the adsorbed oxygen, thereby having a mild oxygen decoupling property.
(2) In the embodiment of the disclosure, the preparation method of the oxygen decoupling oxygen carrier provided by the disclosure is simple, and raw materials are cheap and easy to obtain.
(3) In the embodiment of the disclosure, the oxygen decoupling oxygen carrier provided by the disclosure has a faster oxygen absorption rate which is far higher than the oxygen release rate, and has good circulation stability and activity.
Drawings
FIG. 1 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And non-oxygen decoupling oxygen carrier Ca in comparative example 1 2 Fe 2 O 5 X-ray photoelectron spectroscopy full spectrum of (2);
FIG. 2A is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And comparative example 1 non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 O1s plot of x-ray photoelectron spectroscopy of (c);
FIG. 2B example 1 oxygen decoupling oxygen carrier Mn/Ca of the present disclosure 2 Fe 2 O 5 And comparative example 1 non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 An Fe 2 p-plot of an x-ray photoelectron spectrum of (c);
FIG. 3 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 Mn 2p 3/2 map of x-ray photoelectron spectroscopy of (C);
FIG. 4 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And comparative example 1 non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 Is a temperature programming reducing chart;
FIG. 5 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And non-oxygen decoupling oxygen carrier Ca in comparative example 1 2 Fe 2 O 5 Thermal weight graph with 5 oxygen decoupling and regeneration.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same.
Based on the defects existing when the current Ca-Fe-based oxygen carrier participates in the chemical chain gasification reaction and the wide application of the chemical chain oxygen decoupling technology in the chemical chain combustion field, the Ca-Fe-based oxygen carrier is modified by the oxygen decoupling oxygen carrier and applied to the chemical chain gasification, and an effective method for improving the performance of the Ca-Fe-based oxygen carrier is provided. The oxygen decoupling oxygen carrier can release lattice oxygen into oxygen at a certain temperature and oxygen partial pressure, and the solid-solid reaction between the lattice oxygen of the traditional oxygen carrier and fuel is converted into the gas-solid reaction between molecular oxygen and fuel, so that the cracking of tar and coke is promoted, and the gasification reaction effect is enhanced.
Mn, cu and Co-based oxygen carriers all have certain oxygen decoupling capacity, wherein the Cu-based oxygen carriers are widely applied to chemical looping combustion due to the extremely strong oxygen decoupling capacity, but the extremely strong oxidizing property and the extremely high oxygen decoupling rate can cause the peroxidation of the synthesis gas in chemical looping gasification, so that the quality of the synthesis gas is reduced. The reaction of the Co-based oxygen carrier with carbon is an endothermic reaction, which can lead to a decrease in the temperature of the fuel reactor, thereby affecting the oxygen decoupling performance of the oxygen carrier and reducing the oxygen partial pressure in the fuel reactor. The Mn-based oxygen carrier is a mild oxygen decoupling property adapted to chemical chain gasification and has a low oxygen decoupling temperature. In addition, the Mn-based oxygen carrier has the characteristics of no toxicity, low price, high mechanical strength, higher activity and the like. Based on the advantages of Mn element and Ca-Fe based oxygen carrier, the present disclosure provides a Mn/Ca 2 Fe 2 O 5 An oxygen decoupling oxygen carrier, a preparation method and application thereof.
According to an embodiment of the present disclosure, an oxygen decoupling oxygen carrier includes: ca (Ca) 2 Fe 2 O 5 A substrate; doped to Ca 2 Fe 2 O 5 Mn element on the matrix, and the molecular formula of the oxygen-decoupling oxygen carrier is as follows: mn/Ca 2 Fe 2 O 5 Wherein, the mole ratio of Mn, ca and Fe is 1:1: 1-2: 1:1.
the oxygen-decoupling oxygen carrier prepared by limiting the ratio of Mn, ca and Fe in the range has mild and slow oxygen decoupling capability suitable for chemical chain gasification by the embodiment of the disclosure, wherein Mn/Ca 2 Fe 2 O 5 The mild and slow oxygen decoupling capacity of (2) is represented by Mn/Ca 2 Fe 2 O 5 Oxygen release amount of oxygen carrier<2, and Mn/Ca 2 Fe 2 O 5 The oxygen carrier releases oxygen for a time much longer than the regeneration time.
According to the embodiment of the present disclosure, mn element is uniformly supported on Ca 2 Fe 2 O 5 The surface and bulk phases of the matrix.
According to embodiments of the present disclosure, the oxygen-decoupled oxygen carrier comprises active oxygen between lattice oxygen and adsorbed oxygen.
Through the embodiment of the disclosure, the oxygen in the lattice oxygen in the oxygen carrier can be released by utilizing the oxygen decoupling performance of Mn, so that the oxygen carrier has the oxygen decoupling performance.
According to an embodiment of the present disclosure, a method for preparing an oxygen-decoupled oxygen carrier includes: s1, mixing ferric nitrate, calcium nitrate and manganese nitrate and preparing nitrate solution; s2, adding a complexing agent into the nitrate solution, adding the complexing agent into the nitrate solution, adjusting the pH value of the solution, and heating to form gel; s3, calcining the dried gel at a first preset temperature to decompose nitrate, and heating to a second preset temperature to calcine to obtain Mn/Ca 2 Fe 2 O 5 An oxygen carrier.
According to an embodiment of the present disclosure, the iron nitrate, the calcium nitrate and the manganese nitrate in step S1 are Fe (NO 3 ) 3 ·9H 2 O、Ca(NO 3 ) 2 ·4H 2 O and Mn (NO) 3 ) 2 ·4H 2 O。
According to embodiments of the present disclosure, the molar ratio of manganese ions, calcium ions, and iron ions in the nitrate solution is 1:1: 1-2: 1:1.
according to the embodiment of the disclosure, the complexing agent is citric acid, and the molar ratio of the citric acid to metal ions in nitrate is 1:1-1: 2.
according to an embodiment of the present disclosure, adjusting the pH range of the solution in S2 includes: the pH value is adjusted to 1-2.
By the embodiment of the disclosure, the complexing agent is added into the nitrate solution to firstly change the solution into sol, and then the pH value of the solution is adjusted to be 1 to 2 by ammonia water, so that gel is formed. If the pH value of the solution is too high, precipitation is likely to be formed, and if the pH value of the solution is too low, the complexing effect of metal ions is poor, and gel is not likely to be formed.
According to an embodiment of the present disclosure, the first preset temperature range includes: 500-600 ℃, wherein the first preset temperature can be selected from 500, 550, 600 ℃ and the like; the first preset temperature calcination time range includes: 0.5 to 1.5 hours, optionally 0.5, 1, 1.5 hours, etc.; the second preset temperature range includes: 850-950 ℃, and the temperatures can be selected from 850, 900, 950 ℃ and the like; the calcination time range of the second preset temperature includes: 1-3 h, optionally 1, 2, 3h, etc.; the temperature rising rate of calcination can be selected to be 10 ℃/min.
By the method in the examples of the present disclosure, fe (NO 3 ) 3 ·9H 2 O、Ca(NO 3 ) 2 ·4H 2 O and Mn (NO) 3 ) 2 ·4H 2 O is mixed and formulated into a nitrate solution. Citric acid is used as complexing agent to be added into nitrate solution, ammonia water is used to adjust the pH value of the solution to 1-2, and the solution is heated in water bath at 70 ℃ and stirred continuously until gel is formed. Then, the obtained gel is calcined at 500 to 600 ℃ to decompose nitrate fully, and then the temperature is raised to 850 to 950 ℃ to perform the second calcination, so that the oxygen carrier can be activated. And the preparation method of the oxygen decoupling oxygen carrier adopted by the method is simpler, and the raw materials are cheap and easy to obtain.
According to embodiments of the present disclosure, the calcined oxygen carrier is ground to a powder to a particle size of less than 0.2nm.
According to the embodiment of the disclosure, the dried gel is calcined at the first preset temperature, so that nitrate in the gel can be fully decomposed, and nitrate ions are removed; then, the oxygen carrier can be activated by performing the second calcination at the second preset temperature, so that the oxygen carrier has oxygen decoupling performance. The calcined oxygen carrier is ground into particles with the particle size smaller than 0.2mm, so that the oxygen decoupling oxygen carrier and organic waste (biogas slurry) are uniformly mixed and fully contacted, and the gasification effect of chemical chain gasification reaction is improved.
According to the embodiment of the disclosure, the oxygen decoupling oxygen carrier prepared by the method can be used for biogas residue chemical chain gasification reaction to prepare H 2 And synthesis gas with CO as the main component.
According to the embodiment of the disclosure, in a reaction of an oxygen-decoupled oxygen carrier for chemical looping gasification of biogas residue, a mass ratio of biogas residue to the oxygen-decoupled oxygen carrier is set at 1:1 to 1:2, the oxygen carrier can fully react with the biogas residue within the range, and has higher economic benefit.
According to the embodiment of the disclosure, in the reaction of the oxygen decoupling oxygen carrier for the chemical looping gasification of the biogas residue, the temperature of the reactor is heated to 600-1000 ℃ in advance before the reaction, and nitrogen is introduced to ensure the inert atmosphere in the reactor.
According to the embodiment of the disclosure, the oxygen decoupling oxygen carrier can release lattice oxygen into oxygen under the conditions of a certain temperature and oxygen partial pressure, the released oxygen can participate in a biogas reaction, the solid-solid conversion between the lattice oxygen of the traditional oxygen carrier and fuel is changed into a gas-solid reaction, the reaction rate is improved, and the rapid decrement of biogas residues and the production of high-quality synthetic gas can be realized.
According to the embodiment of the disclosure, the reacted oxygen-decoupling oxygen carrier can be regenerated in an oxygen-containing atmosphere, and the regenerated oxygen-decoupling oxygen carrier can be recycled, wherein the regeneration temperature of the oxygen-decoupling oxygen carrier is preferably 800 ℃, and the atmosphere is preferably an air atmosphere.
In order to make the objects, technical solutions and effects of the present disclosure more apparent, the present disclosure is further described below with reference to specific embodiments and drawings. It should be noted that the illustrated embodiments are merely illustrative of the present disclosure and are not intended to limit the scope of the present disclosure.
The biogas residue selected by the method is taken from a kitchen waste anaerobic digestion plant in Beijing city and is a raw material for chemical chain gasification, and the biogas residue is dried, crushed and screened to a particle size of less than 0.2nm. Industrial analysis, elemental analysis and lower calorific value of biogas residue are shown in table 1.
TABLE 1 Industrial analysis, elemental analysis and Lower Heating Value (LHV) of biogas residues
Example 1
Preparation of oxygen-decoupling oxygen carrier Mn/Ca by sol-gel combustion method 2 Fe 2 O 5 (MCF for short), the specific steps are as follows:
17.52g Mn (NO) 3 ) 2 ·4H 2 O、12.16g Ca(NO 3 ) 2 ·4H 2 O and 28.20g Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 100mL of deionized water according to the ratio of cation 1:1:1, and stirred until the O is completely dissolved, and the O is used as nitrate precursor solution containing metal ions. Next, 40.24g of citric acid was added as a complexing agent to the nitrate precursor solution in a molar ratio of 1:1 of the amount of citric acid added to the amount of metal ions added to the nitrate. Ammonia was slowly added while stirring dropwise to adjust the pH of the solution to 2, and the solution was heated in a water bath at 70 ℃ and stirred continuously until a polymerized gel formed. The resulting wet gel was dried in a forced air drying oven at 105℃for 24 hours until the wet gel in the beaker became a xerogel. Taking out the xerogel, placing the xerogel in a tube furnace, calcining the xerogel at 500 ℃ for 1 hour to fully decompose nitrate, then raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and calcining the xerogel at 900 ℃ for 2 hours to activate the oxygen carrier. Cooling the calcined oxygen carrier to room temperature, grinding into powder until the particle size is smaller than 0.2nm to obtain the final powdered product, namely the oxygen decoupling oxygen carrier Mn/Ca 2 Fe 2 O 5 。
The biogas residue was dried in a forced air drying oven at 105℃for 24h. The oxygen-decoupling oxygen carrier Mn/Ca prepared by the method of example 1 2 Fe 2 O 5 Uniformly mixing the dried biogas residue with Mn/Ca 2 Fe 2 O 5 The mass ratio of (2) is 1:1. And the chemical chain gasification reactor is preheated to 700 ℃, and nitrogen is introduced to ensure the inert atmosphere in the reactor. Then the fuel (biogas residue and oxygen decoupling oxygen carrier Mn/Ca) 2 Fe 2 O 5 ) Pushing into the fuel reactor for gasification. After the reaction is finished, air is introduced into the air reactor, the temperature is maintained at 800 ℃, and Mn/Ca after the reaction is carried out 2 Fe 2 O 5 And (5) performing oxidation regeneration. And then reverseBiogas residues are added into the reactor to continuously carry out chemical chain gasification. The results of the oxygen decoupling oxygen carrier used in biogas residue chemical chain gasification in example 1 are shown in table 2.
