CN113797955B - Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and preparation method thereof Download PDFInfo
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- CN113797955B CN113797955B CN202111242122.8A CN202111242122A CN113797955B CN 113797955 B CN113797955 B CN 113797955B CN 202111242122 A CN202111242122 A CN 202111242122A CN 113797955 B CN113797955 B CN 113797955B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 46
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 28
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 28
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 63
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 11
- -1 ferrous iron ions Chemical class 0.000 claims description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 41
- 239000002994 raw material Substances 0.000 abstract description 24
- 239000011777 magnesium Substances 0.000 abstract description 15
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 229910052742 iron Inorganic materials 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000011229 interlayer Substances 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000001994 activation Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FOGVNFMUZXDMTR-UHFFFAOYSA-N [Mg].Cl Chemical compound [Mg].Cl FOGVNFMUZXDMTR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical group C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910000358 iron sulfate 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
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004711 α-olefin 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of carbon dioxide recycling, and particularly relates to a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and a preparation method thereof. The raw materials of the catalyst comprise iron salt, magnesium salt, organic amine and ammonium bicarbonate, and the catalyst can adapt to a wider raw material carbon-hydrogen ratio and has higher catalytic activity and selectivity. The catalyst has high iron content, organic amine and ammonium bicarbonate are used as raw materials of the catalyst, controllability of a precipitation process is guaranteed, atomic-scale dispersion of iron and magnesium is guaranteed, appropriate active sites are generated, appropriate interlayer ions and molecules are inserted, the size of the interlayer distance is adjusted, and other metal impurity ions cannot be introduced.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide recycling, and particularly relates to a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation and a preparation method thereof.
Background
Carbon dioxide is increasingly attracting attention for people due to climate change. Carbon dioxide is a greenhouse gas, but is also an important carbon source, and the utilization and the conversion of carbon dioxide into fuels and materials are important ways for realizing sustainable development. Hydrogen obtained by utilizing renewable energy sources and carbon dioxide are subjected to hydrogenation reaction, so that various valuable chemicals such as carbon monoxide, methane, low-carbon olefin, gasoline, aromatic hydrocarbon and the like can be obtained. Among them, low-carbon olefins are one of the most basic raw materials in the chemical industry.
The traditional synthesis process of the low-carbon olefin usually takes petroleum, coal or natural gas as raw materials, the carbon dioxide discharged in the process is more, if the carbon dioxide is taken as the raw material and hydrogen obtained by renewable energy is used for hydrogenation reaction, the carbon dioxide is not discharged, various chemical products can be produced, and the process is an important technical route for realizing the aim of carbon neutralization. The core of the successful technical route lies in developing a catalyst for preparing low-carbon olefin by directly hydrogenating high-performance carbon dioxide.
In the prior art, there are various methods for preparing low-carbon olefin catalysts, for example, chinese patent document CN106423263A discloses a catalyst for preparing low-carbon olefin by direct hydrogenation of carbon dioxide, which is formed by mixing two parts of metal oxide and molecular sieve, wherein the metal oxide is ZnO and ZrO 2 And a carrier, wherein the molecular sieve is SAPO-34, H-ZSM-5 or HY. For another example, chinese patent document CN108620089A discloses an iron-based catalyst with a manganese-modified surface for preparing low-carbon olefins by carbon dioxide hydrogenation, which comprises hydrothermally synthesizing magnetic Fe 3 O 4 Nanospheres of Fe 3 O 4 Performing ultrasonic pretreatment on the surfaces of the nanospheres, namely performing immersion method on the pretreated Fe 3 O 4 Manganese additives with different contents are loaded on the surfaces of the nanospheres. For another example, chinese patent document CN104624194A discloses a catalyst for preparing low-carbon olefins by carbon dioxide hydrogenation, the constituent elements of the catalyst are iron, zirconium, potassium and oxygen, and the preparation method of the catalyst comprises the steps of preparing an iron source and a zirconium source aqueous solution, and then carrying out the processes of precipitation, microwave induction, washing, drying, roasting, potassium source impregnation, tabletting, granulation, hydrogen reduction and the like.
