CN1451476A - Catalyst for ethoxylation and use thereof - Google Patents
Catalyst for ethoxylation and use thereof Download PDFInfo
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- CN1451476A CN1451476A CN 03108570 CN03108570A CN1451476A CN 1451476 A CN1451476 A CN 1451476A CN 03108570 CN03108570 CN 03108570 CN 03108570 A CN03108570 A CN 03108570A CN 1451476 A CN1451476 A CN 1451476A
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Abstract
A catalyst for the ethoxylation of feedstock without reactive hydrogen in its terminal group with epoxy ethane contains the oxide of alkali-earth metal (30-90 wt.%), the ions of group III metal (1-40 wt.%), and carrier (1-30 wt.%). Its advantages are less consumption of catalyst, high reaction speed, high conversion of methylester, and high yield of product.
Description
Affiliated field:
The invention belongs to a kind of catalyst and application thereof that end group does not have the ethoxylation synthetic reaction of active hydrogen raw material that be used for.
Background technology:
Generally speaking, by the non-ionic surface active agent of oxirane derivative, end group all contains an active or unsettled hydrogen atom in its hydrophobic raw material, and this hydrogen atom and hetero atom such as O or N link to each other, at base catalyst such as NaOH, KOH or NaOCH
3Deng effect down, this active hydrogen is easy to be removed with alkali and forms an active anion, and the latter is very fast subsequently to generate ethoxylate with oxirane (EO) reaction.And do not contain active raw material such as fatty acid methyl ester for end group, and under above-mentioned base catalyst effect, methyl ester conversion rate is very low, generally equal＜50%, and the product oxyethylene group distributes wide.
Nineteen ninety, Vista chemical company (existing CONDEA Vista company) has developed commercial with composite catalyst (active alkoxide calcium Al catalysts), end group be can effectively finish and the raw material of active hydrogen such as the ethoxylation of fatty acid methyl ester do not contained, the methyl ester conversion rate height, unreacted methyl esters＜1%, Lion company announces that magnesium oxide-based catalyst can reach this effect equally in the near future.
Henkel company also announces to adopt the ethoxylation of calcination hydrotalcite ester under co-catalyst such as ethylene glycol, aliphatic acid, base catalyst effect can reach gratifying reactivity and conversion ratio.
The polyethylene glycol of cocounut oil FMEE (average ethylene oxide base content the is 8) product that the active alkoxide calcium aluminium composite catalyst catalysis of Vista company is synthetic is 2.6%, the unreacted methyl esters is 0.77%, catalyst amount is the 1.0wt% of end-product, average response is fastest only to be 1.21gEO/gcatmin, and reaction temperature is 175 ℃.
The unreacted methyl esters of methyl laurate ethoxylate (average ethylene oxide base content the is 6) product that the metal oxide catalyst of Lion company is synthetic is 2.5%, average response speed 0.92gEO/gcatmin, catalyst amount is the 1.0wt% of end-product, and reaction temperature is 180 ℃.
Though the catalyst of this two company can effectively be finished the ethoxylation that end group does not contain the active hydrogen raw material, catalyst amount is bigger, must filter removal from product, and reaction speed is slower, and average addition speed is about 1gEO/g catmin.
Summary of the invention
It is fast to the objective of the invention is to invent a kind of reaction speed, catalyst that is used for ethoxylation and application thereof that consumption is little.
Catalyst component of the present invention includes alkaline earth oxide, III family metal ion, carrier, and its percentage by weight consists of:
Alkaline earth oxide 30～90%
III family metal oxide 1～40%
Carrier 1～30%
Also include ZnO in the aforesaid catalyst component, it consists of 0.01～1.0% of III family metal ion weight.
The particle diameter of aforesaid catalyst preferably is not more than 0.8mm.
Preparation of catalysts method one of the present invention:
Form by catalyst weight percentage, alkaline earth oxide particle and carrier are mixed to join in the aqueous solution of a kind of III of containing family metal ion, washing is then dryly also sieved after calcination becomes catalyst granules.
Preparation of catalysts method two of the present invention:
Form by catalyst weight percentage, one aqueous solution that contains III family metal ion is mixed with carrier, join in a kind of dispersion liquid of alkaline including earth metal oxide particle, make that the hydroxide of III family metal ion is precipitated to come out and be deposited on carrier surface, with deposit filter, dry, calcination sieves after becoming catalyst granules.
