CN102887884A - Method for producing 2-acetylthiophene with trickle bed reactor - Google Patents
Method for producing 2-acetylthiophene with trickle bed reactor Download PDFInfo
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- CN102887884A CN102887884A CN2012103813315A CN201210381331A CN102887884A CN 102887884 A CN102887884 A CN 102887884A CN 2012103813315 A CN2012103813315 A CN 2012103813315A CN 201210381331 A CN201210381331 A CN 201210381331A CN 102887884 A CN102887884 A CN 102887884A
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Abstract
The invention discloses a method for producing 2-acetylthiophene with a trickle bed reactor, which comprises the following steps: (1) reaction: the trickle bed reactor is filled with a catalyst bed layer, and thiophene and an acylation reagent are sent into the trickle bed reactor to carry out acylation reaction at 20-160 DEG C under the pressure of 0.05-15 MPa, thereby obtaining the 2-acetylthiophene crude product; and (2) refinement: the 2-acetylthiophene crude product is separated and purified by rectification, thereby obtaining the high-purity 2-acetylthiophene product. The invention has the advantages of manageable technical process, mild reaction conditions, low investment cost, high product purity, simple reactor structure, high operation stability and the like, is convenient to control, and can easily implement large-scale and continuous production.
Description
Technical field
The invention belongs to medicine and chemical technology field.Relate to a kind of with the synthetic medicine intermediate 2-acetyl thiophene of trickle-bed reactor production method.
Background technology
The 2-acetyl thiophene is to use wider a kind ofly in the substituted thiophene derivant of α position, is the important intermediate of producing other thiophene derivant.The 2-acetyl thiophene is used widely in medical science, chemistry and food service industry.At medical field, be intermediate 2-thiophene acetic acid, non-steroidal anti-inflammatory analgesics tiaprofenic acid, the 2-acetyl thiophene azine with anti-tumor activity and the transition metal Cu thereof of synthetic broad spectrum antibiotic cefoxitin, Cephaloridine and cefoxitin
2+, Fe
3+The important source material of title complex etc.; At chemical field, it is important chemical reagent, also is the important source material of synthetic organic intermediate thiophene cinnamophenone; In food service industry, owing to the taste of its special similar onion is used as the food aromatizing agent.The 2-acetyl thiophene reacts generation by thiophene and acetylation reagent under catalyst action.The research of synthetic 2-acetyl thiophene both at home and abroad only is confined to the laboratory phase of basic research, about the industrialization case of thiophene by the Friedel-Crafts acylation reaction seldom.
At present, the traditional method of synthetic 2-acetyl thiophene mainly is to be obtained under the condition of phosphoric acid does catalyst by thiophene and diacetyl oxide.Production process is: diacetyl oxide, 85% phosphoric acid and thiophene are mixed to drop in the reactor stir, being heated to reflux temperature is 96～97 ℃, and keeps refluxing 2 hours, and reaction finishes, and will react the production fluid cooling, wash, and removes water layer; The gained oil reservoir is carried out atmospheric and vacuum distillation, separate and purify obtaining the 2-acetyl thiophene of high density.In order to improve the production technique of 2-acetyl thiophene; the researchist attempts using molecular sieve, acidic resins etc. carry out thiophene as catalyzer acylation reaction; but only has the small part catalyzer (such as CT-175; NKC-9 etc.) transformation efficiency of thiophene is reached more than 90%; and the reactor that process adopts is intermittently tank reactor or microreactor; these technology are difficult to overcome that the treatment capacity that traditional method exists is little, process can not be continuous, big for environment pollution etc. defective, can not satisfy the needs that industrial scale is produced.Because technical defective; will cause the Technology take batch still as reactor to be eliminated by the trend of social development; and it is simple in structure; stable operation; be convenient to control; the cost design cost is low, is easy to realize that the reactor of the advantages such as mass-producing and serialization production and Technology thereof will be the trend of the following 2-of production acetyl thiophene.Do not appear in the newspapers and relate to the acylation reaction of thiophene in trickle-bed reactor.
Summary of the invention
The objective of the invention is to overcome the insufficient and deficiencies such as the reaction investment consumption is large, deficiency in economic performance of the reaction of prior art, a kind of method of producing the 2-acetyl thiophene with trickle-bed reactor that makes reaction process mass-producing, environmental protection, is conducive to realize suitability for industrialized production in scale is provided.
