CN116983996B - Method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas - Google Patents
Method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002407 reforming Methods 0.000 title claims abstract description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 117
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000001301 oxygen Substances 0.000 claims abstract description 113
- 239000007789 gas Substances 0.000 claims abstract description 81
- 239000002131 composite material Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 238000005261 decarburization Methods 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910002651 NO3 Inorganic materials 0.000 claims description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 24
- 238000002360 preparation method Methods 0.000 abstract description 12
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000011345 viscous material Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 6
- 238000003980 solgel method Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- -1 ethylene, propylene, butylene Chemical group 0.000 description 4
- 238000005691 oxidative coupling reaction Methods 0.000 description 4
- 230000007017 scission Effects 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
- C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
- C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a composite perovskite type oxygen carrier and a method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas based on the oxygen carrier. The chemical formula of the composite perovskite type oxygen carrier is La x A’ 1‑x Fe y B’ 1‑y O 3 Wherein the A' position is selected from one or more of Li, cs, na, sr, ba; b' is selected from one or two of Mn and W; x is more than 0 and less than 1, and y is more than 0 and less than 1. The composite perovskite type oxygen carrier not only can remarkably improve the selectivity of low-carbon olefin and the conversion rate of methane to low-carbon olefin, but also can be used for being matched with CO 2 Chemical chain splitting is carried out to realize the preparation of high-purity CO. The method sequentially carries out the steps of pretreatment, decarburization treatment, chemical chain reforming, chemical chain cracking and the like on the landfill gas, and finally realizes the preparation of low-carbon olefin and high-purity CO. The method has CH 4 High conversion rate and high CO purity, CH 4 The highest conversion rate can reach 85.37%, and the purity of CO is more than or equal to 96%.
Description
Technical Field
The invention belongs to the technical field of clean conversion of fuel, and particularly relates to a method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas.
Background
Landfill is one of the means commonly used in China for treating urban household garbage. The gas generated by degrading the organic matters in the garbage in the anaerobic process is called garbage landfill gas, and serious malodor, air pollution, greenhouse gas emission and other environmental hazard problems are caused to the periphery of the landfill site from beginning to end. Taking south China as an example, the main component of the urban refuse landfill gas is CH 4 And CO 2 The direct emission of the waste water can generate stronger greenhouse effect and is easy to cause explosion accidents to cause serious loss. The annual output of domestic garbage is more than 10 hundred million tons according to statistics, wherein the domestic garbage occupies two fifths of the total garbage. At present, the landfill gas is mainly used for the purposes of incineration, power generation, heat supply and the like, and the overall utilization rate is not high due to the limited space of urban construction, large investment of power generation projects, longer fund recovery period and other limiting factors,the problem of pollution of greenhouse gases still exists after incineration. Therefore, the research on the new generation of recycling technology of landfill gas is not slow.
The Chinese patent invention discloses a method for preparing methanol by using landfill gas, which reforms the landfill gas into synthesis gas (CH) 4 And CO 2 Combined reforming) by adding H 2 The hydrogen-carbon ratio in the synthesis gas is regulated to synthesize methanol, a part of unreacted gas is recycled, and the other part is used as purge gas and sent to a combustor, so that a scheme of tail gas circulation and comprehensive utilization of energy in the process is integrated. Although the method can ensure the energy efficiency and CO of the process of preparing the methanol from the landfill gas 2 The emission reduction rate is effectively improved, but the working procedures are more, the energy waste is easy to cause, and certain water vapor is additionally required to be supplemented to adjust the hydrogen-carbon ratio required by the methanol synthesis again, so that the operation difficulty is higher.
