CN1887424A - Modified ion exchange resin catalyst and its application - Google Patents
Modified ion exchange resin catalyst and its application Download PDFInfo
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- CN1887424A CN1887424A CN 200610010289 CN200610010289A CN1887424A CN 1887424 A CN1887424 A CN 1887424A CN 200610010289 CN200610010289 CN 200610010289 CN 200610010289 A CN200610010289 A CN 200610010289A CN 1887424 A CN1887424 A CN 1887424A
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- exchange resin
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Abstract
The present invention relates to modified ion exchange resin catalyst, and is especially one kind of tin dichloride modified cation exchange resin catalyst and its application as ammonium lactate esterifying catalyst. The tin dichloride modified cation exchange resin catalyst is prepared through the following steps: 1. drying hydrogen type strong acid cation exchange resin to constant weight; 2. reaction of the dried hydrogen type strong acid cation exchange resin and tin dichloride inside alcohol solution; and 3. washing the modified resin with anhydrous ethanol for several times, drying in a vacuum drier to eliminate ethanol and obtain the modified cation exchange resin catalyst. The catalyst has high esterification yield and no corrosion to the production apparatus.
Description
Technical field
The present invention relates to a kind of by the cation exchange resin catalyst of stannous chloride modification and this catalyst as the ammonium lactate esterification Application of Catalyst.
Background technology
Lactate is the lactic acid derivative that a class has good biodegradability, is widely used in departments such as food, medicine, coating, electronics.Be raw material with lactic acid in traditional lactate synthesis technique, fermentation method is generally adopted in the production of lactic acid, before esterification, must carry out from the technological operation of broth extraction lactic acid, but this technology exists, and process is loaded down with trivial details, accessory substance is many, there are deficiencies such as corrosion in raw material to reaction unit, defines lactate to a certain extent and changes into this reduction.
In lactic fermentation process, make nertralizer with ammoniacal liquor, to obtain tunning-ammonium lactate, ammonium lactate in the zymotic fluid can be directly used in the synthesizing lactic acid ester, save from the technological operation of broth extraction lactic acid, avoided production of by-products, and with ammonium lactate neutral in the zymotic fluid as the esterification initiation material, can prevent the corrosion of equipment, also help the reduction of synthesizing lactic acid ester cost.With ammonium lactate in the lactic fermentation liquid is a kind of up-and-coming method that then is regarded as of synthesizing that raw material directly carries out lactate.
Chinese patent CN1369490A and CN1104254 disclose the employing concentrated sulfuric acid as catalyst, the esterification of catalysis ammonium lactate and alcohol, can obtain desirable esterification yield though make catalyst with the concentrated sulfuric acid, but during esterification with side reactions such as oxidation, sulfurations, and reaction finishes the back also need and carry out water treatment through neutralization for removing unnecessary sulfuric acid, causes production process numerous and diverse.The journal VOL.31.N of Hebei University of Technology 06,7～10,2002. has reported and has used AlCl
3(Lewis acid) is that catalyst esterification ammonium lactate generates ethyl lactate, solved that equipment corrosion is serious, accessory substance many and shortcoming such as aftertreatment technology complexity, but esterification efficient is very low, only is 22.45%.
Summary of the invention
The present invention is in order to solve the deficiency that prior art exists, a kind of modified ion-exchange resin catalyst is provided and has applied it to ammonium lactate and the catalytic esterification of alcohol, this catalyst utilizes the preparation of stannous chloride modified cation-exchange resin, with the esterification of this catalyst replacement sulfur acid catalysis ammonium lactate with alcohol, the equipment corrosion problem of not only esterification yield height, and catalyst-free.The present invention prepares modified ion-exchange resin catalyst according to following step: a, hydro-strong acidic cation exchange resin is dried to constant weight under 100 ℃ in vacuum drying chamber; B, with hydro-strong acidic cation exchange resin after the drying and stannous chloride at C
2～C
5Alcoholic solution in react, hydro-strong acidic cation exchange resin is by chemical modification; C, with the resin after the modification with absolute ethanol washing for several times after, it is dry to put into vacuum drying chamber, removes ethanol, promptly obtains modified ion-exchange resin catalyst, it can be used for the esterification of ammonium lactate and alcohol.
The present invention prepares catalyst with the stannous chloride modified cation-exchange resin, be used for catalysis ammonium lactate and pure esterification, obtained significant catalytic effect: adopt this catalyst system and catalyzing the ammonium lactate esterification efficient under the catalyst-free condition can be improved 12 percentage points (bringing up to 88% from 76%), and the equipment corrosion problem of catalyst-free, be separation and purification of lactic acid from the zymotic fluid that contains ammonium lactate, and the synthesizing lactic acid ester provides highly active catalyst.
