CN118546083B - A method and system for synthesizing indole and its derivatives by alcoholamine method - Google Patents
A method and system for synthesizing indole and its derivatives by alcoholamine method Download PDFInfo
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- CN118546083B CN118546083B CN202411014527.XA CN202411014527A CN118546083B CN 118546083 B CN118546083 B CN 118546083B CN 202411014527 A CN202411014527 A CN 202411014527A CN 118546083 B CN118546083 B CN 118546083B
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title claims abstract description 236
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title claims abstract description 159
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 116
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 207
- 239000002994 raw material Substances 0.000 claims abstract description 161
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 128
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000000047 product Substances 0.000 claims abstract description 81
- 230000009467 reduction Effects 0.000 claims abstract description 58
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 21
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 21
- -1 alcohol amine Chemical class 0.000 claims abstract description 20
- 150000001448 anilines Chemical class 0.000 claims abstract description 18
- 238000011069 regeneration method Methods 0.000 claims abstract description 18
- 230000008929 regeneration Effects 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 4
- 230000008016 vaporization Effects 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 469
- 238000006243 chemical reaction Methods 0.000 claims description 266
- 239000001257 hydrogen Substances 0.000 claims description 223
- 229910052739 hydrogen Inorganic materials 0.000 claims description 223
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 185
- 239000012752 auxiliary agent Substances 0.000 claims description 98
- 239000012071 phase Substances 0.000 claims description 87
- 239000007789 gas Substances 0.000 claims description 74
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 47
- 229910021645 metal ion Inorganic materials 0.000 claims description 47
- ONYNOPPOVKYGRS-UHFFFAOYSA-N 6-methyl-1h-indole Chemical compound CC1=CC=C2C=CNC2=C1 ONYNOPPOVKYGRS-UHFFFAOYSA-N 0.000 claims description 44
- 150000002431 hydrogen Chemical class 0.000 claims description 43
- 238000000926 separation method Methods 0.000 claims description 40
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 38
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 31
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 30
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 30
- 239000012298 atmosphere Substances 0.000 claims description 29
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 26
- 238000004064 recycling Methods 0.000 claims description 22
- 229960004063 propylene glycol Drugs 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical group C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000012856 packing Methods 0.000 claims description 17
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical group C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 claims description 16
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical group C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 235000013772 propylene glycol Nutrition 0.000 claims description 11
- 150000002475 indoles Chemical class 0.000 claims description 9
- 239000012263 liquid product Substances 0.000 claims description 9
- QRRKZFCXXBFHSV-UHFFFAOYSA-N 1-ethylindole Chemical group C1=CC=C2N(CC)C=CC2=C1 QRRKZFCXXBFHSV-UHFFFAOYSA-N 0.000 claims description 8
- YPKBCLZFIYBSHK-UHFFFAOYSA-N 5-methylindole Chemical group CC1=CC=C2NC=CC2=C1 YPKBCLZFIYBSHK-UHFFFAOYSA-N 0.000 claims description 8
- KGWPHCDTOLQQEP-UHFFFAOYSA-N 7-methylindole Chemical group CC1=CC=CC2=C1NC=C2 KGWPHCDTOLQQEP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001041 indolyl group Chemical group 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005191 phase separation Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims 2
- 239000000969 carrier Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000009849 deactivation Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 127
- 238000011068 loading method Methods 0.000 description 29
- 238000003746 solid phase reaction Methods 0.000 description 27
- 239000012299 nitrogen atmosphere Substances 0.000 description 26
- 239000007858 starting material Substances 0.000 description 26
- 239000011949 solid catalyst Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000001704 evaporation Methods 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 13
- 238000010924 continuous production Methods 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000009776 industrial production Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/007—Energy recuperation; Heat pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/146—Multiple effect distillation
-
- 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
- B01J23/72—Copper
-
- 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
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0285—Heating or cooling the reactor
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Indole Compounds (AREA)
Abstract
The invention provides a method and a system for synthesizing indole and derivatives thereof by an alcohol amine method, belonging to the technical field of heterocyclic compound synthesis. The preparation method comprises the steps of filling a Cu-based multi-phase catalyst into a fixed bed reactor, introducing H 2/N2 mixed gas for reduction, mixing raw materials of aniline or aniline derivatives, polyalcohols and water, vaporizing, introducing the mixture into the reactor for catalytic reaction, and cooling, separating and purifying reaction products to obtain purified indole and derivative products thereof. The Cu-based multi-phase catalyst can be subjected to in-situ deactivation and regeneration, then reduced and then continuously used for catalytic reaction, and meanwhile, synthesis reaction and purification are carried out through an specially-arranged synthesis system. The invention can continuously synthesize indole and derivatives thereof under the conditions of easily available raw materials and relatively low temperature, simultaneously uses a catalyst without noble metal, can be deactivated and regenerated in situ, and is suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of heterocyclic compound synthesis, in particular to a method and a system for synthesizing indole and derivatives thereof by an alcohol amine method.
Background
Indole and indole ring compounds are important organic raw materials and chemical products, and have very wide application in the fields of industry, agriculture, medicine and the like. As indole and indole derivatives have the advantages of high theoretical hydrogen production rate, stable chemical structure, long cycle life and the like, can be used as an organic liquid hydrogen storage material, and attracts more and more researchers' attention. In general, the pure indole can be obtained by separating and purifying indole-containing substances such as flower essential oil or coal tar. The most reported preparation method of indole is to separate and purify indole from coal tar. But the separation steps for purifying indole from coal tar are numerous and the process cost is high. In addition, the catalyst can be prepared by multistage reaction of o-toluidine and formic acid. Although the reaction condition is mild, the reaction steps are numerous, the operation process is complex, the production cost is high, and inorganic salt and a large amount of sewage are generated in the reaction, so that the environment is seriously polluted, and the environment is not in accordance with the requirements of green chemistry. This approach is not the best way to produce indole today with emphasis on sustainable development and environmental friendliness.
In the middle nineties, a new method for industrial production of indole is developed in japan, and indole is synthesized by one-step catalysis of aniline and ethylene glycol. The reaction has three advantages of (1) cheap and easily available reaction raw materials. And (2) the reaction steps are few, and the production cost is low. (3) The reaction does not generate inorganic salt and other wastes, has no pollution to the environment and is widely paid attention to.
But is limited by various factors such as catalyst preparation, process synthesis method, reaction temperature, synthesis equipment control and the like. The preparation of indoles from simple anilines and ethylene glycol is attractive, however the biggest limitation is the reaction temperature, which necessitates high demands on industrial equipment and energy consumption. Although the use of ethanolamine or an epoxy compound as a substitute for ethylene glycol has reduced temperature requirements, the availability of raw materials has become a new problem. As another example, matsuda et al found that catalysts such as Cd, cu, ag and Zn have certain activity on aniline and ethylene glycol for synthesizing indole in one step. The yield of indole in the fixed bed reaction reaches more than 20 percent at the temperature of 350 ℃ and normal pressure, wherein the yield of indole of the Ag-based catalyst reaches more than 40 percent. However, the catalyst of the synthesis process is rapidly deactivated within several hours of reaction, resulting in a linear decrease in yield. In addition, the synthesis of indole derivatives is also limited to batch mode and is used on a laboratory scale.
Therefore, it is very important to develop a process for continuously synthesizing high-purity indole and its derivatives by using inexpensive and easily available raw materials and stable catalysts.
Disclosure of Invention
In view of the above, the present invention provides a method and a system for synthesizing indole and its derivatives by alcohol amine method, which adopts a molecular optimal synthesis route, uses a large amount of easily available raw materials, continuously synthesizes indole and its derivatives at a relatively low temperature, uses a catalyst containing no noble metal, and can be deactivated and regenerated in situ, thus being suitable for industrial mass production.
In order to achieve the above object, the present invention provides a method for synthesizing indole and its derivatives by alcohol amine method, which is characterized by comprising the following steps:
S1, filling a Cu-based multi-phase catalyst into a fixed bed reactor, and introducing H 2/N2 mixed gas for reduction, wherein the Cu-based multi-phase catalyst comprises a CuO main body and a ZrO 2 auxiliary agent;
S2, mixing raw material aniline or aniline derivatives, polyalcohols and water, then introducing the mixture into a preheater for vaporization to form vaporized mixed gas, introducing the vaporized mixed gas into a reactor for catalytic reaction with a reduced Cu-based multi-phase catalyst, and obtaining a reaction product containing indole or derivatives thereof, wherein the reaction temperature of the obtained reaction product containing indole is 230-290 ℃;
S3, condensing the reaction product, separating water and hydrogen, and separating and purifying the residual product to obtain indole or a derivative product thereof;
When the Cu-based multi-phase catalyst is deactivated or the activity is reduced, introducing regeneration gas into the reactor for in-situ regeneration, and then reducing according to the step S1 to continue to be used for catalytic reaction.
The method adopts aniline or derivatives thereof and polyol as raw materials, has the advantages of easy obtainment, low price, low production cost, less environmental pollution waste caused in the reaction process, obvious advantages, adopts the Cu-based multi-phase catalyst, the main body of which is CuO, and the auxiliary agent comprises ZrO 2, and the CuO is used as the main body to be matched with ZrO 2, so that the stability of the Cu-based catalyst is obviously improved, the catalytic activity is high, and a fixed bed gas-solid process is adopted, so that the method not only can realize continuous production, simple operation and high production efficiency, but also can realize long-time stable production, and realize large-scale continuous production of indole compounds by a one-step method, solve the problems of insufficient output and low purity of the indole compounds at present, and can also realize the synthesis of indole and the indole derivatives according to different choices of aniline or aniline derivatives and polyols, and has high selectivity and flexibility. The method has the advantages that the reaction can be carried out at a relatively low temperature, particularly the reaction temperature for synthesizing indole is 230-290 ℃, high-temperature high-pressure high-energy consumption is not needed, the difficulty for synthesizing indole derivatives is higher, the temperature is slightly higher, but the synthesis temperature is still lower than that of the existing production method, meanwhile, the catalyst can be regenerated in situ, excessive loss of the catalyst is avoided, long-time stable output can be ensured, and further high-efficiency continuous conversion and high yield are realized.
The invention reduces by using H 2/N2 mixed gas, has high selectivity by utilizing hydrogen and strong reducibility, can reduce the catalyst well and has high activity, and meanwhile, the hydrogen is friendly to the environment and does not generate harmful byproducts. Note that pure hydrogen reduction cannot be used because the catalyst is reduced to a strongly exothermic reaction, and too high a hydrogen concentration gives off significantly heat, and high temperatures can affect the catalyst structure, affecting catalyst activity and lifetime.
Preferably, the aniline derivative is one of N-methylaniline, N-ethylaniline, o-methylaniline, m-methylaniline and p-methylaniline, and the polyalcohol is one of ethylene glycol, glycerol and 1, 2-propylene glycol.
Preferably, the auxiliary agent of the Cu-based multi-phase catalyst further comprises one or more of ZnO, mgO, caO, mnO, baO, ceO 2 and NiO, and the carrier of the Cu-based multi-phase catalyst is at least one of Al 2O3、SiO2 and carbon black.
