CN102887884B - 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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- CN102887884B CN102887884B CN201210381331.5A CN201210381331A CN102887884B CN 102887884 B CN102887884 B CN 102887884B CN 201210381331 A CN201210381331 A CN 201210381331A CN 102887884 B CN102887884 B CN 102887884B
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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 trickle-bed reactor produce synthesis medicine intermediate 2-acetyl thiophene method.
Background technology
2-acetyl thiophene applies wider one in the substituted thiophene derivant of α position, is the important intermediate of producing other thiophene derivant.2-acetyl thiophene is used widely in medical science, chemistry and food service industry.At medical field, be the intermediate 2-thiophene acetic acid of synthesis broad spectrum antibiotic cefoxitin, Cephaloridine and cefoxitin, non-steroidal anti-inflammatory analgesics tiaprofenic acid, the 2-acetyl thiophene azine with anti-tumor activity and transition metal Cu thereof
2+, Fe
3+the important source material of title complex etc.; At chemical field, it is important chemical reagent, is also the important source material of synthesis organic intermediate thiophene cinnamophenone; In food service industry, due to its special similar onion taste and be used as food aromatizing agent.2-acetyl thiophene carries out reaction by thiophene and acetylation reagent and generates under catalyst action.The research of domestic and international synthesis 2-acetyl thiophene is only confined to laboratory phase of basic research, little by the industrialization case of Friedel-Crafts acylation reaction about thiophene.
At present, the traditional method of synthesizing 2-acetyl thiophene is mainly obtained under the condition of phosphoric acid does catalyst by thiophene and diacetyl oxide.Production process is: by diacetyl oxide, 85% phosphoric acid and thiophene mixing drop in reactor and stir, being heated to reflux temperature is 96 ~ 97 DEG C, and keeps backflow 2 hours, and reaction terminates, and will react production fluid cooling, wash, and remove water layer; Gained oil reservoir is carried out atmospheric and vacuum distillation, is separated and purifies and obtain the 2-acetyl thiophene of high density.In order to improve the production technique of 2-acetyl thiophene; researchist attempts applying molecular sieve, acidic resins etc. carry out thiophene acylation reaction as catalyzer; but only have small part catalyzer (as CT-175; NKC-9 etc.) transformation efficiency of thiophene can be made to reach more than 90%; and the reactor that process adopts is batch 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. defect, the needs that industrial scale is produced can not be met.Due to technical defect; the Technology of reactor will cause with batch still for will be eliminated by the trend of social development; and structure is simple; stable operation; be convenient to control; cost design cost is low, and the reactor and the Technology thereof that are easy to realize the advantage such as mass-producing and continuous prodution will be following trend of producing 2-acetyl thiophene.And relate to the acylation reaction of thiophene in trickle-bed reactor and do not appear in the newspapers.
Summary of the invention
The object of the invention is to overcome the deficiencies such as the reaction of prior art insufficient and reaction investment consumption is large, deficiency in economic performance, provide a kind of and make reaction process mass-producing, environmental protection, in scale, be conducive to realizing the method for producing 2-acetyl thiophene with trickle-bed reactor of suitability for industrialized production.
Concrete technical scheme of the present invention is summarized as follows:
Produce a method for 2-acetyl thiophene with trickle-bed reactor, comprise the steps:
(1) reacting workshop section: in trickle-bed reactor, beds being housed, is 20 ~ 160 DEG C in temperature, and pressure is under the condition of 0.05 ~ 15MPa, obtaining 2-acetyl thiophene crude product by carrying out acylation reaction in thiophene and acylating reagent feeding trickle-bed reactor;
(2) refinement: described 2-acetyl thiophene crude product is carried out rectifying separation purification, obtains highly purified 2-acetyl thiophene product.
Good thiophene and acylating reagent are in molar ratio for the ratio of 1:0.8 ~ 10.0 is pre-mixed the described trickle-bed reactor of even feeding or sends into described trickle-bed reactor respectively.
In trickle-bed reactor, also solvent is sent 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 step (1), described beds type of feed is loose heap-type or regular type.
