CN102059133A - Recovery method of catalyst for preparing epoxy fatty acid methyl ester (FAME) - Google Patents
Recovery method of catalyst for preparing epoxy fatty acid methyl ester (FAME) Download PDFInfo
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- CN102059133A CN102059133A CN 201010581445 CN201010581445A CN102059133A CN 102059133 A CN102059133 A CN 102059133A CN 201010581445 CN201010581445 CN 201010581445 CN 201010581445 A CN201010581445 A CN 201010581445A CN 102059133 A CN102059133 A CN 102059133A
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- acid methyl
- catalyst
- methyl ester
- aliphatic acid
- epoxy aliphatic
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Abstract
The invention provides a recovery method of a catalyst for preparing epoxy fatty acid methyl ester (FAME), and relates to a recovery method of a catalyst. The recovery method comprises the following steps: adding H2O2 to unsaturated FAME and the catalyst for preparing the epoxy FAME, and allowing the obtained mixture to react; and removing a water layer after the reaction to obtain a crude product of the epoxy FAME, washing the crude product of the epoxy FAME with water, filtering to obtain precipitate and filtrate, drying the precipitate to obtain the catalyst for preparing the epoxy FAME, and carrying out reduced pressure distillation on the filtrate to obtain the epoxy FAME. The recovery method has the advantages of high catalyst recovery rate under normal temperature and normal pressure in the presence of a solvent, simple process and greatly lowered production cost, and overcomes the defects of the existing industrial technology; and the recovered catalyst has high repeated utilization factor, and the obtained epoxy FAME has better quality.
Description
Technical field
The present invention relates to the recovery method of catalyst, particularly a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester.
Background technology
Along with the develop rapidly of plastics industry, also increasing to the demand of plasticizer.The common plasticizers phthalate has potential carcinogenic danger, and therefore, the plasticizer of development of new asepsis environment-protecting becomes the focus that people pay close attention to.Epoxy aliphatic acid methyl ester is a kind of novel non-toxic plasticizer of succeeding in developing recently, and its exploitation prospect is very extensive.
At present, industrial main employing peroxycarboxylic acid oxidizing process is produced epoxy aliphatic acid methyl ester, Chinese patent CN86104989A discloses a kind of method of synthesizing epoxy soybean oil, its course of reaction is consistent with the production epoxy aliphatic acid methyl ester, this method uses glacial acetic acid to be the carrier of oxygen, hydrogen peroxide is the oxygen species, generates peroxycarboxylic acid under the effect of the catalyst concentrated sulfuric acid, and direct then and unrighted acid methyl esters reaction generates epoxidized soybean oil.The method exists that reaction stability is poor, product color is dark, to shortcomings such as equipment corrosion and environmental pollution are serious.Chinese patent CN1996497A discloses a kind of method of producing epoxy aliphatic acid methyl ester, and this method is synthesized peroxycarboxylic acid with aluminum sulfate catalysis carboxylic acid and hydrogen peroxide, and direct then and unrighted acid methyl esters reaction generates epoxy aliphatic acid methyl ester.The major defect of this method is that a spot of ferrous ion is unfavorable for epoxidised carrying out in catalyst, makes reaction temperature be difficult to control, and course of reaction is safety inadequately.Though Chinese patent CN101235021A has introduced the method for preparing epoxidized soybean oil or epoxyfatty acid first (second) ester with heteropolyacid liquid phase catalysis, but its catalyst can't reclaim, but be dissolved in the product fully, this has greatly improved production cost, reduced the quality of product, can only be confined to the laboratory and use, not solve the problem that exists in the present industrial production technology process.
Summary of the invention
The object of the present invention is to provide a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester.
Described a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester may further comprise the steps:
1) with H
2O
2Join the unrighted acid methyl esters and the preparation epoxy aliphatic acid methyl ester catalyst in react;
2) reaction is removed water layer after finishing, and promptly gets the epoxy aliphatic acid methyl ester crude product, after the epoxy aliphatic acid methyl ester crude product is washed with water, filter sediment and filtrate, after the sediment oven dry, promptly get the catalyst for preparing epoxy aliphatic acid methyl ester, with the filtrate decompression distillation, promptly get epoxy aliphatic acid methyl ester.