Preferably, the Cu-based multi-phase catalyst comprises 10-35% of Cu by mass, 10-25% of metal ions by mass and 40-80% of carrier by mass.
The Cu-based multi-phase catalyst can be prepared into catalytic particles in special shapes such as sphere, cylinder, honeycomb and the like through a molding process, and is loaded in a reactor to continuously synthesize indole and indole ring derivatives through gas-solid reaction.
After the catalyst is deactivated or the activity is reduced, air or mixed gas containing oxygen and nitrogen is introduced to regenerate the catalyst, the catalyst can be regenerated in situ in a fixed bed reactor, the regeneration procedure is simple, the catalyst is prevented from being lost due to transfer or excessive and complicated regeneration operation, and the catalyst is ensured to be stable and simultaneously continuous production is facilitated.
Preferably, the catalyst is regenerated as follows,
Introducing air or nitrogen containing oxygen into the reactor, wherein the gas space velocity is 50h -1~1000h-1, heating and preserving heat of the catalyst in an in-situ mode, the heating rate is 10-20 ℃ per hour, heating to 200-400 ℃ and preserving heat for 2-20 h, and reducing according to the step S1 after regeneration is finished, and continuing to be used for catalytic reaction.
Preferably, when the polyalcohol is glycol, aniline and glycol are adopted as raw materials, and the final reaction product is indole.
Preferably, the Cu-based multi-phase catalyst is composed of CuO as a main body, the auxiliary agent comprises ZrO 2, the Cu is loaded in an amount of 20% -35% by mass, the metal ions in the auxiliary agent are loaded in an amount of 10% -25% by mass, and the carrier is 50% -70% by mass.
Preferably, in the step S1, the volume content of hydrogen in the H 2/N2 mixed gas is 1% -20%, the airspeed is 100H -1~1000h-1, the reduction temperature is 100 ℃ -300 ℃, and the reduction time is 1H-50H;
In the step S2, the molar ratio of raw material aniline to ethylene glycol is 4:1-10:1, the reaction temperature is 230-290 ℃, the reaction pressure is 0-1.0 MPa, the temperature set by the preheater is 190-250 ℃, the feeding airspeed of raw materials is 0.2h -1～1.0h-1, and the water feeding airspeed is 0.06h -1～0.33h-1.
Preferably, when the aniline derivative is N-methylaniline and the polyalcohol is ethylene glycol, the reaction product is N-methylindole.
Preferably, the Cu-based multi-phase catalyst is composed of CuO as a main body, znO and CaO as auxiliary agents, wherein the Cu is 10% -25% by weight, the metal ions in the auxiliary agents are 15% -35% by weight, and the carrier is 50% -75% by weight.
Preferably, in the step S2, the molar ratio of the raw material N-methylaniline to the ethylene glycol is 4:1-8:1, the reaction temperature is 230-280 ℃, the reaction pressure is 0-0.5 MPa, the temperature set by the preheater is 190-240 ℃, the feeding airspeed of the raw material is 0.4h -1～1.0h-1, and the water feeding airspeed is 0.06h -1～0.25h-1.
Preferably, when the aniline derivative is N-ethylaniline and the polyalcohol is ethylene glycol, the reaction product is N-ethylindole.
Preferably, the Cu-based multi-phase catalyst is mainly composed of CuO, the auxiliary agent further comprises CaO, the Cu is loaded by 20% -35%, the metal ions in the auxiliary agent are loaded by 10% -20%, and the content of the carrier is 55% -70%.
Preferably, in the step S2, the molar ratio of the raw material N-ethylaniline to the ethylene glycol is 5:1-10:1, the reaction temperature is 280-350 ℃, the reaction pressure is 0.2-0.6 MPa, the temperature set by the preheater is 200-220 ℃, the feeding airspeed of the raw material is 0.2h -1～0.4h-1, and the water feeding airspeed is 0.1h -1～0.2h-1.
Preferably, when the aniline derivative is o-methylaniline and the polyalcohol is ethylene glycol, the reaction product is 7-methylindole.
Preferably, the Cu-based multi-phase catalyst body is CuO, the auxiliary agent further comprises MgO, baO, znO, the load mass percentage of Cu is 20% -30%, the load mass percentage of metal ions in the auxiliary agent is 10% -25%, and the content of the carrier is 45% -70%.
Preferably, in the step S2, the molar ratio of raw material o-methylaniline to ethylene glycol is 4:1-9:1, the reaction temperature is 250-280 ℃, the reaction pressure is 0-0.5 MPa, the temperature set by the preheater is 210-250 ℃, the feeding airspeed of the raw material is 0.4h -1～0.8h-1, and the water feeding airspeed is 0.2h -1～0.3h-1.
Preferably, when the aniline derivative is m-methylaniline and the polyalcohol is ethylene glycol, the reaction product is 4-methylindole and/or 6-methylindole.
Preferably, the Cu-based multi-phase catalyst body is CuO, the auxiliary agent further comprises MgO and BaO, when the molar ratio of Mg 2+：Ba2+ is more than 3:1, the load mass percent of Cu is 10% -20%, the load mass percent of metal ions in the auxiliary agent is 15% -20%, the content of the carrier is 60% -75%, and the reaction product is mainly 4-methylindole.
Preferably, the molar ratio of raw materials of m-methylaniline to ethylene glycol is 2:1-5:1, the reaction temperature is 230-280 ℃, the reaction pressure is 0-0.5 MPa, and the temperature set by the preheater is 210-250 ℃.
Preferably, the Cu-based multi-phase catalyst body is CuO, the auxiliary agent further comprises MgO and BaO, when the molar ratio of Mg 2+：Ba2+ is smaller than 3:1, the load mass percent of Cu is 25% -35%, the load mass percent of metal ions in the auxiliary agent is 20% -25%, the content of the carrier is 40% -55%, and the reaction product is mainly 6-methylindole.
Preferably, in the step S2, the molar ratio of raw materials of m-methylaniline to ethylene glycol is 5:1-10:1, the reaction temperature is 280-320 ℃, the reaction pressure is 0-0.5 MPa, and the temperature set by the preheater is 240-280 ℃.
Preferably, when the aniline derivative is p-methylaniline and the polyol is ethylene glycol, the reaction product is 5-methylindole.
Preferably, the Cu-based multi-phase catalyst is composed of CuO as a main body, znO and MgO as auxiliary agents, wherein the Cu is 10% -15% by weight, the metal ions in the auxiliary agents are 20% -25% by weight, and the carrier is 60% -70% by weight.
Preferably, in the step S2, the molar ratio of the raw materials of the para-methylaniline to the ethylene glycol is 6:1-10:1, the reaction temperature is 240-290 ℃, the reaction pressure is 0-0.4 MPa, the temperature set by the preheater is 230-280 ℃, the feeding airspeed of the raw materials is 0.2h -1～0.8h-1, and the water feeding airspeed is 0.25h -1～0.30h-1.
Preferably, when the starting material is aniline and the polyol is glycerol, the reaction product is 3-methylindole.
Preferably, the Cu-based multi-phase catalyst is composed of CuO as a main body, mgO as an auxiliary agent, the Cu as a load mass percentage is 25% -35%, the metal ions in the auxiliary agent as a load mass percentage is 15% -25%, and the carrier is 50% -60%.
Preferably, in the step S2, the molar ratio of the raw material aniline to the glycerol is 4:1-8:1, the reaction temperature is 230-260 ℃, the reaction pressure is 0-0.4 MPa, the temperature set by the preheater is 200-250 ℃, the feeding airspeed of the raw material is 0.6h -1～1.0h-1, and the water feeding airspeed is 0.06h -1～0.15h-1.
Preferably, when the starting material is aniline and the polyol is 1, 2-propanediol, the reaction product is 2-methylindole.
Preferably, the Cu-based multi-phase catalyst is composed of CuO as a main body, znO as an auxiliary agent, wherein the Cu is loaded in an amount of 25-35% by mass, the metal ions in the auxiliary agent are loaded in an amount of 15-25% by mass, and the carrier is 50-60% by mass.
Preferably, in the step S2, the molar ratio of the raw material aniline to the 1, 2-propylene glycol is 6:1-10:1, the reaction temperature is 230-280 ℃, the reaction pressure is 0-0.6 MPa, the temperature set by the preheater is 190-220 ℃, the feeding airspeed of the raw material is 0.2h -1～0.6h-1, and the water feeding airspeed is 0.06h -1～0.2h-1.
Preferably, the catalytic reaction in the step S2 is performed under a hydrogen atmosphere, and the vaporized mixed gas and hydrogen are introduced into the reactor together for catalytic reaction, wherein the hydrogen space velocity is 50h -1～500h-1.
Preferably, in the step S3, condensation treatment is performed on the reaction product, after condensation, flash evaporation is performed on the reaction product, water and hydrogen are separated, the hydrogen is returned to the reactor from a top pipeline for recycling, the remaining bottom liquid product enters a rectifying tower for separation, light component raw materials are separated from the top of the rectifying tower for recycling, and purified indole and derivatives thereof are obtained from the bottom of the rectifying tower.
In order to continuously synthesize indole and derivatives thereof more conveniently and efficiently and recycle raw materials and remove impurities, the invention also provides a synthesis system for continuously synthesizing indole and derivatives thereof, which comprises a preheating reaction unit, a hydrogen separation unit and a rectification unit which are connected in sequence;
And carrying out raw material preheating vaporization and catalytic reaction through the preheating reaction unit to obtain a mixed product, carrying out gas-liquid separation on the mixed product through the hydrogen separation unit, separating water and hydrogen for recycling, and carrying out dehydration and impurity removal on the residual product through the rectification unit to obtain indole and derivatives thereof.
The production program is reasonable and convenient in design, can realize high-efficiency recycling of hydrogen and raw materials, avoids waste, and has high purity of separated indole or derivative thereof.
Preferably, the preheating reaction unit comprises a feeding preheating unit and a reaction unit, raw materials are preheated and vaporized through the feeding preheating unit and then enter the reaction unit for catalytic reaction to obtain a mixed product, and the reaction unit is a fixed bed reactor.
Preferably, the reaction unit is a fixed bed reactor.
Preferably, it also comprises a crystallization unit consisting of at least one separation crystallizer and of at least one melting crystallizer;
The rectification unit is a two-tower rectification unit and comprises a first rectification tower, a second rectification tower, a tower top condenser connected with the top of the rectification tower and a tower bottom reboiler positioned at the bottom of the rectification tower, wherein the first rectification tower and the second rectification tower are used for dewatering and recovering light component substances, and then low-purity solutions of indole and derivatives thereof are obtained from the tower bottom.
Preferably, the materials at the bottom of the second rectifying tower are sent into a separation crystallizer, a crystallization additive is added and mixed uniformly, the crystallization additive is water and methanol, solution crystallization is carried out by controlling the proportion of the water, the methanol and the materials at the bottom of the second rectifying tower, indole crystals are obtained, the indole crystals are sent into a melting crystallizer, the cooling rate, the crystallization end point and the heating rate are controlled, and the indole and the derivative products thereof in a high-purity solid state are obtained through cooling crystallization, heating purification.