The low-carbon olefin (ethylene, propylene, butylene, etc.) is used as the core of petrochemical industry, has huge social demand and diversified end markets, and is the basic raw material of synthetic plastics, synthetic fibers, synthetic rubber, new chemical materials and daily chemical products. Currently, industrially used ethylene is mainly obtained by pyrolysis of naphtha or light diesel. The production of ethylene in China cannot meet domestic requirements at present due to the limitations of production scale, raw material resources and other conditions, and a new way for synthesizing ethylene by using landfill gas is developed and developed to become a key of the torsion situation of the low-carbon olefin in China. The method for preparing the low-carbon olefin by using methane at the present stage is mainly divided into 2 types (methane oxidative coupling and methane anaerobic conversion), wherein the method for preparing the olefin by using the methane oxidative coupling through one-step method is more favorable in thermodynamics and has higher feasibility in industrial application. Oxygen supply mode and CO using chemical chain as guide and oxygen carrier to replace molecular oxygen 2 The weak oxidative coupling of (2) realizes the selective activation and directional conversion of methane, and the technology for preparing olefin by oxidative coupling of chemical chains of methane is developed. Carbon monoxide is the main component in synthesis gas and coal gas, and is an important raw material for synthesizing a series of basic organic chemical products and intermediates, such as: organic chemicals such as formic acid, oxalic acid, acetic anhydride, and the like.
Thus, how to realizeCH in landfill gas 4 And CO 2 The catalytic co-conversion is used for preparing the low-carbon olefin and co-producing the high-purity carbon monoxide, and has great promotion effect on improving the energy utilization structure and the environmental pollution problem.
Disclosure of Invention
In view of the above-described problems of the prior art, a primary object of the present invention is to provide a composite perovskite-type oxygen carrier which can not only significantly improve the selectivity of lower olefins and the conversion of methane to lower olefins, but also be compatible with CO 2 Chemical chain cracking is carried out to realize the preparation of high-purity CO.
A second object of the present invention is to provide a method for producing the above-described composite perovskite type oxygen carrier.
The third object of the present invention is to provide an exogenous metal-modified composite perovskite type oxygen carrier.
The fourth object of the invention is to provide the application of the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier in preparing low-carbon olefin and/or carbon monoxide.
The fifth aim of the invention is to provide a method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas.
In order to achieve the above object, the present invention is realized by the following technical scheme:
a compound perovskite type oxygen carrier has a chemical formula of La x A’ 1-x Fe y B’ 1- y O 3 Wherein the A' position is selected from one or more of Li, cs, na, sr, ba; b' is selected from one or two of Mn and W; x is more than 0 and less than 1, and y is more than 0 and less than 1.
The invention adopts a citric acid sol-gel method to construct a composite perovskite type oxygen carrier. The chemical formula is La x A’ 1-x Fe y B’ 1-y O 3 When a specific metal is selected at the A' position, the composite perovskite type oxygen carrier can remarkably improve the selectivity of low-carbon olefin and reduce low-carbon alkane and low-carbon alkaneThe amount of high alkane produced. When the B' position selects specific Mn or W, the composite perovskite type oxygen carrier can lead CH to be 4 The activation generates C-H bond breaking, in-situ dehydrogenation and partial oxidation reaction dehydration with active oxygen molecules to obtain olefin products. The conversion rate of methane to low-carbon olefin can be obviously improved, and the yield of the low-carbon olefin is further improved. The composite perovskite type oxygen carrier can be well applied to the treatment of landfill gas, can be used for converting the landfill gas into low-carbon olefin directly in a clean and efficient way, and can be used for cracking carbon dioxide in both landfill gas raw materials and tail gas after combustion to generate CO.
Preferably, wherein the A 'position is selected from Sr and the B' position is selected from Mn; x is more than or equal to 0.3 and less than or equal to 0.9,0.3, y is more than or equal to 0.9. Further preferably, 0.7.ltoreq.x.ltoreq. 0.9,0.7.ltoreq.y.ltoreq.0.9; most preferably, x is 0.8 and y is 0.8.
Furthermore, the invention claims a preparation method of the composite perovskite type oxygen carrier, la (NO 3 ) 3 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O, A 'nitric acid solution and B' oxide are dissolved in deionized water, nitrate solution is obtained by mixing, citric acid and nitrate solution are mixed, a uniform gel system is obtained by water bath aging hydrolysis, and a compound perovskite type oxygen carrier precursor is obtained by post-treatment; the compound perovskite type oxygen carrier precursor is calcined at 800-1000 ℃, crushed, screened and separated to obtain the compound perovskite type oxygen carrier.