Temperature is preferably 30 ~ 100 DEG C, preferably 80 DEG C.
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, acetic acid, and 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, product purity advantages of higher; Meanwhile, structure of reactor is simple, stable operation, is convenient to control, is easy to realize mass-producing and continuous prodution.
Accompanying drawing explanation
Fig. 1 is that the first produces the schematic flow sheet of 2-acetyl thiophene (refinement employing continuous rectification) with trickle-bed reactor.In figure: 1 is reaction solution storage tank, 2 is take away pump device, 3 is trickle-bed reactor upper inlet, 4 is heat source medium outlet, 5 is beds, 6 is trickle-bed reactor, 7 is heat source medium import, 8 is reaction production fluid storage tank, 9 is the first take away pump, 10 is the second take away pump, 11 is the first container for storing liquid, 12 is light constituent recovery tower, 13, 14, 21, 22 are pipeline, 15 is byproduct treating tower, 16 is the second container for storing liquid, 17 is the 3rd take away pump, 18 is the 4th take away pump, 19 is the 3rd container for storing liquid, 20 is acylating reagent recovery tower, 23 is 2-acetyl thiophene treating tower, 24 is the 4th container for storing liquid, 25 is the 5th take away pump.
Fig. 2 is that the second produces the refinement schematic diagram of 2-acetyl thiophene with trickle-bed reactor.In figure: 31 for rectifying tower reactor, and 32 is electric heating bag, 34 refine rectifying tower for 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
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
The first produces the method for 2-acetyl thiophene (refinement employing continuous rectification) with trickle-bed reactor.(see figure 1)
(1) workshop section is reacted:
Beds 5 is housed in 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 in trickle-bed reactor 6 through trickle-bed reactor upper inlet 3 and carry out acylation reaction, obtaining 2-acetyl thiophene crude product enters in reaction production fluid storage tank 8, the bottom of trickle-bed reactor is provided with heat source medium import 7, be provided with heat source medium outlet 4 on the top of trickle-bed reactor, heat source medium can select thermal oil or de-salted water etc.;
(2) refinement: described 2-acetyl thiophene crude product is carried out continuous rectification separating-purifying, obtains highly purified 2-acetyl thiophene product.
The flow process of continuous rectification is:
The 2-acetyl thiophene crude product be stored in reaction production fluid storage tank 8 reaction workshop section obtained is delivered in 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 from the tower top of light constituent recovery tower through pipeline 13; 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.
The material stored at the first container for storing liquid 11 is delivered in byproduct treating tower 15 through the second take away pump 10, the by product that rectifying obtains from the tower top 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.
The material stored at the second container for storing liquid 16 is delivered in acylating reagent recovery tower 20 through the 3rd take away pump 17, and the acylating reagent that rectifying obtains is delivered to the 4th container for storing liquid 24 from the tower top of acylating reagent recovery tower through pipeline 21; 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.
The material stored at the 3rd container for storing liquid 19 is delivered in 2-acetyl thiophene treating tower 23 through the 4th take away pump 18, the 2-acetyl thiophene that rectifying obtains from the tower top of 2-acetyl thiophene treating tower through pipeline 22 extraction.
In the 4th container for storing liquid 24, the recovered material (thiophene and acylating reagent) of storage delivers to recycle in reaction solution storage tank 1 through the 5th take away pump 25.
The following examples 1-5 is the first employing produces 2-acetyl thiophene (refinement employing continuous rectification) method with trickle-bed reactor.Equipment connection is as Fig. 1.
