CN101643444A - Method and reaction device for preparing indole - Google Patents
Method and reaction device for preparing indole Download PDFInfo
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- CN101643444A CN101643444A CN200810041392A CN200810041392A CN101643444A CN 101643444 A CN101643444 A CN 101643444A CN 200810041392 A CN200810041392 A CN 200810041392A CN 200810041392 A CN200810041392 A CN 200810041392A CN 101643444 A CN101643444 A CN 101643444A
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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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Abstract
The invention relates to a method and a reaction device for preparing indole. In the preparation method, the continuous gas-solid catalytic reaction process of a fixed bed reactor is adopted, o-aminoethylbenzene is gasified at a temperature of between 210 and 300 DEG C, the liquid space velocity is 0.02 to 0.15h<-1>, carbon dioxide and the o-aminoethylbenzene are quickly mixed at a temperature ofbetween 210 and 300 DEG C according to a molar ratio of between 4:1 and 40:1, the mixture is pre-heated to the temperature of between 560 and 640 DEG C, and the mixture enters a catalyst bed layer inthe reactor and is subjected to oxidative dehydrogenation at a temperature of between 560 and 640 DEG to generate a liquid reaction product mainly containing indole. The method has the advantages of simple flow, continuous and convenient operation, low cost, low energy consumption, and environment friendliness, and fully recycles greenhouse gas CO2 and provides a new way for synthesizing the indole.
Description
Technical field
The invention belongs to chemical field, specifically, relate to a kind of preparation method and reaction unit thereof of indoles.
Background technology
Indoles has in fields such as medicine, agricultural chemicals, spices, food and feed additive, dyestuffs widely to be used, in recent years along with the fast development of indoles derived product with and constantly the deriving of new Application Areas, make the market outlook of indoles enlarge day by day; And present global indoles production mainly concentrates on industrially developed country such as the U.S., West Europe, Japan and area.Therefore, it is simple that China presses for technology, and the production technique of chemosynthesis indoles with low cost and eco-friendly satisfies the demand in market.
Industrialized at present indoles synthetic technology mainly contains ortho-chlorotolu'ene method, aniline process and adjacent aminoethylbenzene method.The ortho-chlorotolu'ene method is exactly that ortho-chlorotolu'ene makes dihydroindole through chlorination, cyaniding, ammonification, dehydration, and dehydrogenation obtains indoles then.This method synthesis step is many, sepn process is complicated, by product is many, energy consumption is big, causes cost higher; And use chlorine and hypertoxic prussiate in the building-up process, environmental pollution is serious.Aniline process also claims aniline-glycol method, and this method research is comparatively extensive, and aniline, ethylene glycol is basic organic chemical industry's product, has stable raw material sources, is beneficial to large-scale industrial production.But its shortcoming needs a large amount of aniline to make thinner, the large usage quantity of aniline for avoiding the polyreaction of ethylene glycol under the high temperature, if can not well solve the recycling of aniline, cost will have tangible increase, and aniline, ethylene glycol all belongs to poisonous raw material, and production security requires high.
Reported that with adjacent aminoethylbenzene be raw material in the document (Guangdong chemical industry 1990 No.2 29～32); in temperature is 550 ℃ and nitrogen protection; and have under the condition of aluminum nitrate (or aluminium sesquioxide) existence; carry out dehydrocyclization; obtain indoline through underpressure distillation again; in 640 ℃ of following dehydrogenations, promptly get product subsequently.The shortcoming of this method is the easy inactivation of catalyzer, and synthesis step is various, severe reaction conditions and cost height.Report that by adjacent aminoethylbenzene be raw material in the European patent (EP1362510), under rare gas element, water vapour and air atmosphere, single stage method prepares indoles, still adopts inert atmosphere, and the easy carbon deposit of catalyzer makes the easy inactivation of catalyzer.Document (chemical industry journal 2004 Vol.55 No.7 1201～1205) has reported that also water vapour is the influence of the different content of catalyst component B/Cu/Al under the thinner condition to the indoles yield.At temperature of reaction 873K～923K, bed air speed 0.1h
-1The mol ratio of water/adjacent aminoethylbenzene is under 10 conditions, the indoles yield can reach 78% (obtaining pure product indoles by separation means), its transformation efficiency is at (in adjacent aminoethylbenzene) more than 95%, selectivity is higher than 90% (in indoles), this catalyzer transformation efficiency and selectivity are all higher, though adopt water vapour can suppress caused poisoning of catalyst such as carbon deposit, prolong the work-ing life of catalyzer; But need a large amount of water vapour as thinner, the energy consumption height, product separation must carry out oily water separation earlier, adopts technology such as rectifying or extraction to carry out the separation of oil phase substance then, causes separation costs significantly to increase, and makes that the synthesis of indole cost improves under the water vapour; Adopt air atmosphere to cause the indoles deep oxidation easily, product yield is low.Therefore, simple, the economic Indomethacin synthetic technology of exploitation is very necessary.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, thus provide a kind of economical and practical be the method for feedstock production indoles with adjacent aminoethylbenzene and carbonic acid gas.
