CN1197791A - new process for producing ethyl propionate - Google Patents
new process for producing ethyl propionate Download PDFInfo
- Publication number
- CN1197791A CN1197791A CN 97103265 CN97103265A CN1197791A CN 1197791 A CN1197791 A CN 1197791A CN 97103265 CN97103265 CN 97103265 CN 97103265 A CN97103265 A CN 97103265A CN 1197791 A CN1197791 A CN 1197791A
- Authority
- CN
- China
- Prior art keywords
- ethyl propionate
- propionic acid
- ethanol
- pharmaceutical grade
- preparation
- 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.)
- Granted
Links
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 19
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 18
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 11
- 235000013599 spices Nutrition 0.000 claims description 10
- 241000282326 Felis catus Species 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 230000007306 turnover Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing ethyl propionate uses propionic acid and alcohol as raw materials, sulfuric acid as catalyst and features use of specific proportioning and operating conditions to make the production of ethyl propionate continuous. The yield of the propionic acid reaches more than 94.5 percent, and the method has the advantages of low raw material consumption, large equipment production capacity, good product quality and the like, and is particularly suitable for the production of spice-grade and medicinal-grade ethyl propionate.
Description
The present invention relates to the production technique of ethyl propionate, be applicable to the production of spices level and pharmaceutical grade ethyl propionate.
Ethyl propionate is used to prepare food flavour and superior cosmetics essence in the day chemical industry, be used as organic synthesis intermediate in pharmaceutical industry, and as the solvent of various natural and synthetic resins, or the like.
Relevant documents both at home and abroad such as U.S. chemical abstract (C.A.), world patent abstract (WPI, WPA), Chinese patent index CD-ROM CD and Chinese patent classification annual index by retrieval, result for retrieval shows: the domestic report of extremely not seeing as yet so far about ethyl propionate producing technology.Though abroad relevant for adopting carboxylic acid and alcohol to carry out the bibliographical information that esterification prepares ester continuously for raw material, but raw material is limited to unsaturated carboxylic acid or high-boiling point alcohol, in addition, the liquid material of recirculation backflow contains the azeotropic mixture of unreacted alcohol or alcohol and water or pure and mild ester.Therefore, to so far, do not see the ethyl propionate production technique similar abroad as yet with the present invention yet.
More representational document about the ethyl propionate production technique, for example: (1). " the organic volume of practical fine chemicals handbook (on) (Zhang Sigui chief editor, Chemical Industry Press, June in 1996 the 1st edition, 1327 pages) in introduced the production method of the ethyl propionate of domestic six tame factories; (2). put down in writing the preparation method of ethyl propionate in " organic synthesis topical reference book " (Fan Nengting writes, press of Beijing Institute of Technology, January in 1992 the 1st edition, 366 pages) and the productive rate of propionic acid is 70%; (3). " synthetic flavor handbook (U.S.'s " Fenaroli spices handbook third part " synthetic perfume " translation, the compiling of Jinan City light industry institute, light industry press, September in 1985 the 1st edition, 436～437 pages) in also introduced the synthetic method of ethyl propionate, but the present invention and these production technique and inequality.
Present domestic ethyl propionate manufacturer adopts single pot of intermittently esterification technique mostly, this technology is summarized as follows: with propionic acid (content 98～99%) and excess ethanol (content 92～93%, moisture 7～8%) be raw material, with sulfuric acid is catalyzer, adopt benzene, toluene or chloroform are solvent, make solvent and ethanol, water forms ternary azeotrope, take away the water that the water that contains in the feed ethanol and esterification generate with the form of component distillation, or the employing Calcium Chloride Powder Anhydrous is a dewatering agent, the water that water that contains in the form absorption feed ethanol with generation hydration calcium chloride and esterification generate, thus the balance of esterification is moved to the direction that generates ethyl propionate.After the backflow esterification about 10 hours, esterification finishes.Distill out the ethyl propionate crude product,,, get the ethyl propionate finished product again with rectifying behind Anhydrous potassium carbonate or the anhydrous magnesium sulfate drying with sodium carbonate solution neutralization, clear water washing.The propionic acid productive rate of this technology only is about 70%.
The object of the present invention is to provide that a kind of productive rate height, good economy performance, equipment capacity are big, good product quality and the reliable ethyl propionate production technique of stable operation.