TABLE 2 implementation results of biogas residue chemical chain gasification based on oxygen-decoupled oxygen carrier
Example 2
The oxygen-decoupled oxygen carrier of example 2 was prepared in the same manner as in example 1, except that the chemical looping gasification reactor of example 2 was heated to 800℃and the rest of the operations were the same as in example 1. The results of the chemical looping gasification reaction of biogas residues of the oxygen-decoupled oxygen carrier in example 2 are shown in table 3.
TABLE 3 implementation results of biogas residue chemical chain gasification based on mild oxygen decoupling oxygen carrier
Example 3
The oxygen-decoupled oxygen carrier of example 3 was prepared in the same manner as in example 1, except that the temperature of the chemical looping gasification reactor of example 3 was heated to 900 c, and the rest of the operations were the same as in example 1. The results of the chemical looping gasification reaction of biogas residues of the oxygen-decoupled oxygen carrier in example 3 are shown in table 4.
TABLE 4 implementation results of biogas residue chemical chain gasification based on mild oxygen decoupling oxygen carrier
Comparative example 1
Preparation of non-oxygen decoupling oxygen carrier Ca by sol-gel combustion method 2 Fe 2 O 5 (CF for short), the specific steps are as follows:
19.22g of Ca (NO) 3 ) 2 ·4H 2 O and 44.58g Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 100mL of deionized water according to the ratio of cation 1:1, and stirred until the O is completely dissolved, and the O is used as nitrate precursor solution containing metal ions. Next, 42.41g of citric acid as a complexing agent was added to the nitrate precursor solution in a molar ratio of the added amount of citric acid to the added amount of metal ions in the nitrate of 1:1. Ammonia was slowly added and the solution was stirred while dropping until the pH of the solution was adjusted to 2. The solution was heated in a water bath at 70 ℃ and stirred continuously until a polymerized gel formed. The resulting wet gel was dried in a forced air drying oven at 105℃for 24 hours until the wet gel in the beaker became a xerogel. Taking out the xerogel, placing the xerogel in a tube furnace, calcining the xerogel at 500 ℃ for 1 hour to fully decompose nitrate, then raising the temperature to 900 ℃ at the heating rate of 10 ℃/min, and calcining the xerogel at 900 ℃ for 2 hours to activate the oxygen carrier. Cooling the calcined oxygen carrier to room temperature, grinding into powder until the particle size is smaller than 0.2nm to obtain the final powdered product, namely the non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 。
The biogas residue was dried in a forced air drying oven at 105℃for 24h. The non-oxygen decoupling oxygen carrier Ca prepared by the method of comparative example 1 2 Fe 2 O 5 Uniformly mixing the dried biogas residue with Ca, wherein the biogas residue and Ca 2 Fe 2 O 5 The mass ratio of (2) is 1:1. And the reactor temperature was previously heated to 700 c and nitrogen was introduced to ensure an inert atmosphere within the reactor. Then the fuel (biogas residue and non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 ) Pushing into the fuel reactor for gasification. After the reaction is finished, air is introduced into the air reactor, the temperature is maintained at 800 ℃, and the reacted Ca 2 Fe 2 O 5 And (5) performing oxidation regeneration. And then adding biogas residues into the reactor to continuously carry out chemical-looping gasification. The results of the chemical looping gasification reaction of biogas residues of the oxygen-decoupled oxygen carrier in comparative example 1 are shown in table 5.
TABLE 5 biogas residue chemical chain gasification implementation results based on non-oxygen decoupled oxygen carrier
Comparative example 2
The non-oxygen decoupling oxygen carrier in comparative example 2 was prepared in the same manner as in comparative example 1, except that the temperature of the chemical looping gasification reactor in comparative example 2 was heated to 800 deg.c, and the rest of the operations were the same as in comparative example 1. The results of the chemical looping gasification reaction of biogas residues of the oxygen-decoupled oxygen carrier in comparative example 2 are shown in table 6.
TABLE 6 implementation results of biogas residue chemical chain gasification based on non-oxygen decoupled oxygen carrier
Comparative example 3
The non-oxygen decoupled oxygen carrier of comparative example 3 was prepared in the same manner as in comparative example 1, except that the temperature of the chemical looping gasification reactor of comparative example 3 was heated to 900 c, and the rest of the operations were the same as in comparative example 1. The results of the chemical looping gasification reaction of biogas residues of the oxygen-decoupled oxygen carrier in comparative example 3 are shown in table 7.