Concrete technical scheme of the present invention is summarized as follows:
A kind of method of producing the 2-acetyl thiophene with trickle-bed reactor comprises the steps:
(1) reaction workshop section: beds is housed in the trickle-bed reactor, is 20～160 ℃ in temperature, and pressure is under the condition of 0.05～15MPa, thiophene and acylating reagent is sent into carried out acylation reaction in the trickle-bed reactor and obtain 2-acetyl thiophene crude product;
(2) refining workshop section: described 2-acetyl thiophene crude product is carried out rectifying separation purify, obtain highly purified 2-acetyl thiophene product.
Thiophene and acylating reagent are evenly to send into described trickle-bed reactor or send into respectively described trickle-bed reactor for the ratio of 1:0.8～10.0 is pre-mixed in molar ratio preferably.
In trickle-bed reactor, also send into solvent in described reaction workshop section.
The preferred acetic acid of described solvent, benzene, 1,2-ethylene dichloride, tetramethylene sulfone, chlorobenzene or toluene, preferably tetramethylene sulfone.
In the step (1), described beds type of feed is loose heap type or regular type.
Temperature is preferably 30～100 ℃, preferably 80 ℃.
Pressure is preferably 0.1～10MPa, preferably 0.1MPa.
The mol ratio of thiophene and acylating reagent is more preferably 1:1.2～8.0, preferably 1:2.
Acylating reagent can be Acetyl Chloride 98Min., diacetyl oxide, and acetic acid, methyl aceto acetate or ethyl acetate can also adopt other acylating reagent, preferably select Acetyl Chloride 98Min. or diacetyl oxide.
Rectifying can be continuous rectification or batch fractionating.
Advantage of the present invention:
It is simple to operate that the present invention has technical process, and reaction conditions is gentle, and cost of investment is low, the product purity advantages of higher; Simultaneously, structure of reactor is simple, and stable operation is convenient to control, is easy to realize mass-producing and serialization production.
Description of drawings
Fig. 1 is the first is produced 2-acetyl thiophene (refining workshop section adopts continuous rectification) with trickle-bed reactor schematic flow sheet.Among the figure: 1 is the reaction solution storage tank, and 2 is the take away pump device, and 3 is the trickle-bed reactor upper inlet; 4 are the heat source medium outlet, and 5 is beds, and 6 is trickle-bed reactor; 7 is the heat source medium import, and 8 are reaction production fluid storage tank, and 9 is the first take away pump; 10 is the second take away pump, and 11 is the first container for storing liquid, and 12 is the light constituent recovery tower; 13,14,21; 22 are pipeline; 15 is the byproduct treating tower, and 16 is the second container for storing liquid, and 17 is the 3rd take away pump; 18 is the 4th take away pump; 19 is the 3rd container for storing liquid, and 20 is the acylating reagent recovery tower, and 23 is 2-acetyl thiophene treating tower; 24 is the 4th container for storing liquid, and 25 is the 5th take away pump.
Fig. 2 is the second is produced the 2-acetyl thiophene with trickle-bed reactor refining workshop section schematic diagram.Among the figure: 31 are the rectifying tower reactor, and 32 is the electric heating bag, and 34 are the refining rectifying tower of 2-acetyl thiophene, and 35 is tower head, and 39 is reflux ratio controller, and 40 is discharge port, and 41 is vacuum pump.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
The first is produced the method for 2-acetyl thiophene (refining workshop section adopts continuous rectification) with trickle-bed reactor.(see figure 1)
(1) reaction workshop section:
Beds 5 is housed in the trickle-bed reactor, under the condition of certain temperature and pressure, thiophene and acylating reagent are mixed in reaction solution storage tank 1, by take away pump device 2, deliver to through trickle-bed reactor upper inlet 3 and to carry out acylation reaction in the trickle-bed reactor 6, obtaining 2-acetyl thiophene crude product enters in the reaction production fluid storage tank 8, be provided with heat source medium import 7 in the bottom of trickle-bed reactor, be provided with heat source medium outlet 4 on the top of trickle-bed reactor, heat source medium can be selected thermal oil or de-salted water etc.;
(2) refining workshop section: described 2-acetyl thiophene crude product is carried out the continuous rectification separating-purifying, obtain highly purified 2-acetyl thiophene product.
The flow process of continuous rectification is:
The 2-acetyl thiophene crude product that is stored in the reaction production fluid storage tank 8 that reaction workshop section obtains is delivered in the light constituent recovery tower 12 through the first take away pump 9, and the light constituent thiophene that rectifying obtains is delivered to the 4th container for storing liquid 24 through pipeline 13 from the cat head of light constituent recovery tower; The acylating reagent that the tower reactor of light constituent recovery tower obtains and by product and 2-acetyl thiophene crude product enter in the first container for storing liquid 11.