Preferably, the molar ratio of metal cations in the citric acid and nitrate solution is 2:1 to 1.3:1, a step of; further preferably, the molar ratio of metal cations in the citric acid and nitrate solution is 1.3:1.
preferably, the water bath Chen Huawei: stirring under the condition of constant-temperature water bath, evaporating water and hydrolyzing to obtain a uniform gel system.
Preferably, the temperature of the thermostatic water bath is 75-85 ℃.
Preferably, the post-treatment includes, but is not limited to, post-treatment steps such as drying.
Further, the invention requests protection of an exogenous metal modified composite perovskite type oxygen carrier, the composite perovskite type oxygen carrier or the composite perovskite type oxygen carrier prepared by the preparation method is mixed with ion doping auxiliary agents under the water bath condition, oscillated, completely immersed and dried, calcined at 800-1000 ℃, crushed, screened and separated to obtain the exogenous metal modified composite perovskite type oxygen carrier; the ion doping auxiliary agent is a metal salt solution, and the metal in the metal salt solution is selected from Na + 、K + 、Ca 2+ 、Li + 、Mg 2+ One or more of the following.
The inventor finds that the exogenous metal modified composite perovskite type oxygen carrier can be prepared by adding ion doping auxiliary agents into the composite perovskite type oxygen carrier through an impregnation method. The ion doping auxiliary agent can inhibit secondary reaction of surface carbon and olefin, and improve the yield and selectivity of low-carbon olefin. The combined use of the composite perovskite type oxygen carrier and the ion doping auxiliary agent can directionally regulate and control the matching of the transmission speed of active oxygen and the activation speed of C-H bond, the matching of the generation speed of reduced metal active site and the coupling speed of C-C bond, promote the coupling of methyl free radical to generate low-carbon olefin (such as ethylene) and inhibit the multiphase oxidation of the methyl free radical and the active oxygen to generate CO x Has the advantage of high comprehensive conversion efficiency of resources. The exogenous metal modified composite perovskite type oxygen carrier can be well applied to the treatment of landfill gas, can not only clean and efficiently convert the landfill gas into low-carbon olefin directly, but also crack carbon dioxide in both landfill gas raw materials and tail gas after combustion to generate CO.
Preferably, the metal salt solution is selected from NaCl solution, KCl solution, caCl 2 Solution, liCl solution, mgCl 2 One or more of the solutions. Further preferably, the metal salt solution is MgCl 2 A solution.
Preferably, the calcination time is 3 to 5 hours.
Preferably, the temperature of the water bath is 55-65 ℃. Further preferably, the temperature of the water bath is 60 ℃.
Preferably, the particle size of the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier ranges from 40 meshes to 80 meshes, and the pore size ranges from 50 nm to 100nm.
Furthermore, the invention also claims the application of the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier in preparing low-carbon olefin and/or carbon monoxide.
Furthermore, the invention also discloses a method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas, which comprises the following steps:
s1, decarburization treatment: performing pressure swing adsorption treatment on the pretreated landfill gas to remove CO in the landfill gas 2 Separating to obtain CO 2 And contain CH 4 Is a gas phase product of (a);
s2, chemical chain reforming: the step S1 contains CH 4 The gas phase product of (2) and the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier are subjected to chemical chain reforming in a reactor at 600-1000 ℃ to obtain a low-carbon olefin product;
s3, chemical chain splitting: the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier after the reaction in the step S2 and CO in the step S1 2 Carrying out chemical chain cracking at 600-1000 ℃ to obtain CO;
s3, oxygen carrier regeneration: calcining the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier after the reaction in the step S3 in air, recovering the initial state of the oxygen carrier, and then entering the step S2 for cyclic reaction.
