CN116371417B - Catalyst for synthesizing 3, 4-dimethyl pyrrole and preparation method and application thereof - Google Patents
Catalyst for synthesizing 3, 4-dimethyl pyrrole and preparation method and application thereof Download PDFInfo
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- CN116371417B CN116371417B CN202310202615.1A CN202310202615A CN116371417B CN 116371417 B CN116371417 B CN 116371417B CN 202310202615 A CN202310202615 A CN 202310202615A CN 116371417 B CN116371417 B CN 116371417B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- OJFOWGWQOFZNNJ-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC=C1C OJFOWGWQOFZNNJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 17
- 230000002194 synthesizing effect Effects 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims abstract description 45
- PLGIHTNXEHZXOP-UHFFFAOYSA-N [Zr].[Cr].[Zn].[Cu] Chemical compound [Zr].[Cr].[Zn].[Cu] PLGIHTNXEHZXOP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011651 chromium Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940102253 isopropanolamine Drugs 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 100
- 239000002243 precursor Substances 0.000 claims description 48
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 23
- 230000005070 ripening Effects 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 239000012691 Cu precursor Substances 0.000 claims description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 229910052726 zirconium Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 235000017550 sodium carbonate Nutrition 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 229910019580 Cr Zr Inorganic materials 0.000 claims description 5
- 229910019817 Cr—Zr Inorganic materials 0.000 claims description 5
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 4
- GDXUIKAGNJJWND-UHFFFAOYSA-O [Cr].[N+](=O)([O-])[O-].[NH4+] Chemical compound [Cr].[N+](=O)([O-])[O-].[NH4+] GDXUIKAGNJJWND-UHFFFAOYSA-O 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 claims description 4
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 4
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 230000000694 effects Effects 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000007036 catalytic synthesis reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- -1 2, 5-bis (methoxycarbonyl) -3, 4-dimethylpyrrole Chemical compound 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- UQJPYEMQAMHPFF-UHFFFAOYSA-N 1,3,4-trimethylpyrrole Chemical compound CC1=CN(C)C=C1C UQJPYEMQAMHPFF-UHFFFAOYSA-N 0.000 description 1
- CRAIERWZHKRDOK-UHFFFAOYSA-N 1-amino-3,4-dimethylpyrrole-2-carboxamide Chemical compound CC1=CN(N)C(C(N)=O)=C1C CRAIERWZHKRDOK-UHFFFAOYSA-N 0.000 description 1
- JUCRWFBISXIQHF-UHFFFAOYSA-N 2,5-diethyl-1H-pyrrole-3,4-dicarboxylic acid Chemical compound C(C)C=1NC(=C(C=1C(=O)O)C(=O)O)CC JUCRWFBISXIQHF-UHFFFAOYSA-N 0.000 description 1
- IEOJTKFLLYADNV-UHFFFAOYSA-N 3,4-dimethyl-1h-pyrrole-2-carboxylic acid Chemical compound CC1=CNC(C(O)=O)=C1C IEOJTKFLLYADNV-UHFFFAOYSA-N 0.000 description 1
- PAMCVZRNKYZZIQ-UHFFFAOYSA-N 5-bromo-3,4-dimethyl-1h-pyrrole-2-carbaldehyde Chemical compound CC=1C(C)=C(C=O)NC=1Br PAMCVZRNKYZZIQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 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
- 230000018109 developmental process Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- XUIPYRXOVPTMHC-UHFFFAOYSA-N ethyl 3,4-dimethyl-1h-pyrrole-2-carboxylate Chemical compound CCOC(=O)C=1NC=C(C)C=1C XUIPYRXOVPTMHC-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000010198 maturation time Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
-
- 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
-
- 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
Abstract
The invention discloses a copper zinc chromium zirconium catalyst, which comprises the components of CuO-ZnO-Cr 2 O 3 ‑ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the content of CuO is 1-90%, the content of ZnO is 1-90%, cr 2 O 3 The content of (3) is 1% -90%, zrO 2 The content of (2) is 1% -90%. The copper zinc chromium zirconium catalyst can catalyze isopropanolamine and epoxypropane to synthesize 3, 4-dimethylpyrrole, can convert 100% of isopropanolamine serving as a raw material, has a yield of up to 95.2%, and has the characteristics of high conversion rate, high selectivity and high yield.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for synthesizing 3, 4-dimethyl pyrrole, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
3, 4-dimethyl pyrrole is a key intermediate of various medicines and organic functional materials, and is used for synthesizing raw materials of 3, 4-dimethyl-1H-pyrrole-2-carboxyaldehyde, 5-bromo-3, 4-dimethyl-1H-pyrrole-2-formaldehyde, 1,3, 4-trimethyl pyrrole, 1-amino-3, 4-dimethyl-1H-pyrrole-2-carboxamide and pyrrole derivatives, so that the 3, 4-dimethyl pyrrole has very broad market application prospect.