Another object of the present invention is to provide a kind of reaction unit that is used to realize above-mentioned preparation method.
The preparation method of indoles of the present invention adopts the continuous gas-solid catalyzed reaction technology of fixed-bed reactor, with adjacent aminoethylbenzene 210～300 ℃ of vaporizations, liquid air speed 0.02～0.15h
-1, then with carbonic acid gas and adjacent aminoethylbenzene with 4: 1～40: 1 ratio of mol ratio, in 210～300 ℃ of short mix, after being preheating to 560～640 ℃, advance the beds in the reactor,, generate the liquid reacting product that mainly contains indoles 560～640 ℃ of following oxidation catalysis dehydrogenations.
The preparation method of indoles of the present invention, described reaction atmosphere adopts carbon dioxide atmosphere.
The preparation method of indoles of the present invention, described catalyzer is manganese-aluminium base heterogeneous catalyst.
The preparation method of indoles of the present invention, the pressure of described oxidation catalysis dehydrogenation reaction is normal pressure or negative pressure.
The preparation method of indoles of the present invention comprises that also the liquid reactants to obtaining carries out rectifying or extraction, with separated product indoles, the adjacent aminoethylbenzene of unreacted raw material and the adjacent amino cinnamic step of byproduct of reaction.
The preparation method of indoles of the present invention, the adjacent aminoethylbenzene of unreacted raw material, carbonic acid gas and the adjacent amino-benzene ethene of by product are recycled.
The present invention also provides a kind of reaction unit that is used to prepare indoles, comprises the vaporizing chamber, mixing section, preheating chamber, reactor, water cooler, product holding tank, the collection and confinement of gases jar that set gradually.
According to the device of preparation indoles of the present invention, described product holding tank further is connected with rectifying or extraction plant.
According to the device of preparation indoles of the present invention, a raw material storage tank links to each other with described vaporizing chamber by a pump.
According to the device of preparation indoles of the present invention, described collection and confinement of gases jar is connected with a compressor.
According to the device of preparation indoles of the present invention, described compressor links to each other with gas storage cabinet with water cooler.
According to the device of preparation indoles of the present invention, establish a well heater between described water cooler and preheating chamber.
The invention has the beneficial effects as follows: CO
2Can generate CO with the C reaction, reduce the generation of carbon deposit, thereby effectively suppress the inactivation of catalyzer, prolong life of catalyst.Introduce CO in the system
2After, can consume product H
2, broken through the thermodynamics equilibrium limit of pure dehydrogenation reaction to a certain extent, help of the conversion of adjacent aminoethylbenzene to indoles, improved the transformation efficiency of adjacent aminoethylbenzene, the selectivity and the yield of indoles.Make thinner with water and compare, it separates link at product and has reduced energy consumption; Simultaneously, make full use of the heat of reaction product, effectively reduced energy consumption.With CO
2Be the synthetic valuable organism of raw material, fully recycle greenhouse gases CO
2, effectively reduce the preparation cost of indoles.
Description of drawings
Fig. 1 is the synoptic diagram of the basic device of preparation indoles of the present invention.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only are used to the present invention is described but not are used to limit scope of the present invention.
The transformation efficiency of adjacent aminoethylbenzene
Inlet amount * 100% of=(inlet amount of adjacent aminoethylbenzene-unreacted adjacent aminoethylbenzene amount)/adjacent aminoethylbenzene.
Inlet amount * 100% of the amount/adjacent aminoethylbenzene of the yield of indoles=required adjacent aminoethylbenzene of generation indoles.
The selectivity of indoles=
Generate amount/(inlet amount of adjacent aminoethylbenzene-unreacted adjacent aminoethylbenzene amount) * 100% of the required adjacent aminoethylbenzene of indoles.
The device of embodiment 1, preparation indoles
As shown in Figure 1, the basic device for preparation indoles of the present invention is provided with successively:
Vaporizing chamber 5, adjacent aminoethylbenzene is used to vaporize;
Mixing section 7 is used for short mix CO
2Gas and adjacent aminoethylbenzene raw material;
Preheating chamber 8 is used for preheating material and reaches the required temperature of reactor;
Reactor 9, interior filling manganese-aluminium base heterogeneous catalyst is used to finish the catalytic dehydrogenation cyclization;
Collection and confinement of gases jar 15 is used to collect the unnecessary CO in reaction back
2Gas.