However, the prior art still has some technical problems to be solved, (1) the low carbon selectivity is low, and a large amount of alkane and long-chain olefin exist in the product; (2) The catalyst activity is not high, and a large amount of circulation is needed in the reaction, so that the energy consumption is high; (3) The renewable energy has the characteristic of fluctuation, the hydrogen production amount of the electrolytic hydrogen production is unstable, the hydrogen-carbon ratio in the raw material has a large variation range, and the problems of poor product selectivity, carbon deposition inactivation and the like are caused. In the prior art, a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, which can tolerate the fluctuation of a large range of hydrogen-carbon ratio and has high conversion rate and high selectivity, is still lacked.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the low-carbon olefin catalyst in the prior art is not tolerant to the fluctuation range of the hydrogen-carbon ratio, and the activity and selectivity of the low-carbon olefin catalyst are poor, so that the invention provides the catalyst for preparing the low-carbon olefin by carbon dioxide hydrogenation and the preparation method thereof.
Therefore, the invention provides the following technical scheme.
The invention provides a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, which comprises iron salt, magnesium salt, organic amine and ammonium bicarbonate.
The molar ratio of the organic amine to the ammonium bicarbonate is (1-100): (1-100);
the organic amine is diethylamine, triethylamine or tetraethylammonium hydroxide.
The ferric salt comprises ferrous salt and ferric salt;
the ratio of the total molar amount of ferrous iron ions and magnesium ions to the molar amount of ferric iron ions is (1.5-5): 1;
the ratio of the total molar amount of ferrous ions and ferric ions to the molar amount of magnesium ions is (1-3): 1.
in the catalyst, 3Fe 3+ 、2Fe 2+ And 2Mg 2+ The ratio of the total molar weight of the organic amine to the total molar weight of the organic amine is (0.1-1) to (0.1-10); wherein, 3Fe 3+ Means 3 times of molar weight of ferric ions, 2Fe 2+ 2Mg which is 2 times of the molar weight of ferrous ions 2+ Means 2 times the molar amount of magnesium ions.
The invention also provides a preparation method of the catalyst for preparing the low-carbon olefin by carbon dioxide hydrogenation, which comprises the following steps,
(1) Forming a mixed solution A by using iron salt and magnesium salt; organic amine and ammonium bicarbonate form a mixed solution B; mixing the mixed solution A and the mixed solution B to obtain a mixture C;
(2) Crystallizing and roasting the mixture C to obtain a catalyst;
in the step (2), the roasting atmosphere comprises O 2 And H 2 O。
O in the atmosphere of the calcination 2 The volume fraction of (A) is 0.001-2%;
h in the roasting atmosphere 2 The volume fraction of O is 0.001-5%.
The firing atmosphere also includes inert atmospheres such as nitrogen, argon, and the like.
The mixed solution A and the mixed solution B are mixed at 60-90 ℃ under the atmosphere of carbon dioxide.
The specific steps of mixing the mixed solution A and the mixed solution B comprise the steps of firstly adding part of the mixed solution B into water, dropwise adding the mixed solution A and the rest of the mixed solution B into the water under the atmosphere of carbon dioxide, and obtaining a mixture C after the dropwise adding is finished; wherein, the amount of the part of the mixed solution B added in advance in water is not specifically limited, and when the mixture C is prepared, the 3Fe in the mixed solution A and the mixed solution B is only required 3+ 、2Fe 2+ And 2Mg 2+ The ratio of the total molar quantity of the organic amine to the total molar quantity of the organic amine is (0.1-1) to (0.1-10).
The crystallization temperature is 80-180 ℃, and the crystallization time is 2-96h.
The roasting temperature is 500-950 ℃, and the roasting time is 0.1-20h.
The iron salt can be, but is not limited to, iron salt hydrochloride, iron nitrate, iron sulfate, and the like; the magnesium salt may be, but is not limited to, magnesium hydrochloride, magnesium nitrate, magnesium sulfate, and the like.
The low-carbon olefin refers to an olefin product with the carbon number of 2-4.
The technical scheme of the invention has the following advantages:
1. the catalyst for preparing the low-carbon olefin by the carbon dioxide hydrogenation comprises the raw materials of iron salt, magnesium salt, organic amine and ammonium bicarbonate, can adapt to a wider raw material carbon-hydrogen ratio, and simultaneously has higher catalytic activity and selectivity. The catalyst has high iron content, organic amine and ammonium bicarbonate are used as raw materials of the catalyst, controllability of a precipitation process is guaranteed, atomic-level dispersion of iron and magnesium is guaranteed, appropriate active sites are generated, appropriate interlayer ions and molecules are inserted, the size of the interlayer distance is adjusted, and other metal impurity ions cannot be introduced. Organic amine is used as a raw material of the catalyst, and the catalyst is carbonized and nitrided to generate active sites in the activation process, so that the adsorption of carbon dioxide and hydrogen is enhanced. Furthermore, water is generated in the catalytic reaction process, and the ordered lamellar structure of the catalyst can generate reversible surface hydroxylation under the action of the water, so that the catalyst can adapt to a wider raw material hydrogen-carbon ratio, and the catalytic activity and selectivity of the catalyst are improved.
2. The catalyst for preparing the low-carbon olefin by carbon dioxide hydrogenation has the advantages that the microenvironment in the precipitation process is relatively stable by controlling the molar ratio of organic amine to ammonium bicarbonate through the buffering action of ion pairs, so that iron and magnesium in the catalyst can be dispersed in an atomic level, and a high-activity and high-selectivity catalytic crystal face structure surface can be formed in a controllable manner.
The diethylamine, triethylamine and tetraethyl ammonium hydroxide are common organic amines, the source is wide, the price is low, the unique space structure can effectively regulate and control the lamellar structure of the catalyst precursor, and the activity and the selectivity of the catalyst are improved.
By regulating and controlling the molar ratio of ferrous ions, ferric ions and magnesium ions, the iron content in the catalyst can be improved, so that the catalyst forms a catalyst precursor with an ordered lamellar structure, and the selectivity of the catalyst is improved.
3. The invention provides a preparation method of a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, which comprises the following steps of (1) forming a mixed solution A by iron salt and magnesium salt; organic amine and ammonium bicarbonate form a mixed solution B; mixing the mixed solution A and the mixed solution B to obtain a mixture C; (2) crystallizing and roasting the mixture C to obtain a catalyst; in the step (2), the roasting atmosphere comprises O 2 And H 2 And O. The precursor of the catalyst prepared by the method has an ordered lamellar structure, and the obtained catalyst can perform reversible surface hydroxylation reaction under the action of water, can adapt to a wider raw material hydrogen-carbon ratio, and simultaneously has higher catalytic activityAnd selectivity.
When the catalyst is prepared, organic amine and ammonium bicarbonate are added, so that controllability of a precipitation process can be guaranteed, atomic-level dispersion of iron and magnesium is guaranteed, a proper active site is generated, proper interlayer ions and molecules are inserted, the interlayer spacing of a hydrotalcite-like compound structure is adjusted, other metal impurity ions cannot be introduced, the organic amine is carbonized and nitrided in an activation process of the catalyst to generate the active site, adsorption of carbon dioxide and hydrogen is enhanced, and selectivity and activity of the catalyst are improved.
The activation process of the catalyst can be effectively controlled by controlling the atmosphere in the roasting process, high-efficiency active sites are generated by carbonization and nitridation, the electron transfer in the oxidation-reduction process of the catalyst is promoted, the generation of byproducts is inhibited, and the selectivity is improved;
in the mixing process of the mixed solution A and the mixed solution B, the atomic-level dispersion of iron and magnesium can be realized, and the crystal face orientation of the catalyst can be controlled.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are conventional reagent products which are commercially available, and manufacturers are not indicated.
