CN103539719B - Method for producing indole by taking phenylamine and ethylene glycol as raw materials - Google Patents
Method for producing indole by taking phenylamine and ethylene glycol as raw materials Download PDFInfo
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- CN103539719B CN103539719B CN201210239873.9A CN201210239873A CN103539719B CN 103539719 B CN103539719 B CN 103539719B CN 201210239873 A CN201210239873 A CN 201210239873A CN 103539719 B CN103539719 B CN 103539719B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a method for producing indole by taking phenylamine and ethylene glycol as raw materials and mainly aims to solve the problems of lower indole yield and difficulty in realizing continuous operation in the prior art. The problems are better solved through the technical scheme that the method for producing indole by taking phenylamine and ethylene glycol as raw materials comprises the steps: enabling the raw materials, i.e., phenylamine and ethylene glycol, to enter a reaction region to be in contact with a catalyst to generate an indole-containing product; enabling the catalyst in the reaction region to enter a stripping region; enabling the stripped catalyst to enter a regenerating region under the conveyance of a conveying medium A through a conveying pipe; enabling the regenerated catalyst to enter a degassing region; enabling the degassed catalyst to return to the reaction region under the conveyance of a conveying medium B through a conveying pipe. The method can be used for the industrial production of indole.
Description
Technical field
The present invention relates to it is a kind of with aniline, ethylene glycol as raw material production indole method.
Background technology
Indole is the important source material of each medicine of system, pesticide, spice, dyestuff and feed additive, is that important heterocycle is fine
Chemical intermediate.The production capacity in the whole world is 7000t/a at present.With the development of its applied research, derived by which many heavy
The medicine of the high added value wanted and pesticide, the particularly current market demand rapid development of indole derivativeses tryptophan, only this one
The global distant view demand of item is in 100000t/a.Therefore, the market prospect of indole is very wide.
It is industrial at present mainly to adopt ortho-chlorotolu'ene multistep processes synthesis of indole.It is ortho-chlorotolu'ene Jing chlorinations, cyaniding, ammonification, de-
Water is obtained dihydroindole, then dehydrogenation and indole.As synthesis step is various, separation process is numerous and diverse, and energy consumption is big, high cost, and
And preparation process produces substantial amounts of garbage and causes environmental pollution.China is at present mainly using the method production Yin of this backwardness
Diindyl, and at the same time, China successfully realizes the industrialization of fourth indole synthesis tryptophan now, therefore, the technique for being badly in need of substituting
Simply, the new technique of the inexpensive synthesis of indole of environmental friendliness and cost.
With aniline and ethylene glycol as raw material heterogeneous catalysiss One Step Synthesis of Indole not only low in raw material price, production cost
Low, operating procedure is simple, and environmental friendliness, with clear advantage, is the most promising one kind of synthesis of indole.The eighties in 20th century
Japan has carried out substantial amounts of correlational study to the catalyst.Matsuda etc. find the catalyst such as Cd, Cu, Ag and Zn to aniline and
The reaction of ethylene glycol One Step Synthesis of Indole all has certain activity (United States Patent (USP) 4436917).Under 350 DEG C, normal pressure, Gu
In fixed bed reaction, the yield of indole is all more than 20% (because of aniline excess, in terms of ethylene glycol).Wherein Ag/SiO2- ZnO catalyst
Indole yield reach more than 40%.But experiment is it has also been found that a main problem：Catalyst was inactivated in a few hours, and yield is straight
Line declines.This all contains the N atoms for possessing lone pair electrons, the change on a catalyst of these materials mainly due to aniline and indole
Learn absorption especially strong, it is difficult to be desorbed, it is easy to cause catalyst carbon deposition to inactivate.
T.Honda etc. have developed Ag-Co/SiO2- ZnO catalyst (European patent 0427287).He first with waterglass and
Zinc nitrate coprecipitation prepares specific surface for 240m2The SiO of/g2- ZnO carriers, then with sub-dip method elder generation back loading 0.6%Co and
11%Ag, is obtained Ag-Co/SiO2- ZnO catalyst.As a result show, under the conditions of 1.0MPa, 375 DEG C, in fixed bed reactors
In, Ag-Co/SiO2On-ZnO catalyst, the yield of aniline and ethylene glycol One Step Synthesis of Indole reaches 78%, while catalyst
Stability is relatively good.And the mesh catalyst can be basically unchanged by charcoal regeneration, the performance of regenerated catalyst.