At present, the synthesis of 3, 4-dimethylpyrrole mainly adopts an intermittent kettle type process, and raw materials comprise diethyl 3, 4-pyrrole dicarboxylic acid, ethyl 3, 4-dimethyl-1H-pyrrole-2-carboxylate, 3, 4-dimethyl-1H-pyrrole-2-carboxylic acid, 2, 5-bis (methoxycarbonyl) -3, 4-dimethylpyrrole and the like, the preparation process is complicated, and the production efficiency is low, so that the development of a method for continuously preparing 3, 4-dimethylpyrrole with high conversion rate and high yield is particularly important.
Disclosure of Invention
In order to overcome the problems, the invention provides a catalyst for synthesizing 3, 4-dimethylpyrrole, and a preparation method and application thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a Cu-Zn-Cr-Zr catalyst, which comprises CuO-ZnO-Cr 2 O 3 -ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the content of CuO is 1-90%, the content of ZnO is 1-90%, cr 2 O 3 The content of (3) is 1% -90%, zrO 2 The content of (2) is 1% -90%.
In a second aspect of the present invention, a method for preparing the copper zinc chromium zirconium catalyst is provided, which comprises:
s1, respectively adding a copper precursor, a zinc precursor, a chromium precursor and a zirconium precursor into a solvent, and dissolving to obtain a copper precursor solution, a zinc precursor solution, a chromium precursor solution and a zirconium precursor solution;
s2, adding a precipitant into the chromium precursor solution prepared in the step S1, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH of the solution unchanged in the curing process;
s3, adding a zinc precursor solution into the mixed solution obtained in the step S2, then adding a precipitator, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
s4, adding a copper precursor solution into the mixed solution obtained in the step S3, then adding a precipitant, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
s5, adding a zirconium precursor solution into the mixed solution obtained in the step S4, then adding a precipitant, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
and S6, dehydrating, drying, grinding and calcining the suspension obtained in the step S5 to obtain the Cu-Zn-Cr-Zr catalyst.
In a third aspect, the invention provides an application of the copper zinc chromium zirconium catalyst and/or the copper zinc chromium zirconium catalyst prepared by the preparation method in synthesizing 3, 4-dimethylpyrrole.
In a fourth aspect of the invention, a method for synthesizing 3, 4-dimethylpyrrole is provided, wherein isopropanolamine and propylene oxide are used as raw materials, 3, 4-dimethylpyrrole is catalyzed and synthesized, and the catalyst used is the copper-zinc-chromium-zirconium catalyst and/or the copper-zinc-chromium-zirconium catalyst prepared by the preparation method.
One or more technical solutions provided in the embodiments of the present invention at least have the following technical effects or advantages:
(1) The copper zinc chromium zirconium catalyst provided by the invention has catalytic dehydrogenation and dehydration performances, propylene oxide and isopropanolamine undergo ring opening reaction to generate hydramine, one hydroxyl group of the hydramine compound is dehydrogenated to form carbon-oxygen double bond under the prepared copper catalyst, double bond carbon and the other hydroxyl carbon are condensed to form a ring to generate hydroxyl, and two molecules of hydroxyl are dehydrated to generate 3, 4-dimethylpyrrole under the action of the catalyst at high temperature.