In step 1), the mass ratio of the catalyst of described preparation epoxy aliphatic acid methyl ester and unrighted acid methyl esters can be 3: 100, described unrighted acid methyl esters and H
2O
2Mol ratio can be 1: 1, the catalyst of described preparation epoxy aliphatic acid methyl ester can be the phosphotungstic acid hexadecanyl trimethyl quaternary ammonium salt, and (molecular formula is for [(C
16H
33) N (CH
3)
3]
3PW
12O
40), the condition of described reaction can be: stir speed (S.S.) is 400rpm, and temperature is 40 ℃, and the time is 4h.
In step 2) in, the described time that washes with water can be 5～30min, and the described number of times that washes with water can be 1～10 time; The volume ratio of the consumption of described water and epoxy aliphatic acid methyl ester crude product can be 0.5～2; The temperature of described decompression distillation can be 80 ℃.
The present invention relates to the epoxidation reaction of unrighted acid methyl esters, the influence factor of the catalyst recovery of preparation epoxy aliphatic acid methyl ester mainly contains 2 points: the one, and the polarity of quaternary ammonium salt in the catalyst; The 2nd, the remaining quantity of hydrogen peroxide in the reaction system.Quaternary ammonium salt is got over oleophylic in the catalyst, and then catalyst is easy more is dissolved in the middle of the raw oil material, and mass transfer velocity is faster, react rapider, separate out but catalyst is also difficult more, the present invention is through experiment screening, choice reaction active with separate out all phosphotungstic acid hexadecanyl trimethyl quaternary ammonium salts preferably of degree.Catalyst is insoluble to reaction system before reaction, under the effect of hydrogen peroxide, catalyst becomes [(C
16H
33) N (CH
3)
3]
3{ PO
4[W (O)
2(O
2)]
4, be the epoxidation activity species, dissolve in the reaction system, when hydrogen peroxide exhausted along with the carrying out of double bond epoxidation reaction, catalyst returned to initial state again and separates out, so the remaining quantity of hydrogen peroxide in system directly affects the amount of separating out of catalyst.
The present invention reclaims the catalyst of preparation epoxy aliphatic acid methyl ester under the solvent-free condition of normal temperature and pressure, the catalyst recovery yield height, the catalyst recycling rate of waterused height that reclaims, the quality of the epoxy aliphatic acid methyl ester behind the recovery catalyst is better, in addition, technology of the present invention is simple, greatly reduces production cost, has overcome the shortcoming in the present industrial technology.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
Get the catalyst of 0.5g, 20ml unrighted acid methyl esters and 6ml 30%H
2O
2Join in the uncovered beaker, keep 40 ℃ of temperature, stir revolution 400rpm, reaction 4h stops reaction.Separate water layer, spend the epoxy aliphatic acid methyl ester that the deionised water reaction obtains, the consumption of deionized water and the volume ratio of epoxy aliphatic acid methyl ester are 1: 1, and washing 10min filters the catalyst of separating out, and removes water layer.Repeat operation more than 3 times, the catalyst detergent oven dry back weighing of separating out is obtained 0.45g, the rate of recovery reaches 90%, and 80 ℃ of following decompression distillation, the epoxide number that obtains refining epoxy aliphatic acid methyl ester is 3.7 with the epoxy aliphatic acid methyl ester crude product, and iodine number is 8.The catalyst that reclaims is pressed the reaction of ingredient proportion input, and reaction condition is the same, and reusing the epoxide number that records refining epoxy aliphatic acid methyl ester after 5 times is 3.5, and iodine number is 9, catalyst recovery 0.43g, and the rate of recovery reaches 86%.
Embodiment 2
Reaction condition is with embodiment 1, and reaction finishes the back and separates water layer, spends the epoxy aliphatic acid methyl ester that the deionised water reaction obtains, and the consumption of deionized water and the volume ratio of epoxy aliphatic acid methyl ester are 1: 1, and washing 20min filters the catalyst of separating out, and removes water layer.Repeat operation more than 3 times, the catalyst detergent oven dry back weighing of separating out is obtained 0.47g, the rate of recovery reaches 94%, and 80 ℃ of following decompression distillation, the epoxide number that obtains refining epoxy aliphatic acid methyl ester is 3.8 with the epoxy aliphatic acid methyl ester crude product, and iodine number is 6.The catalyst that reclaims is pressed the reaction of ingredient proportion input, and reaction condition is with embodiment 1, and reusing the epoxide number that records refining epoxy aliphatic acid methyl ester after 5 times is 3.6, and iodine number is 8, catalyst recovery 0.45g, and the rate of recovery reaches 90%.