The specific embodiment
The specific embodiment one: present embodiment is prepared as follows ammonium lactate esterification catalyst: a, hydro-strong acidic cation exchange resin is dried to constant weight under 100 ℃ in vacuum drying chamber; B, with dried hydro-strong acidic cation exchange resin and stannous chloride at C
2～C
5Alcoholic solution in react, hydro-strong acidic cation exchange resin is by chemical modification; C, with the resin after the modification with absolute ethanol washing for several times after, it is dry to put into vacuum drying chamber, removes ethanol, promptly obtains can be used for the modified ion-exchange resin catalyst of esterification of ammonium lactate.
The specific embodiment two: present embodiment is achieved in that
One, prepares catalyst with the stannous chloride modified cation-exchange resin: a: 15 gram Hydrogen polystyrene storng-acid cation exchange resins are dried to constant weight under 100 ℃ in vacuum drying chamber; B: with hydro-strong acidic cation exchange resin after the drying and 40 the gram anhydrous stannous chloride, 60 the gram butanol solutions in the reaction 5 hours, hydro-strong acidic cation exchange resin is by chemical modification.C: behind the usefulness of the resin after modification absolute ethanol washing 4 times, it is dry to put into vacuum drying chamber, removes ethanol, promptly obtains can be used for the modified ion-exchange resin catalyst of esterification of ammonium lactate.
Two, be that 1: 3 ammonium lactate and n-butanol are inserted in the reactor that has water knockout drum, agitator, thermometer and a condenser pipe with mass ratio, the modified resin catalyst that adds 1.5wt% (being equivalent to total reactant), reaction temperature rises to 132 ℃ gradually from 100 ℃, reaction time is 6.5 hours, and esterification yield is 88%.
The specific embodiment three: present embodiment is achieved in that
One, prepares catalyst with the stannous chloride modified cation-exchange resin: a, 15 gram Hydrogen polystyrene storng-acid cation exchange resins are dried to constant weight under 100 ℃ in vacuum drying chamber; B, with hydro-strong acidic cation exchange resin after the drying and 40 the gram anhydrous stannous chloride, 60 the gram butanol solutions in the reaction 5 hours, hydro-strong acidic cation exchange resin is by chemical modification; C, with the resin after the modification with behind the absolute ethanol washing 4 times, it is dry to put into vacuum drying chamber, removes ethanol, promptly obtains can be used for the modified ion-exchange resin catalyst of esterification of ammonium lactate.
Two, be that 1: 3 ammonium lactate and isobutanol are inserted in the reactor that has water knockout drum, agitator, thermometer and a condenser pipe with mass ratio, the modified resin catalyst that adds 1.5wt% (being equivalent to total reactant), reaction temperature rises to 127 ℃ gradually from 100 ℃, reaction time is 6.5 hours, and esterification yield is 75%.
The specific embodiment four: present embodiment is achieved in that
One, prepares catalyst with the stannous chloride modified cation-exchange resin: a, 15 gram Hydrogen polystyrene storng-acid cation exchange resins are dried to constant weight under 100 ℃ in vacuum drying chamber; B, with hydro-strong acidic cation exchange resin after the drying and 40 the gram anhydrous stannous chloride, 60 the gram butanol solutions in the reaction 5 hours, hydro-strong acidic cation exchange resin is by chemical modification; C, with the resin after the modification with behind the absolute ethanol washing 4 times, it is dry to put into vacuum drying chamber, removes ethanol, promptly obtains can be used for the modified ion-exchange resin catalyst of esterification of ammonium lactate.
Two, be that 1: 3 ammonium lactate and isobutanol are inserted in the reactor that has water knockout drum, agitator, thermometer and a condenser pipe with mass ratio, the modified resin catalyst that adds 1.0wt% (being equivalent to total reactant), reaction temperature rises to 132 ℃ gradually from 100 ℃, reaction time is 6.5 hours, and esterification yield is 83%.
The specific embodiment five: present embodiment is achieved in that
One, prepares catalyst with the stannous chloride modified cation-exchange resin: a, 15 gram Hydrogen polystyrene storng-acid cation exchange resins are dried to constant weight under 100 ℃ in vacuum drying chamber; B, with hydro-strong acidic cation exchange resin after the drying and 40 the gram anhydrous stannous chloride, 60 the gram butanol solutions in the reaction 5 hours, hydro-strong acidic cation exchange resin is by chemical modification; C, with the resin after the modification with behind the absolute ethanol washing 4 times, it is dry to put into vacuum drying chamber, removes ethanol, promptly obtains can be used for the modified ion-exchange resin catalyst of esterification of ammonium lactate.