The invention provides a method for preparing low-carbon olefin and CO-producing high-purity carbon monoxide by chemical chain reforming of landfill gas, which comprises the steps of decarbonizing the landfill gas after pretreatment, and carrying out CO treatment 2 Gas phase product (containing CH 4 ) Separation, followed by gas phase product and CO 2 Respectively and sequentially carrying out chemical chain reforming and chemical chain cracking reaction with the composite perovskite type oxygen carrier (or the exogenous metal modified composite perovskite type oxygen carrier), and combining the reaction process to realize the reactionThe preparation of low-carbon olefin and high-purity CO is finally realized by controlling the process conditions. In addition, the method also has CH 4 High conversion rate and high CO purity, CH 4 The highest conversion rate can reach 85.37%, and the purity of CO is more than or equal to 96%. The method provided by the invention can not only clean and efficiently convert the landfill gas into the low-carbon olefin directly, but also convert CO in the landfill gas raw material and the tail gas after combustion 2 Are cracked to form CO. The method has the advantages of low cost, convenient operation, easy mass production, carbon emission and the like. The obtained low-carbon olefin product can be used as a chemical synthesis raw material, and the obtained CO product has high purity and can be used as fuel or a reducing agent.
Preferably, in the pretreated landfill gas, H 2 The volume content of S is less than or equal to 0.1ppm.
Preferably, in the step S1, the temperature of the pressure swing adsorption treatment is 20 to 40 ℃. More specifically, after pressure swing adsorption treatment, the gas phase product CH 4 With CO 2 The volume ratio of (2) is 4:3, the gas phase product also contains trace CO and H 2 、N 2 、NH 3 And H 2 S, etc. The main component of the real landfill gas is methane CH 4 (40-65%) and CO 2 (30-45%), and trace amounts of CO and H 2 、N 2 、NH 3 And H 2 S, etc. The control of methane and carbon dioxide in the gas phase product in the above ratio can more truly simulate actual landfill gas.
Preferably, in the step S2, chemical chain reforming is performed at 800 to 850 ℃.
Preferably, in the step S3, chemical chain cleavage is performed at a temperature of 750 to 850 ℃.
Preferably, in the step S2, the reaction time of the chemical chain reforming is 3 to 25min. Further preferably, the reaction time of the chemical chain reforming is 20 to 25 minutes.
Preferably, in the step S3, the time for the cleavage of the chemical chain is 10 to 30min. Further preferably, the chemical chain cleavage time is 25 to 30 minutes.
Preferably, the pretreatment includes, but is not limited to, pretreatment procedures conventionally performed on landfill gas in the art, such as desulfurization and deacidification treatment, dust removal treatment, VOCs adsorption treatment, and the like. And the components such as hydrogen sulfide, nitrogen, VOCs and the like in the landfill gas are primarily removed by the pretreatment.
Preferably, in the step S3, the calcination is performed in air at a temperature of 800 to 1000 ℃.
Preferably, in the step S3, the calcination is performed in air for 30 to 90 minutes.
In the invention, the reaction heat obtained in the calcination process is circulated through the composite perovskite type oxygen carrier to provide heat for the process of preparing olefin by chemical chains and preparing carbon monoxide. The part of the whole system with insufficient heat realizes heat balance by burning partial gas phase products of landfill gas, and at the same time, the tail gas CO after burning 2 Can enter chemical chain to crack CO.