Preparation of catalysts method three of the present invention:
Form by catalyst weight percentage, alkaline earth oxide particle and carrier are mixed to join a kind of III of containing family's metal ion and Zn
2+The aqueous solution in, washing is then sieved after dry and calcination becomes catalyst granules.
Aforesaid alkaline earth oxide is MgO, CaO, SrO or BaO.
Aforesaid III family metal oxide is Al
2O
3, Ga
2O
3Or In
2O
3
Aforesaid carrier is diatomite or 4A zeolite.
Catalyst of the present invention is used for end group does not have the raw material of active hydrogen and the ethoxylation synthetic reaction that oxirane carries out, catalyst amount is generally 0.1～0.8% of end-product, be preferably 0.2～0.3%, operating temperature is 120～200 ℃, be preferably 140～175 ℃, operating pressure is 0.01～20Mpa, is preferably 0.3～0.5Mpa.
The raw material that aforesaid end group does not have active hydrogen is a fatty acid ester.
Aforesaid fatty acid ester has fatty acid methyl ester, fatty-acid ethyl ester, isopropyl fatty acid ester, fatty acid butyl ester, fatty acid isooctyl etc.
Aforesaid fatty acid methyl ester has cocounut oil methyl esters, methyl laurate, palm oil methyl esters, cotton oil acid methyl esters, butter methyl esters, methyl stearate etc.
Aforesaid fatty-acid ethyl ester has cocounut oil ethyl ester, ethyl laurate etc.
Aforesaid isopropyl fatty acid ester has isopropyl myristate, isopropyl palmitate, isopropyl stearate etc.
Aforesaid fatty acid butyl ester has tetradecylic acid butyl ester, hexadecylic acid butyl ester, butyl stearate etc.
Aforesaid fatty acid isooctyl has isooctyl palmitate, the different monooctyl ester of stearic acid etc.
The present invention compared with prior art has following advantage:
Catalyst is used for end group, and not have the ethoxylation synthetic reaction consumption that active hydrogen raw material and oxirane carries out few, only is 0.1～0.8wt% of end-product; Reaction speed is fast, and average addition speed can reach 8～16gEO/g catmin; The methyl ester conversion rate height; The product yield height; It is synthetic to belong to one-step method, and synthetic route is brief; Course of reaction can be finished on existing any ethoxylation device.
The specific embodiment:
Embodiment 1
MgO 68.4g and diatomite 28g are mixed, and adding contains among the aqueous solution 400ml of aluminium chloride 23g, stirs 1hr, and washing, drying at 500 ℃ of following calcination 1hr, are ground, and sieve, and get a Mg-Al composite catalyst.This catalyst fines contains magnesia 65%, aluminium oxide 8.4%, diatomite 26.6%.
Above-mentioned catalyst 1.0g is joined in the 154g cocounut oil methyl esters, drop in the 1L autoclave N while stirring
2Replace three times, be warming up to 130 ℃, import oxirane (EO), keep 170 ℃ of reaction temperatures, 0.3MPa, reacting about 26min to EO addition is 277g, aging 10min is cooled to 70 ℃, emits material, the 431g that weighs obtains average ethylene oxide base content and is 9.0 product---cocounut oil FMEE.
Embodiment 2
With being dissolved with the aqueous solution 300ml of aluminum nitrate 85g and diatomite 27g, being added dropwise among the dispersion liquid 150ml that contains 58g CaO, stir 1hr under the room temperature, get a mixed catalyst slip, this slip is removed NO through strong-base anion-exchange resin
- 3, after ion-exchange is finished, catalyst is separated from ion exchange resin, drying, at 500 ℃ of following calcination 1hr, grinding sieves makes a Ca-Al composite catalyst.This catalyst fines contains calcium oxide 60%, aluminium oxide 12%, diatomite 28%.
With above-mentioned catalyst 1.8g, add the 182g methyl laurate, drop into the 1L autoclave while stirring, N
2Replace three times, be heated to 140 ℃, import EO, keep 175 ℃ of reaction temperatures simultaneously, 0.4MPa, reacting about 18min to EO addition is 300g, aging 10min is cooled to 70 ℃, emits material, the 483g that weighs obtains average ethylene oxide base content and is 8.0 product---lauryl FMEE.
