CN102491900A - Method for preparing diethylene glycol dibenzoate - Google Patents
Method for preparing diethylene glycol dibenzoate Download PDFInfo
- Publication number
- CN102491900A CN102491900A CN2011104079127A CN201110407912A CN102491900A CN 102491900 A CN102491900 A CN 102491900A CN 2011104079127 A CN2011104079127 A CN 2011104079127A CN 201110407912 A CN201110407912 A CN 201110407912A CN 102491900 A CN102491900 A CN 102491900A
- Authority
- CN
- China
- Prior art keywords
- diethylene glycol
- glycol dibenzoate
- tower
- preparing
- catalytic rectifying
- 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing diethylene glycol dibenzoate, and relates to the diethylene glycol dibenzoate. The invention provides a method which has a simple production process, is low in investment and energy-saving, is suitable for large-scale production and is used for preparing the diethylene glycol dibenzoate. The method comprises the following steps of: mixing benzoic acid and diethylene glycol in a batching kettle, heating, and inputting the mixture to the upper part of a catalytic rectifying tower by a pump; adding a catalyst from a feed inlet of the catalytic rectifying tower, and reacting by a catalytic rectifying section to obtain the diethylene glycol dibenzoate in a tower kettle; discharging water generated in reaction out of a liquid separation tank by a tower top material, and recovering the unreacted benzoic acid. The prepared diethylene glycol dibenzoate is high in purity and does not contain the diethylene glycol, and a subsequent process is avoided. The diethylene glycol dibenzoate is faint yellow liquid, is not needed to be decolorized further, is small in loss of a catalyst and small in corrosivity on equipment, does not have pollution on environment, and has high application value.
Description
Technical field
The present invention relates to a kind of diethylene glycol dibenzoate, especially relate to a kind of method that adopts catalytic distillation to prepare diethylene glycol dibenzoate.
Background technology
Diethylene glycol dibenzoate (DEDB) is a kind of novel softening agent for having a little lurid transparent oily liquid.DEDB compares with conventional plasticizers phthalic acid fat (DOP); Have characteristics such as consistency is good, winter hardiness is good, static resistance, antifouling property is remarkable, thermostability is outstanding, volatility is low, fast light discolouration is good; And toxicity is low; The softening agent of contact food wrapping material is thought can be used for by departments such as external related food, hospital, makeup, has good market outlook.
At present; The method of synthetic DEDB mainly is that employing phenylformic acid and glycol ether are raw material in the industry; Make catalyzer with the vitriol oil, heteropolyacid or toluenesulphonic acids or alkali alumina and produce, use toluene as the band aqua, this technology side reaction is serious; The product color is dark, has increased trouble to subsequent disposal.Employing alkali aluminas such as Gao Yonghui are made catalyzer, utilize YLENE to make the band aqua, and DEDB is synthesized in catalysis, and this method temperature of reaction is high, and product DEDB is thickness relatively, and loss is big.Chinese patent CN101407461A discloses a kind of preparing diethylene glycol dibenzoate, as catalyzer, adopts saturated hydrocarbons as the band aqua with heteropolyacid, toluenesulphonic acids and hydrochloric acid etc., and pure content is high in the thick ester; Chinese patent CN101492372A discloses a kind of working method of diethylene glycol dibenzoate, adopts the mixture of composite catalyst, titanium isopropylate and solid titanium based compound, catalyzer, and after 220～250 ℃ of the temperature of reaction, the reaction times is longer.Chinese patent CN102172533A discloses the method for the solid acid catalyst of a kind of synthetic DEDB, this technological process before several technologies simple, but the catalyzer cost is higher relatively.The process of the synthetic diethylene glycol dibenzoate of phenylformic acid and glycol ether is reversible thermo-negative reaction, therefore needs in the reaction constantly another kind of product water to be got rid of from reactive system, just can make reaction proceed the transformation efficiency that reaches required.The process of draining is very slow in common tank reactor, make the conversion that reacts completely needed chronic.Reaction rectification technique is applied in the phenylformic acid esterification reaction process, will reacts the water and the diethylene glycol dibenzoate that generate by means of rectifying and separate from reaction zone in time, can reach the purpose that improves speed of reaction.
Summary of the invention
The object of the present invention is to provide the preparing diethylene glycol dibenzoate that a kind of production technique is simple, invest low, energy-conservation, suitable scale operation.