Specifically, the low-carbon olefin is olefin with 2-4 carbon atoms, namely the general name of small molecular olefins such as ethylene, propylene, butylene and the like.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a composite perovskite type oxygen carrier and an exogenous metal modified composite perovskite type oxygen carrier, which can remarkably improve the selectivity of low-carbon olefin, reduce the production of low-carbon alkane and high-carbon alkane, remarkably improve the conversion rate of methane to low-carbon olefin and further improve the yield of low-carbon olefin. The composite perovskite type oxygen carrier can be well applied to the treatment of landfill gas, can be used for converting the landfill gas into low-carbon olefin directly in a clean and efficient way, and can be used for cracking carbon dioxide in both landfill gas raw materials and tail gas after combustion to generate CO. Furthermore, the invention also provides a method for preparing the low-carbon olefin and CO-producing the high-purity carbon monoxide by the chemical chain reforming of the landfill gas based on the oxygen carrier, which sequentially carries out the steps of pretreatment, decarburization treatment, chemical chain reforming, chemical chain cracking and the like on the landfill gas, and finally realizes the preparation of the low-carbon olefin and the high-purity carbon monoxide. The method has CH 4 High conversion rate and high CO purity, CH 4 The highest conversion rate can reach 85.37%, and the purity of CO is more than or equal to 96%. The method provided by the invention can not only clean and efficiently convert the landfill gas into the low-carbon olefin directly, but also convert CO in the landfill gas raw material and the tail gas after combustion 2 Are cracked to form CO. The method has the advantages of low cost, convenient operation, easy mass production, carbon emission and the like.
Drawings
FIG. 1 is a flow chart for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1 preparation of a composite perovskite oxygen Carrier
(1) Constructing a composite perovskite type oxygen carrier by adopting a citric acid sol-gel method:
weighing a certain amount of La (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O and Sr (NO 3) 2 are denoted as A 1 ，Fe(NO 3 ) 3 ·9H 2 O and Mn 2 O 3 Denoted as B 1 Dissolving with deionized water, mixing to obtain nitrate solution, wherein the total ion concentration in the nitrate solution is 0.5mol/L; wherein, la/Sr=8/2 at the A position and Fe/Mn=8/2 at the B position. The citric acid was weighed and dissolved and the nitrate solution was added to obtain a mixed solution (citric acid: metal cation=1.3). Stirring the mixed solution under the condition of constant temperature water bath at 80 ℃, evaporating water, stirring for 7 hours to form a viscous substance, and then placing the viscous substance into a vacuum drying oven at 80 ℃ for drying for about 24 hours to obtain the composite perovskite type oxygen carrier precursor.
(2) Calcining the precursor of the composite perovskite type oxygen carrier in the step (1) at 1000 ℃ for 3 hours, then crushing, and screening to obtain the composite perovskite type oxygen carrier La with the particle size range of 40-60 meshes 0.8 Sr 0.2 Fe 0.8 Mn 0.2 O 3 。
Example 2 preparation of an exogenous Metal-modified composite perovskite oxygen Carrier
(1) Constructing a composite perovskite type oxygen carrier by adopting a citric acid sol-gel method:
weighing a certain amount of La (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O and Sr (NO 3) 2 are denoted as A 1 ，Fe(NO 3 ) 3 ·9H 2 O and Mn 2 O 3 Denoted as B 1 Dissolving with deionized water, and mixing to obtain nitrate solution; la/sr=8/2 at position a and Fe/mn=8/2 at position b. The citric acid was weighed and dissolved and the nitrate solution was added to obtain a mixed solution (citric acid: metal cation=1.3). Stirring the mixed solution under the condition of constant temperature water bath at 80 ℃, evaporating water, stirring for 7 hours to form a viscous substance, and then placing the viscous substance into a vacuum drying oven at 80 ℃ for drying for about 24 hours to obtain the composite perovskite type oxygen carrier precursor.
(2) The compound perovskite type oxygen carrier precursor in the step (1) is crushed and sieved after reacting for 3 hours at 1000 ℃ to obtain the compound perovskite type oxygen carrier La with the particle size range of 40-60 meshes 0.8 Sr 0.2 Fe 0.8 Mn 0.2 O 3 。
(3) Mixing the composite perovskite type oxygen carrier in the step (2) with 10ml of NaCl solution under the water bath condition of 60 ℃ and vibrating for 24 hours to ensure complete impregnation, then drying for 24 hours under the condition of 120 ℃, calcining for 3 hours under the temperature of 950 ℃ by adopting a muffle furnace, and screening to obtain Na + Modifying the composite perovskite type oxygen carrier.