Embodiment 3
20g MgO powder is mixed with 9g 4A zeolite, adds and to contain among the aqueous solution 500ml of 1.9% gallium nitrate, the powerful 1hr that stirs, at 110 ℃ of dry 2hr down, 500 ℃ of following calcination 1hr grind, sieve, a MgO composite catalyst that contains gallium ion.This catalyst fines contains magnesia 61.6%, gallium oxide 10.7%, 4A zeolite 27.7%.
Above-mentioned catalyst 3.5g is joined in the 220g cocounut oil methyl esters, drop in the 1L autoclave N while stirring
2Replace three times, be warming up to 130 ℃, import oxirane (EO), keep 165 ℃ of reaction temperatures, 0.3MPa, reacting about 13min to EO addition is 352g, aging 10min is cooled to 70 ℃, emits material, the 574.5g that weighs obtains average ethylene oxide base content and is 8.0 product---cocounut oil FMEE.
Embodiment 4
MgO 68.4g and diatomite 28g are mixed, and adding contains among the aqueous solution 400ml of aluminium chloride 23g and zinc chloride 0.9g, stirs 1hr, and washing, drying at 500 ℃ of following calcination 1hr, are ground, and sieve, and get a Mg-Al-Zn composite catalyst.This catalyst fines contains magnesia 64.7%, aluminium oxide 8.3%, diatomite 26.5%, zinc chloride 0.5%.
With above-mentioned catalyst 1.5g, add the 182g methyl laurate, drop into 11 autoclaves while stirring, N
2Replace three times, be heated to 120 ℃, import EO, keep 160 ℃ of reaction temperatures simultaneously, 0.3MPa, reacting about 12min to EO addition is 300g, aging 10min is cooled to 70 ℃, emits material, the 483g that weighs obtains average ethylene oxide base content and is 8.0 product---lauryl FMEE.
Embodiment 5
1 catalyst 1.8g joins in the 178.8g palm oil methyl esters with the foregoing description, drops in the 1L autoclave N while stirring
2Replace three times, be warming up to 150 ℃, import oxirane (EO), keep 180 ℃ of reaction temperatures, 0.5MPa, reacting about 15min to EO addition is 343g, aging 10min is cooled to 70 ℃, emits material, the 524g that weighs obtains average ethylene oxide base content and is 13.0 product---palm oil FMEE.
Embodiment 6
2 catalyst 1.6g join in the 192g cotton oil acid methyl esters with the foregoing description, drop in the 1L autoclave N while stirring
2Replace three times, be warming up to 150 ℃, import oxirane (EO), keep 185 ℃ of reaction temperatures, 0.6MPa, reacting about 20min to EO addition is 316g, aging 10min is cooled to 70 ℃, emits material, the 509g that weighs obtains average ethylene oxide base content and is 12.0 product---cotton oil acid FMEE.
Embodiment 7
3 catalyst 1.5g join in the 180.8g cocounut oil ethyl ester with the foregoing description, drop in the 1L autoclave N while stirring
2Replace three times, be warming up to 150 ℃, import oxirane (EO), keep 180 ℃ of reaction temperatures, 0.5MPa, reacting about 30min to EO addition is 387g, aging 10min is cooled to 70 ℃, emits material, the 568g that weighs obtains average ethylene oxide base content and is 11.0 product---cocounut oil ethyl ester ethoxylate.
Embodiment 8
4 catalyst 2.6g join in the 179.4g isopropyl palmitate with the foregoing description, drop in the 1L autoclave N while stirring
2Replace three times, be warming up to 150 ℃, import oxirane (EO), keep 175 ℃ of reaction temperatures, 0.4MPa, reacting about 20min to EO addition is 396g, aging 10min is cooled to 70 ℃, emits material, the 576g that weighs obtains average ethylene oxide base content and is 15.0 product---isopropyl palmitate ethoxylate.
Embodiment 9
1 catalyst 2.0g joins in the different monooctyl ester of 181.4g stearic acid with the foregoing description, drops in the 1L autoclave N while stirring
2Replace three times, be warming up to 150 ℃, import oxirane (EO), keep 190 ℃ of reaction temperatures, 0.6MPa, reacting about 22min to EO addition is 316g, aging 10min is cooled to 70 ℃, emits material, the 443g that weighs obtains average ethylene oxide base content and is 16.0 product---the different monooctyl ester ethoxylate of stearic acid.