The pilot plant can be used for convenient research, test and development and production of a small amount of products, but can be used for industrial production rectification units, such as three-tower rectification units, when the amount is large and the industrial production is formally carried out.
Preferably, the device also comprises a vacuum unit externally connected for manufacturing a high vacuum rectification environment, wherein the rectification unit is a three-tower rectification unit and comprises a dehydration tower, a raw material recovery tower and a product tower which are connected in sequence.
Preferably, the mixed product is cooled and separated from gas and liquid through a hydrogen separation unit, water and hydrogen are separated, the rest product is dehydrated and light component impurities are removed through a water removal tower, then the light component raw materials are separated through a raw material recovery tower and recovered, finally the light component raw materials enter a product tower for further purification, and the high-purity liquid indole and derivative products thereof are obtained at the top of the tower.
Preferably, the water removal tower adopts a reducing tower, the number of tower plates is 25-35, efficient silk screen structured packing is adopted in the tower, the tower top pressure is 95-105 kPa, and the reflux ratio is controlled to be 0.4-2.
Preferably, the raw material recovery tower adopts a mode of gas-liquid phase separation into a tower, the number of tower plates is 35-50, corrugated packing with metal pore plates is adopted in the tower, the tower top pressure is 10-25 kPa, and the reflux ratio is controlled to be 0.7-1.5.
Preferably, the product tower is used for purifying the product indole, the number of tower plates is 35-50, corrugated metal plate packing is adopted in the tower, the tower top pressure is 5-15 kPa, and the reflux ratio is controlled to be 0.4-1.6.
The pressure at the top of the tower is absolute pressure.
The novel filler has larger specific surface area, better plate efficiency such as filler separation, the corrugated angle and the opening direction are optimized, fluctuation under larger working conditions is adapted, larger gas load is adapted, and the operation elasticity can be increased and the tower height can be reduced. The raw material recovery tower adopts a mode of gas-liquid phase separation into the tower, and the gas phase enters the upper part of the distributor to prevent the phenomenon that partial filler cannot be wetted and utilized due to the disturbance of the liquid phase distribution of the distributor, and the liquid phase enters the distributor. The height of the integral packing is about 20m, the rectifying section is the same as the stripping section tower plate, the integral separation recovery rate is more than 97%, the raw materials are fully reused, and the integral packing can be used as the outlet heat exchange of a front-stage reactor.
The device optimizes the mixing and separating modes, adopts a mixer and a single preheater in a feeding preheating unit, avoids the waste of raw materials in repeated preheating, can aim at adjusting the preheating load when synthesizing heat release, reduces the energy consumption cost, adopts a novel efficient regular plate corrugated packing tower in a separating and purifying part, effectively reduces the height of the tower by more than 30 percent compared with the traditional random packing or plate rectifying tower, and performs energy thermal coupling design with a front section, thereby greatly reducing the energy consumption of an integral product and the production and emission of waste liquid, and the byproduct hydrogen can be used as cyclic supply, continuous recycling and the like.
When the industrial continuous production is carried out, excessive raw materials produced at the top of the rectifying tower are circulated into a raw material mixer for continuous production.
The technical scheme of the invention at least comprises the following beneficial effects:
1. The invention adopts aniline or its derivative and polyhydric alcohol as raw materials, the aniline or its derivative and polyhydric alcohol are easy to obtain and low in price, the production cost is low, and the environmental pollution waste caused in the reaction process is less, at the same time, the copper-based multi-phase catalyst designed by the invention is adopted, and the gas-solid reaction technology is adopted, so that the reaction is carried out at relatively low temperature, high temperature and high energy consumption are not needed, indole and its derivative can be continuously and efficiently synthesized, and indole and its derivative can be synthesized according to different choices of aniline or aniline derivative and polyhydric alcohol, the selectivity is strong, and the flexibility is high.
2. Meanwhile, the copper-based multi-phase catalyst in the scheme is not easy to deactivate, the stable output of the device can be ensured for a long time, the yield of indole and derivatives thereof is higher, and the catalyst can be deactivated and regenerated in situ, so that the problem that the catalyst is easy to deactivate and regenerate is solved, the service cycle of the catalyst is greatly prolonged, the cost of catalyst replacement is reduced, the efficient and continuous conversion and the high yield of indole are realized, and the method has important significance for realizing the industrial synthesis of indole.
3. The invention reduces by using nitrogen containing hydrogen, which has high selectivity and strong reducibility, can reduce the catalyst well and has high activity, and simultaneously, the hydrogen is friendly to the environment and does not generate harmful byproducts.
4. The device optimizes the mixing and separating modes, adopts a mixer and a single preheater in a feeding preheating unit, avoids the waste of raw materials in repeated preheating, can aim at adjusting the preheating load when synthesizing heat release, reduces the energy consumption cost, adopts a novel efficient regular plate corrugated packing tower in a separating and purifying part, effectively reduces the height of the tower by more than 30 percent compared with the traditional random packing or plate rectifying tower, and performs energy thermal coupling design with a front section, thereby greatly reducing the energy consumption of an integral product and the production and discharge of waste liquid, and the byproduct hydrogen can be used as circulation supply and continuous recycling, thereby being suitable for industrial production.
Drawings
FIG. 1 is a schematic diagram of a synthesis system used for production in example 1 of the present invention;
FIG. 2 is a schematic diagram of the synthesis system according to embodiment 30 of the present invention;
FIG. 3 is a mass spectrum of the sample of the reaction result of example 1 of the present invention;
FIG. 4 is a mass spectrum of the sample of the reaction result of example 4 of the present invention;
FIG. 5 is a mass spectrum of the sample of the reaction result of example 7 of the present invention;
FIG. 6 is a mass spectrum of the sample of the reaction result of example 10 of the present invention;
FIG. 7 is a mass spectrum of the sample of the reaction result of example 16 of the present invention;
FIG. 8 is a mass spectrum of the sample of the reaction result of example 19 of the present invention;
FIG. 9 is a chart showing the detection of a sample of the reaction result in example 22 of the present invention;
FIG. 10 is a mass spectrum of the sample of the reaction result of example 25 of the present invention.
In the figure, M, a mixer, E1, a preheater, R, a reactor, E2, a condenser, F, a flash evaporator, I, a first rectifying tower, II, a second rectifying tower, V1, a separation crystallizer, V2, a melting crystallizer, T1, a water removal tower, T2, a raw material recovery tower, T3 and a product tower.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which are obtained by a person skilled in the art based on the described embodiments of the invention, fall within the scope of protection of the invention.
The existing method for synthesizing indole generally has the defects of high reaction temperature, high requirement on industrial equipment and high energy consumption. The other method for synthesizing indole includes such steps as putting raw materials of aniline and glycol into reaction zone, contacting with catalyst to generate indole product, putting the stripped catalyst in reaction zone into stripping zone, delivering nitrogen to regeneration zone, delivering regenerated catalyst into degassing zone, delivering the degassed catalyst back to reaction zone, and contact reaction with raw materials. The reaction process is complex, the actual operation is inconvenient, the catalyst loss is large, and the actual industrial continuous production is difficult to realize.
Based on the above, the invention is provided after a great deal of experimental investigation, aniline and glycol are used as raw materials, a Cu-based multi-phase catalyst is adopted, the raw materials are filled into a fixed bed reactor, H 2/N2 mixed gas is introduced for reduction, the raw materials of aniline and glycol are mixed with water and then vaporized, the raw materials of aniline and glycol are introduced into the reactor for catalytic reaction, and the reaction products are cooled, separated and purified to obtain purified indole products, wherein the specific implementation mode is as follows:
Example 1
Using the synthesis system shown in FIG. 1, the reaction was performed under the following reaction conditions to prepare indole.
The indole is prepared by a one-step method of aniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 30mL, the Cu-based catalyst is reduced in a nitrogen atmosphere containing hydrogen, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2 as an auxiliary agent and SiO 2 as a carrier, wherein the mass ratio of Cu is 35%, the mass ratio of metal ions in the auxiliary agent is 25%, the mass ratio of the carrier is 65%, the Cu-based multi-phase catalyst is reduced under the condition that the hydrogen accounts for 10% of the mixed gas of nitrogen and hydrogen, the space velocity is 100h -1, the reduction temperature is 150 ℃, and the reduction time is 10h.
After the reduction was completed, the raw materials aniline and ethylene glycol were fed into the reaction mixer M at a 7:1 molar ratio using a plunger pump, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer using a plunger pump at a space velocity of 0.13h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater E1. The temperature of the preheater E1 is 200 ℃, the hydrogen entering the preheater entrains vaporized aniline, ethylene glycol and water at the flow rate of 200h -1, the reaction temperature is 230 ℃, the reaction pressure is 0.2MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 200h -1, the hydrogen enters the preheater E1 through a one-way valve, and then the mixed gas phase raw material reacts in the fixed bed reactor R.
The reaction product is changed into a part of liquid product from gas after being condensed by a condenser E2, the gas and the vapor are discharged after flash evaporation in a flash evaporator F, the gas can return to a hydrogen gas inlet pipeline for recycling, the product at the bottom of the flash evaporation tank enters a rectifying tower for separation, the light component at the top of the tower is used as a raw material for recycling, and the product at the bottom of the tower is sampled and analyzed. The reaction results were analyzed and shown in FIG. 3, and the results showed that the ethylene glycol conversion was 99% and the indole yield was 85% (based on ethylene glycol).
Referring to the rectification and purification part in fig. 1, the purification process for obtaining high-purity indole is as follows:
Rectifying, namely sequentially feeding the synthesized product into a first rectifying tower I and a second rectifying tower II to recover substances such as aniline, ethylene glycol and the like. The tower bottom material of the first rectifying tower I continuously enters a second rectifying tower II for treatment, the tower bottom material of the second rectifying tower II is 35, the reflux ratio is 20, the tower top pressure (absolute pressure) is 0.05Mpa, the tower top collection of the second rectifying tower II is aniline, the purity of the aniline is 98.5%, the aniline is recycled and used as the raw material for synthesis production, and the tower bottom of the second rectifying tower II is 88.5% of low-purity indole solution;
(2) Solution crystallization, namely transferring low-purity indole extracted from the tower bottom of a second rectifying tower II into a separation crystallizer V1, performing solution crystallization under the condition that the ratio of water to methanol to low-purity indole is 1:1:1, and returning a solvent into the separation crystallizer after solid-liquid separation, and discharging crystals to obtain 98.7% indole crystals;
(3) The melting crystallization comprises the steps of conveying indole obtained by solution crystallization into a melting crystallizer V2, crystallizing in a gradual cooling mode, enabling the surface of a crystallization tube to form crystals, enabling the cooling rate to be 3 ℃ per hour, enabling the cooling time to be 5 hours, enabling the cooling time to be 37.5 ℃, stopping cooling, keeping the temperature for 1 hour, gradually heating to melt, enabling the heating rate to be 1 ℃ per hour, heating to 42 ℃, keeping the temperature for 1 hour, discharging liquid, recycling, continuously heating to enable the crystals to be completely melted, discharging the obtained product from the bottom of the melting crystallizer, and obtaining the high-purity solid indole with the purity of 99.92%.