(2) The copper-zinc-chromium-zirconium catalyst provided by the invention has the characteristics of simple preparation method, wide raw material sources, low cost, capability of converting 100% of raw material isopropanolamine, high yield up to 95.2%, high conversion rate, high selectivity and high yield.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof. It is to be understood that the scope of the invention is not limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
In a first exemplary embodiment of the present invention, a Cu-Zn-Cr-Zr catalyst is provided, the composition of the catalyst is CuO-ZnO-Cr 2 O 3 -ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the content of CuO is 1-90%, the content of ZnO is 1-90%, cr 2 O 3 The content of (3) is 1% -90%, zrO 2 The content of (2) is 1% -90%.
In one or more embodiments, the CuO is present in an amount of 20% to 45%, the ZnO is present in an amount of 20% to 75%, and the Cr 2 O 3 The content of (C) is 10% -65%, zrO 2 The content of (2) is 10% -50%.
In a second exemplary embodiment of the present invention, a method for preparing the copper zinc chromium zirconium catalyst is provided, including:
s1, respectively adding a copper precursor, a zinc precursor, a chromium precursor and a zirconium precursor into a solvent, and dissolving to obtain a copper precursor solution, a zinc precursor solution, a chromium precursor solution and a zirconium precursor solution;
s2, adding a precipitant into the chromium precursor solution prepared in the step S1, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH of the solution unchanged in the curing process;
s3, adding a zinc precursor solution into the mixed solution obtained in the step S2, then adding a precipitator, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
s4, adding a copper precursor solution into the mixed solution obtained in the step S3, then adding a precipitant, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
s5, adding a zirconium precursor solution into the mixed solution obtained in the step S4, then adding a precipitant, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
and S6, dehydrating, drying, grinding and calcining the suspension obtained in the step S5 to obtain the Cu-Zn-Cr-Zr catalyst.
In one or more embodiments, in the step S1, the copper precursor includes one or more of copper acetate, copper nitrate, copper chloride, and copper oxalate; preferably one or more of copper oxalate, copper acetate and copper nitrate.
In one or more embodiments, in step S1, the zinc precursor includes one or more of zinc acetate, zinc oxalate, and zinc nitrate.
In one or more embodiments, in the step S1, the chromium precursor includes one or more of chromium sulfate, chromium acetate, chromium chloride, chromium oxalate, chromium nitrate, and chromium ammonium nitrate; preferably one or more of chromium acetate, chromium oxalate, chromium nitrate, chromium ammonium nitrate.
In one or more embodiments, in the step S1, the zirconium precursor includes one or more of zirconium acetate, zirconium nitrate, zirconium chloride, zirconium oxalate; preferably one or more of zirconium oxalate, zirconium acetate and zirconium nitrate.
In one or more embodiments, in the step S1, the solvent includes one or more of water, methanol, ethanol, acetonitrile; preferably one or two of water and ethanol.
Preferably, in the step S1, the solvents of the copper precursor solution, the zinc precursor solution, the chromium precursor solution, and the zirconium precursor solution may be the same or different.
In one or more embodiments, in the step S2, the precipitant includes one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, or sodium hydroxide; preferably one or more of ammonia, sodium bicarbonate and sodium carbonate.
In one or more embodiments, in the step S2, the temperature of the solution during the ripening is 25 to 95 ℃, preferably 25 to 50 ℃.
In one or more embodiments, in step S2, the pH of the solution is 2 to 13, preferably 8 to 11.
In one or more embodiments, in the step S2, the curing time is 0.05 to 24 hours, preferably 0.1 to 3 hours.
In one or more embodiments, in the step S3, the precipitant includes one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, or sodium hydroxide; preferably one or more of ammonia, sodium bicarbonate and sodium carbonate.
In one or more embodiments, in the step S3, the temperature of the solution during the ripening is 25 to 95 ℃, preferably 25 to 50 ℃.
In one or more embodiments, in step S3, the pH of the solution is 2 to 13, preferably 8 to 11.
