CN103772260B - Produce the method for indoles - Google Patents
Produce the method for indoles Download PDFInfo
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- CN103772260B CN103772260B CN201210412555.8A CN201210412555A CN103772260B CN 103772260 B CN103772260 B CN 103772260B CN 201210412555 A CN201210412555 A CN 201210412555A CN 103772260 B CN103772260 B CN 103772260B
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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
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Abstract
The present invention relates to a kind of method of producing indoles, mainly solve the problem that in prior art, indoles yield is lower.The present invention is by adopting a kind of method of producing indoles, comprise aniline, the raw material of ethylene glycol enters reaction zone, with catalyst exposure, generate the product comprising indoles, in reaction zone, described catalyzer enters stripping zone, and the catalyzer after stripping enters reduction zone, and the catalyzer after reduction enters breeding blanket, the technical scheme that catalyzer after regeneration returns to reaction zone solves the problems referred to above preferably, can be used in the industrial production of indoles.
Description
Technical field
The present invention relates to a kind of method of producing indoles.
Background technology
Indoles is the important source material of system each medicine, agricultural chemicals, spices, dyestuff and fodder additives, is important heterocycle fine-chemical intermediate.The throughput in the current whole world is 7000t/a.Along with the development of its applied research, derived medicine and the agricultural chemicals of many important high added values by it, particularly the market requirement rapid development of current indole derivatives tryptophane, only this item whole world distant view demand is at 100000t/a.Therefore, the market outlook of indoles are very wide.
Current industrial main employing ortho-chlorotolu'ene multistep processes synthesis of indole.Ortho-chlorotolu'ene obtains dihydroindole through chlorination, cyaniding, ammonification, Dehydration, then dehydrogenation and indoles.Because synthesis step is various, sepn process is numerous and diverse, and energy consumption is large, and cost is high, and preparation process produces a large amount of wastes and causes environmental pollution.The method that China mainly applies this backwardness at present produces indoles, and meanwhile, China successfully realizes the industrialization of fourth indole synthesis tryptophane now, and therefore, the technique being badly in need of substituting is simple, the new technology of environmental friendliness and the inexpensive synthesis of indole of cost.
With aniline and ethylene glycol for raw material heterogeneous catalyst One Step Synthesis of Indole not only low in raw material price, production cost is low, and operating procedure is simple, and environmental friendliness, has obvious advantage, is the most promising one of synthesis of indole.The eighties in 20th century, Japan carried out a large amount of correlative studys to this catalyzer.Matsuda etc. find that the reactions of catalyzer to aniline and ethylene glycol One Step Synthesis of Indole such as Cd, Cu, Ag and Zn all have certain activity (United States Patent (USP) 4436917).350 DEG C, under normal pressure, in fixed bed reaction, the yield of indoles all more than 20% (because aniline is excessive, in ethylene glycol).Wherein Ag/SiO
2the indoles yield of-ZnO catalyst reaches more than 40%.But experiment also finds a main problem: catalyzer is at a few hours inactivation, and yield straight line declines.This is mainly because aniline and indoles are all containing the atom N having lone-pair electron, and these materials chemisorption is on a catalyst strong especially, is difficult to desorption, is easy to cause catalyst carbon deposition inactivation.
T.Honda etc. have developed Ag-Co/SiO
2-ZnO catalyst (European patent 0427287).First he prepare specific surface by water glass and zinc nitrate coprecipitation method is 240m
2the SiO of/g
2-ZnO carrier, then uses first back loading 0.6%Co and 11%Ag of sub-dip method, obtained Ag-Co/SiO
2-ZnO catalyst.Result shows, under 1.0MPa, 375 DEG C of conditions, in fixed-bed reactor, and Ag-Co/SiO
2on-ZnO catalyst, the yield of aniline and ethylene glycol One Step Synthesis of Indole reaches 78%, and the stability of catalyzer is relatively good simultaneously.And this catalyzer of order can pass through charcoal regeneration, the performance of regenerated catalyst is substantially constant.
Recently, domestic also beginning has carried out this research.Bibliographical information (catalysis journal .2003, V24 (6), 471-474) pickling process have developed Ag/SiO
2and Cu/SiO
2catalyzer, and the catalytic performance having investigated aniline, ethylene glycol One Step Synthesis of Indole.The indoles yield of two kinds of catalyzer can reach about 80%, but the very fast inactivation of catalyzer, and the yield reacting 3 hours rear catalysts declines a lot.
