CN113861005A - Method for continuously synthesizing citral through tubular reactor - Google Patents
Method for continuously synthesizing citral through tubular reactor Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- citral
- tubular reactor
- continuously
- catalyst
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for continuously synthesizing citral through a tubular reactor, which comprises the following steps: the method comprises the steps of pre-complexing dehydrolinalool and a copper catalyst to form a homogeneous system, adding a titanium catalyst and an acid catalyst into the homogeneous system to form a homogeneous solution, continuously pumping the homogeneous solution into a tubular reactor from a feed inlet at a certain flow rate through a plug-in pump, standing in the tubular reactor for reaction, continuously flowing out a crude product after standing reaction from the other port to obtain a crude citral product continuously, and carrying out reduced pressure rectification on the crude citral product to obtain the citral product. According to the method, the tubular reactor is adopted to continuously synthesize the citral, so that the continuous production of the citral is realized, the time cost and the labor cost of production are saved, and the industrial production is facilitated; the safety accident caused by violent reaction and heat release in large-scale production is avoided, and the safety 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)
1. A method for continuously synthesizing citral through a tubular reactor is characterized by comprising the following steps:
the method comprises the steps of pre-complexing dehydrolinalool and a copper catalyst to form a homogeneous system, adding a titanium catalyst and an acid catalyst into the homogeneous system to form a homogeneous solution, 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.
2. The method for continuously synthesizing citral through the tubular reactor according to claim 1, wherein: the temperature of the retention reaction is 140-180 ℃, and the time is 2-5 min.
3. The method for continuously synthesizing citral through the tubular reactor according to claim 1, wherein: the copper catalyst is one or the mixture of cuprous bromide and cuprous chloride.
4. The method for continuously synthesizing citral through the tubular reactor according to claim 1, wherein: the temperature of the pre-complexing is 50-100 ℃.
5. The method for continuously synthesizing citral through the tubular reactor according to claim 1, wherein: the titanium catalyst is titanium acetylacetonate.
6. The method for continuously synthesizing citral through the tubular reactor according to claim 1, wherein: the acid catalyst is one or a mixture of more than two of cinnamic acid, sorbic acid and tiglic acid.
7. The method for continuously synthesizing citral through the tubular reactor according to claim 1, wherein: 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).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111348475.6A CN113861005A (en) | 2021-11-15 | 2021-11-15 | Method for continuously synthesizing citral through tubular reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111348475.6A CN113861005A (en) | 2021-11-15 | 2021-11-15 | Method for continuously synthesizing citral through tubular reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113861005A true CN113861005A (en) | 2021-12-31 |
Family
ID=78984630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111348475.6A Pending CN113861005A (en) | 2021-11-15 | 2021-11-15 | Method for continuously synthesizing citral through tubular reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113861005A (en) |
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 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109731612B (en) | Functionalized ionic liquid and method for preparing all-trans vitamin A acetate | |
| CN106565659B (en) | A method of preparing vitamin e acetate | |
| CN107602357A (en) | A kind of method for preparing menthones | |
| CN113233979B (en) | Preparation method of 4-acetoxyl-2-methyl-2-butenal | |
| CN113861005A (en) | Method for continuously synthesizing citral through tubular reactor | |
| CN113956138A (en) | Method for continuously synthesizing isopropenal through tubular reactor | |
| CN107805201B (en) | Preparation method of methyl dihydrojasmonate | |
| CN104311405A (en) | Preparation method of benzaldehyde | |
| CN110330421B (en) | Method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as raw material | |
| CN113559935B (en) | Catalyst system and method for preparing hydroxycitronellal from citronellal epoxide | |
| CN101209415B (en) | Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate | |
| CN108794314A (en) | A kind of method of citral hydrogenation synthesis citronellal | |
| CN1295201C (en) | Method for preparing alpha, beta unsaturated alcohol from compound of ketone or aldehyde containing carbonyl | |
| CN113999098A (en) | Method for synthesizing 2,3, 5-trimethylbenzoquinone | |
| CN101475447B (en) | Method for synthesizing 2,4,6-pseudocuminol | |
| CN111196755A (en) | Preparation method of natural benzaldehyde | |
| CN106554268B (en) | A kind of method of aqueous catalysis synthesizing methyl succinic acid | |
| CN111004091A (en) | Method for preparing 4,4,5,5, 5-penta-fluoropentanol | |
| CN113248345B (en) | Preparation method of 2-butenol | |
| CN105541544A (en) | 3-methyl-3-buten-1-ol production method | |
| CN113666810B (en) | Green synthesis method of hydroxycitronellal | |
| CN117884186B (en) | Catalyst for preparing optically active citronellal, and preparation method and application thereof | |
| CN115677460B (en) | Method for preparing citronellal by dehydrogenation of citronellol | |
| CN108864170B (en) | Preparation method of ethyltrimethoxysilane | |
| CN1379005A (en) | Process for oligomerizing isobutylene in ionic liquid [Hmim] +BF-(4) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |