CN1114600C - Process for continuously synthesizing coumarin - Google Patents
Process for continuously synthesizing coumarin Download PDFInfo
- Publication number
- CN1114600C CN1114600C CN 00127109 CN00127109A CN1114600C CN 1114600 C CN1114600 C CN 1114600C CN 00127109 CN00127109 CN 00127109 CN 00127109 A CN00127109 A CN 00127109A CN 1114600 C CN1114600 C CN 1114600C
- Authority
- CN
- China
- Prior art keywords
- tower
- salicylic aldehyde
- reaction
- reaction tower
- continuously
- 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.)
- Expired - Lifetime
Links
Abstract
The present invention discloses a method for continuously synthesizing coumarin, which uses salicylic aldehyde and acetic anhydride as raw materials, and uses an alkaline substance as a catalyst. The salicylic aldehyde and the alkaline catalyst are continuously introduced into a reaction tower from the top of the reaction tower, and the acetic anhydride is continuously introduced into the reaction tower from the lower part of the reaction tower. The generated coumarin is continuously discharged by a tower kettle, and is refined by a conventional method. The method has the advantages of continuous reaction, high production efficiency and low raw material consumption, and the quantity of waste water is largely reduced.
Description
Technical field
The invention belongs to the production method of spices, relate in particular to a kind of production method of tonka bean camphor.
Background technology:
Tonka bean camphor is a kind of synthetic perfume, and consumption is very big in essence is produced, and year consumption is about more than 2000 tons.Its structural formula is as follows:
At present, tonka bean camphor in the world generally all adopts by the Perkin method of Pan Jin (Perkin) invention and produces.Other different operational path also has corresponding report, and as document " practical synthetic perfume ", the technology of (Ding Desheng, Gong Juan take turns work, and Science and Technology of Shanghai press publishes) report all because of defectives such as raw material or waste water, is difficult to carry out large-scale industrial production.
There is fairly obvious shortcoming in the method for Perkin method and above-mentioned bibliographical information:
1) be rhythmic reaction, can't realize serialization, production efficiency is low;
2) raw material consumption height, every 1kg tonka bean camphor finished product consumes salicylic aldehyde 1.17kg, acetic anhydride 2.9kg;
3) wastewater flow rate is big, the about 3kg phenolic wastewater of per kilogram finished product, and bad environment pollution is serious.
Summary of the invention
The object of the present invention is to provide a kind of method of continuous production tonka bean camphor,, satisfy the production needs of perfume industry to overcome the defective that existing in prior technology production efficiency is low, raw material consumption is high and environmental pollution is serious.
Design of the present invention is such:
Said tonka bean camphor is to be that former section carries out synthetic with salicylic aldehyde and acetic anhydride, and its reaction formula is:
By above-mentioned reaction formula as seen, entire reaction is finished by two steps and is constituted, the esterification reaction temperature of the first step is generally 140 ℃～170 ℃, the temperature of reaction of the second step condensation is 180 ℃～220 ℃, the present invention utilizes two different temperature sections of above-mentioned reaction process, reaction process is carried out in a tower reactor, carry out on the top that makes the lower the first step of temperature of reaction be reflected at tower reactor, and the second higher step of temperature of reaction is reflected at and carries out in the bottom of tower reactor and the tower still, thereby can realize the serialization of production process.
The present invention also is achieved in that
Continuously introduce tower in from the top of reaction tower salicylic aldehyde and catalyzer, continuously introduce tower in from the bottom of reaction tower acetic anhydride, the service temperature of reaction tower is 140 ℃～170 ℃, the temperature of tower still is 180 ℃～220 ℃, acetic anhydride is heated the back vaporization in the bottom of tower, upwards flow, in reaction tower, carry out esterification, generate the salicylic aldehyde carboxylate, flow downward with mobile salicylic aldehyde counter current contact from top to bottom, finally enter the tower still, in the tower still, carry out condensation reaction, generate target product---tonka bean camphor, discharging continuously, be sent to follow-up refining step, adopt conventional method to make with extra care;
The easy polymerization of salicylic aldehyde, therefore generally with adding in the tower after the acetoxyphenyl dilution, the weight percent concentration after the dilution is 45%～60% again.Salicylic aldehyde is similar to routine techniques to the feed molar ratio of acetic anhydride, and weight ratio is generally 1: 1.1～1.2, and said catalyzer is an acetate catalyst, and as Potassium ethanoate or sodium-acetate etc., consumption and routine techniques are similar, are generally 3%～4% of salicylic aldehyde;
For guaranteeing reaction efficiency, the residence time of salicylic aldehyde in reaction tower is 3～6 hours, and its theoretical tray is advisable with 12～20;
In addition, take out of in order to prevent the cat head raw material, cat head is provided with the condenser that reclaims acetic acid, and with acetic acid condensation in condenser of vaporizing in the production process, partial reflux enters in the tower, and suitable reflux ratio is 3: 1～2: 1.
The reaction tower that is adopted can adopt tower commonly used on the engineering, the interior tray column of filling general ceramic packing or adopting other of tower.
The above-mentioned method for preparing tonka bean camphor disclosed by the invention has very significant advantage, and the present invention is a successive reaction, the production efficiency height, and raw material consumption is low simultaneously, and every 1kg tonka bean camphor finished product consumes salicylic aldehyde 1.117kg, acetic acid 2.0kg; Wastewater flow rate significantly reduces, the about 0.5kg phenolic wastewater of per kilogram finished product.
Embodiment
Below will be further described related content of the present invention by embodiment.