TABLE 7 implementation results of biogas residue chemical chain gasification based on non-oxygen decoupled oxygen carrier
FIG. 1 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And non-oxygen decoupling oxygen carrier Ca in comparative example 1 2 Fe 2 O 5 X-ray photoelectron spectroscopy (x-ray photoelectron spectroscopy) spectrum (x-ray photoelectron spectroscopy) full spectrum (x-ray photoelectron spectroscopy (x-ray photoelectron.
As shown in FIG. 1, mn/Ca 2 Fe 2 O 5 (MCF) mainly contains Fe, mn, O, ca, which shows that Mn element is successfully doped into Ca 2 Fe 2 O 5 In a matrix; and the non-oxygen decoupling oxygen carrier mainly contains elements such as Fe, O, ca and the like.
FIG. 2A is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And comparative example 1 non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 O1s plot of x-ray photoelectron spectroscopy of (c).
As shown in FIG. 2A, the oxygen decoupler Mn/Ca in example 1 2 Fe 2 O 5 The oxygen binding energy of the medium lattice is higher than that of Ca 2 Fe 2 O 5 The mid-lattice oxygen binding energy was shifted to the left by 0.6eV, indicating Mn/Ca 2 Fe 2 O 5 The activity of the medium oxygen is stronger than Ca 2 Fe 2 O 5 The activity of oxygen, illustrating that the oxygen-decoupling oxygen carrier in example 1 of the present disclosure may release lattice oxygen into oxygen. As can also be seen from FIG. 2A, ca is caused by doping of Mn element 2 Fe 2 O 5 The lattice oxygen in (a) is converted into an active oxygen between the adsorbed oxygen and the lattice oxygen, and under certain conditions, the active oxygen can show oxygen decoupling performance, and when the binding energy is higher, the oxidizing property is stronger, so that the chemical chain gasification reaction is facilitated.
FIG. 2B is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And comparative example 1 non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 Fe 2 p-plot of x-ray photoelectron spectroscopy of (c).
As shown in FIG. 2B, ca is known to 2 Fe 2 O 5 The Fe element in the alloy is mainly Fe 2+ And Fe (Fe) 3+ Is present in the form of (c).
FIG. 3 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 Mn 2p 3/2 map of the x-ray photoelectron spectrum of (C).
As shown in FIG. 3, the Mn element in example 1 is mainly Mn in the oxygen-decoupling oxygen carrier 4+ And Mn of 3+ Is present in the form of (c).
FIG. 4 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And comparative example 1 non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 Is a temperature programmed reduction map.
As shown in FIG. 4, the reduction peak area of low temperature Duan Qingqi in the temperature-programmed reduction chart was larger, which means that the oxidation was stronger, but that of example 1The oxygen-decoupling oxygen carrier has a larger reduction peak at a low temperature section, which indicates that the oxygen-decoupling oxygen carrier Mn/Ca 2 Fe 2 O 5 Has stronger oxidizing property.
FIG. 5 is an oxygen-decoupling oxygen carrier Mn/Ca of example 1 of the present disclosure 2 Fe 2 O 5 And non-oxygen decoupling oxygen carrier Ca in comparative example 1 2 Fe 2 O 5 Thermal weight graph with 5 oxygen decoupling and regeneration.
Inert gas is simulated by using a thermal weight reactor to explore the weight loss of the oxygen decoupling oxygen carrier and the non-oxygen decoupling oxygen carrier in the reaction process, and the oxygen decoupling oxygen carrier and the non-oxygen decoupling oxygen carrier after weight loss are regenerated by using air (oxygen-containing gas). As shown in FIG. 5, oxygen-decoupling oxygen carrier Mn/Ca was carried out in the first 10min 2 Fe 2 O 5 And a non-oxygen decoupling oxygen carrier Ca 2 Fe 2 O 5 Weight loss occurs, which is caused by the adsorbed components in the oxygen carrier. Mn/Ca under inert gas Ar atmosphere 2 Fe 2 O 5 At constant weight loss, it is explained that Mn/Ca 2 Fe 2 O 5 Oxygen is released during the reaction, the amount of released oxygen is less than 2% (calculated by mass loss), representing Mn/Ca 2 Fe 2 O 5 The oxygen carrier has oxygen decoupling performance; while Ca in comparative example 2 Fe 2 O 5 No significant weight loss during the reaction process, indicating that it does not have oxygen decoupling properties. Next, mn/Ca after the reaction 2 Fe 2 O 5 And Ca 2 Fe 2 O 5 Air (containing oxygen) is introduced into the reactor, mn/Ca with oxygen decoupling performance is obtained 2 Fe 2 O 5 Ca that adsorbs oxygen to regenerate it under oxygen-enriched conditions without oxygen decoupling performance 2 Fe 2 O 5 There was no significant change in the oxygen enriched conditions. It can also be seen from fig. 5 that the oxygen-decoupling oxygen carrier provided by the present disclosure has a faster oxygen uptake rate, which is far higher than the rate of releasing oxygen, thereby making the regeneration rate faster, and due to Mn/Ca 2 Fe 2 O 5 The time of releasing oxygen of the oxygen carrier is longer than that of regeneration, which is also beneficial to the preparation of synthesis by chemical chain gasification reaction in practical applicationAnd (3) air. In addition, after continuous 5 times of oxygen decoupling and regeneration, the oxygen decoupling oxygen carrier Mn/Ca prepared by the method provided by the present disclosure is found 2 Fe 2 O 5 The quality of the catalyst is not obviously lost, and the oxygen decoupling performance of the catalyst has higher stability, so the catalyst has good recycling property.
The temperature in fig. 5 is the reaction temperature in the thermogravimetric reactor, and this temperature was used to simulate the temperature of the chemical chain gasification reaction and the temperature used for regenerating the oxygen carrier.
When Mn/Ca 2 Fe 2 O 5 The molar ratio of Mn, ca and Fe is greater than 2:1:1, mn/Ca as Mn content increases 2 Fe 2 O 5 Enhancement of oxygen carrier oxidability, CO and H in chemical chain gasification reactions 2 To a certain extent can be converted into CO 2 Resulting in CO and H 2 Yield decreases, CO 2 The yield is increased and the quality of the synthesis gas is reduced.
While the foregoing is directed to embodiments of the present disclosure, other and further details of the invention may be had by the present application, it is to be understood that the foregoing description is merely exemplary of the present disclosure and that no limitations are intended to the scope of the disclosure, except insofar as modifications, equivalents, improvements or modifications may be made without departing from the spirit and principles of the present disclosure.
Claims (8)
1. An oxygen-decoupled oxygen carrier for use in biogas residue chemical chain gasification applications, the oxygen-decoupled oxygen carrier comprising:
Ca 2 Fe 2 O 5 a substrate;
doped to the Ca 2 Fe 2 O 5 The Mn element on the substrate is a compound of Mn,
the molecular formula of the oxygen decoupling oxygen carrier is as follows:
Mn/Ca 2 Fe 2 O 5 ，
wherein, the mole ratio of Mn, ca and Fe is 1:1: 1-2: 1:1, a step of;
the Mn element is uniformly supported on the Ca 2 Fe 2 O 5 The surface and bulk phases of the matrix, and the oxygen-decoupling oxygen carrier comprises active oxygen between lattice oxygen and adsorbed oxygen.
2. A method of preparing the oxygen-decoupled oxygen carrier of claim 1, comprising:
s1, mixing ferric nitrate, calcium nitrate and manganese nitrate and preparing nitrate solution;
s2, adding a complexing agent into the nitrate solution, adding a pH regulator solution, and heating to form gel;
s3, calcining the dried gel at a first preset temperature to decompose nitrate, and heating to a second preset temperature to calcine to obtain Mn/Ca 2 Fe 2 O 5 An oxygen carrier.
3. The method of claim 2, wherein the nitrate solution has a molar ratio of manganese ions, calcium ions, and iron ions of 1:1: 1-2: 1:1, a step of;
the complexing agent is citric acid, and the molar ratio of the citric acid to metal ions in nitrate is 1:1-1: 2.
4. the method of claim 2, wherein said adjusting the pH range of the solution in S2 comprises: the pH value is adjusted to 1-2.
5. The method of claim 2, wherein,
the first preset temperature range includes: 500-600 ℃;
the first preset temperature calcination time range includes: 0.5 to 1.5 hours;
the second preset temperature range includes: 850-950 ℃;
the calcination time range of the second preset temperature includes: and 1-3 h.
6. The method of claim 2, further comprising grinding the calcined oxygen carrier to a powder to a particle size of less than 0.2nm.
7. Use of an oxygen-decoupled oxygen carrier according to any of claims 1 for biogas residue chemical chain gasification.
8. The use according to claim 7, comprising:
mixing biogas residue with the oxygen decoupling oxygen carrier, and carrying out biogas residue chemical chain gasification reaction at 600-1000 ℃ to prepare H 2 And synthesis gas with CO as the main component.
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