Claims (15)
1. a catalyst that is used for ethoxylation is characterized in that catalyst component includes alkaline earth oxide, III family metal ion, carrier, and its percentage by weight consists of:
Alkaline earth oxide 30～90%
III family metal oxide 1～40%
Carrier 1～30%
2. a kind of catalyst that is used for ethoxylation as claimed in claim 1 is characterized in that also including ZnO in the described catalyst agent component, and it consists of 0.01～1.0% of III family metal ion weight.
3. a kind of catalyst that is used for ethoxylation as claimed in claim 1 or 2 is characterized in that described catalyst particle size is not more than 0.8mm.
4. a kind of catalyst that is used for ethoxylation as claimed in claim 1 is characterized in that described alkaline earth oxide is MgO, CaO, SrO or BaO.
5. a kind of catalyst that is used for ethoxylation as claimed in claim 1 is characterized in that described III family metal oxide is Al
2O
3, Ga
2O
3Or In
2O
3
6. a kind of catalyst that is used for ethoxylation as claimed in claim 1 is characterized in that described carrier is diatomite or 4A zeolite.
7. as each described a kind of Application of Catalyst method that is used for ethoxylation of claim 1～6, it is characterized in that comprising the steps: that described catalyst is used for end group and does not have the raw material of active hydrogen and the ethoxylation synthetic reaction that oxirane carries out, catalyst amount is 0.1～0.8Wt% of end-product, operating temperature is 120～200 ℃, and operating pressure is 0.01～20Mpa.
8. a kind of Application of Catalyst method that is used for ethoxylation as claimed in claim 7 is characterized in that described catalyst amount is that end-product is 0.2～0.3Wt%, and operating pressure is 0.3～0.5Mpa, and operating temperature is 140～175 ℃.
9. as claim 7 or 8 described a kind of Application of Catalyst methods that are used for ethoxylation, it is characterized in that the raw material that described end group does not have an active hydrogen is a fatty acid ester.
10. a kind of Application of Catalyst method that is used for ethoxylation as claimed in claim 9 is characterized in that described fatty acid ester has fatty acid methyl ester, fatty-acid ethyl ester, isopropyl fatty acid ester, fatty acid butyl ester or fatty acid isooctyl.
11. a kind of Application of Catalyst method that is used for ethoxylation as claimed in claim 10 is characterized in that described fatty acid methyl ester has cocounut oil methyl esters, methyl laurate, palm oil methyl esters, cotton oil acid methyl esters or butter methyl esters.
12. a kind of Application of Catalyst method that is used for ethoxylation as claimed in claim 10 is characterized in that aforesaid fatty-acid ethyl ester has cocounut oil ethyl ester or ethyl laurate.
13. a kind of Application of Catalyst method that is used for ethoxylation as claimed in claim 10 is characterized in that aforesaid isopropyl fatty acid ester has isopropyl myristate, isopropyl palmitate or isopropyl stearate.
14. a kind of Application of Catalyst method that is used for ethoxylation as claimed in claim 10 is characterized in that aforesaid fatty acid butyl ester has tetradecylic acid butyl ester, hexadecylic acid butyl ester or butyl stearate.
15. a kind of Application of Catalyst method that is used for ethoxylation as claimed in claim 10 is characterized in that aforesaid fatty acid isooctyl has isooctyl palmitate or the different monooctyl ester of stearic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03108570 CN1190265C (en) | 2003-03-28 | 2003-03-28 | Catalyst for ethoxylation and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03108570 CN1190265C (en) | 2003-03-28 | 2003-03-28 | Catalyst for ethoxylation and use thereof |
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|---|---|
| CN1451476A true CN1451476A (en) | 2003-10-29 |
| CN1190265C CN1190265C (en) | 2005-02-23 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357248C (en) * | 2004-12-17 | 2007-12-26 | 辽宁奥克化学集团有限公司 | Fatty acid ester alkoxylating method and dedicated equipment therefor |
| CN100391597C (en) * | 2004-12-17 | 2008-06-04 | 辽宁奥克化学集团有限公司 | Fatty acid ester alkoxylating catalyst and its preparation method |
| CN102503841A (en) * | 2011-10-08 | 2012-06-20 | 中国日用化学工业研究院 | Ethoxylate ester quaternary ammonium salt and its preparation method |
| CN103724611A (en) * | 2013-10-10 | 2014-04-16 | 桐乡市恒隆化工有限公司 | Preparation and usage method of fatty alcohol ethoxylation reaction catalyst |