Example 3 preparation of an exogenous Metal-modified composite perovskite oxygen Carrier
(1) Constructing a composite perovskite type oxygen carrier by adopting a citric acid sol-gel method:
weighing a certain amount of La (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O and Sr (NO 3) 2 are denoted as A 1 ，Fe(NO 3 ) 3 ·9H 2 O and Mn 2 O 3 Denoted as B 1 Dissolving and mixing with deionized water to obtain nitrate solution; la/sr=8/2 at position a, fe/mn=8 +.2. The citric acid was weighed and dissolved and the nitrate solution was added to obtain a mixed solution (citric acid: metal cation=1.3). Stirring the mixed solution under the condition of constant temperature water bath at 80 ℃, evaporating water, stirring for 7 hours to form a viscous substance, and then placing the viscous substance into a vacuum drying oven at 80 ℃ for drying for about 24 hours to obtain the composite perovskite type oxygen carrier precursor.
(2) The compound perovskite type oxygen carrier precursor in the step (1) is crushed and sieved after reacting for 3 hours at 1000 ℃ to obtain the compound perovskite type oxygen carrier La with the particle size range of 40-60 meshes 0.8 Sr 0.2 Fe 0.8 Mn 0.2 O 3 。
(3) The composite perovskite type oxygen carrier in the step (2) is mixed with 10ml MgCl under the water bath condition of 60 DEG C 2 Mixing the solutions, oscillating for 24 hours to ensure complete impregnation, drying at 120deg.C for 24 hours, calcining at 950 deg.C for 3 hours by using a muffle furnace, and sieving to obtain Mg 2+ Modifying the composite perovskite type oxygen carrier.
Example 4 preparation of an exogenous Metal-modified composite perovskite oxygen Carrier
(1) Constructing a composite perovskite type oxygen carrier by adopting a citric acid sol-gel method:
weighing a certain amount of La (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O and LiNO 3 Is marked as A 1 ，Fe(NO 3 ) 3 ·9H 2 O and Mn 2 O 3 Denoted as B 1 Dissolving and mixing with deionized water to obtain nitrate solution; la/li=8/2 at position a and Fe/mn=8/2 at position b. The citric acid was weighed and dissolved and the nitrate solution was added to obtain a mixed solution (citric acid: metal cation=1.3). Stirring the mixed solution under the condition of constant temperature water bath at 80 ℃, evaporating water, stirring for 7 hours to form a viscous substance, and then placing the viscous substance into a vacuum drying oven at 80 ℃ for drying for about 24 hours to obtain the composite perovskite type oxygen carrier precursor.
(2) The compound perovskite type oxygen carrier precursor in the step (1) is crushed and sieved after reacting for 3 hours at 1000 ℃ to obtain the compound perovskite type oxygen carrier La with the particle size range of 40-60 meshes 0.8 Li 0.2 Fe 0.8 Mn 0.2 O 3 。
(3) The composite perovskite type oxygen carrier in the step (2) is mixed with 10ml MgCl under the water bath condition of 60 DEG C 2 Mixing the solutions, oscillating for 24 hours to ensure complete impregnation, drying at 120deg.C for 24 hours, calcining at 950 deg.C for 3 hours by using a muffle furnace, and sieving to obtain Mg 2+ Modifying the composite perovskite type oxygen carrier.
Example 5 preparation of an exogenous Metal-modified composite perovskite oxygen Carrier
(1) Constructing a composite perovskite type oxygen carrier by adopting a citric acid sol-gel method:
weighing a certain amount of La (NO) according to stoichiometric ratio 3 ) 3 ·6H 2 O and Ba (NO 3) 2 are denoted as A 1 ，Fe(NO 3 ) 3 ·9H 2 O and Mn 2 O 3 Denoted as B 1 Dissolving and mixing with deionized water to obtain nitrate solution; la/ba=8/2 at position a and Fe/mn=8/2 at position b. The citric acid was weighed and dissolved and the nitrate solution was added to obtain a mixed solution (citric acid: metal cation=1.3). Stirring the mixed solution under the condition of constant temperature water bath at 80 ℃, evaporating water, stirring for 7 hours to form a viscous substance, and then placing the viscous substance into a vacuum drying oven at 80 ℃ for drying for about 24 hours to obtain the composite perovskite type oxygen carrier precursor.