Embodiment 1
Reaction workshop section: Mont-K10 beds is housed in trickle-bed reactor, beds type of feed is loose heap-type; It is 80 DEG C in temperature, pressure is under the condition of 0.5MPa, is pre-mixed evenly, carries out the thiophene and the diacetyl oxide that are 1:1.2 in molar ratio acylation reaction and obtain 2-acetyl thiophene crude product in feeding trickle-bed reactor, the transformation efficiency of thiophene is the yield of 99.9%, 2-acetyl thiophene is 99%;
Refinement: described 2-acetyl thiophene crude product is carried out continuous rectification separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Embodiment 2
Reaction workshop section: CT-175 resin catalyst bed is housed in trickle-bed reactor, beds type of feed is loose heap-type; It is 30 DEG C in temperature, pressure is under the condition of 0.1MPa, is pre-mixed evenly, carries out the thiophene and the Acetyl Chloride 98Min. that are 1:3 in molar ratio acylation reaction and obtain 2-acetyl thiophene crude product in feeding trickle-bed reactor, the transformation efficiency of thiophene is the yield of 98%, 2-acetyl thiophene is 98.3%;
Refinement: described 2-acetyl thiophene crude product is carried out continuous rectification separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.5%.
Embodiment 3
Reaction workshop section: H-ZSM-5 beds is housed in trickle-bed reactor, beds type of feed is loose heap-type; Be 100 DEG C in temperature, pressure is under the condition of 10MPa, is that the thiophene of 1:8 and acetic acid are sent into respectively in trickle-bed reactor and carried out acylation reaction and obtain 2-acetyl thiophene crude product by mol ratio, and the transformation efficiency of thiophene is the yield of 99.2%, 2-acetyl thiophene is 98.5%;
Refinement: described 2-acetyl thiophene crude product is carried out continuous rectification separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.1%.
Embodiment 4
Reaction workshop section: HY beds is housed in trickle-bed reactor, and beds type of feed is regular type; It is 20 DEG C in temperature, pressure is under the condition of 0.05MPa, be that the thiophene of 1:0.8:0.5, methyl aceto acetate and solvent sulfolane are pre-mixed evenly by mol ratio, carry out acylation reaction in feeding trickle-bed reactor and obtain 2-acetyl thiophene crude product, the transformation efficiency of methyl aceto acetate is the yield of 99.5%, 2-acetyl thiophene is 99.3%;
Refinement: described 2-acetyl thiophene crude product is carried out continuous rectification separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Embodiment 5
Reaction workshop section: load Zn is housed in trickle-bed reactor
2+zSM-5 beds, beds type of feed is regular type; It is 160 DEG C in temperature, pressure is under the condition of 15MPa, be thiophene, the ethyl acetate and 1 of 1:10:0.5 by mol ratio, 2-ethylene dichloride is pre-mixed evenly, deliver in trickle-bed reactor and carry out acylation reaction and obtain 2-acetyl thiophene crude product, the transformation efficiency of thiophene is the yield of 92%, 2-acetyl thiophene is 99.0%;
Refinement: described 2-acetyl thiophene crude product is carried out continuous rectification separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Experiment proves, also can obtain 2-acetyl thiophene product with 1, the 2-ethylene dichloride that acetic acid, benzene, chlorobenzene or toluene substitute in the present embodiment.
The second produces the method for 2-acetyl thiophene (refinement employing batch fractionating) with trickle-bed reactor.
(1) workshop section is reacted:
With the reaction workshop section of first method;
(2) refinement: described 2-acetyl thiophene crude product is carried out batch fractionating separating-purifying, obtains highly purified 2-acetyl thiophene product.(see figure 2)
The flow process of batch fractionating is:
The 2-acetyl thiophene crude product be stored in reaction production fluid storage tank 8 reaction workshop section obtained loads in rectifying tower reactor 31, heat through electric heating bag 32, material is refined rectifying tower 34 through 2-acetyl thiophene and is separated, under the control of reflux ratio controller 39, at discharge port 40 place's extraction product 2-acetyl thiophene of tower head 35; Tower head is connected with vacuum pump 41.
The following examples 6-10 is the second adopted produces 2-acetyl thiophene (refinement employing batch fractionating) method with trickle-bed reactor.Equipment connection is as Fig. 2.