Concrete steps of the present invention are following:
The batching still in phenylformic acid and glycol ether Hybrid Heating; Be input to catalytic rectifying tower top through pump; Catalyzer is added by catalytic rectifying tower opening for feed top, after the reaction of catalytic distillation section, obtains diethylene glycol dibenzoate (DEDB) at the tower still; The water discharge that the cat head material generates through dividing flow container to react, and reclaim unreacted phenylformic acid.Prepared diethylene glycol dibenzoate (DEDB) purity is high, does not contain glycol ether, has saved postprocessing working procedures.
Said batching still can adopt the conventional commercially available batching still that heats; The temperature of said heating can be 100～150 ℃;
Said catalyzer can be selected from tetrabutyl titanate etc., can realize homogeneous reaction in the tower, has saved the problem of loading difficulty in the solid catalyst tower.
The add-on of said catalyzer can be 0.6%～1.0% of material total mass.
The reflux ratio of said catalytic rectifying tower can be (2～4): 1.
Said glycol ether and benzoic mol ratio can be 1: (1.8～2.2).
The condition of the operating process of said catalytic rectifying tower can be: the top vacuum degree is 0.09～0.1MPa, and tower top temperature is 120～140 ℃.
Load filler in the said catalytic rectifying tower, every at a distance from liquid distributor of 3m filler installation, to guarantee that Liquid Distribution is even, reaction is carried out smoothly.
The present invention carries out catalyzed reaction through phenylformic acid and glycol ether to generate diethylene glycol dibenzoate in catalytic rectifying tower.Through the catalytic distillation effect, obtain DEDB purity more than 98% at the tower still.The DEDB product that the present invention obtains is a weak yellow liquid, does not need further decolouring, and the catalyst loss amount is little, and is little to equipment corrosion, and environmentally safe has good using value.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.In Fig. 1, respectively be labeled as: 1 raw material; 2 batching stills; 3 fresh feed pumps; 4 catalytic rectifying towers; 5 cat head materials; The 6DEDB product; 7 overhead condensers; 8 return tanks; 9 fens flow containers; 10 water; 11 phenylformic acid; 12 catalyst make-up mouths.
Fig. 2 is embodiment of the invention diethylene glycol dibenzoate (DEDB) standard specimen color atlas.
Fig. 3 is the color atlas of the embodiment of the invention 1 diethylene glycol dibenzoate (DEDB).
Fig. 4 is the color atlas of the embodiment of the invention 2 diethylene glycol dibenzoates (DEDB).
Fig. 5 is the color atlas of the embodiment of the invention 3 diethylene glycol dibenzoates (DEDB).
In Fig. 2～5, X-coordinate is time (min), and ordinate zou is voltage (mV).
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further explain, but the present invention is not limited to this.
Adopt the mode of connection of Fig. 1, phenylformic acid and diglycol material 1 join in the batching still 2, are dissolved in the glycol ether fully through phenylformic acid after the preheating; Join catalytic rectifying tower 4 tops through fresh feed pump 3, get into return tank 8 through cat head material 5 behind the catalytic distillation tower reaction rectification through cold overhead condenser 7, in a part of feed back to the catalytic rectifying tower 4; Another part material gets into and divides flow container 9; Separate with phenylformic acid through static back water, water 10 is in the 9 top extraction of minute flow container, and phenylformic acid 11 returns raw material 1 in the 9 lower section extraction of minute flow container; The extraction material is a DEDB product 6 at the bottom of catalytic rectifying tower 4 towers, and catalyzer is added by catalyst make-up mouth 12.
Adopt flow process shown in Figure 1, charging glycol ether and benzoic mol ratio are: 1: 1.8, and 100 ℃ of batching still Heating temperatures; Catalyzer metatitanic acid four butyl ester add-ons are 0.9% of material total amount; Catalytic rectifying tower reflux ratio 2: 1, top vacuum degree are 0.09MPa, 140 ℃ of temperature.Load filler in the catalytic rectifying tower, whenever a liquid distributor is installed at a distance from 3 meters fillers.The gained result is following: water 90% in the cat head material, phenylformic acid 10%, and it is as shown in Figure 3 through the chromatogram detection to obtain the DEDB product at the bottom of the tower, and after DEDB standard specimen (referring to Fig. 2) comparison, product purity can reach 99%.