Two, be that 1: 2 ammonium lactate and n-amyl alcohol are inserted in the reactor that has water knockout drum, agitator, thermometer and a condenser pipe with mass ratio, the modified resin catalyst that adds 1.5wt% (being equivalent to total reactant), reaction temperature rises to 132 ℃ gradually from 100 ℃, reaction time is 6.5 hours, and esterification yield is 83.2%.
Claims (6)
1, modified ion-exchange resin catalyst is characterized in that described modified ion-exchange resin catalyst obtains as follows: a, hydro-strong acidic cation exchange resin is dried to constant weight under 100 ℃ in vacuum drying chamber; B, with dried hydro-strong acidic cation exchange resin and stannous chloride at C
2～C
5Alcoholic solution in react; C, with the resin after the modification with absolute ethanol washing for several times after, it is dry to put into vacuum drying chamber.
2, modified ion-exchange resin catalyst according to claim 1 is characterized in that described hydro-strong acidic cation exchange resin is a Hydrogen polystyrene storng-acid cation exchange resin.
3, modified ion-exchange resin catalyst according to claim 1, it is 10: 1～1: 1 that the mass ratio that it is characterized in that stannous chloride and cationic ion-exchange resin in the described reaction system closes.
4, modified ion-exchange resin catalyst according to claim 1 is characterized in that the concentration of described stannous chloride in alcoholic solution is 10%～45%.
5, modified ion-exchange resin catalyst according to claim 1 is characterized in that 2～5 hours reaction time in alcoholic solution of described stannous chloride and cationic ion-exchange resin.
6, the described modified ion-exchange resin catalyst of claim 1 is as the ammonium lactate esterification Application of Catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610010289 CN1887424A (en) | 2006-07-14 | 2006-07-14 | Modified ion exchange resin catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610010289 CN1887424A (en) | 2006-07-14 | 2006-07-14 | Modified ion exchange resin catalyst and its application |
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| CN1887424A true CN1887424A (en) | 2007-01-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798260A (en) * | 2010-02-08 | 2010-08-11 | 浙江新化化工股份有限公司 | Method for applying catalyst to synthesize lyral by myrac aldehyde |
| CN101898965A (en) * | 2010-08-23 | 2010-12-01 | 孝感市易生新材料有限公司 | Two-step method for producing propyl lactate with high content and high optical purity |
| CN101906041A (en) * | 2010-08-23 | 2010-12-08 | 孝感市易生新材料有限公司 | Method for producing high-content and high optical purity amyl ester lactate by using two-step method |
| CN103992207A (en) * | 2014-05-09 | 2014-08-20 | 常州大学 | Method for preparing vicinal diol by catalytic oxidation of alkene in hydrogen peroxide/cationic resin system |
-
2006
- 2006-07-14 CN CN 200610010289 patent/CN1887424A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798260A (en) * | 2010-02-08 | 2010-08-11 | 浙江新化化工股份有限公司 | Method for applying catalyst to synthesize lyral by myrac aldehyde |
| CN101798260B (en) * | 2010-02-08 | 2012-09-05 | 浙江新化化工股份有限公司 | Method for applying catalyst to synthesize lyral by myrac aldehyde |
| CN101898965A (en) * | 2010-08-23 | 2010-12-01 | 孝感市易生新材料有限公司 | Two-step method for producing propyl lactate with high content and high optical purity |
| CN101906041A (en) * | 2010-08-23 | 2010-12-08 | 孝感市易生新材料有限公司 | Method for producing high-content and high optical purity amyl ester lactate by using two-step method |
| CN101898965B (en) * | 2010-08-23 | 2013-07-10 | 孝感市易生新材料有限公司 | Two-step method for producing propyl lactate with high content and high optical purity |
| CN101906041B (en) * | 2010-08-23 | 2013-07-10 | 孝感市易生新材料有限公司 | Method for producing high-content and high optical purity amyl ester lactate by using two-step method |
| CN103992207A (en) * | 2014-05-09 | 2014-08-20 | 常州大学 | Method for preparing vicinal diol by catalytic oxidation of alkene in hydrogen peroxide/cationic resin system |
| CN103992207B (en) * | 2014-05-09 | 2017-05-03 | 常州大学 | Method for preparing vicinal diol by catalytic oxidation of alkene in hydrogen peroxide/cationic resin system |
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