In addition, product holding tank 13 of the present invention can also further be connected with rectifying or extraction plant, is used to isolate product indoles, the adjacent aminoethylbenzene of unreacted raw material and the adjacent amino-benzene ethene of by product.As adopt rectifying separation, can isolate the mixture of adjacent aminoethylbenzene, adjacent amino-benzene ethene and indoles earlier, and then rectifying separation goes out to consist of adjacent aminoethylbenzene and adjacent amino cinnamic mixture and product indoles, this belongs to conventional means for a person skilled in the art, therefore is not further described in detail herein.Adjacent aminoethylbenzene of described unreacted raw material and the adjacent amino-benzene ethene of by product can be recycled.Can also establish a well heater 10 between described water cooler 11 and the preheating chamber 8.
Further, raw material storage tank 1 links to each other with described vaporizing chamber 5 by pump 2, and adjacent aminoethylbenzene places described raw material storage tank 1, by pump 2 input vaporizing chambers; Described collection and confinement of gases jar 15 is connected with a compressor 16, is used to compress reacted CO
2Gas; Fresh CO
2Atmosphere storage is reacted back CO in gas storage cabinet 4
2After compressed machine 16 compressions of gas, with fresh CO
2The gas mixed cycle is utilized.The CO gas that reaction produces generates CO through peroxidation
2Gas carries out recycle as reactant gases then again.
Use the concrete reaction process of this device preparation indoles as follows: adjacent aminoethylbenzene is measured in the back input vaporizing chambers 5 through under meter 3 by raw material storage tank 1 by certain flow with pump 2; CO
2By compressed in the gas storage cabinet 4 and under meter 6 controls, and by the CO after compressor 16 compressions
2After gas enters water cooler 11 preheatings by a certain percentage jointly, by well heater 10 heating, wherein a part of then gas is by the vaporizing chamber 5 adjacent aminoethylbenzene of vaporizing, and in mixing section 7 and adjacent aminoethylbenzene short mix, then in preheating chamber 8 with the CO of another part
2Carry out contact preheating and mixing, the beds that flows at last in the reactor 9 carries out oxidation catalysis dehydrogenation and cyclisation generation indoles; Reaction product is through supercooler 11,14 coolings, liquid reacting product is collected by holding tank 13, separate through technology such as rectifying or extractions then, adjacent aminoethylbenzene of the unreacted raw material of gained and the adjacent amino-benzene ethene of by product (adjacent amino-benzene ethene can take off a hydrogen by adjacent aminoethylbenzene and obtain, and cyclisation also can generate indoles after it took off a hydrogen again) carry out circulating reaction; Gas advances holding tank 15 collections after compressor 16 compressions are controlled its flows by under meter 12, then with a certain amount of fresh CO
2Gas mixes, and carries out recycle.
The preparation of embodiment 2-6, indoles
Pressing shown in the table 1, is 0.02～0.15h with the adjacent aminoethylbenzene of raw material with liquid air speed
-1With pump delivery to vaporizing chamber, 210～300 ℃ of vaporizations, advance then in the mixing section in 210～300 ℃ and carbonic acid gas short mix, the mol ratio of carbonic acid gas and adjacent aminoethylbenzene is 4: 1～40: 1, advances preheating chamber then and is preheating to 560～640 ℃, flows to the beds in the reactor at last, at 560～640 ℃, react under normal pressure or the negative pressure, generation contains indoles and the adjacent amino cinnamic liquid reacting product of by product, and reaction formula is as follows:
Table 1
| Embodiment | ????2 | ????3 | ????4 | ????5 | ????6 |
| Liquid air speed (h -1) | ????0.05 | ????0.05 | ????0.02 | ????0.15 | ????0.05 |
| ??CO 2Molar concentration rate with adjacent aminoethylbenzene | ????20∶1 | ????8∶1 | ????40∶1 | ????8∶1 | ????4∶1 |
| Pressure (Pa) | ????0.613×10 5 | ????1.013×10 5 | ????0.413×10 5 | ????1.013×10 5 | ????0.713×10 5 |
| Vaporization temperature (℃) | ????210 | ????250 | ????300 | ????250 | ????210 |
| Mixing temperature (℃) | ????210 | ????250 | ????300 | ????250 | ????300 |
| Preheating temperature (℃) | ????625 | ????560 | ????625 | ????625 | ????640 |
| Temperature of reaction (℃) | ????625 | ????560 | ????625 | ????625 | ????640 |
| Adjacent aminoethylbenzene transformation efficiency (%) | ????94.68 | ????55.41 | ????63.33 | ????84.00 | ????97.27 |
| Indoles yield (%) | ????70.89 | ????43.54 | ????56.23 | ????51.43 | ????76.13 |
| Indoles selectivity (%) | ????74.87 | ????78.58 | ????88.78 | ????61.23 | ????78.27 |
By the result of table 1 as seen, the peak rate of conversion of adjacent aminoethylbenzene can reach about 97%, selectivity also can reach about 88%, the yield of indoles is up to more than 76%, though the yield of the transformation efficiency of adjacent aminoethylbenzene or indoles is very not high under listed some processing condition of table 1, but by suitable means such as raw materials cost control, indole preparation method of the present invention is enough to satisfy industrial production requirement.