| CN105268482A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Preparation method of fatty acid methyl ester oxyalkylation catalyst |
| CN105268481A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN105498842A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst and application thereof |
| CN106390977A (en) * | 2016-08-29 | 2017-02-15 | 上海多纶化工有限公司 | Soybean phospholipid ethoxylation catalyst, and synthesis method of soybean phospholipid ethoxylate |
| CN107159177A (en) * | 2017-06-05 | 2017-09-15 | 浙江皇马科技股份有限公司 | A kind of preparation of alkaline composite oxide catalysts and its application process |
| CN107282135A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN107790189A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | Catalyst for fatty acid methyl ester ethoxylation |
| CN109627431A (en) * | 2018-12-06 | 2019-04-16 | 上海多纶化工有限公司 | The production method of fatty acid methyl ester APEO |
| CN115814800A (en) * | 2022-12-09 | 2023-03-21 | 万华化学集团股份有限公司 | Preparation method and application of fatty acid methyl ester ethoxylation catalyst |
-
2003
- 2003-03-28 CN CN 03108570 patent/CN1190265C/en not_active Expired - Lifetime
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391597C (en) * | 2004-12-17 | 2008-06-04 | 辽宁奥克化学集团有限公司 | Fatty acid ester alkoxylating catalyst and its preparation method |
| CN100357248C (en) * | 2004-12-17 | 2007-12-26 | 辽宁奥克化学集团有限公司 | Fatty acid ester alkoxylating method and dedicated equipment therefor |
| CN102503841A (en) * | 2011-10-08 | 2012-06-20 | 中国日用化学工业研究院 | Ethoxylate ester quaternary ammonium salt and its preparation method |
| CN103724611A (en) * | 2013-10-10 | 2014-04-16 | 桐乡市恒隆化工有限公司 | Preparation and usage method of fatty alcohol ethoxylation reaction catalyst |
| CN103724611B (en) * | 2013-10-10 | 2015-12-02 | 桐乡市恒隆化工有限公司 | The method of preparation and use of fatty alcohol ethoxylate catalysts |
| CN105268481B (en) * | 2014-07-24 | 2018-02-13 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN105268482A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Preparation method of fatty acid methyl ester oxyalkylation catalyst |
| CN105268481A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN105268482B (en) * | 2014-07-24 | 2018-02-13 | 中国石油化工股份有限公司 | The preparation method of fatty acid methyl ester alkoxylating catalyst |
| CN105498842A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst and application thereof |
| CN105498842B (en) * | 2014-09-25 | 2018-06-08 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst and its application |
| CN107282135A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN107282135B (en) * | 2016-04-12 | 2020-01-03 | 中国石油化工股份有限公司 | Fatty acid methyl ester ethoxylation catalyst |
| CN107790189A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | Catalyst for fatty acid methyl ester ethoxylation |
| CN106390977A (en) * | 2016-08-29 | 2017-02-15 | 上海多纶化工有限公司 | Soybean phospholipid ethoxylation catalyst, and synthesis method of soybean phospholipid ethoxylate |
| CN106390977B (en) * | 2016-08-29 | 2018-10-19 | 上海多纶化工有限公司 | The synthetic method of soybean lecithin ethoxylation catalyst and soybean lecithin ethoxylate |
| CN107790189B (en) * | 2016-08-29 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for fatty acid methyl ester ethoxylation |
| CN107159177A (en) * | 2017-06-05 | 2017-09-15 | 浙江皇马科技股份有限公司 | A kind of preparation of alkaline composite oxide catalysts and its application process |
| CN107159177B (en) * | 2017-06-05 | 2020-01-10 | 浙江皇马新材料科技有限公司 | Preparation and application method of alkaline composite oxide catalyst |
| CN109627431A (en) * | 2018-12-06 | 2019-04-16 | 上海多纶化工有限公司 | The production method of fatty acid methyl ester APEO |
| CN115814800A (en) * | 2022-12-09 | 2023-03-21 | 万华化学集团股份有限公司 | Preparation method and application of fatty acid methyl ester ethoxylation catalyst |
| CN115814800B (en) * | 2022-12-09 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method and application of fatty acid methyl ester ethoxylation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1190265C (en) | 2005-02-23 |
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Application publication date: 20031029 Assignee: SINOLIGHT SURFACTANTS TECHNOLOGY CO.,LTD. Assignor: China Research Institute of Daily Chemical Industry Contract record no.: 2013310000091 Denomination of invention: Catalyst for ethoxylation and use thereof Granted publication date: 20050223 License type: Exclusive License Record date: 20130807 |
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