The purifying device comprises a first rectifying tower I, a second rectifying tower II, a tower top condenser connected with the top of the rectifying tower and a tower bottom reboiler positioned at the bottom of the rectifying tower, wherein in the process of separating a bottom liquid product in the rectifying tower, the rectifying tower is adopted to refine the product, and a qualified tower bottom product is separated;
The tower top condenser, rectifying section cold source, condensing light component material in rectifying section and partial reflux to ensure the tower top temperature, tower kettle reboiler, stripping section heat source to provide heat source for the whole rectifying tower, partial gas-liquid phase balance formed on each column plate via heat supply to maintain the tower bottom temperature, rectifying tower to provide platform for gas-liquid phase mass transfer and heat transfer in the specific product refining site and to separate out qualified tower top product. When the industrial continuous production is carried out, excessive raw materials produced at the top of the rectifying tower are circulated into the raw material mixer M for continuous production.
Example 2
Using the synthesis system shown in FIG. 1, the reaction was performed under the following reaction conditions to prepare indole.
The indole is prepared by a one-step method of aniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 30mL, the Cu-based multi-phase catalyst is reduced in a nitrogen atmosphere containing hydrogen, cuO is used as a main body, zrO 2 is used as an auxiliary agent, siO 2 is used as a carrier, wherein the mass ratio of Cu is 20%, the mass ratio of metal ions in the auxiliary agent is 10%, the mass ratio of the carrier is 70%, the Cu-based multi-phase catalyst is reduced under the condition that the hydrogen accounts for 10% of mixed gas of nitrogen and hydrogen, the space velocity is 1000h -1, the reduction temperature is 300 ℃, and the reduction time is 1h.
After the reduction was completed, the raw materials aniline and ethylene glycol were fed into the reaction mixer M at a molar ratio of 9:1 using a plunger pump, the space velocity of the liquid was maintained at 0.6h -1, water was pumped into the mixer using a plunger pump at a space velocity of 0.13h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater E1. The temperature of the preheater E1 is 230 ℃, the hydrogen entering the preheater entrains vaporized aniline, ethylene glycol and water at the flow rate of 200h -1, the reaction temperature is 290 ℃, the reaction pressure is 1.0MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 200h -1, the hydrogen enters the preheater E1 through a one-way valve, and then the mixed gas phase raw material reacts in the fixed bed reactor R.
The reaction product is changed into a part of liquid product from gas after being condensed by a condenser E2, the gas and the vapor are discharged after flash evaporation in a flash evaporator F, the gas can return to a hydrogen gas inlet pipeline for recycling, the product at the bottom of the flash evaporation tank enters a rectifying tower for separation, the light component at the top of the tower is used as a raw material for recycling, and the product at the bottom of the tower is sampled and analyzed. The reaction result samples are subjected to detection analysis, and the result shows that the conversion rate of the ethylene glycol is 99 percent, and the indole yield is 88 percent (calculated by the ethylene glycol).
Example 3
Using the synthesis system shown in FIG. 1, the reaction was performed under the following reaction conditions to prepare indole.
The indole is prepared by a one-step method of aniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 20mL, the Cu-based catalyst is reduced in a nitrogen atmosphere containing hydrogen, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2 as an auxiliary agent and carbon black as a carrier, wherein the Cu accounts for 30% by mass, the metal ions in the auxiliary agent account for 20% by mass, and the carrier accounts for 50% by mass, and the Cu-based multi-phase catalyst is reduced under a nitrogen and hydrogen mixed gas with the hydrogen accounting for 20% by mass, the space velocity is 500h -1, the reduction temperature is 200 ℃, and the reduction time is 50h.
After the reduction was completed, the raw materials aniline and ethylene glycol were fed into the reaction mixer M at a 5:1 molar ratio using a plunger pump, the liquid space velocity was maintained at 0.5h -1, water was pumped into the mixer using a plunger pump at a space velocity of 0.13h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater E1. The temperature of the preheater E1 is 250 ℃, the hydrogen entering the preheater entrains vaporized aniline, ethylene glycol and water at a flow rate of 200h -1, the reaction temperature is 260 ℃, the reaction pressure is 0.2MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 200h -1, the hydrogen enters the preheater E1 through a one-way valve, and then the mixed gas phase raw material reacts in the fixed bed reactor R.
The reaction product is changed into a part of liquid product from gas after being condensed by a condenser E2, the gas and the vapor are discharged after flash evaporation in a flash evaporator F, the gas can return to a hydrogen gas inlet pipeline for recycling, the product at the bottom of the flash evaporation tank enters a rectifying tower for separation, the light component at the top of the tower is used as a raw material for recycling, and the product at the bottom of the tower is sampled and analyzed. The reaction result samples were subjected to detection analysis, and the results show that the conversion rate of ethylene glycol is 97% and the indole yield is 82% (calculated as ethylene glycol).
Example 4
The synthesis system shown in FIG. 1 was used to prepare N-methylindole by the reaction under the following reaction conditions.
N-methylindole is prepared by a one-step method of N-methylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 20mL, the Cu-based catalyst is reduced in a nitrogen atmosphere containing hydrogen, the Cu-based catalyst takes CuO as a main body, zrO 2, znO and CaO as auxiliary agents and Al 2O3 as a carrier, wherein the mass ratio of Cu is 15%, the mass ratio of metal ions in the auxiliary agents is 25%, the mass ratio of the carrier is 60%, the Cu-based catalyst is reduced under the condition that the hydrogen accounts for 20% of the mixed gas of nitrogen and hydrogen, the space velocity is 100h -1, the reduction temperature is 150 ℃, and the reduction time is 10h.
After the reduction was completed, the raw materials N-methylaniline and ethylene glycol were fed into the reaction mixer with a plunger pump at a molar ratio of 6:1, the space velocity of the liquid was maintained at 0.8h -1, water was pumped into the mixer with a plunger pump at a space velocity of 0.06h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 240 ℃, the vaporized N-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 100h -1, the reaction temperature is 280 ℃, the reaction pressure is 0.5MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed.
The reaction product is changed into partial liquid product from gas after being condensed by a condenser, the gas and the vapor are discharged after flash evaporation, the gas can return to a hydrogen gas inlet pipeline for recycling, the product at the bottom of the flash evaporation tank enters a rectifying tower for separation, the light component at the top of the tower is used as raw material for recycling, and the product at the bottom of the tower is sampled and analyzed. The reaction results were analyzed and shown in FIG. 4, and the results showed that the ethylene glycol conversion was 98% and the N-methylindole yield was 80% (based on ethylene glycol).
Example 5
The synthesis system shown in FIG. 1 was used to prepare N-methylindole by the reaction under the following reaction conditions.
N-methylindole is prepared by a one-step method of N-methylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 30mL, the Cu-based catalyst is reduced in a nitrogen atmosphere containing hydrogen, cuO is used as a main body, zrO 2, znO and CaO are used as auxiliary agents, al 2O3 is used as a carrier, wherein the mass ratio of Cu is 10%, the mass ratio of metal ions in the auxiliary agents is 15%, the mass ratio of the carrier is 75%, the Cu-based catalyst is reduced under the condition that the hydrogen accounts for 20% of mixed gas of nitrogen and hydrogen, the space velocity is 100h -1, the reduction temperature is 150 ℃, and the reduction time is 10h.
After the reduction was completed, the raw materials N-methylaniline and ethylene glycol were fed into the reaction mixer with a plunger pump at a molar ratio of 4:1, the space velocity of the liquid was maintained at 0.8h -1, water was pumped into the mixer with a plunger pump at a space velocity of 0.13h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 240 ℃, the vaporized N-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 100h -1, the reaction temperature is 230 ℃, the reaction pressure is 0.1MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed.
The reaction product is changed into partial liquid product from gas after being condensed by a condenser, the gas and the vapor are discharged after flash evaporation, the gas can return to a hydrogen gas inlet pipeline for recycling, the product at the bottom of the flash evaporation tank enters a rectifying tower for separation, the light component at the top of the tower is used as raw material for recycling, and the product at the bottom of the tower is sampled and analyzed. The reaction result samples are subjected to detection analysis, and the result shows that the conversion rate of the ethylene glycol is 95%, and the yield of the N-methylindole is 78% (calculated by the ethylene glycol).
Example 6
The synthesis system shown in FIG. 1 was used to prepare N-methylindole by the reaction under the following reaction conditions.
N-methylindole is prepared by a one-step method of N-methylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 20mL, the Cu-based catalyst is reduced in a nitrogen atmosphere containing hydrogen, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2 and ZnO, caO, mnO as auxiliary agents and carbon black as a carrier, wherein the mass ratio of Cu is 25%, the mass ratio of metal ions in the auxiliary agents is 25%, the mass ratio of the carrier is 50%, the Cu-based multi-phase catalyst is reduced under the condition that the hydrogen accounts for 10% of the mixed gas of nitrogen and hydrogen, the space velocity is 100h -1, the reduction temperature is 150 ℃, and the reduction time is 10h.
After the reduction was completed, the raw materials N-methylaniline and ethylene glycol were fed into the reaction mixer with a plunger pump at a molar ratio of 8:1, maintaining a liquid space velocity of 0.8h -1, pumping water into the mixer with a plunger pump at a space velocity of 0.13h -1, and then the two raw materials and water mixture were vaporized together in the preheater. The temperature of the preheater is 240 ℃, the vaporized N-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 100h -1, the reaction temperature is 250 ℃, the reaction pressure is 1.0MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed.
The reaction product is changed into partial liquid product from gas after being condensed by a condenser, the gas and the vapor are discharged after flash evaporation, the gas can return to a hydrogen gas inlet pipeline for recycling, the product at the bottom of the flash evaporation tank enters a rectifying tower for separation, the light component at the top of the tower is used as raw material for recycling, and the product at the bottom of the tower is sampled and analyzed. The reaction result sample was subjected to detection analysis, and the result showed that the conversion of ethylene glycol was 98% and the yield of N-methylindole was 83% (based on ethylene glycol).
Example 7
N-ethylindole is prepared in a one-step process from N-ethylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2 and CaO as auxiliary agents and SiO 2 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 20%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 60%.
After completion of the reduction in the same manner as in example 4, the raw materials N-ethylaniline and ethylene glycol were fed into the reaction mixer in a 5:1 molar ratio by means of a plunger pump, the space velocity of the liquid was maintained at 0.3h -1, water was pumped into the mixer by means of a plunger pump at a space velocity of 0.2h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 220 ℃, the vaporized N-ethylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 280 ℃, the reaction pressure is 0.2MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed. As shown in FIG. 5, the reaction results showed that the conversion of ethylene glycol was 85% and the yield of N-ethylindole was 75% (based on ethylene glycol). The subsequent steps after the completion of the reaction are the same as those of example 4, and will not be described again.
