CN113861005A - A kind of method for continuously synthesizing citral by tubular reactor - Google Patents
A kind of method for continuously synthesizing citral by tubular reactor Download PDFInfo
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- CN113861005A CN113861005A CN202111348475.6A CN202111348475A CN113861005A CN 113861005 A CN113861005 A CN 113861005A CN 202111348475 A CN202111348475 A CN 202111348475A CN 113861005 A CN113861005 A CN 113861005A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
- B01J31/0208—Ketones or ketals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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Abstract
本发明公开了一种通过管式反应器连续化合成柠檬醛的方法，包括以下步骤：将去氢芳樟醇与铜催化剂预络合，形成均相体系，再向均相体系中加入钛催化剂和酸催化剂形成均相溶液，最后将上述均相溶液通过注塞泵以一定流速从进料口连续不断的打入管式反应器中，在管式反应器中停留反应，停留反应后的粗品从另一端口连续流出，即可源源不断的连续得到柠檬醛粗产品，柠檬醛粗产品通过减压精馏即可得到柠檬醛产品。本发明采用管式反应器连续化合成柠檬醛，实现了柠檬醛的连续化生产，节约了生产的时间成本和劳动成本，利于工业化生产；避免了在大规模生产中因反应剧烈放热而导致的安全事故的发生，安全性高。The invention discloses a method for continuously synthesizing citral through a tubular reactor. and acid catalyst to form a homogeneous solution. Finally, the above homogeneous solution is continuously pumped into the tubular reactor from the feed port through a syringe pump at a certain flow rate, and the reaction is stopped in the tubular reactor, and the crude product after the reaction is retained. Continuously flowing out from another port, the crude citral product can be continuously obtained continuously, and the crude citral product can be obtained by vacuum distillation. The invention adopts the tubular reactor to continuously synthesize citral, realizes the continuous production of citral, saves the time cost and labor cost of production, and is beneficial to industrialized production; The occurrence of safety accidents is high.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to the synthesis of spices, and particularly relates to a method for continuously synthesizing citral through a tubular reactor.
Background
Citral is one of the most important representatives of open-chain monoterpenes, and is a colorless or yellowish liquid with a strong lemon flavor. Citral can be used for preparing citrus-flavored food flavor, and also for synthesizing isopulegol, hydroxycitronellal and ionone, which is a raw material for synthesizing vitamin A.
At present, the synthesis methods of citral mainly comprise:
(1) CN112642489A reports that linalool is used as a raw material to prepare citral under the condition of bimetallic catalytic oxidation, but the method uses precious metals such as ruthenium, rhodium, iridium, gold, platinum, palladium and the like, and is expensive;
(2) CN104292087 reports that dehydrolinalool is used as a raw material, and a catalyst 1, 2-bis (diphenylphosphino) ethane-bis (2-methylpropenyl) ruthenium is added to perform a catalytic rearrangement reaction in the presence of a solvent ethylbenzene and a cocatalyst carboxylic acid to prepare citral, wherein ethylbenzene is used as the solvent in the method, the volatility of the ethylbenzene is strong, the environment is damaged, and the method also uses a noble metal ruthenium and has poor economical efficiency;
(3) US3912656 reports the synthesis of citral with a catalyst consisting of triphenylsiloxanium oxide and triphenylsilanol, and US3994936 reports the introduction of an electron-withdrawing group into triphenylsiloxanium oxide or trialkylsilyl alcohol to further improve the catalyst activity. However, the triphenyl siloxy vanadium oxide is easy to hydrolyze and has poor stability, the reaction is required to be carried out under anhydrous condition, and the reaction condition is harsh, and meanwhile, the method uses a large amount of expensive trialkyl silanol, so that the method is not suitable for industrial production;
(4) CN104292087A reports that a catalyst prepared from dehydrolinalool as a raw material, molybdenum dioxide bisacetylacetonate and weakly acidic cation exchange resin, petroleum ether as a solvent and dimethyl sulfoxide as a cosolvent react for 9 hours at 120 ℃ to prepare citral.
Therefore, the method for synthesizing citral, which has the advantages of high safety, low cost, high efficiency, environmental protection and no pollution, is developed, and has important practical significance for promoting the industrial production of citral.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the method for continuously synthesizing the citral through the tubular reactor, the method is high in safety, can avoid potential safety hazards caused by severe heat release in the ton-level production process, and is low in cost, high in efficiency, environment-friendly, pollution-free and easy to industrially produce.
