CN103173291A - Method for preparing cottonseed oil carbonic ester lubricating base oil by using carbon dioxide - Google Patents
Method for preparing cottonseed oil carbonic ester lubricating base oil by using carbon dioxide Download PDFInfo
- Publication number
- CN103173291A CN103173291A CN2013101187735A CN201310118773A CN103173291A CN 103173291 A CN103173291 A CN 103173291A CN 2013101187735 A CN2013101187735 A CN 2013101187735A CN 201310118773 A CN201310118773 A CN 201310118773A CN 103173291 A CN103173291 A CN 103173291A
- Authority
- CN
- China
- Prior art keywords
- oil
- cottonseed oil
- gas
- epoxy
- lubricating base
- 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
Landscapes
- Lubricants (AREA)
Abstract
The invention relates to a method for preparing cottonseed oil carbonic ester lubricating base oil by using carbon dioxide. The method comprises the steps of: by adopting quaternary ammonium salt as a catalyst at a solvent-free condition, preparing cottonseed oil carbonic ester lubricating base oil by addition reaction of epoxy cottonseed oil and CO2; adding the epoxy cottonseed oil and the quaternary ammonium salt into a high-pressure kettle with a magnetic stirrer; sealing the high-pressure kettle and then vaccumizing to remove dissolved oxygen in the epoxy cottonseed oil, then putting the high-pressure kettle in an oil bath pan with the magnetic stirrer; stirring and heating; inhaling CO2 gas to continue the reaction after heating to the reaction temperature; fully cooling the high-pressure kettle by using the oil bath after the reaction is ended; slowly exhausting CO2 gas; opening the kettle; adding an organic solvent to dissolve cottonseed oil carbonic ester; pouring the mixed solvent to a separating funnel; washing with warm water so as to remove the catalyst; and pumping the solvent to obtain the final product cottonseed oil carbonic ester lubricating base oil, and then treating the final product with a lubricating oil property test by a conventional method.
Description
Technical field
The present invention relates to a kind of method that carbonic acid gas prepares Oleum Gossypii semen carbonic ether lubricating base oil, the method under condition of no solvent take quaternary ammonium salt as catalyzer, epoxy cottonseed oil and CO
2Addition prepares Oleum Gossypii semen carbonic ether lubricating base oil.
Background technology
The mineral based lubricating oil has occupied the very large portion of Lube Oil Market because of its ripe technique and cheap price, but the environmental pollution that causes due to leak, overflow and infiltration etc. in its production, use and discharge process is more and more serious, and the bio-based lubricating oil with biological degradability is renewable because of it, environmentally friendly, meet the Sustainable development requirement and get more and more people's extensive concerning.
Five-membered cyclic carbonate ester is the very important chemical products of a class and chemical intermediate.The same with the synthetic method of other chemical, the synthetic technology of five-membered ring carbonate ester has experienced by falling behind the advanced process that progressively becomes.The preparation of industrialization five-membered ring carbonate ester is to adopt phosgenation the earliest, except the raw material phosgene has severe toxicity, and by-product hydrochloric acid etching apparatus, the use that has been under an embargo of this method.Also can prepare five-membered ring carbonate ester by ester-interchange method, but be subjected to the restriction of economical in reaction and catalytic erosion, ester-interchange method also is eliminated gradually.CO
2Also can prepare five-membered ring carbonate ester with glycol reaction, but the water that generates is difficult for removing, carries out to the positive reaction direction thereby suppressed reaction, restricted the yield of product.Present industrial preparation five-membered ring carbonate ester mainly adopts epoxy compounds and CO
2The direct addition method, this method no coupling product generates, if in reaction process not with an organic solvent, be the atom economy type reaction that meets the Green Chemistry standard.
Epoxy compounds and CO
2The standby corresponding cyclic carbonate of direct addition legal system be applied to bio-based lubricating oil field, under condition of no solvent, with bio-based Epoxy oil and CO
2Reaction preparation bio-based carbonic ether, the physico-chemical property of research bio-based carbonic ether, investigating its application prospect in the lubricating base oil field will be a very significant technology and research.