Still there is the lower shortcoming of indoles yield in prior art, the present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that the indoles yield that exists in prior art is lower, provides a kind of method of production indoles newly.The method is used for, in the production of indoles, having the advantage that in product, indoles yield is higher.
For solving the problem, the technical solution used in the present invention is as follows: a kind of method of producing indoles, comprise aniline, the raw material of ethylene glycol enters reaction zone, with catalyst exposure, generate the product comprising indoles, in reaction zone, described catalyzer enters stripping zone, and the catalyzer after stripping enters reduction zone, catalyzer after reduction enters breeding blanket, and the catalyzer after regeneration returns to reaction zone.
In technique scheme, described reaction zone, stripping zone, reduction zone, breeding blanket are fluidized-bed.Described catalyzer is the based fluidized bed catalyst of Cu; The load quality percentage ratio of Cu is 0.5 ~ 30%, and preferable range is 5 ~ 25%; Carrier is SiO
2or Al
2o
3; Catalyst buildup density is 350 ~ 1000 grams per liters, and preferable range is 450 ~ 900 grams per liters.Described reaction zone reaction conditions is: temperature of reaction 300 ~ 450 DEG C, and preferable range is 350 ~ 400 DEG C; Reaction pressure counts 0 ~ 1MPa with gauge pressure, and preferable range is 0 ~ 0.8MPa; Aniline and ethylene glycol charge-mass ratio are 1 ~ 15, and preferable range is 4 ~ 12.Add the water vapour that massfraction is 1 ~ 50% in described reaction zone feeds, the addition preferable range of water vapour is 5 ~ 40%.The stripping fluid of described stripping zone adopts water vapour.The reducing medium of reduction zone adopts hydrogen volume mark to be the gas mixture of 1 ~ 100%, and reduction temperature is between 50 ~ 500 DEG C.The regenerating medium of described breeding blanket is be nitrogen and the oxygen mixture of 0.1 ~ 10% oxygen containing volume fraction, and regeneration temperature is 300 ~ 450 DEG C.
Cu of the present invention is catalyst based adopts conventional pickling process preparation, selects commercially available carrier.
Catalyst reaction of the present invention, stripping, reduction, regenerative process can operate continuously, relies on plug valve or guiding valve to control catalyst flow, also can periodical operation.
The present inventor is found by research, and aniline, ethylene glycol are in the process being converted into indoles, and a part for the carbon distribution of formation can be removed by method of reducing, and a part needs with oxygen recovery with removing.Adopt method of the present invention, reacted catalyzer is through stripping, the reaction product that stripping goes out to carry and raw material, then enter reduction zone, reduce in a hydrogen atmosphere, remove a part of carbon distribution, then breeding blanket is promoted to, regenerate under oxygen atmosphere, the final activity recovering catalyzer, return to reaction zone and continue to participate in reaction.Method of the present invention adopts fluid bed mode, easy temperature control, not only can realize the operate continuously that indoles is produced, and can improve the yield of indoles simultaneously.
Adopt technical scheme of the present invention: described reaction zone, stripping zone, reduction zone, breeding blanket are fluidized-bed; Described catalyzer is the based fluidized bed catalyst of Cu, and the load quality percentage ratio of Cu is 0.5 ~ 30%, and carrier is SiO
2or Al
2o
3, catalyst buildup density is 350 ~ 1000 grams per liters; Described reaction zone reaction conditions is: temperature of reaction 300 ~ 450 DEG C, and reaction pressure counts 0 ~ 1Mpa with gauge pressure, and aniline and ethylene glycol charge-mass ratio are 1 ~ 15:1; The water vapour that massfraction is 1 ~ 50% is added in described reaction zone feeds; The stripping fluid of described stripping zone adopts water vapour; The reducing medium of reduction zone adopts hydrogen volume mark to be the gas mixture of 1 ~ 100%, and reduction temperature is between 50 ~ 500 DEG C; The regenerating medium of described breeding blanket is be nitrogen and the oxygen mixture of 0.1 ~ 10% oxygen containing volume fraction, and regeneration temperature is 300 ~ 450 DEG C, and indoles mass yield reaches 85.4%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention;
In Fig. 1,1 is regenerated flue gas outlet; 2 for adding agent line; 3 is strainer; 4 is breeding blanket, stripping zone; 5 is regeneration gas; 6 is plug valve; 7 is feedstock; 8 is reaction zone outlet line; 9 is product pipeline; 10 is reaction zone; 11 is stripping gas outlet; 12 for promoting circuit; 13 is plug valve; 14 is strainer; 15 is stripping zone; 16 is stripping fluid entrance; 17 for promoting medium inlet; 18 is plug valve; 19 is strainer; 20 return gas product pipeline for stripping gas; 21 is reduction zone outlet line; 22 is strainer; 23 is reduction zone; 24 is reducing medium source line; 25 is plug valve.