The invention is realized by the following technical scheme:
a method for continuously synthesizing citral through a tubular reactor, comprising the following steps:
the method comprises the steps of pre-complexing dehydrolinalool and a copper catalyst to form a homogeneous system, then adding a titanium catalyst and an acid catalyst into the homogeneous system to form a homogeneous solution, finally continuously pumping the homogeneous solution into a tubular reactor from a feed inlet at a certain flow rate through a plug-injection pump, standing in the tubular reactor for reaction, continuously flowing out a crude product after standing reaction from the other port, and performing reduced pressure rectification on the crude product after reaction to obtain a citral product.
The invention further improves the scheme as follows:
the temperature of the retention reaction is 140-180 ℃, and the time is 2-5 min.
Further, the copper catalyst is one or a mixture of cuprous bromide and cuprous chloride.
Further, the temperature of the pre-complexing is 50-100 ℃.
Further, the titanium catalyst is titanium acetylacetonate oxide.
Further, the acid catalyst is one or a mixture of more than two of cinnamic acid, sorbic acid and tiglic acid.
Further, the mass ratio of the dehydrolinalool to the copper catalyst to the titanium catalyst to the acid catalyst is 500: (0.5-4): (2-8): (20-60).
The chemical reaction equation is as follows:
the invention has the following beneficial effects:
the reaction efficiency is greatly improved by mixing the type of the catalyst, the proportion of the catalyst and the reaction temperature, the continuous reaction is facilitated, the continuous production of the citral is realized through a simple tubular reactor, and the problem of violent heat release in large-scale production is solved because the tubular reactor has the characteristics of small volume, large specific surface area and quick heat dissipation;
compared with the traditional method, the invention realizes the continuous production of the citral and saves the time cost and the labor cost of the production; reacting in a tubular reactor for 2-5min to obtain a crude product with the citral content of 92%, wherein the tonnage capacity can be achieved within several minutes, and the industrial production is facilitated; secondly, the required equipment is simple, the occupied space of the equipment is small, and the investment cost of industrial equipment is reduced; compared with the traditional intermittent reaction, the continuous reaction has the characteristics of high safety and avoidance of safety accidents caused by violent exothermic reaction in large-scale production; and the catalyst has the characteristics of recycling, environmental protection, no pollution and the like.
Detailed Description
Example 1
Adding 500 g of dehydrolinalool and 2 g of cuprous bromide into a 1000 mL single-mouth bottle in sequence, stirring uniformly, heating to 80 ℃ until the cuprous bromide is completely dissolved in the solution, then adding 8 g of titanium acetylacetonate and 40 g of cinnamic acid into the solution, stirring uniformly, injecting the mixed solution into a tubular reactor preheated to 160 ℃ through a plug pump, controlling the flow rate at 75 mL/min, controlling the time of the solution flowing through the tubular reactor to be 2 min, detecting and analyzing through gas chromatography, wherein the conversion rate of the raw material dehydrolinalool is 100%, the content of the product citral is 92%, collecting the solution flowing out of the tubular reactor, and obtaining 450 g of citral through reduced pressure rectification, wherein the yield is 90%.
Example 2
Adding 500 g of dehydrolinalool and 2 g of cuprous chloride into a 1000 mL single-mouth bottle in sequence, stirring uniformly, heating to 80 ℃ until cuprous bromide is completely dissolved in the solution, then adding 8 g of titanyl acetylacetonate and 40 g of cinnamic acid into the solution, stirring uniformly, injecting the mixed solution into a tubular reactor preheated to 160 ℃ through a plug pump, controlling the flow rate at 75 mL/min, controlling the time of the solution flowing through the tubular reactor to be 2 min, detecting and analyzing through gas chromatography, wherein the conversion rate of the raw material dehydrolinalool is 100%, the content of the product citral is 91%, collecting the solution flowing out of the tubular reactor, and obtaining 445 g of citral through reduced pressure rectification, wherein the yield is 89%.