(2) The compound perovskite type oxygen carrier precursor in the step (1) is crushed and sieved after reacting for 3 hours at 1000 ℃ to obtain the compound perovskite type oxygen carrier La with the particle size range of 40-60 meshes 0.8 Ba 0.2 Fe 0.8 Mn 0.2 O 3 。
(3) The composite perovskite type oxygen carrier in the step (2) is mixed with 10ml MgCl under the water bath condition of 60 DEG C 2 Mixing the solutions, oscillating for 24 hours to ensure complete impregnation, drying at 120deg.C for 24 hours, calcining at 950 deg.C for 3 hours by using a muffle furnace, and sieving to obtain Mg 2+ Modifying the composite perovskite type oxygen carrier.
Example 6 method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas
(1) Pretreatment: as shown in FIG. 1, the landfill gas sourceThe material is subjected to desulfurization and deacidification treatment, dust removal treatment, VOCs adsorption treatment, primary removal of components such as large-particle dust, hydrogen sulfide, nitrogen, VOCs and the like, and H in landfill gas is controlled 2 S volume content is less than or equal to 0.1ppm, and the pretreated landfill gas is obtained.
(2) Decarburization treatment: performing PSA pressure swing adsorption treatment on the pretreated landfill gas at 20-40 ℃ to remove CO in the landfill gas 2 Separating to obtain CO 2 And contain CH 4 Is a gas phase product of (a) a gas phase product of (b).
(3) Chemical chain reforming: the step (2) contains CH 4 The gas phase product of (2) and the composite perovskite type oxygen carrier prepared in the embodiment 1 are reformed in a fixed bed of landfill gas simulated atmosphere at 700 ℃, active components in the gas phase product react with oxygen carrier lattice oxygen, the oxygen carrier is reduced into lower oxides, the reaction time is 20min, the low-carbon olefin product is obtained, and the reformed tail gas can be burnt for supplying heat to a system.
(4) Preparing CO by chemical chain cleavage: the oxygen carrier of the suboxide in the reduced state after the reaction in the step (3) is separated from the CO in the step (2) 2 CO at 780 DEG C 2 And (3) carrying out chemical chain cracking in a fixed bed in the atmosphere, wherein the reaction time is 25min, and obtaining the high-purity CO.
(5) Oxygen carrier regeneration: and (3) regenerating and calcining the oxygen carrier reacted in the step (4) in a high-temperature air atmosphere, wherein the calcining temperature is 900 ℃, the calcining time is 60 minutes, the initial state of the oxygen carrier is recovered, and then the composite perovskite type oxygen carrier enters the step (3) for cyclic reaction. In the regeneration process, the generated heat is circularly transported to the process of preparing olefin by chemical chains and preparing carbon monoxide by chemical chains through the composite perovskite type oxygen carrier.
EXAMPLES 7-10A method for preparing low-carbon olefins and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas
Examples 7 to 10 differ from example 6 in that: the exogenous metal-modified composite perovskite type oxygen carriers prepared in examples 2 to 5 were used, respectively, and the differences of other specific reaction conditions are shown in the following table 1.