In one or more embodiments, in the step S3, the curing time is 0.05 to 24 hours, preferably 0.1 to 3 hours.
In one or more embodiments, in the step S4, the precipitant includes one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, or sodium hydroxide; preferably one or more of ammonia, sodium bicarbonate and sodium carbonate.
In one or more embodiments, in the step S4, the temperature of the solution during the ripening is 25 to 95 ℃, preferably 25 to 50 ℃.
In one or more embodiments, in step S4, the pH of the solution is 2 to 13, preferably 8 to 11.
In one or more embodiments, in the step S4, the curing time is 0.05 to 24 hours, preferably 0.1 to 3 hours.
In one or more embodiments, in the step S5, the precipitant includes one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, or sodium hydroxide; preferably one or more of ammonia, sodium bicarbonate and sodium carbonate.
In one or more embodiments, in the step S5, the temperature of the solution during the ripening is 25 to 95 ℃, preferably 25 to 50 ℃.
In one or more embodiments, in step S5, the pH of the solution is 2 to 13, preferably 8 to 11.
In one or more embodiments, in the step S5, the curing time is 0.05 to 24 hours, preferably 0.1 to 3 hours.
In one or more embodiments, the precipitants used in S2-S5 may be different from each other, and the solution temperature and pH during the ripening process may be preferably uniform from one time to the next.
In one or more embodiments, in step S6, the calcination temperature is 300 to 600 ℃, preferably 400 to 550 ℃; the calcination time is 1.0 to 24 hours, preferably 2 to 10 hours.
In one or more embodiments, in the step S6, the drying conditions are: drying at 80-150 deg.c.
In a third exemplary embodiment of the present invention, there is provided the use of the copper zinc chromium zirconium catalyst described above and/or the copper zinc chromium zirconium catalyst prepared by the preparation method described above for the synthesis of 3, 4-dimethylpyrrole.
In a fourth exemplary embodiment of the present invention, a method for synthesizing 3, 4-dimethylpyrrole is provided, wherein isopropanolamine and propylene oxide are used as raw materials, and 3, 4-dimethylpyrrole is synthesized by catalysis, wherein the catalyst is the copper-zinc-chromium-zirconium catalyst and/or the copper-zinc-chromium-zirconium catalyst prepared by the preparation method.
In one or more embodiments, the steps of catalytic synthesis of 3, 4-dimethylpyrrole are:
(1) Activation of the catalyst; the activation method comprises the following steps: filling a catalyst in a fixed bed reactor, introducing nitrogen into the fixed bed reactor at room temperature until air is exhausted, introducing hydrogen diluted by the nitrogen into the fixed bed reactor, controlling the pressure to be 0.1-1Mpa, raising the reaction temperature of the fixed bed to 120 ℃ at a heating rate of 1.5-3 ℃/min and keeping the temperature for 2 hours, raising the reaction temperature of the fixed bed to 170 ℃ at a heating rate of 1.5-3 ℃/min and keeping the temperature for 2 hours, raising the reaction temperature of the fixed bed to 220 ℃ at a heating rate of 1.5-3 ℃/min and keeping the temperature for 4 hours, and raising the reaction temperature of the fixed bed to 270 ℃ at a heating rate of 1.5-3 ℃/min and keeping the reaction temperature of the fixed bed for 10 hours; preferably, the volume percentage of the hydrogen after the nitrogen is diluted is 1-15%;
(2) Maintaining the temperature of the fixed bed reactor at 270 ℃, controlling the pressure to be 0.5MPa, passing the mixed propylene oxide and isopropanolamine through a preheater at 250 ℃, and entering the fixed bed reactor to react with a catalyst to generate 3, 4-dimethylpyrrole;
(3) Sending the reaction liquid generated in the step (2) into a condenser for condensation, and sending the condensed material into a gas-liquid separator for separation to obtain 3, 4-dimethylpyrrole reaction liquid;
(4) And (3) rectifying and purifying the 3, 4-dimethylpyrrole reaction liquid obtained in the step (3) to obtain the 3, 4-dimethylpyrrole reaction liquid.