Summary of the invention
The purpose of this invention is to provide a kind of method that carbonic acid gas prepares Oleum Gossypii semen carbonic ether lubricating base oil, the method is take quaternary ammonium salt as catalyzer, with epoxy cottonseed oil and CO under condition of no solvent
2Addition prepares Oleum Gossypii semen carbonic ether lubricating base oil, epoxy cottonseed oil and catalyzer quaternary ammonium salt are added in autoclave with magnetic stirring, vacuumize the dissolved oxygen of removing in epoxy cottonseed oil after the enclosed high pressure still, then autoclave is put into the oil bath pan with magnetic agitation, stir, heating after reaching temperature of reaction, is poured CO
2Gas continues reaction, after question response finishes, fully cooling with ice bath after, slowly discharge CO
2Gas is driven still, adds organic solvent dissolution Oleum Gossypii semen carbonic ether, pour separating funnel into, wash to remove catalyzer with warm water, obtain end product Oleum Gossypii semen carbonic ether lubricating base oil after extracting solvent, then with ordinary method, final product is lubricated the oil nature test.
A kind of carbonic acid gas of the present invention prepares the method for Oleum Gossypii semen carbonic ether lubricating base oil, follows these steps to carry out:
A, be that Tetrabutyl amonium bromide, cetyl trimethylammonium bromide or four octyl group brometo de amonios add in autoclave with magnetic stirring with epoxy cottonseed oil and catalyzer quaternary ammonium salt, vacuumize 30 minutes after the enclosed high pressure still to remove the dissolved oxygen in epoxy cottonseed oil;
B, autoclave is put into oil bath pan with magnetic agitation, stir and be heated to temperature 100-160 ℃, after reaching temperature of reaction, pour CO
2Gas 1-10MPa replenishes CO again after pressure decreased
2Gas, reaction times 2-24 hour;
After c, question response finish, fully cooling with ice bath after, slowly discharge CO
2Gas, drive still, adding organic solvent is ethyl acetate or petroleum ether dissolution Oleum Gossypii semen carbonic ether, will add the still material after solvent to pour separating funnel into, to remove catalyzer, obtain end product Oleum Gossypii semen carbonic ether lubricating base oil after extracting solvent with warm water washing 3-6 time.
The mol ratio of the epoxy group(ing) in the epoxy cottonseed oil in step a and catalyzer quaternary ammonium salt is 16-100:1.
CO in step b
2The purity of gas is technical grade.
In step c, the volume ratio of organic solvent and warm water is 1:1.
Description of drawings
Fig. 1 is the thermogravimetric curve figure of epoxy cottonseed oil of the present invention and Oleum Gossypii semen carbonic ether, and wherein dotted line represents epoxy cottonseed oil, and solid line represents the Oleum Gossypii semen carbonic ether.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited only to described embodiment;
Embodiment 1
Be that in epoxy cottonseed oil, the mol ratio of epoxy group(ing) and catalyzer Tetrabutyl amonium bromide is 100:1 with epoxy cottonseed oil 100g and catalyzer Tetrabutyl amonium bromide 1.5g(), add in the autoclave with magnetic stirring, vacuumize 30 minutes after the enclosed high pressure still to remove the dissolved oxygen in epoxy cottonseed oil;
Autoclave is put into oil bath pan with magnetic agitation, stir and be heated to 100 ℃ of temperature, after reaching temperature of reaction, pour technical grade CO
2Gas 3MPa replenishes CO again after pressure decreased
2Gas, the reaction times is 6 hours;
After question response finishes, fully cooling with ice bath after, slowly discharge CO
2Gas, drive still, add organic solvent and warm water for 1:1 by volume, with organic solvent acetic acid ethyl dissolution Oleum Gossypii semen carbonic ether, pour separating funnel into, with warm water washing 3 times, remove the catalyzer Tetrabutyl amonium bromide, obtain end product Oleum Gossypii semen carbonic ether lubricating base oil after extracting solvent, then record oxirane value by volumetry, the transformation efficiency that calculates epoxy cottonseed oil is 25%.