Deliver in the byproduct treating tower 15 through the second take away pump 10 at the material that the first container for storing liquid 11 is stored, the by product that rectifying obtains from the cat head of byproduct treating tower through pipeline 14 extraction; The acylating reagent that the tower reactor of byproduct treating tower obtains and 2-acetyl thiophene crude product enter in the second container for storing liquid 16.
Deliver in the acylating reagent recovery tower 20 through the 3rd take away pump 17 at the material that the second container for storing liquid 16 is stored, the acylating reagent that rectifying obtains is delivered to the 4th container for storing liquid 24 through pipeline 21 from the cat head of acylating reagent recovery tower; The 2-acetyl thiophene crude product that the tower reactor of acylating reagent recovery tower obtains enters in the 3rd container for storing liquid 19.
Deliver in the 2-acetyl thiophene treating tower 23 through the 4th take away pump 18 at the material that the 3rd container for storing liquid 19 is stored, the 2-acetyl thiophene that rectifying obtains from the cat head of 2-acetyl thiophene treating tower through pipeline 22 extraction.
The recovered material (thiophene and acylating reagent) of storing in the 4th container for storing liquid 24 is delivered to recycle in the reaction solution storage tank 1 through the 5th take away pump 25.
The following examples 1-5 is the first of employing is produced 2-acetyl thiophene (refining workshop section adopts continuous rectification) with trickle-bed reactor method.Equipment connection such as Fig. 1.
Embodiment 1
Reaction workshop section: the Mont-K10 beds is housed in the trickle-bed reactor, and the beds type of feed is loose heap type; It is 80 ℃ in temperature, pressure is under the condition of 0.5MPa, carries out acylation reaction in the trickle-bed reactor and obtains 2-acetyl thiophene crude product being pre-mixed evenly for the thiophene of 1:1.2 and diacetyl oxide in molar ratio, sending into, the transformation efficiency of thiophene is that the yield of 99.9%, 2-acetyl thiophene is 99%;
Refining workshop section: described 2-acetyl thiophene crude product is carried out the continuous rectification separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Embodiment 2
Reaction workshop section: CT-175 resin catalyst bed is housed in the trickle-bed reactor, and the beds type of feed is loose heap type; It is 30 ℃ in temperature, pressure is under the condition of 0.1MPa, carries out acylation reaction in the trickle-bed reactor and obtains 2-acetyl thiophene crude product being pre-mixed evenly for the thiophene of 1:3 and Acetyl Chloride 98Min. in molar ratio, sending into, the transformation efficiency of thiophene is that the yield of 98%, 2-acetyl thiophene is 98.3%;
Refining workshop section: described 2-acetyl thiophene crude product is carried out the continuous rectification separating-purifying, obtain purity and be 99.5% 2-acetyl thiophene product.
Embodiment 3
Reaction workshop section: the H-ZSM-5 beds is housed in the trickle-bed reactor, and the beds type of feed is loose heap type; Be 100 ℃ in temperature, pressure is under the condition of 10MPa, is that the thiophene of 1:8 and acetic acid are sent into respectively and carried out acylation reaction in the trickle-bed reactor and obtain 2-acetyl thiophene crude product with mol ratio, and the transformation efficiency of thiophene is that the yield of 99.2%, 2-acetyl thiophene is 98.5%;
Refining workshop section: described 2-acetyl thiophene crude product is carried out the continuous rectification separating-purifying, obtain purity and be 99.1% 2-acetyl thiophene product.
Embodiment 4
Reaction workshop section: the HY beds is housed in the trickle-bed reactor, and the beds type of feed is regular type; It is 20 ℃ in temperature, pressure is under the condition of 0.05MPa, be after thiophene, methyl aceto acetate and the solvent sulfolane of 1:0.8:0.5 is pre-mixed evenly with mol ratio, send into and carry out acylation reaction in the trickle-bed reactor and obtain 2-acetyl thiophene crude product, the transformation efficiency of methyl aceto acetate is that the yield of 99.5%, 2-acetyl thiophene is 99.3%;
Refining workshop section: described 2-acetyl thiophene crude product is carried out the continuous rectification separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Embodiment 5
Reaction workshop section: load Zn is housed in the trickle-bed reactor
2+The ZSM-5 beds, the beds type of feed is regular type; It is 160 ℃ in temperature, pressure is under the condition of 15MPa, be thiophene, the ethyl acetate and 1 of 1:10:0.5 with mol ratio, the 2-ethylene dichloride is pre-mixed evenly, deliver to and carry out acylation reaction in the trickle-bed reactor and obtain 2-acetyl thiophene crude product, the transformation efficiency of thiophene is that the yield of 92%, 2-acetyl thiophene is 99.0%;
Refining workshop section: described 2-acetyl thiophene crude product is carried out the continuous rectification separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Experiment showed, with acetic acid, benzene, chlorobenzene or toluene to substitute 1 in the present embodiment, the 2-ethylene dichloride also can obtain 2-acetyl thiophene product.