Preferably, the molar ratio of propylene oxide to isopropanolamine in step (2) is (0.1-7.5): 1, preferably in a molar ratio of (1.5-5): 1, a step of;
preferably, the isopropanolamine in the step (2) has a mass space velocity of 0.01h -1 ～0.55h -1 。
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
In the following examples, the catalyst activity was tested as follows: loading 12.5g of catalyst into a stainless steel reactor, placing the stainless steel reactor into an electric heating furnace, introducing nitrogen into the fixed bed reactor at room temperature to exhaust air, introducing hydrogen diluted by nitrogen into the fixed bed reactor, controlling the volume concentration of the hydrogen in the reaction gas to be 10%, controlling the pressure to be 0.5Mpa, heating the reaction temperature of the fixed bed to 120 ℃ at a heating rate of 2 ℃/min and keeping the temperature for 2h, heating the reaction temperature of the fixed bed to 170 ℃ at a heating rate of 2 ℃/min and keeping the temperature for 4h, heating the reaction temperature of the fixed bed to 220 ℃ at a heating rate of 2 ℃/min and keeping the reaction temperature of the fixed bed to 270 ℃ at a heating rate of 2 ℃/min and keeping the reaction temperature for 10h; the temperature in the reactor is controlled to 270 ℃, and the isopropanolamine feed mass space velocity is 0.2h -1 The molar ratio of the epoxypropane to the isopropanolamine is 1.2:1, and the total space velocity of the gas is 4500h -1 The conversion rate and the yield are used as the activity index of the catalyst.
Example 1
Preparation of copper zinc chromium zirconium catalyst:
s1, adding a certain amount of copper nitrate, zinc nitrate, chromium nitrate and zirconium nitrate into water respectively, and dissolving to obtain a copper precursor solution, a zinc precursor solution, a chromium precursor solution and a zirconium precursor solution;
s2, adding ammonia water into the chromium precursor solution prepared in the step S1 at the temperature of 25 ℃, adjusting the pH value of the solution to 9, and stirring and curing for 0.5h;
s3, adding a zinc precursor solution into the mixed solution obtained in the step S2, adding precipitator ammonia water to adjust the PH to 9, and stirring and curing for 0.5h;
s4, adding a copper precursor solution into the mixed solution obtained in the step S3, adding precipitator ammonia water to adjust the PH to 9, and stirring and curing for 0.5h;
s5, adding a zirconium precursor solution into the mixed solution obtained in the step S4, adding precipitator ammonia water to adjust the PH to 9, and stirring and curing for 0.75h;
the temperature of the solution is kept at 25 ℃ and the PH is kept at 9 in the ripening process of S2-S5, and meanwhile, the beaker is covered to prevent excessive evaporation of water in the ripening process;
and S6, continuously stirring the suspension obtained in the step S5 for 2 hours at 70 ℃ to be sticky under the state of opening the cover of the beaker, and drying, grinding and calcining at 110 ℃ to obtain the copper-zinc-chromium-zirconium catalyst.
The catalytic activity of the catalysts with different contents for the catalytic synthesis of 3, 4-dimethylpyrrole by adjusting the content of each metal element in the copper zinc chromium zirconium catalyst is shown in table 1.
TABLE 1 CuZnCrZr catalyst Activity at different mass fractions
Example 2
The temperature and pH of the solution during the ripening in the steps S2 to S5 were adjusted, and the other synthesis methods were the same as in example 1, except that the catalytic activity of the catalyst for the catalytic synthesis of 3, 4-dimethylpyrrole was as shown in Table 2.
TABLE 2 CuZnCrZr catalyst Activity at different curing temperatures and pH
Example 3
The time for curing in the steps S2 to S5 was adjusted, and the other synthesis methods were the same as those in example 1, except that the catalytic activities of the catalysts for the catalytic synthesis of 3, 4-dimethylpyrrole were as shown in Table 3.
TABLE 3 CuZnCrZr catalyst Activity at different maturation times
Example 4
The catalytic activities of the CuZnCrZr catalyst for catalyzing and synthesizing 3, 4-dimethylpyrrole under different loading sequences are studied by adjusting different metal loading sequences in different S2-S5 steps as shown in table 4.