Comprise aniline, the raw material of ethylene glycol enters reaction zone 10 through pipeline 7, with catalyst exposure, generate the product comprising indoles, centrifugal station is entered through pipeline 9, catalyzer in reaction zone 10 enters stripping zone 15, catalyzer after stripping enters reduction zone 23, and the catalyzer after reduction enters breeding blanket 4 through promoting circuit 12, and the catalyzer after regeneration returns to reaction zone 10.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, aniline and ethylene glycol enter reaction zone with mass ratio 15:1, the water vapour that massfraction is 50% is added in charging, with catalyst exposure, generate the product comprising indoles, the catalyzer in reaction zone enters stripping zone, and the catalyzer after stripping enters reduction zone, catalyzer after reduction enters breeding blanket, and the catalyzer after regeneration returns to reaction zone.Reaction zone, stripping zone, reduction zone, breeding blanket are fluidized-bed, and catalyzer is the based fluidized bed catalyst of Cu, and the load quality percentage ratio of Cu is 30%, and carrier is Al
2o
3, catalyst buildup density is 1000 grams per liters.Reaction zone reaction conditions is: temperature of reaction 450 DEG C, reaction pressure counts 0Mpa with gauge pressure.The stripping fluid of stripping zone adopts water vapour, and the reducing medium of reduction zone adopts the hydrogen of 100%, and adopt temperature-programmed mode, reduction temperature is between 50 ~ 500 DEG C.The regenerating medium of breeding blanket is be nitrogen and the oxygen mixture of 10% oxygen containing volume fraction, and regeneration temperature is 450 DEG C.Product adopts gas chromatographic analysis, and indoles mass yield is 70.5% (based on ethylene glycol).
[embodiment 2]
According to the condition described in [embodiment 1] and step, aniline and ethylene glycol enter reaction zone with mass ratio 1:1, add the water vapour that massfraction is 1% in charging, and in catalyzer, the load quality percentage ratio of Cu is 0.5%, and carrier is SiO
2, catalyst buildup density is 350 grams per liters.Reaction zone reaction conditions is: temperature of reaction 300 DEG C, reaction pressure counts 0Mpa with gauge pressure.The reducing medium of reduction zone adopts hydrogen volume mark to be the gas mixture of 1%.The regenerating medium of breeding blanket is be nitrogen and the oxygen mixture of 0.1% oxygen containing volume fraction, and regeneration temperature is 300 DEG C.Product adopts gas chromatographic analysis, and indoles mass yield is 64.8% (based on ethylene glycol).
[embodiment 3]
According to the condition described in [embodiment 1] and step, aniline and ethylene glycol enter reaction zone with mass ratio 7:1, add the water vapour that massfraction is 20% in charging, and in catalyzer, the load quality percentage ratio of Cu is 18%, and carrier is SiO
2, catalyst buildup density is 650 grams per liters.Reaction zone reaction conditions is: temperature of reaction 375 DEG C, reaction pressure counts 0Mpa with gauge pressure.The reducing medium of reduction zone adopts hydrogen volume mark to be the gas mixture of 10%, and the regenerating medium of breeding blanket is be nitrogen and the oxygen mixture of 8% oxygen containing volume fraction, and regeneration temperature is 400 DEG C.Product adopts gas chromatographic analysis, and indoles mass yield is 85.4% (based on ethylene glycol).
[embodiment 4]
According to the condition described in [embodiment 3] and step, aniline and ethylene glycol enter reaction zone with mass ratio 5:1, add the water vapour that massfraction is 10% in charging, and in catalyzer, the load quality percentage ratio of Cu is 16%, and carrier is SiO
2, catalyst buildup density is 600 grams per liters.Reaction zone reaction conditions is: temperature of reaction 386 DEG C, reaction pressure counts 1Mpa with gauge pressure.The reducing medium of reduction zone adopts hydrogen volume mark to be the gas mixture of 20%, and the regenerating medium of breeding blanket is be nitrogen and the oxygen mixture of 18% oxygen containing volume fraction, and regeneration temperature is 400 DEG C.Product adopts gas chromatographic analysis, and indoles mass yield is 80.7% (based on ethylene glycol).