Example 8
N-ethylindole is prepared in a one-step process from N-ethylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, takes ZrO 2 and CaO as auxiliary agents and takes SiO 2 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 20%, the mass ratio of metal ions in the auxiliary agents is 10%, and the mass ratio of the carrier is 70%.
After completion of the reduction in the same manner as in example 4, the raw materials N-ethylaniline and ethylene glycol were fed into the reaction mixer in a molar ratio of 10:1 by means of a plunger pump, the space velocity of the liquid was maintained at 0.2h -1, water was fed into the mixer by means of a plunger pump at a space velocity of 0.1h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 220 ℃, the vaporized N-ethylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 350 ℃, the reaction pressure is 0.6MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed. The reaction results showed that the conversion of ethylene glycol was 88% and the yield of N-ethylindole was 72% (based on ethylene glycol). The subsequent steps after the completion of the reaction are the same as those of example 4, and will not be described again.
Example 9
N-ethylindole is prepared in a one-step process from N-ethylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, takes ZrO 2 and CaO as auxiliary agents and takes SiO 2 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 35%, the mass ratio of metal ions in the auxiliary agents is 10%, and the mass ratio of the carrier is 55%.
After completion of the reduction in the same manner as in example 4, the raw materials N-ethylaniline and ethylene glycol were fed into the reaction mixer in a molar ratio of 7:1 by means of a plunger pump, the space velocity of the liquid was maintained at 0.25h -1, water was fed into the mixer by means of a plunger pump at a space velocity of 0.15h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 220 ℃, the vaporized N-ethylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 280 ℃, the reaction pressure is 0.2MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed. The reaction result showed 86% conversion of ethylene glycol and 75% yield of N-ethylindole (calculated as ethylene glycol). The subsequent steps after the completion of the reaction are the same as those of example 4, and will not be described again.
Example 10
The method prepares 7-methylindole by o-methylaniline and ethylene glycol by a one-step method. The Cu-based catalyst is adopted, the catalyst loading is 50mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and MgO, baO, znO as auxiliary agents and Al 2O3 as a carrier after reduction in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 25%, the mass ratio of metal ions in the auxiliary agents is 15%, and the mass ratio of the carrier is 60%.
After completion of the reduction in the same manner as in example 1, the raw materials o-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump at a molar ratio of 8:1, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.25h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 250 ℃, the vaporized o-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 500h -1, the reaction temperature is 270 ℃, the reaction pressure is 0.1MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 500h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. As shown in FIG. 6, the results showed that the conversion of ethylene glycol was 80% and the yield of 7-methylindole was 76% (based on ethylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 11
The method prepares 7-methylindole by o-methylaniline and ethylene glycol by a one-step method. The Cu-based catalyst is adopted, the catalyst loading is 50mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and MgO, baO, znO as auxiliary agents and Al 2O3 as a carrier after reduction in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 20%, the mass ratio of metal ions in the auxiliary agents is 10%, and the mass ratio of the carrier is 70%.
After completion of the reduction in the same manner as in example 1, the raw materials o-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump in a molar ratio of 4:1, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.3h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 210 ℃, the vaporized o-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 500h -1, the reaction temperature is 250 ℃, the reaction pressure is 0.5MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 500h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. The results showed that the conversion of ethylene glycol was 70% and the yield of 7-methylindole was 68% (based on ethylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 12
The method prepares 7-methylindole by o-methylaniline and ethylene glycol by a one-step method. The Cu-based catalyst is adopted, the catalyst loading is 50mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and MgO, baO, znO as auxiliary agents and Al 2O3 as a carrier after reduction in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 30%, the mass ratio of metal ions in the auxiliary agents is 25%, and the mass ratio of the carrier is 45%.
After completion of the reduction in the same manner as in example 1, the raw materials o-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump at a molar ratio of 6:1, the space velocity of the liquid was maintained at 0.8h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.3h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 250 ℃, the vaporized o-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 500h -1, the reaction temperature is 260 ℃, the reaction pressure is 0.3MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 500h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. The results showed 75% conversion of ethylene glycol and 73% yield of 7-methylindole (based on ethylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 13
The preparation of 4-methylindole and 6-methylindole from m-methylaniline and ethylene glycol in one step. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2, baO and MgO as auxiliary agents (the molar ratio of Mg 2+：Ba2+ is more than 3:1), and Al 2O3 as a carrier, wherein the mass ratio of Cu is 20%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 60%.
After completion of the reduction in the same manner as in example 1, the starting materials m-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump in a molar ratio of 4:1, the space velocity of the liquid was maintained at 0.6h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.1h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 230 ℃, the hydrogen entering the preheater entrains vaporized m-methylaniline, ethylene glycol and water at the flow rate of 100h -1, the reaction temperature is 280 ℃, the reaction pressure is 0.5MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed. The results showed that the ethylene glycol conversion was 80%, the 4-methylindole yield was 70% (based on ethylene glycol), and the 6-methylindole yield was 5% (based on ethylene glycol).
Example 14
The preparation of 4-methylindole and 6-methylindole from m-methylaniline and ethylene glycol in one step. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and BaO, mgO, niO as auxiliary agents (the molar ratio of Mg 2+：Ba2+ is more than 3:1), and Al 2O3 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 10%, the mass ratio of metal ions in the auxiliary agents is 15%, and the mass ratio of the carrier is 75%.
After completion of the reduction in the same manner as in example 1, the starting materials m-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump in a molar ratio of 2:1, the space velocity of the liquid was maintained at 0.6h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.1h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 210 ℃, the hydrogen entering the preheater entrains vaporized m-methylaniline, ethylene glycol and water into the reactor at the flow rate of 100h -1, the reaction temperature of the water feeding airspeed is 230 ℃ at the flow rate of 0.2h -1, the reaction pressure is 0.05MPa, the gas-solid phase reaction is carried out on the catalyst under the hydrogen atmosphere, the hydrogen flow is controlled by a mass flowmeter, the hydrogen airspeed is 100h -1, the mixture of the gas-phase raw materials is reacted on a solid catalyst bed after passing through a check valve. The results showed that the conversion of ethylene glycol was 70%, the yield of 4-methylindole was 62% (based on ethylene glycol), and the yield of 6-methylindole was 7% (based on ethylene glycol).
Example 15
The preparation of 4-methylindole and 6-methylindole from m-methylaniline and ethylene glycol in one step. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2, baO and MgO as auxiliary agents (the molar ratio of Mg 2+：Ba2+ is more than 3:1), and Al 2O3 as a carrier, wherein the mass ratio of Cu is 15%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 65% after reduction in a nitrogen atmosphere containing hydrogen.
After completion of the reduction in the same manner as in example 1, the starting materials m-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump in a molar ratio of 5:1, the space velocity of the liquid was maintained at 0.6h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.1h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 250 ℃, the hydrogen entering the preheater entrains vaporized m-methylaniline, ethylene glycol and water at the flow rate of 100h -1, the reaction temperature is 250 ℃, the reaction pressure is 0.3MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. The results showed that the conversion of ethylene glycol was 82%, the yield of 4-methylindole was 71% (based on ethylene glycol), and the yield of 6-methylindole was 8% (based on ethylene glycol).
In the above example, the molar ratio of Mg 2+：Ba2+ in the auxiliary agent of the catalyst in example 13 was adjusted to be less than 3:1 to promote the reaction in the direction of preferentially producing 6-methylindole, thereby obtaining a product mainly comprising 6-methylindole, and other specific synthetic routes and steps refer to the method in example 13.
Example 16
The one-step method for preparing the 6-methylindole and the 4-methylindole from m-methylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and BaO, mgO, niO as auxiliary agents (the molar ratio of Mg 2+：Ba2+ is less than 3:1), and Al 2O3 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 25%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 55%.
After completion of the reduction in the same manner as in example 1, the starting materials m-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump in a molar ratio of 10:1, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.2h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 240 ℃, the hydrogen entering the preheater entrains vaporized m-methylaniline, ethylene glycol and water at the flow rate of 100h -1, the reaction temperature is 290 ℃, the reaction pressure is 0.5MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed. As shown in FIG. 7, the results showed that the conversion of ethylene glycol was 80%, and the yield of 6-methylindole was 68% (based on ethylene glycol) and the yield of 4-methylindole was 6% (based on ethylene glycol).
Example 17
The one-step method for preparing the 6-methylindole and the 4-methylindole from m-methylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and BaO, mgO, niO as auxiliary agents (the molar ratio of Mg 2+：Ba2+ is less than 3:1), and Al 2O3 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 30%, the mass ratio of metal ions in the auxiliary agents is 25%, and the mass ratio of the carrier is 40%.
After completion of the reduction in the same manner as in example 1, the starting materials m-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump in a molar ratio of 5:1, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.4h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 280 ℃, the hydrogen entering the preheater entrains vaporized m-methylaniline, ethylene glycol and water at the flow rate of 100h -1, the reaction temperature is 320 ℃, the reaction pressure is 0, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. The results showed 75% conversion of ethylene glycol, 65% yield of 6-methylindole (based on ethylene glycol) and 10% yield of 4-methylindole (based on ethylene glycol).
Example 18
The one-step method for preparing the 6-methylindole and the 4-methylindole from m-methylaniline and ethylene glycol. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and BaO, mgO, niO as auxiliary agents (the molar ratio of Mg 2+：Ba2+ is less than 3:1), and Al 2O3 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 25%, the mass ratio of metal ions in the auxiliary agents is 25%, and the mass ratio of the carrier is 50%.
After completion of the reduction in the same manner as in example 1, the starting materials m-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump in a molar ratio of 10:1, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.2h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 260 ℃, the hydrogen entering the preheater entrains vaporized m-methylaniline, ethylene glycol and water at the flow rate of 100h -1, the reaction temperature is 280 ℃, the reaction pressure is 0.3MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 100h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed. The results showed that the conversion of ethylene glycol was 83%, the yield of 6-methylindole was 70% (based on ethylene glycol), and the yield of 4-methylindole was 8% (based on ethylene glycol).
Example 19
The 5-methylindole is prepared from p-methylaniline and ethylene glycol by a one-step method. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2, znO and MgO as auxiliary agents and Al 2O3 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 15%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 65%.
After completion of the reduction in the same manner as in example 1, the raw materials of p-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump at a molar ratio of 7:1, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.25h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 230 ℃, the vaporized para-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 50h -1, the reaction temperature is 290 ℃, the reaction pressure is 0, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 50h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. As shown in FIG. 8, the results showed that the conversion of ethylene glycol was 90% and the yield of 5-methylindole was 80% (based on ethylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 20
The 5-methylindole is prepared from p-methylaniline and ethylene glycol by a one-step method. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2, znO and MgO as auxiliary agents and Al 2O3 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 10%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 70%.
After completion of the reduction in the same manner as in example 1, the raw materials of p-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump at a molar ratio of 10:1, the space velocity of the liquid was maintained at 0.4h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.3h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 230 ℃, the vaporized para-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 50h -1, the reaction temperature is 240 ℃, the reaction pressure is 0.3MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 50h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. The results showed 94% conversion of ethylene glycol and 82% yield of 5-methylindole (calculated as ethylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 21
The 5-methylindole is prepared from p-methylaniline and ethylene glycol by a one-step method. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2, znO and MgO as auxiliary agents and Al 2O3 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 15%, the mass ratio of metal ions in the auxiliary agents is 25%, and the mass ratio of the carrier is 60%.
After completion of the reduction in the same manner as in example 1, the raw materials of p-methylaniline and ethylene glycol were fed into the reaction mixer by a plunger pump at a molar ratio of 6:1, the space velocity of the liquid was maintained at 0.8h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.25h -1, and then the mixture of the two raw materials and water was vaporized together in the preheater. The temperature of the preheater is 280 ℃, the vaporized para-methylaniline, ethylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 50h -1, the reaction temperature is 290 ℃, the reaction pressure is 0.4MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 50h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. The results showed that the ethylene glycol conversion was 85% and the 5-methylindole yield was 74% (based on ethylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 22
3-Methylindole is prepared from aniline and glycerol in a one-step process. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and MgO as auxiliary agents and SiO 2 as a carrier after reduction in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 25%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 55%.
After completion of the reduction in the same manner as in example 1, the starting materials aniline and glycerol were fed into the reaction mixer with a plunger pump in a 5:1 molar ratio, the space velocity of the liquid was maintained at 0.65h -1, water was pumped into the mixer with a plunger pump at a space velocity of 0.15h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 220 ℃, the vaporized aniline, glycerol and water are entrained by the hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 260 ℃, the reaction pressure is 0.3MPa, the hydrogen and the catalyst are subjected to gas-solid phase reaction under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials are subjected to reaction on a solid catalyst bed. As shown in FIG. 9, the reaction results of the bottoms product showed a glycerol conversion of 85% and a 3-methylindole yield of 75% (calculated as glycerol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 23
3-Methylindole is prepared from aniline and glycerol in a one-step process. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and MgO as auxiliary agents and SiO 2 as a carrier after reduction in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 25%, the mass ratio of metal ions in the auxiliary agents is 15%, and the mass ratio of the carrier is 60%.
After completion of the reduction in the same manner as in example 1, the starting materials aniline and glycerol were fed into the reaction mixer with a plunger pump in a molar ratio of 4:1, the space velocity of the liquid was maintained at 1h -1, water was pumped into the mixer with a plunger pump at a space velocity of 0.1h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 250 ℃, the vaporized aniline, glycerol and water are entrained by the hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 260 ℃, the reaction pressure is 0.1MPa, the hydrogen and the catalyst are subjected to gas-solid phase reaction under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials are subjected to reaction on a solid catalyst bed. The reaction result of the tower kettle product shows that the conversion rate of the glycerol is 82 percent, and the yield of the 3-methylindole is 75 percent (calculated by glycerol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 24
3-Methylindole is prepared from aniline and glycerol in a one-step process. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, takes ZrO 2, znO and MgO as auxiliary agents and takes SiO 2 as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 35%, the mass ratio of metal ions in the auxiliary agents is 15%, and the mass ratio of the carrier is 50%.
After completion of the reduction in the same manner as in example 1, the starting materials aniline and glycerol were fed into the reaction mixer with a plunger pump at a molar ratio of 8:1, maintaining a liquid space velocity of 1h -1, water was pumped into the mixer with a plunger pump at a space velocity of 0.15h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 250 ℃, the vaporized aniline, glycerol and water are entrained by the hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 230 ℃, the reaction pressure is 0.4MPa, the hydrogen and the catalyst are subjected to gas-solid phase reaction under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials are subjected to reaction on a solid catalyst bed. The reaction result of the tower kettle product shows that the conversion rate of the glycerol is 88 percent, and the yield of the 3-methylindole is 73 percent (calculated by glycerol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 25
The 2-methylindole is prepared from aniline and 1, 2-propanediol in a one-step process. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2 and ZnO as auxiliary agents and SiO 2 as a carrier after reduction in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 30%, the mass ratio of metal ions in the auxiliary agents is 20%, and the mass ratio of the carrier is 58%.
After completion of the reduction in the same manner as in example 1, the starting materials aniline and 1, 2-propanediol were fed into the reaction mixer by a plunger pump in a molar ratio of 8:1, the space velocity of the liquid was maintained at 0.2h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.06h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 220 ℃, the vaporized aniline, the vaporized 1, 2-propylene glycol and the water are entrained by the hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 270 ℃, the reaction pressure is 0, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw materials react on a solid catalyst bed. As shown in FIG. 10, the reaction results of the bottoms product showed 85% conversion of 1, 2-propanediol and 75% yield of 2-methylindole (based on 1, 2-propanediol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 26
The 2-methylindole is prepared from aniline and 1, 2-propanediol in a one-step process. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based multi-phase catalyst takes CuO as a main body, zrO 2、ZnO、CeO2 as an auxiliary agent and carbon black as a carrier after being reduced in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 35%, the mass ratio of metal ions in the auxiliary agent is 15%, and the mass ratio of the carrier is 60%.
After completion of the reduction in the same manner as in example 1, the starting materials aniline and 1, 2-propanediol were fed into the reaction mixer by a plunger pump at a molar ratio of 6:1, the space velocity of the liquid was maintained at 0.5h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.06h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 220 ℃, vaporized aniline, 1, 2-propylene glycol and water are entrained by hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 280 ℃, the reaction pressure is 0.4MPa, the hydrogen and the catalyst are subjected to gas-solid phase reaction in the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material is subjected to reaction on a solid catalyst bed. The reaction result of the tower kettle product shows that the conversion rate of the 1, 2-propylene glycol is 80 percent, and the yield of the 2-methylindole is 77 percent (calculated by 1, 2-propylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 27
The 2-methylindole is prepared from aniline and 1, 2-propanediol in a one-step process. The Cu-based catalyst is adopted, the catalyst loading is 60mL, the Cu-based catalyst takes CuO as a main body, zrO 2 and ZnO as auxiliary agents and SiO 2 as a carrier after reduction in a nitrogen atmosphere containing hydrogen, wherein the mass ratio of Cu is 25%, the mass ratio of metal ions in the auxiliary agents is 25%, and the mass ratio of the carrier is 50%.
After completion of the reduction in the same manner as in example 1, the starting materials aniline and 1, 2-propanediol were fed into the reaction mixer by a plunger pump at a molar ratio of 10:1, the space velocity of the liquid was maintained at 0.5h -1, water was pumped into the mixer by a plunger pump at a space velocity of 0.2h -1, and then the mixture of the two starting materials and water was vaporized together in the preheater. The temperature of the preheater is 190 ℃, the vaporized aniline, the vaporized 1, 2-propylene glycol and the water are entrained by the hydrogen entering the preheater at the flow rate of 300h -1, the reaction temperature is 230 ℃, the reaction pressure is 0.6MPa, the gas-solid phase reaction is carried out with the catalyst under the hydrogen atmosphere, the flow rate of the hydrogen is controlled by a mass flowmeter, the space velocity of the hydrogen is 300h -1, the hydrogen enters the preheater through a one-way valve, and then the mixed gas phase raw material reacts on a solid catalyst bed. The reaction result of the tower kettle product shows that the conversion rate of the 1, 2-propylene glycol is 88 percent, and the yield of the 2-methylindole is 72 percent (calculated by 1, 2-propylene glycol). The subsequent steps after the reaction are the same as those in example 1, and will not be described again.
Example 28
Test of the deactivation and regeneration method of Cu-based multi-phase catalyst after the catalyst activity is reduced to less than 50% after a period of time by taking example 1 as an example, the catalyst is subjected to in-situ deactivation and regeneration. And (3) introducing regeneration gas, which can be air or nitrogen containing oxygen, into the reactor, wherein the air is adopted this time, the airspeed is 100h -1, the temperature is raised to 300 ℃ at the temperature rising rate of 20 ℃ per hour, the temperature is kept for 4h, and the regeneration is finished.
The catalyst was re-reduced according to the above-mentioned reduction step after regeneration, and the reaction was continued after repeated reduction regeneration, and the reaction effect of the regenerated catalyst was tested and recorded, and the specific results are shown in table 1 below.
As shown by the test results in Table 1, the Cu-based multi-phase catalyst is used for synthesizing indole by adopting a one-step method of aniline and ethylene glycol in a fixed bed reactor, and in the continuous production process, the catalyst is subjected to deactivation and regeneration and is continuously used, the activity of the catalyst can be better recovered, and the result shows that the ethylene glycol conversion rate and the indole yield can also maintain higher level and the catalytic efficiency is high through multiple times of deactivation and regeneration.
Example 29
Using the reaction synthesis system of example 1 described above, the reaction was carried out under the following reaction conditions. The catalyst loading is 60mL, the reaction temperature is 280 ℃, the reaction pressure is 1.0MPa, the molar ratio of aniline to glycol is 9:1, the liquid space velocity is 0.4H -1, the water space velocity is 0.13H -1, the catalyst and the raw materials are vaporized together, the preheater temperature is 240 ℃, the H 2 space velocity is 300H -1, the reaction is carried out to synthesize indole, sampling analysis is carried out every 50 hours, the result is recorded, the stability experiment is continuously carried out for 500 hours, and the summarized reaction result data are shown in Table 2. The specific reaction process is as described in example 1 and the separation and purification process of the product.
As can be seen from the results in the table 2, under the reaction conditions of the technical scheme, after aniline and ethylene glycol are continuously fed and reacted for 500 hours, the conversion rate of the ethylene glycol and the yield of the synthesized indole are reduced to a certain extent, but the conversion rate and the yield of the synthesized indole can still be kept at higher levels, so that the Cu-based multi-phase catalyst has better stability and obvious industrial application value.
The process adopts a small fixed reactor in a laboratory, can realize continuous production, can increase the diameter of a reaction furnace pipe in large-scale industrial production, improves the loading amount of a catalyst, can carry out cyclic reaction, improves the utilization rate of excessive raw materials, improves the reaction efficiency, can realize resource conservation and achieves the aim of environmental protection.
In this case, in the case of continuous industrial production, the product obtained after the completion of the reaction in the reactor is cooled and flashed, and the product obtained after separation is fed into a rectifying column, and the target product, unreacted raw materials, by-products and the like are separated by the rectifying column.
Example 30
Referring to fig. 2, a synthesis system adopted by the method for synthesizing indole and derivatives thereof by an alcohol amine method comprises a preheating reaction unit, a hydrogen separation unit, a three-tower rectification unit and a vacuum unit externally connected for manufacturing a high-vacuum rectification environment, wherein the preheating reaction unit comprises a feed preheating unit and a reactor;
The raw materials are preheated and vaporized through the feed preheating unit, the raw materials enter a reactor for catalytic reaction, the mixed products are cooled and separated in a hydrogen separation unit, water and hydrogen are separated for recycling, and the purified indole and the derivative products thereof are obtained through dehydration and removal of light component impurities through a water removal tower in a three-tower rectifying unit.