Sequence 1: the loading sequence was as in example 1: chromium-zinc-copper-zirconium.
Sequence 2: exchanging the addition sequence of the copper precursor solution and the zinc precursor solution, wherein the loading sequence is as follows: chromium- & gt copper- & gt zinc- & gt zirconium.
Sequence 3: exchanging the addition sequence of the zinc precursor solution and the chromium precursor solution, wherein the loading sequence is as follows: zinc-chromium-copper-zirconium.
Sequence 4: exchanging the addition sequence of the chromium precursor solution and the copper precursor solution, wherein the loading sequence is as follows: copper→zinc→chromium→zirconium.
TABLE 4 CuZnCrZr catalyst Activity for different load sequences
| Preparation method | Isopropanolamine conversion (%) | Isopropanolamine yield (%) |
| Sequence 1 | 100 | 95.2 |
| Order 2 | 97.1 | 84.2 |
| Sequence 3 | 98.5 | 85.1 |
| Sequence 4 | 99.1 | 83.3 |
Example 5
Copper zinc chromium zirconium catalysts were synthesized by different synthesis methods and compared with the catalysts prepared in example 1 (content ratio of copper zinc chromium zirconium is 5:9:4:2), and the catalytic activity results are shown in table 5.
Coprecipitation method: copper nitrate, zinc nitrate, chromium nitrate and zirconium nitrate with the molar ratio of 5:9:4:2 are dissolved in a certain amount of deionized water, and stirred and dissolved; dissolving a certain amount of sodium carbonate in a certain amount of deionized water, simultaneously dropwise adding a nitrate solution and a sodium carbonate solution, keeping the temperature at 25 ℃ and the PH at 9, curing for 1h, and then aging for 1h; the copper-zinc-chromium-zirconium catalyst is prepared by filtering, washing, drying at 110 ℃, grinding and calcining at 500 ℃.
Carbonate heat treatment process: mixing copper carbonate, zinc carbonate, chromium carbonate, zirconium carbonate and deionized water in a molar ratio of 5:9:4:2 by adopting a ball star mill, and then drying at 110 ℃, milling and calcining at 500 ℃ to prepare the copper zinc chromium zirconium catalyst.
Hydrothermal method: copper nitrate, zinc nitrate, chromium nitrate and zirconium nitrate with the molar ratio of 5:9:4:2 are dissolved in a certain amount of deionized water, and stirred for dissolution; adding a certain amount of ammonia water to adjust the pH to 9, curing for 1.5 hours at room temperature, then placing into an autoclave, stirring for 2 hours at 70 ℃, then evaporating to dryness at 70 ℃, drying at 110 ℃, grinding and screening to obtain the catalyst.
TABLE 5 Activity of CuZnCrZr catalysts prepared by different preparation methods
| Preparation method | Isopropanolamine conversion (%) | Isopropanolamine yield (%) |
| Coprecipitation method | 95.8 | 88.9 |
| Carbonate heat treatment process | 91.5 | 75.4 |
| Hydrothermal process | 79.3 | 69.0 |
| The preparation method of the invention | 100 | 95.2 |
It should be noted that the above examples are only for illustrating the technical solution of the present invention and are not limiting thereof. Although the present invention has been described in detail with reference to the examples given, those skilled in the art can make modifications and equivalents to the technical solutions of the present invention as required, without departing from the spirit and scope of the technical solutions of the present invention.
Claims (36)
1. A copper zinc chromium zirconium catalyst in the synthesis of 3,the application of the 4-dimethylpyrrole is characterized in that the copper zinc chromium zirconium catalyst comprises CuO-ZnO-Cr 2 O 3 -ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the content of CuO is 1-90%, the content of ZnO is 1-90%, and Cr 2 O 3 The content of (3) is 1% -90%, and ZrO 2 The content of (2) is 1% -90%.