The objective of the invention is to realize by following method: with ethanol (content 92～93%) and excessive propionic acid (content 98～99%) is raw material, with sulfuric acid is catalyzer, the bed material proportioning is a propionic acid: ethanol=2.0～6.0: 1 (mol ratio), and dripping the material proportioning is propionic acid: ethanol=0.8～1.1: 1 (mol ratio); After bed material esterification in the question response still reaches balance substantially, control cat head gas temperature is 79～82 ℃, fluid temperature is 104～114 ℃ in the still, the turnover balance of control material is a dripping quantity: quantity of reflux: ester output amount: aquifer yield=1: 0.6～0.8: 0.7～0.9: 0.1～0.2 (volume ratio), to drip material adds in the reactor continuously, simultaneously ethyl propionate and the water form with binary azeotrope is steamed from the knockout tower cat head continuously, after the condensation cooling layering, 35～55% of upper strata ethyl propionate total amount is returned cat head as phegma, lower layer of water is gone whole the branch, remaining upper strata ethyl propionate is taken out, be spices level ethyl propionate, as through rectifying, be the pharmaceutical grade ethyl propionate.
The present invention compared with prior art has a series of outstanding advantages: (1) propionic acid productive rate of the present invention reaches more than 94.5%, and prior art only is about 70%; (2) equipment capacity (reactor with unit volume calculates) improves more than 7 times than prior art; (3) the present invention does not have benzene, toluene, chloroform equal solvent and participates in the technological process, thereby ethyl propionate product purity height, fragrance are just; (4) the present invention does not have " three wastes " discharging substantially; (5) treating process is greatly simplified, and thick ester need not neutralize, washing, rectifying, can reach spices level ethyl propionate standard, as through rectifying, can reach pharmaceutical grade ethyl propionate standard; (6) production cost reduces more than 25% than prior art.
Accompanying drawing is the equipment configuration sketch of ethyl propionate continuous esterification.
The equipment configuration of ethyl propionate continuous esterification comprises: reactor [1], knockout tower [2], condenser [3], water cooler [4], separator [5], under meter [6], [7], [8], [9] and other utility appliance, and as thermometer [T], tensimeter [P] etc.
The present invention is explained in detail by embodiment below in conjunction with accompanying drawing:
Embodiment 1: lot number 87-11-23 (preparation spices level ethyl propionate)
(1), preparation of raw material
1. bed material: 55 kilograms of propionic acid (content 98.6%)
10 kilograms of ethanol (content 92.5%)
0.8 kilogram in sulfuric acid (content 98%)
2. drip material: 300 kilograms of propionic acid (content 98.6%)
200 kilograms of ethanol (content 92.5%)
(2) operating process and controlled variable
In [1] in 100 liters of reactors of above-mentioned bed material adding, open and stir, toward the interior feeding of reacting kettle jacketing steam, the total reflux esterification is after 1 hour, and the tower top temperature of knockout tower [2] is stabilized in 79.4 ℃, promptly begins the continuous esterification operation.The bottom that above-mentioned dropping material is added continuously reactor [1] through under meter [9] by 37～39 liters/hour flow, binary azeotrope with ethyl propionate and water steams from cat head continuously through knockout tower [2] simultaneously, through condenser [3] condensation, after water cooler [4] cooling, entering separator [5] is divided into two-layer up and down, the part of upper strata ethyl propionate passes back into cat head through under meter [8] by 26～28 liters/hour flow, another part of upper strata ethyl propionate takes out through the flow of under meter [6] by 30～32 liters/hour, and lower layer of water is taken out through the flow of under meter [7] by 6～7 liters/hour.In whole continuous esterification process, 80.5～81.5 ℃ of tower top temperatures of control, 107～110 ℃ of temperature in the kettle.
Because of the present invention is a continuous esterification process, present embodiment dripped material with above-mentioned 500 kilograms and all dropwises in the time of 15 hours, when dropwising, take out 401.5 kilograms of ethyl propionates altogether, contain ester amount 97.103%, acid number (mgKOH/g) 0.83, propionic acid productive rate 95.5%.The prepared ethyl propionate of present embodiment need not neutralize, washing, rectifying, has met spices grade standard (U.S. FCC III standard).
Embodiment 2: lot number 88-3-16 (preparation pharmaceutical grade ethyl propionate)
(1) preparation of raw material
1. bed material: 60 kilograms of propionic acid (content 98.9%)
8 kilograms of ethanol (content 92.4%)
0.8 kilogram in sulfuric acid (content 98%)
2. drip material: 350 kilograms of propionic acid (content 98.9%)
250 kilograms of ethanol (content 92.4%)
(2) operating process and controlled variable
Operating process is with embodiment 1.