Comparative example 1
Comparative exampleExample 3 differs in that: in the step (2), a composite perovskite type oxygen carrier precursor La is prepared and obtained 0.8 Cu 0.2 Fe 0.8 Mn 0.2 O 3 。
Comparative example 2
The difference between this comparative example and example 3 is that: in the step (2), a composite perovskite type oxygen carrier precursor La is prepared and obtained 0.8 Sr 0.2 Fe 0.8 Ca 0.2 O 3 。
Comparative example 3
The difference between this comparative example and example 3 is that: in the step (2), a composite perovskite type oxygen carrier precursor La is prepared and obtained 0.8 Ca 0.2 Fe 0.8 Ce 0.2 O 3 。
Comparative examples 4-8A method for preparing low-carbon olefin and co-producing high-purity carbon monoxide by chemical chain reforming of landfill gas
Comparative examples 4 to 6 differ from example 8 in that: the exogenous metal-modified composite perovskite type oxygen carriers prepared in comparative examples 1 to 3 were used, respectively, and the differences of other specific reaction conditions are shown in the following table 1.
Comparative examples 7 to 8 the exogenous metal-modified composite perovskite type oxygen carrier prepared in example 8 was used, and the differences of other specific reaction conditions are shown in table 1 below.
TABLE 1
Test example 1
The products obtained in step (3) and step (4) in examples 6 to 10 and comparative examples 4 to 8 were tested by Gas Chromatography (GC). The test results are shown in table 2 below.
TABLE 2
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The claims that follow are intended to claim the broadest possible scope as conceivable and the embodiments presented herein are demonstrated for the applicant's true test results. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (4)
1. The method for preparing the low-carbon olefin co-production high-purity carbon monoxide by chemical chain reforming of the landfill gas is characterized by comprising the following steps of:
s1, decarburization treatment: performing pressure swing adsorption treatment on the pretreated landfill gas to remove CO in the landfill gas 2 Separating to obtain CO 2 And contain CH 4 Is a gas phase product of (a);
s2, chemical chain reforming: the step S1 contains CH 4 The gas phase product of (2) and the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier are subjected to chemical chain reforming in a reactor at 800-850 ℃ to obtain a low-carbon olefin product; the reaction time of the chemical chain reforming is 20-25 min;
s3, chemical chain splitting: the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier after the reaction in the step S2 and CO in the step S1 2 Performing chemical chain cracking at the temperature of 750-850 ℃ to obtain CO; the reaction time of the chemical chain cracking is 25-30 min;
s3, oxygen carrier regeneration: calcining the composite perovskite type oxygen carrier or the exogenous metal modified composite perovskite type oxygen carrier after the reaction in the step S3 in air, recovering the initial state of the oxygen carrier, and then entering the step S2 for cyclic reaction;
the chemical formula of the composite perovskite type oxygen carrier is La x A’ 1-x Fe y B’ 1-y O 3 Wherein the A 'position is selected from Sr and the B' position is selected from Mn; x is more than or equal to 0.3 and less than or equal to 0.9,0.3, y is more than or equal to 0.9;
mixing the composite perovskite type oxygen carrier with an ion doping auxiliary agent under the water bath condition, vibrating, drying after soaking completely, calcining at 800-1000 ℃, crushing, screening and separating to obtain the exogenous metal modified composite perovskite type oxygen carrier; the ion doping auxiliary agent is a metal salt solution, and the metal in the metal salt solution is selected from Na + 、K + 、Ca 2+ 、Li + 、Mg 2+ One or more of the following.
2. The method according to claim 1, wherein La (NO 3 ) 3 ·6H 2 O、Fe (NO 3 ) 3 ·9H 2 O, A 'nitric acid solution and B' oxide are dissolved in deionized water, nitrate solution is obtained by mixing, citric acid and nitrate solution are mixed, a uniform gel system is obtained by water bath aging hydrolysis, and a compound perovskite type oxygen carrier precursor is obtained by post-treatment; the compound perovskite type oxygen carrier precursor is calcined at 800-1000 ℃, crushed, screened and separated to obtain the compound perovskite type oxygen carrier.
3. The method according to claim 2, characterized in that the molar ratio of metal cations in the citric acid and nitrate solution is 2:1 to 1.3:1.
4. the method according to claim 1, wherein the metal salt solution is selected from the group consisting of NaCl solution, KCl solution, caCl 2 Solution, liCl solution, mgCl 2 One or more of the solutions.
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