Example 3
Adding 500 g of dehydrolinalool and 2 g of cuprous chloride into a 1000 mL single-mouth bottle in sequence, stirring uniformly, heating to 80 ℃ until cuprous bromide is completely dissolved in the solution, then adding 5 g of titanyl acetylacetonate and 30 g of sorbic acid into the solution, stirring uniformly, injecting the mixed solution into a tubular reactor preheated to 160 ℃ through a plug pump, controlling the flow rate at 50 mL/min, controlling the time for the solution to flow through the tubular reactor to be 3 min, detecting and analyzing through gas chromatography, wherein the conversion rate of the raw material dehydrolinalool is 100%, the content of the product citral is 89%, collecting the solution flowing out of the tubular reactor, and carrying out reduced pressure rectification to obtain 440 g of citral, wherein the yield is 88%.
Example 4
Adding 500 g of dehydrolinalool and 2 g of cuprous bromide into a 1000 mL single-mouth bottle in sequence, stirring uniformly, heating to 80 ℃ until the cuprous bromide is completely dissolved in the solution, then adding 5 g of titanyl acetylacetonate and 20 g of tiglic acid into the solution, stirring uniformly, injecting the mixed solution into a tubular reactor preheated to 160 ℃ by using a plug pump, controlling the flow rate at 30 mL/min, controlling the time for the solution to flow through the tubular reactor to be 5min, detecting and analyzing by using a gas chromatography, wherein the conversion rate of the raw material dehydrolinalool is 100%, the content of the product citral is 89%, collecting the solution flowing out of the tubular reactor, and obtaining 437 g of citral by carrying out reduced pressure rectification, wherein the yield is 87.4%.
Example 5
Adding 500 g of dehydrolinalool and 4 g of cuprous chloride into a 1000 mL single-mouth bottle in sequence, stirring uniformly, heating to 80 ℃ until cuprous bromide is completely dissolved in the solution, then adding 8 g of titanyl acetylacetonate and 40 g of tiglic acid into the solution, stirring uniformly, injecting the mixed solution into a tubular reactor preheated to 180 ℃ through a plug pump, controlling the flow rate at 75 mL/min, controlling the time of the solution flowing through the tubular reactor to be 2 min, detecting and analyzing through gas chromatography, wherein the conversion rate of the raw material dehydrolinalool is 100%, the content of the product citral is 92%, collecting the solution flowing out of the tubular reactor, and rectifying under reduced pressure to obtain 448 g of citral, wherein the yield is 89.6%.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111348475.6A CN113861005A (en) | 2021-11-15 | 2021-11-15 | A kind of method for continuously synthesizing citral by tubular reactor |
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| CN202111348475.6A CN113861005A (en) | 2021-11-15 | 2021-11-15 | A kind of method for continuously synthesizing citral by tubular reactor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1381587A (en) * | 1972-07-31 | 1975-01-22 | Givaudan & Cie Sa | Process for the manufacture of citral |
| US4749814A (en) * | 1986-04-03 | 1988-06-07 | Rhone-Poulenc Sante | Process for the preparation of ethylenic carbonyl compounds |
| US4816606A (en) * | 1987-09-30 | 1989-03-28 | Basf Aktiengesellschaft | Continuous preparation of aldehydes and ketones |
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN110407680A (en) * | 2019-08-20 | 2019-11-05 | 万华化学集团股份有限公司 | A method of preparing isoamyl olefine aldehydr |
-
2021
- 2021-11-15 CN CN202111348475.6A patent/CN113861005A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1381587A (en) * | 1972-07-31 | 1975-01-22 | Givaudan & Cie Sa | Process for the manufacture of citral |
| US4749814A (en) * | 1986-04-03 | 1988-06-07 | Rhone-Poulenc Sante | Process for the preparation of ethylenic carbonyl compounds |
| US4816606A (en) * | 1987-09-30 | 1989-03-28 | Basf Aktiengesellschaft | Continuous preparation of aldehydes and ketones |
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN110407680A (en) * | 2019-08-20 | 2019-11-05 | 万华化学集团股份有限公司 | A method of preparing isoamyl olefine aldehydr |
Non-Patent Citations (2)
| Title |
|---|
| 凌立新等: "《化工单元实训操作》", vol. 1, 重庆大学出版社, pages: 379 - 380 * |
| 赵宁波等: ""钛酸异丙酯催化脱氢芳樟醇合成柠檬醛"", 《化工进展》, vol. 35, no. 4, pages 1203 - 1207 * |
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Application publication date: 20211231 |