Taking the synthesis of N-methylindole as an example, the specific process is as follows:
The synthesis system comprises a preheating reaction unit, a hydrogen separation unit, a three-tower rectification unit and a vacuum unit, wherein the preheating reaction unit comprises a feeding preheating unit and a reaction unit, the raw materials are preheated and vaporized through the feeding preheating unit and then enter the reaction unit to perform catalytic reaction to obtain a mixed product, the reaction unit is a fixed bed reactor R, the feeding preheating unit comprises a feeding pump, a mixer M and a preheater E1, the hydrogen separation unit comprises a condenser E2, and the three-tower rectification unit comprises a water removal tower T1, a raw material recovery tower T2 and a product tower T3 which are sequentially connected;
And (3) preheating a reaction unit, namely filling the prepared Cu-based catalyst into a reactor R, feeding ethylene glycol, N-methylaniline and water in a molar ratio of 1:5.5:11, and feeding the three groups of raw materials into the reactor R for catalytic reaction after the three groups of raw materials are vaporized to obtain an outlet flow of the reactor R. In this test, the gas phase stream passing through the outlet of the detection reactor R consists of 64% of N-methylaniline, 23% of water, 1.3% of ethylene glycol and 11.7% of N-methylindole as a product, together with other heavy impurities, by mass.
And the hydrogen separation unit is used for cooling the N-methylaniline and glycol raw materials at the top of the two towers, the total flow is 3311kg/h, the temperature is reduced from 270 ℃ to 184 ℃, the load of the condenser E2 is 160kW, the residual heat of the reaction gas phase is completely utilized to provide a heat source for the circulation of the front-stage aniline, and the reaction gas phase enters the high-efficiency gas-liquid separator for gas-liquid separation after passing through the two-stage cooler, and the condensation temperature is about 90-110 ℃. At this time, the hydrogen is separated to obtain the maximum separation efficiency, and part of the hydrogen is recycled to be collected and purified. The byproduct of the hydrogen product obtained per hour is measured to be more than 50Nm < 3 >, and the hydrogen with the purity of 99% can be obtained as a byproduct through simple absorption and purification.
And the three-tower rectifying unit is used for removing light components such as hydrogen from the cooled stream, then, dehydrating and partially removing light component impurities in a dehydrating tower T1, wherein the theoretical plate number of the dehydrating tower T1 is 30, and the variable diameter tower is adopted to meet the gas-liquid phase load requirement. The pressure (absolute pressure) of the tower top is 101kPa, high-efficiency silk screen structured packing is adopted in the tower, the height of the packing is 15m, the diameter of the tower is 700mm, the reflux ratio is controlled at 1.0, the operation of stably dehydrating and removing light component impurities is carried out, the light impurities such as methanol, water and the like in the product can be removed, the produced liquid phase is split-phase, the organic phase is taken as reflux liquid to enter the tower, the wastewater can be concentrated and evaporated, the wastewater is recycled, and the wastewater discharge amount is greatly reduced.
The theoretical plate number of the raw material recovery tower T2 is 40, and corrugated packing with metal pore plates is adopted in the tower. The corrugated filler of the metal pore plate has larger specific surface area, better plate efficiency such as filler separation, and the like, and the corrugated angle and the opening direction are optimized, so that the corrugated filler adapts to the fluctuation of larger working conditions, adapts to larger gas load, increases the operation elasticity of the corrugated filler and reduces the tower height. The raw material recovery tower T2 adopts a mode of gas-liquid phase separation into a tower, gas phase enters the upper part of the distributor, and the phenomenon that partial filler cannot be wetted and utilized due to disturbance of liquid phase distribution of the distributor is prevented, and liquid phase enters the distributor. The height of the integral packing is 20m, the rectifying section and the stripping section are the same, the pressure is negative pressure operation, the pressure (absolute pressure) of the tower top is 15kPa, the reflux ratio is controlled to be 1.1, the temperature of the tower top is 140-150 ℃, the tower bottom is 190-195 ℃, the integral separation recovery rate is more than 97%, and the raw materials are fully reused and are used as the outlet heat exchange of the front-stage reactor. The N-methylaniline and ethylene glycol raw materials with the purity of more than 99 percent are obtained at the top of the tower.
The theoretical plate number of the product tower T3 is 40, and the tower is internally filled with metal plate corrugated packing. The corrugated metal plate filler has the characteristics of large specific surface, high mass transfer efficiency, moderate liquid holdup and larger and more flexible coping with load. The pressure (absolute pressure) at the top of the tower is 10kPa, so that the grade of a heat source at the bottom of the tower is effectively reduced, and the conventional heat conducting oil boiler can be used. The reflux ratio is controlled at 1.1, and the two feed inlets at the lower part of the middle part of the tower can be flexibly adjusted according to the composition of raw materials. The liquid N-methylindole with the purity of 99.9 percent is obtained at the top of the tower, and the heavy component impurity is obtained at the bottom of the tower and can be used as a mixed raw material of a medical intermediate for sale.
The product is separated and purified by the method to obtain the N-methylindole product 1400t/a, the purity of the product reaches 99.9%, and 1200Nm3 of hydrogen is produced as a byproduct every day. The use amount of the whole public engineering and the matched facilities is small. The energy consumption of the product is 1.5tce/t, which is reduced by more than 30 percent compared with the traditional scheme, the whole energy consumption is lower, the environment is friendly, the large waste water discharge in the traditional process is avoided, the waste gas discharge is avoided, the disposable equipment investment can be effectively saved, the product purity is high, and the industrial competitiveness is good.
Example 31
The difference from the above-mentioned example 30 was that the number of trays, the column top pressure and the reflux ratio were adjusted, namely, the number of trays used in the water removal column was 25, the column top pressure was 95kPa, the reflux ratio was 0.4, the number of trays used in the raw material recovery column was 35, the column top pressure was 10kPa, the reflux ratio was controlled to 0.7, the number of trays used in the product column was 35, the column top pressure was 5kPa, and the reflux ratio was 0.4, and the other apparatuses, methods and procedures used in the example 30 were identical.
Finally, liquid N-methylindole with the purity of 99.5 percent is obtained from the top of the tower, and heavy component impurities are obtained from the bottom of the tower.
Example 32
The difference from the above-mentioned example 30 was that the number of trays, the column top pressure and the reflux ratio were adjusted, namely, the number of trays used in the water removal column was 35, the column top pressure was 105kPa, the reflux ratio was 2, the number of trays used in the raw material recovery column was 50, the column top pressure was 25kPa, the reflux ratio was controlled to 1.5, the number of trays used in the product column was 50, the column top pressure was 15kPa, and the reflux ratio was 1.6, and the other apparatuses, methods and procedures used in the example 30 were identical.
Finally, liquid N-methylindole with the purity of 99.8 percent is obtained from the top of the tower, and heavy component impurities are obtained from the bottom of the tower.
In examples 30 to 32 of the present application, if indole and its derivatives are solid materials, the two-column rectification unit and the crystallization unit described in example 1 are preferably used for separation and purification of the product, and if indole and its derivatives are liquid materials, the three-column rectification unit described in example 30 is preferably used for separation and purification of the product. The three column ranges of the rectification columns implemented in examples 30-32 fully meet the rectification requirements of other liquid indole derivatives, but the data combination at the time of optimal rectification effect can be properly adjusted according to the ranges by a person skilled in the art.
In summary, the invention adopts the molecular optimal synthesis route, utilizes a large amount of easily available raw materials, and adopts a one-step method to catalyze and continuously synthesize indole and derivatives thereof under the condition of relatively low temperature, and has the advantages of simple process, convenient operation, no noble metal catalyst, low catalysis temperature, low production cost, high production efficiency, difficult inactivation of the catalyst and the like, thereby realizing industrial mass production and having considerable economic value and industrial application significance.
The foregoing is a preferred embodiment of the present invention, and the method and system for synthesizing indole and its derivatives by alcohol amine method provided by the present invention are described in detail, wherein specific examples are applied to illustrate the principles and embodiments of the present invention, and the above examples are only used to help understand the method and core idea of the present invention, and meanwhile, the present invention should not be construed as being limited to the present invention in any way, according to the idea of the present invention, by those skilled in the art. The foregoing is a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (36)
1. The method for synthesizing indole and derivatives thereof by alcohol amine method is characterized by comprising the following steps:
S1, filling a Cu-based multi-phase catalyst into a fixed bed reactor, and introducing H 2/N2 mixed gas for reduction, wherein the Cu-based multi-phase catalyst comprises a CuO main body and a ZrO 2 auxiliary agent;
S2, mixing raw material aniline or aniline derivatives, polyalcohols and water, then introducing the mixture into a preheater for vaporization to form vaporized mixed gas, introducing the vaporized mixed gas into a reactor for catalytic reaction with a reduced Cu-based multi-phase catalyst, and obtaining a reaction product containing indole or derivatives thereof, wherein the reaction temperature of the obtained reaction product containing indole is 230-290 ℃;
S3, condensing the reaction product, separating water and hydrogen, and separating and purifying the residual product to obtain indole or a derivative product thereof;
When the Cu-based multi-phase catalyst is deactivated or the activity is reduced, introducing regeneration gas air or nitrogen containing oxygen into the reactor for in-situ regeneration, and then reducing according to the step S1 to continue to be used for catalytic reaction;
the auxiliary agent of the Cu-based multi-phase catalyst also comprises one or more of ZnO, mgO, caO, mnO, baO, ceO 2 and NiO, and the carrier of the Cu-based multi-phase catalyst is at least one of Al 2O3、SiO2 and carbon black.
2. The method for synthesizing indole and derivatives thereof by alcohol amine method according to claim 1, wherein the aniline derivative is one of N-methylaniline, N-ethylaniline, o-methylaniline, m-methylaniline and p-methylaniline, and the polyalcohol is one of ethylene glycol, glycerol and 1, 2-propylene glycol.
3. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 2, wherein the mass ratio of Cu in the Cu-based multi-phase catalyst is 10% -35%, the mass ratio of metal ions in the auxiliary agent is 10% -25%, and the mass ratio of the carrier is 40% -80%.
4. The method for synthesizing indole and derivatives thereof according to claim 2, wherein the catalyst is regenerated as follows;
introducing air or nitrogen containing oxygen into the reactor, wherein the gas space velocity is 50h -1~1000h-1, heating and preserving heat of the catalyst in an in-situ mode, the heating rate is 10-20 ℃ per hour, heating to 200-400 ℃ and preserving heat for 2-20 h, and reducing according to the step S1 after regeneration is finished, and continuing to be used for catalytic reaction.
5. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the polyalcohol is ethylene glycol, aniline and ethylene glycol are used as raw materials, and the final reaction product is indole.
6. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 5, wherein the Cu-based multi-phase catalyst is mainly CuO, the auxiliary agent comprises ZrO 2, the Cu is loaded by 20% -35%, the metal ions in the auxiliary agent are loaded by 10% -25%, and the carrier is 50% -70%.