Recently, the country also begins to carry out this research.Document report (catalysis journal .2003, V24 (6), 471-
474) infusion process have developed Ag/SiO2And Cu/SiO2Catalyst, and investigated aniline, the catalysis of ethylene glycol One Step Synthesis of Indole
Performance.The indole yield of two kinds of catalyst can reach 80% or so, but catalyst is inactivated quickly, react 3 hours rear catalysts
Yield declines a lot.
Prior art yet suffers from the shortcoming that indole yield is relatively low, be difficult to continuous operation, and the present invention is targetedly
Solve the problem.
The content of the invention
The technical problem to be solved is that indole yield is relatively low present in prior art, is difficult to continuous behaviour
The problem of work, there is provided it is a kind of it is new with aniline, ethylene glycol as raw material production indole method.The method is used for the production of indole
In, have the advantages that indole yield is higher in product, can operate continuously.
To solve the above problems, the technical solution used in the present invention is as follows：One kind is with aniline, ethylene glycol as raw material production Yin
The method of diindyl, including the raw material of aniline, ethylene glycol enters reaction zone, contacts with catalyst, generation includes the product of indole, reacts
In area, the catalyst enters stripping zone, and the Jing delivery pipes under the conveying of pumped (conveying) medium A of the catalyst Jing after stripping enter regeneration
Area, catalyst after regeneration enter degassing district, it is degassed after catalyst under pumped (conveying) medium B conveyings Jing delivery pipes return it is anti-
Answer area.
In above-mentioned technical proposal, the reaction zone, stripping zone, degassing district, renewing zone are fluid bed；The catalyst is
The based fluidized bed catalysts of Cu, the load quality percent of Cu is 0.5～30%, and carrier is SiO2Or Al2O3, catalyst buildup density
For 350～1000 g/l；The reaction zone reaction condition is：300～450 DEG C of reaction temperature, reaction pressure is calculated as 0 with gauge pressure
～1Mpa, aniline are 1～15 with ethylene glycol charge-mass ratio:1；It is 1～50% to add mass fraction in the reaction zone feeds
Vapor；The stripping fluid of the stripping zone adopts vapor；The degassing medium of degassing district is vapor；Pumped (conveying) medium A is nitrogen
Gas；Pumped (conveying) medium B is vapor；The regenerating medium of the renewing zone be containing nitrogen that volume fraction is 0.1～10% oxygen and
Oxygen mixture, regeneration temperature are 300～450 DEG C；In the delivery pipe, catalyst is in diluted phase transport state, and in pipe, catalyst is close
Spend for 50～350 kgs/m3。
Cu bases catalyst of the present invention is prepared using conventional infusion process, selects commercially available carrier.
Plug valve or guiding valve control catalyst flow are relied in the present invention.
The present inventor has found that by studying, during indole is converted into, the carbon distribution of formation can lead to for aniline, ethylene glycol
Cross oxygen recovery removing.Using the method for the present invention, reacted catalyst through stripping, be stripped off the product that carries and
Raw material, subsequently into renewing zone, regenerates under oxygen atmosphere, and the final activity for recovering catalyst, the catalyst after regeneration are passed through
After vapor degassing, the nitrogen and oxygen of entrainment are taken off, then Jing vapor is delivered to reaction zone.The method of the present invention is using stream
Change bed pattern, easy temperature control can not only realize the continuous operation of indole production, while the yield of indole can be improved.
Using technical scheme：The reaction zone, stripping zone, degassing district, renewing zone are fluid bed；It is described to urge
Agent is the based fluidized bed catalysts of Cu, and the load quality percent of Cu is 0.5～30%, and carrier is SiO2Or Al2O3, catalyst heap
Product density is 350～1000 g/l；The reaction zone reaction condition is：300～450 DEG C of reaction temperature, reaction pressure is with gauge pressure
0～1Mpa is calculated as, aniline is 1～15 with ethylene glycol charge-mass ratio:1；In the reaction zone feeds add mass fraction be 1～
50% vapor；The stripping fluid of the stripping zone adopts vapor；The degassing medium of degassing district is vapor；Pumped (conveying) medium A
For nitrogen；Pumped (conveying) medium B is vapor；The regenerating medium of the renewing zone is containing the nitrogen that volume fraction is 0.1～10% oxygen
Gas and oxygen mixture, regeneration temperature are 300～450 DEG C；In the delivery pipe, catalyst is in diluted phase transport state, catalysis in pipe
Agent density is 50～350 kgs/m3, indole mass yield reaches 87.4%, achieves preferable technique effect.