Embodiment 2
Be that in cetyl trimethylammonium bromide 4.6g(epoxy cottonseed oil, the mol ratio of epoxy group(ing) and catalyzer cetyl trimethylammonium bromide is 28:1 with epoxy cottonseed oil 100g and catalyzer quaternary ammonium salt) add in the autoclave with magnetic stirring, vacuumize 30 minutes after the enclosed high pressure still to remove the dissolved oxygen in epoxy cottonseed oil;
Autoclave is put into oil bath pan with magnetic agitation, stir and be heated to 120 ℃, after reaching temperature of reaction, pour technical grade CO
2Gas 1MPa replenishes CO again after pressure decreased
2Gas, the reaction times is 10 hours;
After question response finishes, fully cooling with ice bath after, slowly discharge CO
2Gas, drive still, add organic solvent and warm water for 1:1 by volume, with organic solvent petroleum ether dissolution Oleum Gossypii semen carbonic ether, pour separating funnel into, with warm water washing 4 times, remove the catalyzer cetyl trimethylammonium bromide, obtain end product Oleum Gossypii semen carbonic ether lubricating base oil after extracting solvent, then record oxirane value by volumetry, the transformation efficiency that calculates epoxy cottonseed oil is 55%.
Embodiment 3
Be that in Tetrabutyl amonium bromide 5.9g(epoxy cottonseed oil, the mol ratio of epoxy group(ing) and catalyzer Tetrabutyl amonium bromide is 16:1 with epoxy cottonseed oil 100g and catalyzer quaternary ammonium salt) add in the autoclave with magnetic stirring, vacuumize 30 minutes after the enclosed high pressure still to remove the dissolved oxygen in epoxy cottonseed oil;
Autoclave is put into oil bath pan with magnetic agitation, stir and be heated to 140 ℃, after reaching temperature of reaction, pour technical grade CO
2Gas 6MPa replenishes CO again after pressure decreased
2Gas, the reaction times is 24 hours;
After question response finishes, fully cooling with ice bath after, slowly discharge CO
2Gas, drive still, add organic solvent and warm water for 1:1 by volume, with organic solvent petroleum ether dissolution Oleum Gossypii semen carbonic ether, pour separating funnel into, with warm water washing 5 times, remove the catalyzer Tetrabutyl amonium bromide, obtain end product Oleum Gossypii semen carbonic ether lubricating base oil after extracting solvent, then record oxirane value by volumetry, the transformation efficiency that calculates epoxy cottonseed oil is 99.9%.
Embodiment 4
Be that in four octyl group brometo de amonio 4.7g(epoxy cottonseed oils, the mol ratio of epoxy group(ing) and catalyzer four octyl group brometo de amonios is 20:1 with epoxy cottonseed oil 100g and catalyzer quaternary ammonium salt) add in the autoclave with magnetic stirring, vacuumize 30 minutes after the enclosed high pressure still to remove the dissolved oxygen in epoxy cottonseed oil;
Autoclave is put into oil bath pan with magnetic agitation, stir and be heated to 160 ℃, after reaching temperature of reaction, pour technical grade CO
2Gas replenishes CO again to 10MPa after pressure decreased
2Gas, the reaction times is 18 hours;
After question response finishes, fully cooling with ice bath after, slowly discharge CO
2Gas, drive still, add organic solvent and warm water for 1:1 by volume, with organic solvent acetic acid ethyl dissolution Oleum Gossypii semen carbonic ether, pour separating funnel into, with warm water washing 6 times, remove catalyzer four octyl group brometo de amonios, obtain end product Oleum Gossypii semen carbonic ether lubricating base oil after extracting solvent, then record oxirane value by volumetry, the transformation efficiency that calculates epoxy cottonseed oil is 75%.
Embodiment 5
Oleum Gossypii semen carbonic ether lubricating base oil by the described method acquisition of embodiment 1-4, test through physico-chemical property, mainly comprise: it the results are shown in Table 1,2 the test of pour point, flash-point, kinematic viscosity, viscosity index and oxidation stability, abrasion resistance and extreme pressure property, and 3:
Table 1 sample physico-chemical property test result
aThe transformation efficiency of epoxy cottonseed oil=25%;
bThe transformation efficiency of epoxy cottonseed oil=55%;
cThe transformation efficiency of epoxy cottonseed oil=75%;
dThe transformation efficiency of epoxy cottonseed oil=99.9%.
Table 2 sample oxidation stability test result
aThe transformation efficiency of epoxy cottonseed oil=25%;
bThe transformation efficiency of epoxy cottonseed oil=55%;
cThe transformation efficiency of epoxy cottonseed oil=75%;
dThe transformation efficiency of epoxy cottonseed oil=99.9%.