Embodiment 1
Equipment: stainless head tower still, 1000L; Ceramic packing reaction tower, virtual height are 10 meters, and diameter is 0.2 meter;
To introduce continuously in the tower from the top of reaction tower through salicylic aldehyde and Potassium ethanoate (salicylic aldehyde concentration is 50%) after the acetoxyphenyl dilution, flow is 60 kilograms/hour; Acetic anhydride is introduced in the tower continuously from the bottom of reaction tower, and flow is 36 kilograms/hour; The service temperature of reaction tower is 156 ℃, and the temperature of tower still is 205 ℃, and the tonka bean camphor of generation is by the continuous discharging of tower still, through being sent to follow-up refining step after the washing;
The Potassium ethanoate consumption is 35 kilograms of/ton tonka bean camphors;
The acetic acid partial reflux of condensation in the overhead condenser enters in the tower, and reflux ratio is 3: 1.
Per hour produce 72 kilograms of tonka bean camphor crude products, content 5 is 5%;
Unit consumption: salicylic aldehyde 1.117kg/kg tonka bean camphor, acetic acid 2.0kg/kg tonka bean camphor; The phenolic wastewater amount is the 0.5kg/kg tonka bean camphor.
Claims (4)
1. the method for a continuously synthesizing coumarin is a raw material with salicylic aldehyde and acetic anhydride, is catalyzer with acetate, it is characterized in that:
With acetoxyphenyl salicylic aldehyde is diluted, salicylic aldehyde after the dilution and acetate catalyst are introduced in the tower from the top of reaction tower continuously, continuously introduce tower in from the bottom of reaction tower acetic anhydride, the service temperature of reaction tower is 140 ℃～170 ℃, the temperature of tower still is 180 ℃～220 ℃, the tonka bean camphor that generates is by the continuous discharging of tower still, the acetic acid of vaporizing in production process condensation in condenser, and partial reflux enters in the tower;
The residence time of salicylic aldehyde in reaction tower is 3～6 hours.
2. the method for claim 1 is characterized in that, reflux ratio is 3: 1～2: 1.
3. the method for claim 1 is characterized in that, the theoretical tray of reaction tower is 12～20.
4. the method for claim 1 is characterized in that, the weight percent concentration of dilution back salicylic aldehyde is 45%～60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00127109 CN1114600C (en) | 2000-11-01 | 2000-11-01 | Process for continuously synthesizing coumarin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00127109 CN1114600C (en) | 2000-11-01 | 2000-11-01 | Process for continuously synthesizing coumarin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351011A CN1351011A (en) | 2002-05-29 |
| CN1114600C true CN1114600C (en) | 2003-07-16 |
Family
ID=4592128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00127109 Expired - Lifetime CN1114600C (en) | 2000-11-01 | 2000-11-01 | Process for continuously synthesizing coumarin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1114600C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993146B (en) * | 2012-12-04 | 2015-07-15 | 南京工业大学 | Method for continuously synthesizing cumarin by microchannel reactor |
| CN105367566B (en) * | 2015-11-30 | 2018-11-16 | 四川大学 | Substituted cumarin-thiazole orange derivative and its preparation method and application |
| CN106187968B (en) * | 2016-07-11 | 2018-10-26 | 安徽金鹏香精香料有限公司 | A kind of industrial preparative method of cumarin |
-
2000
- 2000-11-01 CN CN 00127109 patent/CN1114600C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1351011A (en) | 2002-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5696303A (en) | Process for the preparation of aliphatic α, ω-diols | |
| CN101693661A (en) | Method for producing propylene glycol methyl ether acetate | |
| CN111875479B (en) | Application of acidic ionic liquid in high-selectivity synthesis of borneol | |
| CN1114600C (en) | Process for continuously synthesizing coumarin | |
| CN102795988A (en) | Method for preparing nonane diacid and biomass diesel from tung oil | |
| CN1928018A (en) | Method of preparing biological diesel oil using solid base catalyst | |
| CN102329233B (en) | Method for catalytically synthesizing diisooctyl terephthalate under action of ionic liquid | |
| CN103159591B (en) | Technique of synthesizing ethanol with acetic acid | |
| CN102060767A (en) | Method for producing caprolactam by methylbenzene | |
| CN1072711C (en) | Industrial production of highly unsaturated fatty acid | |
| US6037504A (en) | Process for producing aliphatic diols | |
| CN111825549A (en) | Synthesis method of n-butyl glycolate | |
| CN209442896U (en) | The glycolic preparation facilities of methyl glycollate Hydrolyze method | |
| CN114181040B (en) | Preparation method of dichloropropanol | |
| CN1193006C (en) | Method for preparing N-ethoxy oxalyl-alanine ethyl ester | |
| CN1548431A (en) | Continuous coumarin synthesizing process | |
| CN1031131C (en) | Process for preparing 6-methoxy naphthyl aldehyde | |
| CN113480401A (en) | Synthesis method of chloro-n-pentane | |
| CN1197790A (en) | Preparation of acetate product | |
| CN107033000A (en) | A kind of continuous liquid of fixed bed method that catalysis prepares lactate admittedly | |
| CN112473736B (en) | Supported polyacid catalyst and application thereof in preparation of levulinate | |
| CN101318900B (en) | Process for synthesizing ethyl propiolate | |
| CN105152858A (en) | Preparation method for aliphatic mixed dihydric alcohol | |
| CN1243713C (en) | Method for synthesizing ethyl ester linoleic acid by catalyzing S 04/T102 solid super strong acid | |
| CN1272298C (en) | Continuous reaction rectifying synthesizing methylene diethyl ether technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030716 |