2. The use according to claim 1, wherein the content of CuO is 20% -45%, the content of ZnO is 20% -75%, and Cr 2 O 3 The content of (C) is 10% -65%, and ZrO 2 The content of (2) is 10% -50%.
3. The use according to claim 1, wherein the preparation method of the copper zinc chromium zirconium catalyst comprises the following steps:
s1, respectively adding a copper precursor, a zinc precursor, a chromium precursor and a zirconium precursor into a solvent, and dissolving to obtain a copper precursor solution, a zinc precursor solution, a chromium precursor solution and a zirconium precursor solution;
s2, adding a precipitant into the chromium precursor solution prepared in the step S1, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH of the solution unchanged in the curing process;
s3, adding a zinc precursor solution into the mixed solution obtained in the step S2, then adding a precipitator, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
s4, adding a copper precursor solution into the mixed solution obtained in the step S3, then adding a precipitant, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
s5, adding a zirconium precursor solution into the mixed solution obtained in the step S4, then adding a precipitant, adjusting the pH value of the solution, curing for a period of time, and keeping the temperature and the pH value of the solution unchanged in the curing process;
and S6, dehydrating, drying, grinding and calcining the suspension obtained in the step S5 to obtain the Cu-Zn-Cr-Zr catalyst.
4. The use according to claim 3, wherein in step S1 the copper precursor comprises one or more of copper acetate, copper nitrate, copper chloride, copper oxalate; or, the zinc precursor comprises one or more of zinc acetate, zinc oxalate and zinc nitrate;
or the chromium precursor comprises one or more of chromium sulfate, chromium acetate, chromium chloride, chromium oxalate, chromium nitrate and ammonium chromium nitrate;
or, the zirconium precursor comprises one or more of zirconium acetate, zirconium nitrate, zirconium chloride and zirconium oxalate; or, the solvent comprises one or more of water, methanol, ethanol and acetonitrile.
5. The method according to claim 4, wherein in the step S1, the copper precursor is one or more of copper oxalate, copper acetate and copper nitrate.
6. The use according to claim 4, wherein the chromium precursor is one or more of chromium acetate, chromium oxalate, chromium nitrate, chromium ammonium nitrate.
7. The use according to claim 4, wherein the zirconium precursor is one or more of zirconium oxalate, zirconium acetate, zirconium nitrate.
8. The use according to claim 4, wherein the solvent is one or both of water and ethanol.
9. The use according to claim 3, wherein in step S2, the precipitant comprises one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate or sodium hydroxide;
or the temperature of the solution in the ripening process is 25-95 ℃;
or the pH value of the solution is 2-13;
or the ripening time is 0.05-24 h.
10. The use according to claim 9, wherein the precipitant is one or more of ammonia water, sodium bicarbonate and sodium carbonate.
11. The use according to claim 9, wherein the temperature of the solution during the ripening is 25-50 ℃.
12. The use according to claim 9, wherein the pH of the solution is 8-11.
13. The use according to claim 9, wherein the ripening time is 0.1 to 3 hours.
14. The use according to claim 3, wherein in step S3, the precipitant comprises one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate or sodium hydroxide;
or the temperature of the solution in the ripening process is 25-95 ℃;
or the pH value of the solution is 2-13;
or the ripening time is 0.05-24 h.
15. The use according to claim 14, wherein the precipitant is one or more of aqueous ammonia, sodium bicarbonate and sodium carbonate.
16. The use according to claim 14, wherein the temperature of the solution during the ripening is 25-50 ℃.
17. The use according to claim 14, wherein the pH of the solution is 8-11.
18. The use according to claim 14, wherein the ripening time is 0.1 to 3 hours.
19. The use according to claim 3, wherein in step S4, the precipitant comprises one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate or sodium hydroxide;
or in the step S4, the temperature of the solution in the ripening process is 25-95 ℃;
or, in the step S4, the pH value of the solution is 2 to 13;
or in the step S4, the ripening time is 0.05-24 h.
20. The use according to claim 19, wherein the precipitant is one or more of aqueous ammonia, sodium bicarbonate and sodium carbonate.