Table 3 sample extreme pressure property test result
Can find out from table 1,2 and 3: epoxy cottonseed oil and CO
2Variation has occured in the physico-chemical property of the Oleum Gossypii semen carbonic ether that addition generates, and along with the kinematic viscosity of the increase product of the transformation efficiency of epoxy cottonseed oil obviously increases, flash-point decreases but still remains on relatively high temperature.It is worth noting, after the carbonic acid esterification, the thermostability of epoxy group(ing) bio oil, oxidation stability and extreme pressure property and abrasion resistance have obtained improving significantly, it are more suitable in the situation that High Temperature High Pressure is used.
Claims (4)
1. a carbonic acid gas prepares the method for Oleum Gossypii semen carbonic ether lubricating base oil, it is characterized in that following these steps to carrying out:
A, be that Tetrabutyl amonium bromide, cetyl trimethylammonium bromide or four octyl group brometo de amonios add in autoclave with magnetic stirring with epoxy cottonseed oil and catalyzer quaternary ammonium salt, vacuumize 30 minutes after the enclosed high pressure still to remove the dissolved oxygen in epoxy cottonseed oil;
B, autoclave is put into oil bath pan with magnetic agitation, stir and be heated to temperature 100-160 ℃, after reaching temperature of reaction, pour CO
2Gas 1-10MPa replenishes CO again after pressure decreased
2Gas, reaction times 2-24 hour;
After c, question response finish, fully cooling with ice bath after, slowly discharge CO
2Gas, drive still, adding organic solvent is ethyl acetate or petroleum ether dissolution Oleum Gossypii semen carbonic ether, will add the still material after solvent to pour separating funnel into, to remove catalyzer, obtain end product Oleum Gossypii semen carbonic ether lubricating base oil after extracting solvent with warm water washing 3-6 time.
2. method according to claim 1 is characterized in that epoxy group(ing) in the epoxy cottonseed oil in step a and the mol ratio of catalyzer quaternary ammonium salt are 10-100:1.
3. method according to claim 1, is characterized in that CO in step b
2The purity of gas is technical grade.
4. method according to claim 1 is characterized in that in step c, the volume ratio of organic solvent and warm water is 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101187735A CN103173291A (en) | 2013-04-07 | 2013-04-07 | Method for preparing cottonseed oil carbonic ester lubricating base oil by using carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101187735A CN103173291A (en) | 2013-04-07 | 2013-04-07 | Method for preparing cottonseed oil carbonic ester lubricating base oil by using carbon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103173291A true CN103173291A (en) | 2013-06-26 |
Family
ID=48633487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101187735A Pending CN103173291A (en) | 2013-04-07 | 2013-04-07 | Method for preparing cottonseed oil carbonic ester lubricating base oil by using carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103173291A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746359A (en) * | 2019-11-11 | 2020-02-04 | 新疆工程学院 | Silica gel supported imidazole ionic liquid catalyst, preparation method and application in preparation of carbonate |
| CN113105935A (en) * | 2021-02-25 | 2021-07-13 | 安徽中天石化股份有限公司 | Carbonate type modified vegetable oil base oil and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040230009A1 (en) * | 2003-02-19 | 2004-11-18 | Wilkes Garth L. | Nonisocyanate polyurethane materials, and their preparation from epoxidized soybean oils and related epoxidized vegetable oils, incorporation of carbon dioxide into soybean oil, and carbonation of vegetable oils |
| CN1880311A (en) * | 2006-05-12 | 2006-12-20 | 中国科学院山西煤炭化学研究所 | Method for generating cyclic carbonates using natural reproducible resource |
| CN1995031A (en) * | 2006-12-20 | 2007-07-11 | 中国科学院山西煤炭化学研究所 | Method for synthesizing five ring carbonate using natural reproducible resource |
| CN102069010A (en) * | 2010-12-14 | 2011-05-25 | 华东理工大学 | Montmorillonite catalyst used in preparation of cyclic carbonate |
| CN102585192A (en) * | 2011-12-31 | 2012-07-18 | 中国林业科学研究院林产化学工业研究所 | Biologic polycarbonate and preparation method thereof |