Embodiment 3
Reaction condition is with embodiment 1, and reaction finishes the back and separates water layer, spends the epoxy aliphatic acid methyl ester that the deionised water reaction obtains, and the consumption of deionized water and the volume ratio of epoxy aliphatic acid methyl ester are 1: 1, and washing 10min filters the catalyst of separating out, and removes water layer.Repeat operation more than 5 times, the catalyst detergent oven dry back weighing of separating out is obtained 0.47g, the rate of recovery reaches 94%, and 80 ℃ of following decompression distillation, the epoxide number that obtains refining epoxy aliphatic acid methyl ester is 3.8 with the epoxy aliphatic acid methyl ester crude product, and iodine number is 7.The catalyst that reclaims is pressed the reaction of ingredient proportion input, and reaction condition is with embodiment 1, and reusing the epoxide number that records refining epoxy aliphatic acid methyl ester after 5 times is 3.6, and iodine number is 9, catalyst recovery 0.44g, and the rate of recovery reaches 88%.
Embodiment 4
Reaction condition is with embodiment 1, and reaction finishes the back and separates water layer, spends the epoxy aliphatic acid methyl ester that the deionised water reaction obtains, and the consumption of deionized water and the volume ratio of epoxy aliphatic acid methyl ester are 1: 1, and washing 20min filters the catalyst of separating out, and removes water layer.Repeat operation more than 5 times, the catalyst detergent oven dry back weighing of separating out is obtained 0.49g, the rate of recovery reaches 98%, and 80 ℃ of following decompression distillation, the epoxide number that obtains refining epoxy aliphatic acid methyl ester is 3.8 with the epoxy aliphatic acid methyl ester crude product, and iodine number is 6.The catalyst that reclaims is pressed the reaction of ingredient proportion input, and reaction condition is with embodiment 1, and reusing the epoxide number that records refining epoxy aliphatic acid methyl ester after 5 times is 3.6, and iodine number is 8, catalyst recovery 0.47g, and the rate of recovery reaches 94%.
Embodiment 5
Reaction condition is with embodiment 1, and reaction finishes the back and separates water layer, spends the epoxy aliphatic acid methyl ester that the deionised water reaction obtains, and the consumption of deionized water and the volume ratio of epoxy aliphatic acid methyl ester are 2: 1, and washing 10min filters the catalyst of separating out, and removes water layer.Repeat operation more than 3 times, the catalyst detergent oven dry back weighing of separating out is obtained 0.47g, the rate of recovery reaches 94%, and 80 ℃ of following decompression distillation, the epoxide number that obtains refining epoxy aliphatic acid methyl ester is 3.8 with the epoxy aliphatic acid methyl ester crude product, and iodine number is 6.The catalyst that reclaims is pressed the reaction of ingredient proportion input, and reaction condition is with embodiment 1, and reusing the epoxide number that records refining epoxy aliphatic acid methyl ester after 5 times is 3.7, and iodine number is 8, catalyst recovery 0.44g, and the rate of recovery reaches 88%.
Embodiment 6
Reaction condition is with embodiment 1, and reaction finishes the back and separates water layer, spends the epoxy aliphatic acid methyl ester that the deionised water reaction obtains, and the consumption of deionized water and the volume ratio of epoxy aliphatic acid methyl ester are 2: 1, and washing 10min filters the catalyst of separating out, and removes water layer.Repeat operation more than 5 times, the catalyst detergent oven dry back weighing of separating out is obtained 0.49g, the rate of recovery reaches 98%, and 80 ℃ of following decompression distillation, the epoxide number that obtains refining epoxy aliphatic acid methyl ester is 3.9 with the epoxy aliphatic acid methyl ester crude product, and iodine number is 6.The catalyst that reclaims is pressed the reaction of ingredient proportion input, and reaction condition is with embodiment 1, and reusing the epoxide number that records refining epoxy aliphatic acid methyl ester after 5 times is 3.6, and iodine number is 8, catalyst recovery 0.46g, and the rate of recovery reaches 92%.