In some embodiments of the present invention, the raw materials of the catalyst for preparing low carbon olefins by carbon dioxide hydrogenation include iron salt, magnesium salt, organic amine and ammonium bicarbonate, wherein the molar ratio of the organic amine to the ammonium bicarbonate is (1-100): (1-100), in other specific embodiments, the molar ratio of organic amine to ammonium bicarbonate can be any of the above ratios, or (20-80): (30-70), and can be (50-60): (40-60), for example, the molar ratio of organic amine to ammonium bicarbonate can be 5.
Example 1
This example provides a catalyst for preparing low carbon olefin by carbon dioxide hydrogenation, the raw material of which comprises Fe (NO) 3 ) 3 、FeSO 4 、Mg(NO 3 ) 2 Triethylamine and ammonium bicarbonate.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
(1) Taking Fe (NO) 3 ) 3 、FeSO 4 、Mg(NO 3 ) 2 Adding water to prepare Fe 3+ 、Fe 2 And Mg 2+ The mixed solution A with the molar concentrations of 0.08mol/L, 0.02mol/L and 0.1mol/L is reserved;
mixing triethylamine, ammonium bicarbonate and water to prepare a mixed solution B, wherein the molar concentrations of the triethylamine and the ammonium bicarbonate in the mixed solution B are respectively 0.1mol/L and 0.1mol/L for later use;
adding 50mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the dropping speed of 1mL/min and 5.5mL/min in the atmosphere of carbon dioxide at 60 ℃ until 100mL of mixed solution A and 550mL of mixed solution B are added to obtain a mixture C;
(2) And transferring the mixture C into a hydrothermal kettle, crystallizing at 100 ℃ for 12h, filtering to obtain a solid-phase product, washing, filtering under a nitrogen protective gas, drying to obtain an intermediate product, placing the intermediate product in a mixed atmosphere of oxygen, water and nitrogen, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 20h, and cooling to obtain the catalyst. Wherein the volume fraction of oxygen in the mixed atmosphere formed by oxygen, water and nitrogen is 0.001%, and the volume fraction of water vapor is 5%.
Example 2
This example provides a catalyst for preparing low carbon olefin by carbon dioxide hydrogenation, the raw material of which comprises FeCl 3 、FeCl 2 、MgCl 2 Diethylamine, and ammonium bicarbonate.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
(1) Taking FeCl 3 、FeCl 2 、MgCl 2 Adding water to prepare Fe 3+ 、Fe 2 And Mg 2+ Mixed solution A with the molar concentrations of 0.1mol/L, 0.35mol/L and 0.15mol/L respectively for standby;
mixing diethylamine, ammonium bicarbonate and water to prepare a mixed solution B, wherein the molar concentrations of the diethylamine and the ammonium bicarbonate in the mixed solution B are respectively 1mol/L and 0.01mol/L for standby;
adding 20mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the dropping speeds of 3mL/min and 4mL/min at 90 ℃ under the atmosphere of carbon dioxide until 150mL of mixed solution A and 200mL of mixed solution B are added to obtain a mixture C;
(2) And transferring the mixture C into a hydrothermal kettle, crystallizing at 180 ℃ for 12h, filtering to obtain a solid-phase product, washing, filtering under an argon protective gas, drying to obtain an intermediate product, placing the intermediate product in a mixed atmosphere of oxygen, water and nitrogen, heating to 900 ℃ at a heating rate of 0.5 ℃/min, roasting for 0.5h, and cooling to obtain the catalyst. Wherein the volume fraction of oxygen in the mixed atmosphere formed by oxygen, water and nitrogen is 2%, and the volume fraction of water vapor is 0.001%.