| CN102698799A (en) * | 2012-06-06 | 2012-10-03 | 湖南大学 | Polymer supported quaternary ammonium salt ion catalyst as well as preparation method and application thereof |
| CN102775378A (en) * | 2011-12-20 | 2012-11-14 | 湖南大学 | Solvent-free catalytic synthesis method of cyclic carbonate |
-
2013
- 2013-04-07 CN CN2013101187735A patent/CN103173291A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040230009A1 (en) * | 2003-02-19 | 2004-11-18 | Wilkes Garth L. | Nonisocyanate polyurethane materials, and their preparation from epoxidized soybean oils and related epoxidized vegetable oils, incorporation of carbon dioxide into soybean oil, and carbonation of vegetable oils |
| CN1880311A (en) * | 2006-05-12 | 2006-12-20 | 中国科学院山西煤炭化学研究所 | Method for generating cyclic carbonates using natural reproducible resource |
| CN1995031A (en) * | 2006-12-20 | 2007-07-11 | 中国科学院山西煤炭化学研究所 | Method for synthesizing five ring carbonate using natural reproducible resource |
| CN102069010A (en) * | 2010-12-14 | 2011-05-25 | 华东理工大学 | Montmorillonite catalyst used in preparation of cyclic carbonate |
| CN102775378A (en) * | 2011-12-20 | 2012-11-14 | 湖南大学 | Solvent-free catalytic synthesis method of cyclic carbonate |
| CN102585192A (en) * | 2011-12-31 | 2012-07-18 | 中国林业科学研究院林产化学工业研究所 | Biologic polycarbonate and preparation method thereof |
| CN102698799A (en) * | 2012-06-06 | 2012-10-03 | 湖南大学 | Polymer supported quaternary ammonium salt ion catalyst as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 唐俊杰: "合成润滑油基础知识讲座之五", 《润滑油》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746359A (en) * | 2019-11-11 | 2020-02-04 | 新疆工程学院 | Silica gel supported imidazole ionic liquid catalyst, preparation method and application in preparation of carbonate |
| CN113105935A (en) * | 2021-02-25 | 2021-07-13 | 安徽中天石化股份有限公司 | Carbonate type modified vegetable oil base oil and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105368574B (en) | Method for reducing acid value of liquid organic mixture | |
| CN111411023B (en) | Vegetable oil polyalcohol and preparation method and application thereof | |
| CN105646225B (en) | A kind of tung oil polylol and preparation method | |
| CN103173291A (en) | Method for preparing cottonseed oil carbonic ester lubricating base oil by using carbon dioxide | |
| CN104388107B (en) | Esterified biological asphalt and preparation method thereof | |
| CN103937616B (en) | Method for extracting high-purity unsaturated fatty acid from soybean oil | |
| CN105523923A (en) | Method of producing estolide using linking agent | |
| CN102399577A (en) | Chemical settling dehydration method for thick oil transition zone ageing oil | |
| CN102796035A (en) | Condensation method of m-,p-mixed di-(tert-butyl isopropyl peroxide)benzene | |
| CN101289627B (en) | Process for reducing acid value of biodiesel | |
| CN104673489A (en) | Method for recycling and treating gutter oil | |
| CN107778175A (en) | The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two | |
| CN104327265A (en) | Long-carbon-chain semi-aromatic nylon PA14T and preparation method thereof | |
| CN103965016A (en) | Method for preparing fatty alcohol through hydrogenation of fatty acid methyl ester in presence of temperature control catalytic system | |
| CN104845739A (en) | Method for preparing grease polyol from epoxy grease and grease polyol | |
| CN104312619A (en) | Method for separating n-alkane from shale oil | |
| CN102492948B (en) | Extract corrosion inhibitor of sweet potato stems and lettuce flower stalks and preparation method thereof | |
| CN101544559A (en) | Method for separating and extracting isostearic acid from monomer acid | |
| CN105732368B (en) | A kind of method using luwa evaporator synthesizing polyatomic alcohol fatty acid ester | |
| CN111269116B (en) | Method for realizing preparation and in-situ separation of ricinoleic acid oligomer | |
| CN103666566A (en) | Preparation method of petroleum corrosion inhibitor | |
| CN104151258A (en) | Method and apparatus for recycling tetrahydrofuran solvent during reduction reaction of L-phenylglycinol | |
| CN104592283A (en) | Synthetic method of silane coupling agent Si-69 | |
| CN105732369B (en) | Using the method for falling film evaporator synthesizing polyatomic alcohol fatty acid ester | |
| CN104592169B (en) | With the method that waste oil prepares epoxy aliphatic acid methyl ester for raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130626 |