Claims (8)
1. recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester is characterized in that may further comprise the steps:
1) with H
2O
2Join the unrighted acid methyl esters and the preparation epoxy aliphatic acid methyl ester catalyst in react;
2) reaction is removed water layer after finishing, and promptly gets the epoxy aliphatic acid methyl ester crude product, after the epoxy aliphatic acid methyl ester crude product is washed with water, filter sediment and filtrate, after the sediment oven dry, promptly get the catalyst for preparing epoxy aliphatic acid methyl ester, with the filtrate decompression distillation, promptly get epoxy aliphatic acid methyl ester.
2. a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester as claimed in claim 1 is characterized in that in step 1) the mass ratio of the catalyst of described preparation epoxy aliphatic acid methyl ester and unrighted acid methyl esters is 3: 100.
3. a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester as claimed in claim 1 is characterized in that in step 1), described unrighted acid methyl esters and H
2O
2Mol ratio be 1: 1.
4. a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester as claimed in claim 1 is characterized in that in step 1) the catalyst of described preparation epoxy aliphatic acid methyl ester is the phosphotungstic acid hexadecanyl trimethyl quaternary ammonium salt.
5. a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester as claimed in claim 1 is characterized in that in step 1) the condition of described reaction is: stir speed (S.S.) is 400rpm, and temperature is 40 ℃, and the time is 4h.
6. a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester as claimed in claim 1 is characterized in that in step 2) in, the described time that washes with water is 5～30min, the described number of times that washes with water is 1～10 time.
7. a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester as claimed in claim 1 is characterized in that in step 2) in, the volume ratio of the amount of described water and described epoxy aliphatic acid methyl ester crude product is 0.5～2.
8. a kind of recovery method for preparing the catalyst of epoxy aliphatic acid methyl ester as claimed in claim 1 is characterized in that in step 2) in, the temperature of described decompression distillation is 80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105814455A CN102059133B (en) | 2010-12-10 | 2010-12-10 | Recovery method of catalyst for preparing epoxy fatty acid methyl ester (FAME) |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105814455A CN102059133B (en) | 2010-12-10 | 2010-12-10 | Recovery method of catalyst for preparing epoxy fatty acid methyl ester (FAME) |
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|---|---|
| CN102059133A true CN102059133A (en) | 2011-05-18 |
| CN102059133B CN102059133B (en) | 2012-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993616A (en) * | 2018-07-20 | 2018-12-14 | 江苏扬农化工集团有限公司 | A kind of regeneration method of phosphorus molybdenum/heteropoly tungstic acid quaternary ammonium salt catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1575203A (en) * | 2001-11-02 | 2005-02-02 | 加利福尼亚技术学院 | Polyoxometallate catalysts and method for the production of carboxylic acids by catalysed partial oxidation of alkanes |
| CN1781598A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for preparing resin assembled heteropoly acid salt catalyst |
| US20070021630A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
| WO2008032459A1 (en) * | 2006-09-13 | 2008-03-20 | Japan Science And Technology Agency | Acid catalyst having organic group bound thereto |
-
2010
- 2010-12-10 CN CN2010105814455A patent/CN102059133B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1575203A (en) * | 2001-11-02 | 2005-02-02 | 加利福尼亚技术学院 | Polyoxometallate catalysts and method for the production of carboxylic acids by catalysed partial oxidation of alkanes |
| CN1781598A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for preparing resin assembled heteropoly acid salt catalyst |
| US20070021630A1 (en) * | 2005-07-25 | 2007-01-25 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
| WO2008032459A1 (en) * | 2006-09-13 | 2008-03-20 | Japan Science And Technology Agency | Acid catalyst having organic group bound thereto |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993616A (en) * | 2018-07-20 | 2018-12-14 | 江苏扬农化工集团有限公司 | A kind of regeneration method of phosphorus molybdenum/heteropoly tungstic acid quaternary ammonium salt catalyst |
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|---|---|
| CN102059133B (en) | 2012-07-04 |
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