Controlled variable is: when the tower top temperature of knockout tower [2] is stabilized in 79.8 ℃, and the operation of beginning continuous esterification; In the continuous esterification process, the control feed rate is 40～42 liters/hour, and return velocity is 28～30 liters/hour, and ester output speed is 32～34 liters/hour, going out water speed is 7～8 liters/hour, 80.8～81.5 ℃ of tower top temperatures of control, 108～112 ℃ of temperature in the kettle; When continuous esterification carried out 16 hours, above-mentioned 600 kilograms dripped material and add, this moment altogether 467 kilograms of ethyl propionates, contain ester amount 97.251%.
With the rectifying in the rectifier unit of packing into of above-mentioned ethyl propionate, collect 98～99 ℃ of cuts, 455 kilograms of smart ethyl propionates, propionic acid productive rate 94.7% contains ester amount 99.380%, moisture 0.0958% meets the pharmaceutical grade standard.Annotate: the leading indicator of spices level (U.S. FCC III) ethyl propionate is: contain ester amount 〉=97.0%,
Acid number (mgKOH/g)≤2.0.
The leading indicator of pharmaceutical grade ethyl propionate is: contain ester amount 〉=98.0%, moisture content≤0.1%.
Claims (3)
1. ethyl propionate producing technology, be particularly related to the preparation of spices level and pharmaceutical grade ethyl propionate, it comprises that with propionic acid and ethanol be raw material, with sulfuric acid is catalyzer, through batching, continuous esterification, and preparation spices level ethyl propionate, or again through rectifying, preparation pharmaceutical grade ethyl propionate, it is characterized in that: the proportioning of bed material is a propionic acid: ethanol=2.0～6.0: 1 (mol ratio), the proportioning that drips material is a propionic acid: ethanol=0.8～1.1: 1 (mol ratio); After treating that the bed material esterification reaches balance substantially, to drip material adds in the reactor continuously, simultaneously ethyl propionate and the water form with binary azeotrope is steamed from the knockout tower cat head continuously, after the condensation cooling layering, 35～55% of upper strata ethyl propionate total amount is returned cat head as phegma, lower layer of water is all divided go, remaining upper strata ethyl propionate is taken out, promptly get spices level ethyl propionate,, promptly get the pharmaceutical grade ethyl propionate as through rectifying.
2. novel process according to claim 1, it is characterized in that controlling the cat head gas temperature is 79～82 ℃, fluid temperature is 104～114 ℃ in the still.
3. novel process according to claim 1, the turnover balance that it is characterized in that controlling material is a dripping quantity: quantity of reflux: ester output amount: aquifer yield=1: 0.6～0.8: 0.7～0.9: 0.1～0.2 (volume ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103265A CN1059199C (en) | 1997-04-28 | 1997-04-28 | ethyl propionate production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103265A CN1059199C (en) | 1997-04-28 | 1997-04-28 | ethyl propionate production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1197791A true CN1197791A (en) | 1998-11-04 |
| CN1059199C CN1059199C (en) | 2000-12-06 |
Family
ID=5166613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97103265A Expired - Fee Related CN1059199C (en) | 1997-04-28 | 1997-04-28 | ethyl propionate production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1059199C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761450A (en) * | 2012-12-20 | 2015-07-08 | 常州市松盛香料有限公司 | Preparation method of ethyl propionate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231222A (en) * | 1991-07-02 | 1993-07-27 | Union Carbide Chemicals & Plastics Technology Corporation | Esterification process |
| CN1039226C (en) * | 1995-04-17 | 1998-07-22 | 国营吴江香料厂 | Semi-continuous production process of ethyl formate |
-
1997
- 1997-04-28 CN CN97103265A patent/CN1059199C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761450A (en) * | 2012-12-20 | 2015-07-08 | 常州市松盛香料有限公司 | Preparation method of ethyl propionate |
| CN104761450B (en) * | 2012-12-20 | 2016-08-24 | 常州市松盛香料有限公司 | The preparation method of ethyl propionate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1059199C (en) | 2000-12-06 |
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| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Zhou Zhiqiang Document name: Notification to Pay the Fees |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20001206 Termination date: 20100428 |