Description of the drawings
Schematic flow sheets of the Fig. 1 for the method for the invention；
In Fig. 1,1 is delivery pipe；2 is feed(raw material)inlet；3 is that reaction zone catalyst enters stripping zone pipeline；4 is reaction zone；5
For filter；6 is pumped (conveying) medium A entrances；7 is stripping zone；8 is gas-solid cyclone separator；9 is decanting zone；10 is products export；
11 is stripped vapor entrance；12 is delivery pipe；13 export for renewing zone；14 is decanting zone；15 is regenerating medium entrance；16 for again
Raw area's catalyst removes degassing district pipeline；17 is filter；18 are degassing medium inlet；19 is pumped (conveying) medium B；20 is degassing district gas
Phase outlet line；21 is gas-solid cyclone separator；22 is degassing district；23 is renewing zone；24 is stripping zone gaseous phase outlet pipeline.
Raw material enters reaction zone 4, contacts with catalyst, and generation includes the product of indole, and in reaction zone 4, the catalyst enters
Enter stripping zone 7, the Jing delivery pipes 12 under the conveying of pumped (conveying) medium A of the catalyst Jing after stripping enter renewing zone 23, after regeneration
Catalyst enter degassing district 22, it is degassed after catalyst pumped (conveying) medium B conveying under Jing delivery pipes 1 return reaction zone 4.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Specific embodiment
【Embodiment 1】
On reaction unit as shown in Figure 1, aniline and ethylene glycol are with mass ratio 15:1 enters reaction zone, adds in charging
Mass fraction is 50% vapor, is contacted with catalyst, and generation includes the product of indole, and the catalyst in reaction zone enters vapour
Area is carried, the catalyst Jing after stripping enters renewing zone, after the degassed area's degassing of the catalyst after regeneration, return to reaction zone.Reaction
Area, stripping zone, degassing district, renewing zone are fluid bed, and catalyst is the based fluidized bed catalysts of Cu, the load quality percent of Cu
For 30%, carrier is Al2O3, catalyst buildup density is 1000 g/l.Reaction zone reaction condition is：300 DEG C of reaction temperature, instead
Pressure is answered to be calculated as 0Mpa with gauge pressure.The stripping fluid of stripping zone adopts vapor, and the degassing medium of degassing district is vapor, is conveyed
Medium A is nitrogen, and pumped (conveying) medium B is vapor.The regenerating medium of renewing zone is containing the nitrogen that volume fraction is 0.1% oxygen
And oxygen mixture, regeneration temperature is 300 DEG C.In delivery pipe, catalyst is in diluted phase transport state, and in pipe, density of catalyst is 50
Kg/m3.Product adopts gas chromatographic analysiss, and indole mass yield is 71.2% (being based on ethylene glycol).
【Embodiment 2】
According to condition and step described in embodiment 1, aniline and ethylene glycol are with mass ratio 1:1 enters reaction zone, in charging
Addition mass fraction is 1% vapor, and in catalyst, the load quality percent of Cu is 0.5%, and carrier is Al2O3, catalyst heap
Product density is 350 g/l.Reaction zone reaction condition is：450 DEG C of reaction temperature, reaction pressure is calculated as 0Mpa with gauge pressure.Renewing zone
Regenerating medium be that containing the nitrogen and oxygen mixture that volume fraction is 10% oxygen, regeneration temperature is 450 DEG C.In delivery pipe
Density of catalyst is 350 kgs/m3.Product adopts gas chromatographic analysiss, and indole mass yield is 73.8% (being based on ethylene glycol).
【Embodiment 3】
According to condition and step described in embodiment 1, aniline and ethylene glycol are with mass ratio 7:1 enters reaction zone, in charging
Addition mass fraction is 15% vapor, and in catalyst, the load quality percent of Cu is 21%, and carrier is SiO2, catalyst heap
Product density is 750 g/l.Reaction zone reaction condition is：380 DEG C of reaction temperature, reaction pressure is calculated as 0Mpa with gauge pressure.Renewing zone
Regenerating medium be that containing the nitrogen and oxygen mixture that volume fraction is 5% oxygen, regeneration temperature is 400 DEG C.Urge in delivery pipe
Agent density is 150 kgs/m3.Product adopts gas chromatographic analysiss, and indole mass yield is 87.4% (being based on ethylene glycol).