7. The method for synthesizing indole and derivatives thereof according to claim 6, wherein in the step S1, the volume content of hydrogen in the H 2/N2 gas mixture is 1% -20%, the space velocity is 100H -1~1000h-1, the reduction temperature is 100 ℃ -300 ℃, and the reduction time is 1H-50H;
In the step S2, the molar ratio of raw material aniline to ethylene glycol is 4:1-10:1, the reaction temperature is 230-290 ℃, the reaction pressure is 0-1.0 MPa, the temperature set by the preheater is 190-250 ℃, the feeding airspeed of raw materials is 0.2h -1～1.0h-1, and the water feeding airspeed is 0.06h -1～0.33h-1.
8. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the aniline derivative is N-methylaniline and the polyhydric alcohol is ethylene glycol, the reaction product is N-methylindole.
9. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 8, wherein the Cu-based multi-phase catalyst is mainly CuO, the auxiliary agent further comprises ZnO and CaO, the Cu is 10% -25% by weight, the metal ions in the auxiliary agent are 15% -35% by weight, and the carrier is 50% -75% by weight.
10. The method for synthesizing indole and derivatives thereof according to claim 9, wherein in the step S2, the molar ratio of raw material N-methylaniline to ethylene glycol is 4:1-8:1, the reaction temperature is 230-280 ℃, the reaction pressure is 0-0.5 MPa, the temperature set by the preheater is 190-240 ℃, the feeding airspeed of raw material is 0.4h -1～1.0h-1, and the water feeding airspeed is 0.06h -1～0.25h-1.
11. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the aniline derivative is N-ethylaniline and the polyhydric alcohol is ethylene glycol, the reaction product is N-ethylindole.
12. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 11, wherein the Cu-based multi-phase catalyst is mainly CuO, the auxiliary agent further comprises CaO, the Cu is loaded by 20% -35%, the metal ions in the auxiliary agent are loaded by 10% -20%, and the carrier is 55% -70%.
13. The method for synthesizing indole and derivatives thereof according to claim 12, wherein in the step S2, the molar ratio of raw material N-ethylaniline to ethylene glycol is 5:1-10:1, the reaction temperature is 280-350 ℃, the reaction pressure is 0.2-0.6 mpa, the temperature set by the preheater is 200-220 ℃, the feeding airspeed of raw material is 0.2h -1～0.4h-1, and the water feeding airspeed is 0.1h -1～0.2h-1.
14. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the aniline derivative is o-methylaniline and the polyalcohol is ethylene glycol, the reaction product is 7-methylindole.
15. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 14, wherein the main body of the Cu-based multi-phase catalyst is CuO, the auxiliary agent further comprises MgO, baO, znO, the load mass percent of Cu is 20% -30%, the load mass percent of metal ions in the auxiliary agent is 10% -25%, and the content of the carrier is 45% -70%.
16. The method for synthesizing indole and derivatives thereof according to claim 15, wherein in the step S2, the molar ratio of raw material o-methylaniline to ethylene glycol is 4:1-9:1, the reaction temperature is 250-280 ℃, the reaction pressure is 0-0.5 MPa, the temperature set by the preheater is 210-250 ℃, the feeding airspeed of raw material is 0.4h -1～0.8h-1, and the feeding airspeed of water is 0.2h -1～0.3h-1.
17. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the aniline derivative is meta-methylaniline and the polyalcohol is ethylene glycol, the reaction product is 4-methylindole and/or 6-methylindole.
18. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 17, wherein the main body of the Cu-based multi-phase catalyst is CuO, the auxiliary agent further comprises MgO and BaO, when the molar ratio of Mg 2+：Ba2+ in the auxiliary agent is more than 3:1, the load mass percent of Cu is 10% -20%, the load mass percent of metal ions in the auxiliary agent is 15% -20%, the content of a carrier is 60% -75%, and the reaction product is mainly 4-methylindole;
In the step S2, the molar ratio of raw materials of m-methylaniline to ethylene glycol is 2:1-5:1, the reaction temperature is 230-280 ℃, the reaction pressure is 0-0.5 MPa, and the temperature set by the preheater is 210-250 ℃.
19. The method for synthesizing indole and derivatives thereof according to claim 18, wherein the main body of the Cu-based multi-phase catalyst is CuO, the auxiliary agent further comprises MgO and BaO, when the molar ratio of Mg 2+：Ba2+ is less than 3:1, the load mass percent of Cu is 25% -35%, the load mass percent of metal ions in the auxiliary agent is 20% -25%, the content of carriers is 40% -55%, and the reaction product is mainly 6-methylindole;
in the step S2, the molar ratio of raw materials of m-methylaniline to ethylene glycol is 5:1-10:1, the reaction temperature is 280-320 ℃, the reaction pressure is 0-0.5 MPa, and the temperature set by the preheater is 240-280 ℃.
20. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the aniline derivative is p-methylaniline and the polyhydric alcohol is ethylene glycol, the reaction product is 5-methylindole.
21. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 20, wherein the Cu-based multi-phase catalyst is mainly CuO, the auxiliary agent further comprises ZnO and MgO, the Cu is 10% -15% by weight, the metal ions in the auxiliary agent are 20% -25% by weight, and the carrier is 60% -70% by weight.
22. The method for synthesizing indole and derivatives thereof according to claim 21, wherein in the step S2, the molar ratio of raw material p-methylaniline to ethylene glycol is 6:1-10:1, the reaction temperature is 240 ℃ to 290 ℃, the reaction pressure is 0-0.4 mpa, the temperature set by the preheater is 230 ℃ to 280 ℃, the feeding airspeed of raw material is 0.2h -1～0.8h-1, and the water feeding airspeed is 0.25h -1～0.30h-1.
23. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the raw material is aniline and the polyhydric alcohol is glycerol, the reaction product is 3-methylindole.
24. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 23, wherein the Cu-based multi-phase catalyst is mainly CuO, the auxiliary agent further comprises MgO, the Cu is loaded by 25% -35%, the metal ions in the auxiliary agent are loaded by 15% -25%, and the carrier is 50% -60%.
25. The method for synthesizing indole and derivatives thereof according to claim 24, wherein in the step S2, the molar ratio of aniline to glycerol is 4:1-8:1, the reaction temperature is 230-260 ℃, the reaction pressure is 0-0.4 mpa, the temperature set by the preheater is 200-250 ℃, the feeding airspeed of the raw materials is 0.6h -1～1.0h-1, and the water feeding airspeed is 0.06h -1～0.15h-1.
26. The method for synthesizing indole and derivatives thereof according to claim 2, wherein when the raw material is aniline and the polyhydric alcohol is 1, 2-propanediol, the reaction product is 2-methylindole.
27. The method for synthesizing indole and derivatives thereof by an alcohol amine method according to claim 26, wherein the Cu-based multi-phase catalyst is mainly CuO, the auxiliary agent further comprises ZnO, the Cu is loaded by 25% -35%, the metal ions in the auxiliary agent are loaded by 15% -25%, and the carrier is 50% -60%.
28. The method for synthesizing indole and derivatives thereof according to claim 27, wherein in the step S2, the molar ratio of aniline as a raw material to 1, 2-propanediol is 6:1-10:1, the reaction temperature is 230-280 ℃, the reaction pressure is 0-0.6 mpa, the temperature set by the preheater is 190-220 ℃, the feeding airspeed of the raw material is 0.2h -1～0.6h-1, and the water feeding airspeed is 0.06h -1～0.2h-1.
29. The method for synthesizing indole and derivatives thereof according to any one of claims 1 to 28, wherein the catalytic reaction in step S2 is performed under a hydrogen atmosphere, and the vaporized mixed gas and hydrogen are introduced into the reactor to perform the catalytic reaction, and the hydrogen space velocity is 50h -1～500h-1.
30. The method for synthesizing indole and derivatives thereof according to any one of claims 1 to 28, wherein in step S3, the reaction product is condensed, the reaction product is flashed and then vented, water and hydrogen are separated, the hydrogen is returned to the reactor from a top pipeline for recycling, the remaining bottom liquid product enters a rectifying tower for separation, light component raw materials are separated from the top of the tower for recycling, and the purified indole and derivatives thereof are obtained from the bottom of the tower.
31. A synthesis system adopted by the method for synthesizing indole and derivatives thereof by an alcohol amine method according to any one of claims 1 to 28, wherein the synthesis system comprises a preheating reaction unit, a hydrogen separation unit and a rectification unit which are connected in sequence;
the mixed product is subjected to gas-liquid separation by a hydrogen separation unit, separated water and hydrogen are recycled, and the residual product is dehydrated and impurity-removed by a rectification unit to obtain indole and a derivative thereof;
the preheating reaction unit comprises a feeding preheating unit and a reaction unit, raw materials are preheated and vaporized through the feeding preheating unit and then enter the reaction unit for catalytic reaction to obtain a mixed product, and the reaction unit is a fixed bed reactor;
The rectification unit is a two-tower rectification unit and comprises a first rectification tower, a second rectification tower, a tower top condenser connected with the top of the rectification tower and a tower bottom reboiler positioned at the bottom of the rectification tower, wherein the tower bottom condenser is used for dehydrating and recovering light component substances through the first rectification tower and the second rectification tower, and then low-purity solutions of indole and derivatives thereof are obtained from the tower bottom.
32. The synthesis system according to claim 31, wherein the material in the second rectifying tower is fed into the separation crystallizer, the crystallization supplement is added and mixed uniformly, the crystallization supplement is water and methanol, the solution crystallization is performed by controlling the ratio of the water, the methanol and the material in the second rectifying tower to obtain indole crystals, the indole crystals are fed into the melting crystallizer, the cooling rate, the crystallization endpoint and the heating rate are controlled, and the indole derivative products in high purity solid state are obtained through cooling crystallization, heating purification.
33. The synthesis system according to claim 31, further comprising a vacuum unit external to the vacuum unit for creating a high vacuum rectification environment;
the rectification unit is a three-tower rectification unit and comprises a water removal tower, a raw material recovery tower and a product tower which are connected in sequence;
The mixed product is cooled by a hydrogen separation unit, gas-liquid separation is carried out, water and hydrogen are separated, the rest product is dehydrated by a water removal tower, light component impurities are removed, light component raw materials are separated by a raw material recovery tower and recovered, finally, the light component raw materials enter a product tower for further purification, and high-purity liquid indole and derivative products thereof are obtained at the top of the tower.
34. The synthesis system of claim 33, wherein the water removal tower is a reducing tower with the number of plates being 25-35, high-efficiency silk screen structured packing is adopted in the tower, the tower top pressure is 95kPa-105kPa, and the reflux ratio is controlled to be 0.4-2.
35. The synthesis system according to claim 33, wherein the raw material recovery tower adopts a gas-liquid phase separation mode, the number of tower plates is 35-50, corrugated packing materials with metal pore plates are adopted in the tower, the tower top pressure is 10 kpa-25 kpa, and the reflux ratio is controlled to be 0.7-1.5.
36. The synthesis system according to claim 33, wherein the product indole is purified by using the product tower, the number of tower plates is 35-50, corrugated metal plate packing is adopted in the tower, the tower top pressure is 5 kpa-15 kpa, and the reflux ratio is controlled to be 0.4-1.6.
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