The second is produced the method for 2-acetyl thiophene (refining workshop section adopts batch fractionating) with trickle-bed reactor.
(1) reaction workshop section:
Reaction workshop section with first method;
(2) refining workshop section: described 2-acetyl thiophene crude product is carried out the batch fractionating separating-purifying, obtain highly purified 2-acetyl thiophene product.(see figure 2)
The flow process of batch fractionating is:
The 2-acetyl thiophene crude product in the reaction production fluid storage tank 8 of being stored in that reaction workshop section obtains is packed in the rectifying tower reactor 31, through 32 heating of electric heating bag, material separates through the refining rectifying tower 34 of 2-acetyl thiophene, under the control of reflux ratio controller 39, at the discharge port 40 places extraction product 2-of tower head 35 acetyl thiophene; Tower head is connected with vacuum pump 41.
The following examples 6-10 is the second of employing is produced 2-acetyl thiophene (refining workshop section adopts batch fractionating) with trickle-bed reactor method.Equipment connection such as Fig. 2.
Embodiment 6
Reaction workshop section: with embodiment 1
Refining workshop section: described 2-acetyl thiophene crude product is carried out the batch fractionating separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Embodiment 7
Reaction workshop section: with embodiment 2
Refining workshop section: described 2-acetyl thiophene crude product is carried out the batch fractionating separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Embodiment 8
Reaction workshop section: with embodiment 3
Refining workshop section: described 2-acetyl thiophene crude product is carried out the batch fractionating separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Embodiment 9
Reaction workshop section: with embodiment 4
Refining workshop section: described 2-acetyl thiophene crude product is carried out the batch fractionating separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Embodiment 10
Reaction workshop section: with embodiment 5
Refining workshop section: described 2-acetyl thiophene crude product is carried out the batch fractionating separating-purifying, obtain purity and be 99.9% 2-acetyl thiophene product.
Claims (10)
1. a method of producing the 2-acetyl thiophene with trickle-bed reactor is characterized in that comprising the steps:
(1) reaction workshop section: beds is housed in the trickle-bed reactor, is 20～160 ℃ in temperature, and pressure is under the condition of 0.05～15MPa, thiophene and acylating reagent is sent into carried out acylation reaction in the trickle-bed reactor and obtain 2-acetyl thiophene crude product;
(2) refining workshop section: described 2-acetyl thiophene crude product is carried out rectifying separation purify, obtain highly purified 2-acetyl thiophene product.
2. method according to claim 1 is characterized in that described thiophene and acylating reagent are evenly to send into described trickle-bed reactor or send into respectively described trickle-bed reactor for the ratio of 1:0.8～10.0 is pre-mixed in molar ratio.
3. method according to claim 1 is characterized in that also sending into solvent in described reaction workshop section in trickle-bed reactor.
4. one of according to claim 1-3 described method is characterized in that in the described step (1), and described beds type of feed is loose heap type or regular type.
5. method according to claim 1 is characterized in that described temperature is 30～100 ℃.
6. method according to claim 1 is characterized in that described pressure is 0.1～10MPa.
7. method according to claim 2, the mol ratio that it is characterized in that described thiophene and acylating reagent is 1:1.2～8.0.
8. according to claim 1,2 or 7 described methods, it is characterized in that described acylating reagent is Acetyl Chloride 98Min., diacetyl oxide, acetic acid, methyl aceto acetate or ethyl acetate.
9. method according to claim 3 is characterized in that described solvent is acetic acid, benzene, 1,2-ethylene dichloride, tetramethylene sulfone, chlorobenzene or toluene.
10. method according to claim 1 is characterized in that described rectifying is continuous rectification or batch fractionating.
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Cited By (2)
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| CN103483311A (en) * | 2013-08-27 | 2014-01-01 | 仙桃市康化科技有限公司 | Automatic production system for 2-acetylthiophene |
| CN106397295A (en) * | 2016-09-06 | 2017-02-15 | 凯莱英医药集团（天津）股份有限公司 | 2-branch acylation method of solid acid continuous loaded catalyzed aromatic heterocyclic compound |
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| CN103483311A (en) * | 2013-08-27 | 2014-01-01 | 仙桃市康化科技有限公司 | Automatic production system for 2-acetylthiophene |
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