Preparation method of the present invention takes circulating reaction, and unreacted adjacent aminoethylbenzene can utilize tail gas CO with the adjacent amino-benzene ethene of byproduct of reaction with the adjacent aminoethylbenzene mixed cycle of fresh raw material after separating
2Through purify, compression back and fresh CO
2Carry out recycle according to a certain ratio again, can realize resources conservation, this reaction process realizes zero release substantially, reaches eco-friendly purpose, meets the theory of current Green Chemistry.This preparation method has made full use of waste heat in addition, effectively reduces production energy consumption.
In sum, it is simple that the reaction process of adjacent aminoethylbenzene and carbon dioxide one-step method catalytic dehydrogenation cyclisation synthesis of indole has flow process, and operation is convenient continuously, with low cost, low, the eco-friendly advantage of energy consumption, and fully recycle greenhouse gases CO
2, provide a synthesis of indole the new technology approach.
Claims (12)
1, a kind of preparation method of indoles is characterized in that, adopts the continuous gas-solid catalyzed reaction technology of fixed-bed reactor, with adjacent aminoethylbenzene 210～300 ℃ of vaporizations, liquid air speed 0.02～0.15h
-1, then with carbonic acid gas and adjacent aminoethylbenzene with 4: 1～40: 1 ratio of mol ratio, in 210～300 ℃ of short mix, after being preheating to 560～640 ℃, advance the beds in the reactor,, generate the liquid reacting product that mainly contains indoles 560～640 ℃ of following oxidation catalysis dehydrogenations.
2, the method for claim 1 is characterized in that, reaction atmosphere adopts carbon dioxide atmosphere.
3, the method for claim 1 is characterized in that, described catalyzer is manganese-aluminium base heterogeneous catalyst.
4, the method for claim 1 is characterized in that, the pressure of described oxidation catalysis dehydrogenation reaction is normal pressure or negative pressure.
5, the method for claim 1 is characterized in that, comprises that also the liquid reactants to obtaining carries out rectifying or extraction, with separated product indoles, the adjacent aminoethylbenzene of unreacted raw material and the adjacent amino cinnamic step of byproduct of reaction.
6, method as claimed in claim 5 is characterized in that, the adjacent aminoethylbenzene of unreacted raw material, the adjacent amino-benzene ethene of by product and carbonic acid gas are recycled.
7, a kind of reaction unit that is used to prepare indoles is characterized in that, described reaction unit comprises vaporizing chamber, mixing section, preheating chamber, reactor, water cooler, product holding tank, the collection and confinement of gases jar that sets gradually.
8, device as claimed in claim 7 is characterized in that, described product holding tank further is connected with rectifying or extraction plant.
9, device as claimed in claim 7 is characterized in that, a raw material storage tank links to each other with described vaporizing chamber by a pump.
10, device as claimed in claim 7 is characterized in that, described collection and confinement of gases jar is connected with a compressor.
11, device as claimed in claim 10 is characterized in that, described compressor links to each other with gas storage cabinet with water cooler.
12, device as claimed in claim 7 is characterized in that, establishes a well heater between described water cooler and preheating chamber.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810041392A CN101643444A (en) | 2008-08-05 | 2008-08-05 | Method and reaction device for preparing indole |
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|---|---|---|---|
| CN200810041392A CN101643444A (en) | 2008-08-05 | 2008-08-05 | Method and reaction device for preparing indole |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878040A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Method for preparing indole from o-toluidine |
| CN112142652A (en) * | 2020-10-13 | 2020-12-29 | 安徽国星生物化学有限公司 | 2,3 dichloropyridine production method and device |
| CN112724067A (en) * | 2021-01-13 | 2021-04-30 | 江苏普洛德化学科技有限公司 | Preparation process of indigo and obtained intermediate indoline |
-
2008
- 2008-08-05 CN CN200810041392A patent/CN101643444A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878040A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Method for preparing indole from o-toluidine |
| CN110878040B (en) * | 2018-09-06 | 2022-08-09 | 中国石油化工股份有限公司 | Method for preparing indole from o-toluidine |
| CN112142652A (en) * | 2020-10-13 | 2020-12-29 | 安徽国星生物化学有限公司 | 2,3 dichloropyridine production method and device |
| CN112724067A (en) * | 2021-01-13 | 2021-04-30 | 江苏普洛德化学科技有限公司 | Preparation process of indigo and obtained intermediate indoline |
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Application publication date: 20100210 |