Obviously, adopt method of the present invention, the object improving indoles yield can be reached, there is larger technical superiority, can be used in the industrial production of indoles.
Claims (4)
1. produce the method for indoles for one kind, comprise aniline, the raw material of ethylene glycol enters reaction zone, with catalyst exposure, generate the product comprising indoles, in reaction zone, described catalyzer enters stripping zone, catalyzer after stripping enters reduction zone, and the catalyzer after reduction enters breeding blanket, and the catalyzer after regeneration returns to reaction zone;
Wherein, described catalyzer is the based fluidized bed catalyst of Cu, and the load quality percentage ratio of Cu is 5 ~ 25%, and carrier is Al
2o
3, catalyst buildup density is 450 ~ 900 grams per liters; Described reaction zone, stripping zone, reduction zone, breeding blanket are fluidized-bed; The water vapour that massfraction is 1 ~ 50% is added in described reaction zone feeds; The stripping fluid of described stripping zone adopts water vapour; The reducing medium of reduction zone adopts hydrogen volume mark to be the gas mixture of 1 ~ 100%, and reduction temperature is between 50 ~ 500 DEG C; The regenerating medium of described breeding blanket is be nitrogen and the oxygen mixture of 0.1 ~ 10% oxygen containing volume fraction, and regeneration temperature is 300 ~ 450 DEG C.
2. produce the method for indoles according to claim 1, it is characterized in that described reaction zone reaction conditions is: temperature of reaction 300 ~ 450 DEG C, reaction pressure counts 0 ~ 1MPa with gauge pressure, and aniline and ethylene glycol charge-mass ratio are 1 ~ 15.
3. produce the method for indoles according to claim 2, it is characterized in that temperature of reaction 350 ~ 400 DEG C, reaction pressure counts 0 ~ 0.8MPa with gauge pressure, and aniline and ethylene glycol charge-mass ratio are 4 ~ 12.
4. produce the method for indoles according to claim 1, it is characterized in that the interpolation massfraction of water vapour in described reaction zone feeds is 5 ~ 40%.
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|---|---|---|---|
| CN201210412555.8A CN103772260B (en) | 2012-10-25 | 2012-10-25 | Produce the method for indoles |
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|---|---|---|---|
| CN201210412555.8A CN103772260B (en) | 2012-10-25 | 2012-10-25 | Produce the method for indoles |
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| CN103772260A CN103772260A (en) | 2014-05-07 |
| CN103772260B true CN103772260B (en) | 2015-12-09 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436917A (en) * | 1981-04-15 | 1984-03-13 | Mitsui Toatsu Chemicals, Inc. | Process for the preparation of indoles |
| CN1034320A (en) * | 1987-12-21 | 1989-08-02 | 法国精制和总分配公司 | The method and apparatus of regenerating catalyst in fluidized bed |
| EP0427287A1 (en) * | 1989-11-10 | 1991-05-15 | MITSUI TOATSU CHEMICALS, Inc. | Preparation process of indoles |
| CN101456783A (en) * | 2007-12-13 | 2009-06-17 | 中国石油化工股份有限公司 | Method for improving light olefins output during catalytic cracking process |
| CN103539717A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Reaction device for producing benzpyrole |
-
2012
- 2012-10-25 CN CN201210412555.8A patent/CN103772260B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436917A (en) * | 1981-04-15 | 1984-03-13 | Mitsui Toatsu Chemicals, Inc. | Process for the preparation of indoles |
| CN1034320A (en) * | 1987-12-21 | 1989-08-02 | 法国精制和总分配公司 | The method and apparatus of regenerating catalyst in fluidized bed |
| EP0427287A1 (en) * | 1989-11-10 | 1991-05-15 | MITSUI TOATSU CHEMICALS, Inc. | Preparation process of indoles |
| CN101456783A (en) * | 2007-12-13 | 2009-06-17 | 中国石油化工股份有限公司 | Method for improving light olefins output during catalytic cracking process |
| CN103539717A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Reaction device for producing benzpyrole |
Non-Patent Citations (2)
| Title |
|---|
| Cu/SiO2催化剂上苯胺和乙二醇一步合成吲哚的研究;孙军明等;《分子催化》;20020630;第16卷(第3期);第229-233页 * |
| Cu-SiO2催化剂在苯胺生产中的应用;姜新亮;《氯碱工业》;20090930;第45卷(第9期);第30-34页 * |
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