Example 3
This example provides a catalyst for preparing low carbon olefin by carbon dioxide hydrogenation, the raw material of which comprises Fe 2 (SO 4 ) 3 、FeSO 4 、MgSO 4 Tetraethylammonium hydroxide and ammonium bicarbonate.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
(1) Taking Fe 2 (SO 4 ) 3 、FeSO 4 、MgSO 4 Adding water to prepare Fe 3+ 、Fe 2 And Mg 2+ The molar concentrations are respectively 0.003mol/L, 0.005mol/L and 0.004mol/L of mixed solution A for standby;
mixing tetraethyl ammonium hydroxide solution, ammonium bicarbonate and water to prepare mixed solution B, wherein the molar concentrations of the tetraethyl ammonium hydroxide solution and the ammonium bicarbonate in the mixed solution B are 0.01mol/L and 1mol/L respectively for later use;
adding 50mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the temperature of 60 ℃ and in the atmosphere of carbon dioxide, wherein the dropwise adding speed is 0.5mL/min and 1.5mL/min respectively until 100mL of mixed solution A and 300mL of mixed solution B are added to obtain a mixture C;
(2) And transferring the mixture C into a hydrothermal kettle, crystallizing at 80 ℃ for 96h, filtering to obtain a solid-phase product, washing, filtering under a helium protective gas, drying to obtain an intermediate product, placing the intermediate product in a mixed atmosphere of oxygen, water and nitrogen, heating to 660 ℃ at a heating rate of 1 ℃/min, roasting for 24h, and cooling to obtain the catalyst. Wherein the volume fraction of oxygen in the mixed atmosphere formed by oxygen, water and nitrogen is 1%, and the volume fraction of water vapor is 2%.
Comparative example 1
The comparative example provides a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, and the raw material of the catalyst comprises Fe (NO) 3 ) 3 、FeSO 4 、Mg(NO 3 ) 2 Sodium hydroxide and ammonium bicarbonate.
The amount and preparation method of the raw materials in the catalyst are the same as those in example 1, and the amount of sodium hydroxide is the same as that of triethylamine.
Comparative example 2
The comparative example provides a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation, and the raw material of the catalyst comprises Fe (NO) 3 ) 3 、FeSO 4 、Mg(NO 3 ) 2 Triethylamine and sodium carbonate.
The amount and preparation method of the raw materials in the catalyst are the same as those in example 1, and the amount of sodium carbonate is the same as that of ammonium bicarbonate.
Comparative example 3
The comparative example provides a carbon dioxide hydrogenation processThe raw material of the catalyst for low-carbon olefin comprises Fe (NO) 3 ) 3 、FeSO 4 、Mg(NO 3 ) 2 Triethylamine and ammonium bicarbonate.
The preparation method of the catalyst comprises the following steps:
(1) Taking Fe (NO) 3 ) 3 、FeSO 4 、Mg(NO 3 ) 2 Adding water to prepare Fe 3+ 、Fe 2 And Mg 2+ The mixed solution A with the molar concentrations of 0.08mol/L, 0.02mol/L and 0.1mol/L is reserved;
mixing triethylamine, ammonium bicarbonate and water to prepare a mixed solution B, wherein the molar concentrations of the triethylamine and the ammonium bicarbonate in the mixed solution B are respectively 0.1mol/L and 0.1mol/L for later use;
adding 50mL of mixed solution B into 200mL of deionized water, and dropwise adding the mixed solution A and the mixed solution B at the same time at the temperature of 60 ℃ and under the atmosphere of carbon dioxide at the dropping speed of 1mL/min and 5.5mL/min respectively until 100mL of mixed solution A and 550mL of mixed solution B are added to obtain a mixture C;
(2) And transferring the mixture C into a hydrothermal kettle, crystallizing at 100 ℃ for 12h, filtering to obtain a solid-phase product, washing, filtering under a nitrogen protective gas, drying to obtain an intermediate product, placing the intermediate product in a pure nitrogen atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min, roasting for 20h, and cooling to obtain the catalyst.