Embodiment 6
Reaction workshop section: with embodiment 1
Refinement: described 2-acetyl thiophene crude product is carried out batch fractionating separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Embodiment 7
Reaction workshop section: with embodiment 2
Refinement: described 2-acetyl thiophene crude product is carried out batch fractionating separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Embodiment 8
Reaction workshop section: with embodiment 3
Refinement: described 2-acetyl thiophene crude product is carried out batch fractionating separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Embodiment 9
Reaction workshop section: with embodiment 4
Refinement: described 2-acetyl thiophene crude product is carried out batch fractionating separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Embodiment 10
Reaction workshop section: with embodiment 5
Refinement: described 2-acetyl thiophene crude product is carried out batch fractionating separating-purifying, obtains the 2-acetyl thiophene product that purity is 99.9%.
Claims (7)
1. produce a method for 2-acetyl thiophene with trickle-bed reactor, it is characterized in that comprising the steps:
(1) reacting workshop section: in trickle-bed reactor, beds being housed, is 20 ~ 160 DEG C in temperature, and pressure is under the condition of 0.05 ~ 15MPa, obtaining 2-acetyl thiophene crude product by carrying out acylation reaction in thiophene and acylating reagent feeding trickle-bed reactor; Described thiophene and acylating reagent are in molar ratio for the ratio of 1:0.8 ~ 10.0 is pre-mixed the described trickle-bed reactor of even feeding or sends into described trickle-bed reactor respectively;
(2) refinement: described 2-acetyl thiophene crude product is carried out rectifying separation purification, obtains highly purified 2-acetyl thiophene product; The mol ratio of described thiophene and acylating reagent is 1:1.2 ~ 8.0, and described acylating reagent is Acetyl Chloride 98Min., diacetyl oxide, acetic acid, methyl aceto acetate or ethyl acetate.
2. method according to claim 1, is characterized in that in trickle-bed reactor, also sending into solvent in described reaction workshop section.
3. method according to claim 1 and 2, is characterized in that in described step (1), and described beds type of feed is loose heap-type or regular type.
4. method according to claim 1, is characterized in that described temperature is 30 ~ 100 DEG C.
5. method according to claim 1, is characterized in that described pressure is 0.1 ~ 10MPa.
6. method according to claim 2, is characterized in that described solvent is acetic acid, benzene, 1,2-ethylene dichloride, tetramethylene sulfone, chlorobenzene or toluene.
7. method according to claim 1, is characterized in that described rectifying is continuous rectification or batch fractionating.
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| CN103483311B (en) * | 2013-08-27 | 2018-10-30 | 仙桃市康化科技有限公司 | 2- acetyl thiophene Automatic Production Systems |
| CN106397295B (en) * | 2016-09-06 | 2019-04-23 | 凯莱英医药集团（天津）股份有限公司 | A kind of method that solid acid continuous load is catalyzed heteroaromatic compounds 2- acylation |
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| CN1954913A (en) * | 2005-10-19 | 2007-05-02 | 辽宁石油化工大学 | Appalication of solid acid used for synthetic 2-acetylthiphene catalyst |
| CN101406840A (en) * | 2008-10-24 | 2009-04-15 | 中国科学院大连化学物理研究所 | Catalyst for producing 1,2-cyclohexane dicarboxylic acid diesters |
| CN102388019A (en) * | 2008-12-03 | 2012-03-21 | 帝斯曼知识产权资产管理有限公司 | Production of lactams and carboxylic acid amides by beckman rearrangement of oximes in the presence of nb catalysts |
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Patent Citations (4)
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| CN1660497A (en) * | 2004-12-30 | 2005-08-31 | 浙江工业大学 | Application of cesium phosphotungstic acid as catalyst for synthesizing acetyl thiophene |
| CN1954913A (en) * | 2005-10-19 | 2007-05-02 | 辽宁石油化工大学 | Appalication of solid acid used for synthetic 2-acetylthiphene catalyst |
| CN101406840A (en) * | 2008-10-24 | 2009-04-15 | 中国科学院大连化学物理研究所 | Catalyst for producing 1,2-cyclohexane dicarboxylic acid diesters |
| CN102388019A (en) * | 2008-12-03 | 2012-03-21 | 帝斯曼知识产权资产管理有限公司 | Production of lactams and carboxylic acid amides by beckman rearrangement of oximes in the presence of nb catalysts |
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