【Embodiment 4】
According to condition and step described in embodiment 3, simply reaction zone pressure is calculated as 1Mpa with gauge pressure.Product adopts gas phase
Chromatography, indole mass yield are 82.5% (being based on ethylene glycol).
Obviously, using the method for the present invention, the purpose for improving indole yield can be reached, with larger technical advantage,
Can be used in the commercial production of indole.
Claims (3)
1. it is a kind of with aniline, ethylene glycol as raw material production indole method, including the raw material of aniline, ethylene glycol enters reaction zone,
Contact with catalyst, generation includes the product of indole, and in reaction zone, the catalyst enters stripping zone, the catalyst Jing after stripping
Under the conveying of pumped (conveying) medium A, Jing delivery pipes enter renewing zone, and catalyst after regeneration enters degassing district, it is degassed after urge
Agent Jing delivery pipes under pumped (conveying) medium B conveyings return to reaction zone；
Wherein, the stripping fluid of the stripping zone adopts vapor；The degassing medium of degassing district is vapor；Pumped (conveying) medium A is
Nitrogen；Pumped (conveying) medium B is vapor；In the delivery pipe catalyst be in diluted phase transport state, pipe in density of catalyst be 50～
350 kgs/m3；The reaction zone, stripping zone, degassing district, renewing zone are fluid bed；The reaction zone reaction condition is：Instead
300～450 DEG C of temperature, reaction pressure is answered to be calculated as 0～1Mpa with gauge pressure, aniline is 1～15 with ethylene glycol charge-mass ratio:1；
Wherein, the catalyst is the based fluidized bed catalysts of Cu, and the load quality percent of Cu is 0.5～30%, and carrier is SiO2
Or Al2O3, catalyst buildup density is 350～1000 g/l.
2. according to claim 1 with aniline, ethylene glycol as raw material production indole method, it is characterised in that the reaction zone
Add the vapor that mass fraction is 1～50% in charging.
3. according to claim 1 with aniline, ethylene glycol as raw material production indole method, it is characterised in that the renewing zone
Regenerating medium be that containing the nitrogen and oxygen mixture that volume fraction is 0.1～10% oxygen, regeneration temperature is 300～450
℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210239873.9A CN103539719B (en) | 2012-07-12 | 2012-07-12 | Method for producing indole by taking phenylamine and ethylene glycol as raw materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210239873.9A CN103539719B (en) | 2012-07-12 | 2012-07-12 | Method for producing indole by taking phenylamine and ethylene glycol as raw materials |
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| CN103539719A CN103539719A (en) | 2014-01-29 |
| CN103539719B true CN103539719B (en) | 2017-04-19 |
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| CN112279799B (en) * | 2019-07-26 | 2022-02-22 | 中石化南京化工研究院有限公司 | Method for preparing spice-grade indole by extraction crystallization |
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| JPS6287566A (en) * | 1985-10-14 | 1987-04-22 | Mitsui Toatsu Chem Inc | Production of indole |
| US4831158A (en) * | 1984-11-08 | 1989-05-16 | Mitsui Toatsu Chemicals, Incorporated | Preparation process indoles |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4831158A (en) * | 1984-11-08 | 1989-05-16 | Mitsui Toatsu Chemicals, Incorporated | Preparation process indoles |
| JPS6287566A (en) * | 1985-10-14 | 1987-04-22 | Mitsui Toatsu Chem Inc | Production of indole |
| CN1356299A (en) * | 2001-12-14 | 2002-07-03 | 清华大学 | Process and system for preparing low-carbon olefin from methanol or dimethylether |
| CN101007779A (en) * | 2006-01-26 | 2007-08-01 | 中国科学院大连化学物理研究所 | Method and device for making indole |
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| CN102295507A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for converting methanol or dimethyl ether into low-carbon olefin |
| CN101913996A (en) * | 2010-08-16 | 2010-12-15 | 中国天辰工程有限公司 | Fluidized bed reaction method for preparing dimethyl ether by methyl alcohol in presence of intermittently regenerated catalyst |
| CN102463084A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Reaction device for preparing dimethylbenzene from methanol or dimethyl ether and methylbenzene |
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