Adopt flow process shown in Figure 1, charging glycol ether and benzoic mol ratio are: 1: 2.2, and 150 ℃ of batching still Heating temperatures; Catalyzer metatitanic acid four butyl ester add-ons are 0.6% of material total amount; Catalytic rectifying tower reflux ratio 4: 1, top vacuum degree are 0.1MPa, 120 ℃ of temperature.Load filler in the catalytic rectifying tower, whenever a liquid distributor is installed at a distance from 3 meters fillers.The gained result is following: water 85% in the cat head material, phenylformic acid 15%, and it is as shown in Figure 4 through the chromatogram detection to obtain the DEDB product at the bottom of the tower, and after DEDB standard specimen (referring to Fig. 2) comparison, product purity can reach 99%.
Adopt flow process shown in Figure 1, charging glycol ether and benzoic mol ratio are: 1: 2.0, and 120 ℃ of batching still Heating temperatures; Catalyzer metatitanic acid four butyl ester add-ons are 1.0% of material total amount; Catalytic rectifying tower reflux ratio 3: 1, top vacuum degree are 0.09MPa, 140 ℃ of temperature.Load filler in the catalytic rectifying tower, whenever a liquid distributor is installed at a distance from 3 meters fillers.The gained result is following: water 85% in the cat head material, phenylformic acid 15%, and it is as shown in Figure 5 through the chromatogram detection to obtain the DEDB product at the bottom of the tower, and after DEDB standard specimen (referring to Fig. 2) comparison, product purity can reach 99%.
The catalytic distillation production technique of the diethylene glycol dibenzoate that the present invention proposes; Be described through embodiment; Person skilled obviously can be changed or suitably change and combination system and method as herein described in not breaking away from content of the present invention, spirit and scope, realizes technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as and are included in spirit of the present invention, scope and the content.
Claims (7)
1. preparing diethylene glycol dibenzoate is characterized in that its concrete steps are following:
In the batching still, with phenylformic acid and glycol ether Hybrid Heating, be input to catalytic rectifying tower top through pump, catalyzer is added by catalytic rectifying tower opening for feed top, after the reaction of catalytic distillation section, obtains diethylene glycol dibenzoate at the tower still.
2. a kind of preparing diethylene glycol dibenzoate as claimed in claim 1, the temperature that it is characterized in that said heating is 100～150 ℃.
3. a kind of preparing diethylene glycol dibenzoate as claimed in claim 1 is characterized in that said catalyzer is a tetrabutyl titanate.
4. a kind of preparing diethylene glycol dibenzoate as claimed in claim 1, the add-on that it is characterized in that said catalyzer is 0.6%～1.0% of a material total mass.
5. a kind of preparing diethylene glycol dibenzoate as claimed in claim 1, the reflux ratio that it is characterized in that said catalytic rectifying tower is 2～4: 1.
6. a kind of preparing diethylene glycol dibenzoate as claimed in claim 1 is characterized in that said glycol ether and benzoic mol ratio are 1: 1.8～22.
7. a kind of preparing diethylene glycol dibenzoate as claimed in claim 1, it is characterized in that the condition of the operating process of said catalytic rectifying tower is: the top vacuum degree is 0.09～0.1MPa, tower top temperature is 120～140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104079127A CN102491900A (en) | 2011-12-08 | 2011-12-08 | Method for preparing diethylene glycol dibenzoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104079127A CN102491900A (en) | 2011-12-08 | 2011-12-08 | Method for preparing diethylene glycol dibenzoate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102491900A true CN102491900A (en) | 2012-06-13 |
Family
ID=46183770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104079127A Pending CN102491900A (en) | 2011-12-08 | 2011-12-08 | Method for preparing diethylene glycol dibenzoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102491900A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
| CN104592027A (en) * | 2015-02-13 | 2015-05-06 | 厦门大学 | Method for preparing methyl benzoate |
| CN106146314A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of preparation method of dibenzoic acid binary alcohol esters plasticizer |
| CN106187754B (en) * | 2015-05-06 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of method of catalytic distillation production aromatic esters |
| CN116328790A (en) * | 2023-04-10 | 2023-06-27 | 浙江大学 | Preparation method of solid acid catalyst and application of solid acid catalyst in diethylene glycol dibenzoate synthesis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107136A (en) * | 1994-07-16 | 1995-08-23 | 广西大学 | Method and equipment for continuous catalyzing rectifying production of n-butyester acetate |
| CN101560151A (en) * | 2009-05-22 | 2009-10-21 | 南京大学 | Process for continuously generating methyl acetate by reactive distillation taking ionic liquid as catalyst |
-
2011
- 2011-12-08 CN CN2011104079127A patent/CN102491900A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107136A (en) * | 1994-07-16 | 1995-08-23 | 广西大学 | Method and equipment for continuous catalyzing rectifying production of n-butyester acetate |
| CN101560151A (en) * | 2009-05-22 | 2009-10-21 | 南京大学 | Process for continuously generating methyl acetate by reactive distillation taking ionic liquid as catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 宋桂贤等: "一缩二乙二醇二苯甲酸酯的合成", 《化工文摘》 * |
| 盛奎龙等: "催化反应精馏制备乙酸乙酯", 《精细石油化工进展》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086891A (en) * | 2013-02-22 | 2013-05-08 | 厦门大学 | Preparation method of plasticizer diethylene glycol dibenzoate |
| CN103086891B (en) * | 2013-02-22 | 2015-12-23 | 厦门大学 | The preparation method of elasticizer diethylene glycol dibenzoate |
| CN104592027A (en) * | 2015-02-13 | 2015-05-06 | 厦门大学 | Method for preparing methyl benzoate |
| CN106146314A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of preparation method of dibenzoic acid binary alcohol esters plasticizer |
| CN106187754B (en) * | 2015-05-06 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of method of catalytic distillation production aromatic esters |
| CN116328790A (en) * | 2023-04-10 | 2023-06-27 | 浙江大学 | Preparation method of solid acid catalyst and application of solid acid catalyst in diethylene glycol dibenzoate synthesis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102491900A (en) | Method for preparing diethylene glycol dibenzoate | |
| CN105367368B (en) | The method that high-purity isobutylene is prepared from C_4 hydrocarbon | |
| CN110256476B (en) | Method for synthesizing 1,1,1,3,5,5, 5-heptamethyltrisiloxane by using hydrogen-containing silicone oil low-boiling-point substance | |
| CN106748651A (en) | A kind of coal-ethylene glycol process for refining and system | |
| CN100393677C (en) | Process for extracting 1-methylnaphthalene and 2-methylnaphthalene from tar | |
| CN102584544B (en) | Process for separating ethylene glycol monomethyl ether and water with intermittent azeotropic distillation method | |
| CN101941887A (en) | Method for indirectly synthesizing ethanol by using carbon monoxide and hydrogen | |
| CN104592030A (en) | Method for synthesizing phthalate compounds | |
| CN103030564A (en) | Method for carrying out high-efficiency catalytic alcoholysis on polyethylene terephthalate (PET) by multi-component catalyst | |
| CN104178092A (en) | High-temperature organic heat carrier and production technology thereof | |
| CN102796002B (en) | Method for catalytically alcoholizing polyethylene terephthalate | |
| CN102134191A (en) | Process method for producing ethyl acetate by catalytic rectification | |
| CN101085711B (en) | Method for synthesizing ethyl benzene and diethyl benzene | |
| CN102875382B (en) | Method for catalytically alcoholizing polyethylene terephthalate (PET) by metallic acetate ion liquid | |
| CN102372610A (en) | Extraction and rectification technology and preparation apparatus of high-density methylal | |
| CN101260016A (en) | Refining device for preparing high-pure isobutene by cracking methyl tertiary butyl ether and technique thereof | |
| CN103159591B (en) | Technique of synthesizing ethanol with acetic acid | |
| CN104193598A (en) | Multi-reflux environment-friendly dimethoxymethane preparation process | |
| CN104230676A (en) | Process for preparing methylal | |
| CN106146299B (en) | The method for producing acetic acid esters and ethylene glycol | |
| CN104592027A (en) | Method for preparing methyl benzoate | |
| CN103601639A (en) | O-chlorobenzoic acid synthesis process | |
| CN107573216A (en) | A kind of synthetic method of absolute ethyl alcohol | |
| CN107698542A (en) | Prepare the device and method of gamma butyrolactone | |
| CN101838192A (en) | Trimethylacetic acid crude product refining process and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120613 |