Test examples
The test example provides performance tests and test results of the catalysts prepared in the examples and comparative examples.
1mL of each catalyst prepared in examples and comparative examples was charged into a fixed bed reactor, and the reaction was carried out at 350 ℃ and 5MPa in the presence of CO 2 The flow rate is 3000mL h -1 The reaction evaluation is carried out under the conditions that in order to simulate wider hydrogen-carbon ratio change, hydrogen with different flow rates is respectively introduced at 1 hour, 2 hours and 3 hours, the hydrogen-carbon ratio (the molar ratio of the hydrogen to the carbon dioxide) is respectively 3, 0.2 and 6, the product composition is detected by gas chromatography, and the space-time yield and the low-carbon olefin (ethylene, propylene, 1-butylene, cis-2-butylene, trans-plus-alpha-olefin) are calculated2-butene, isobutene).
TABLE 1 Performance test results of catalysts of examples and comparative examples
Through the test results of comparative example 1 and comparative example 2 recorded in table 1, it can be shown that the catalyst for preparing low carbon olefins by hydrogenation of carbon dioxide of the present invention uses organic amine and ammonium bicarbonate as raw materials, so that the catalyst can adapt to a wider raw material hydrogen-carbon ratio, and the selectivity and activity of the catalyst can be improved.
Through the test result of the comparative example 3, the invention can obviously improve the selectivity and the activity of the catalyst and adapt to a wider hydrogen-carbon ratio under a specific roasting atmosphere when preparing the catalyst.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (9)
1. A preparation method of a catalyst for preparing low-carbon olefin by carbon dioxide hydrogenation is characterized by comprising the following steps:
(1) Forming a mixed solution A by using iron salt and magnesium salt; organic amine and ammonium bicarbonate form a mixed solution B; mixing the mixed solution A and the mixed solution B to obtain a mixture C; the iron salt comprises ferrous salt and ferric salt; the organic amine is diethylamine, triethylamine or tetraethylammonium hydroxide;
(2) Crystallizing and roasting the mixture C to obtain a catalyst;
in the step (2), the roasting atmosphere comprises O 2 And H 2 O, also including inert atmosphere;
the roasting gasO in the atmosphere 2 The volume fraction of (A) is 0.001-2%;
h in the roasting atmosphere 2 The volume fraction of O is 0.001-5%.
2. The method according to claim 1, wherein the mixed solution a and the mixed solution B are mixed at 60 to 90 ℃ under an atmosphere of carbon dioxide.
3. The preparation method according to claim 1 or 2, wherein the mixing of the mixed solution A and the mixed solution B comprises the steps of adding a part of the mixed solution B into water, and dropwise adding the mixed solution A and the rest of the mixed solution B into the water under the atmosphere of carbon dioxide to obtain a mixture C after the dropwise adding.
4. The method according to claim 1 or 2, wherein the crystallization temperature is 80-180 ℃ and the crystallization time is 2-96 hours.
5. The method of claim 1 or 2, wherein the roasting temperature is 500-950 ℃ and the roasting time is 0.1-20h.
6. The method according to claim 1 or 2, wherein the molar ratio of the organic amine to the ammonium bicarbonate is (1-100): (1-100).
7. The production method according to claim 1 or 2, wherein a ratio of a total molar amount of ferrous iron ions and magnesium ions to a molar amount of ferric iron ions is (1.5-5): 1;
the ratio of the total molar amount of ferrous ions and ferric ions to the molar amount of magnesium ions is (1-3): 1.
8. the method according to claim 1 or 2, wherein 3Fe 3+ 、2Fe 2+ And 2Mg 2+ Total molar amount of (2) and molar amount of organic amineThe ratio of (1) - (0.1) - (10) is.
9. The use of the catalyst for preparing lower olefins by hydrogenation of carbon dioxide, prepared by the preparation method of any one of claims 1 to 8, in the preparation of lower olefins by hydrogenation of carbon dioxide.
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