21. The use according to claim 19, wherein the temperature of the solution during the ripening is 25-50 ℃.
22. The use according to claim 19, wherein the pH of the solution is 8-11.
23. The use according to claim 19, wherein the ripening time is 0.1 to 3 hours.
24. The use according to claim 3, wherein in step S5, the precipitant comprises one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate or sodium hydroxide;
or in the step S5, the temperature of the solution in the ripening process is 25-95 ℃;
or, in the step S5, the pH value of the solution is 2 to 13;
or, in the step S5, the curing time is 0.05-24 h.
25. The use according to claim 24, wherein the precipitant is one or more of aqueous ammonia, sodium bicarbonate and sodium carbonate.
26. The use according to claim 24, wherein the temperature of the solution during the ripening is 25-50 ℃.
27. The use according to claim 24, wherein the pH of the solution is 8 to 11.
28. The use according to claim 24, wherein the ripening time is 0.1 to 3 hours.
29. The use according to claim 3, wherein in step S6, the calcination temperature is 300 to 600 ℃; the calcination time is 1.0-24 h;
or, the drying conditions are as follows: and drying at 80-150 ℃.
30. The use according to claim 24, wherein the calcination temperature is 400-550 ℃; the calcination time is 2-10 h.
31. A method for synthesizing 3, 4-dimethylpyrrole is characterized in that isopropanolamine and propylene oxide are used as raw materials in the method, 3, 4-dimethylpyrrole is catalyzed and synthesized, a catalyst is the copper-zinc-chromium-zirconium catalyst in claim 1, and the copper-zinc-chromium-zirconium catalyst comprises CuO-ZnO-Cr 2 O 3 -ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the content of CuO is 1-90%, the content of ZnO is 1-90%, and Cr 2 O 3 The content of (3) is 1% -90%, and ZrO 2 The content of (2) is 1% -90%.
32. The method of claim 31, wherein the method comprises:
(1) Activation of the catalyst; the activation method comprises the following steps: filling a catalyst in a fixed bed reactor, introducing nitrogen into the fixed bed reactor at room temperature until air is exhausted, introducing hydrogen diluted by the nitrogen into the fixed bed reactor, controlling the pressure to be 0.1-1mpa, raising the reaction temperature of the fixed bed to 120 ℃ at a heating rate of 1.5-3 ℃/min and keeping the temperature for 2 hours, raising the reaction temperature of the fixed bed to 170 ℃ at a heating rate of 1.5-3 ℃/min and keeping the temperature for 2 hours, raising the reaction temperature of the fixed bed to 220 ℃ at a heating rate of 1.5-3 ℃/min and keeping the temperature for 4 hours, and raising the reaction temperature of the fixed bed to 270 ℃ at a heating rate of 1.5-3 ℃/min and keeping the reaction temperature of the fixed bed for 10 hours;
(2) Maintaining the temperature of the fixed bed reactor at 270 ℃, controlling the pressure to be 0.5MPa, passing the mixed propylene oxide and isopropanolamine through a preheater at 250 ℃, and entering the fixed bed reactor to react with a copper-zinc-chromium-zirconium catalyst to generate 3, 4-dimethylpyrrole;
(3) Sending the reaction liquid generated in the step (2) into a condenser for condensation, and sending the condensed material into a gas-liquid separator for separation to obtain 3, 4-dimethylpyrrole reaction liquid;
(4) And (3) rectifying and purifying the 3, 4-dimethylpyrrole reaction liquid obtained in the step (3) to obtain the 3, 4-dimethylpyrrole reaction liquid.
33. The method of claim 31, wherein the molar ratio of the propylene oxide to the isopropanolamine in step (2) is (0.1 to 7.5): 1.
34. the method of claim 33, wherein the molar ratio of the propylene oxide to the isopropanolamine in step (2) is (0.5 to 5): 1.
35. the process of claim 31, wherein the isopropanolamine in step (2) has a mass space velocity of 0.01h -1 ~0.55h -1 。
36. The method of claim 31, wherein in step (1), the volume percentage of hydrogen diluted with nitrogen is 1% -15%.
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