CN102977244B - Bio-based polyester synthetic oil and preparation method thereof - Google Patents
Bio-based polyester synthetic oil and preparation method thereof Download PDFInfo
- Publication number
- CN102977244B CN102977244B CN201210486521.3A CN201210486521A CN102977244B CN 102977244 B CN102977244 B CN 102977244B CN 201210486521 A CN201210486521 A CN 201210486521A CN 102977244 B CN102977244 B CN 102977244B
- Authority
- CN
- China
- Prior art keywords
- fumaric acid
- furfural
- preparation
- furfuryl
- raw material
- 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.)
- Active
Links
Landscapes
- Developing Agents For Electrophotography (AREA)
- Furan Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Lubricants (AREA)
Abstract
The invention relates to a preparation method of bio-based polyester synthetic oil. The molecular structure of the bio-based polyester synthetic oil is shown in the description, R=CmH2m+1 (m>=1), n=2-20, and the molecular mass is 700-7000. The preparation method comprises the steps of: hydrolyzing by taking agricultural and forestry waste as a raw material to obtain furfural; carrying out catalytic oxidation on the furfural to prepare fumaric acid; carrying out ZSM-5 catalytic esterification on furfuryl alcohol prepared by hydrogenation of the furfural and fumaric acid to prepare 2-furan methyl ester fumarate; and carrying out polymerization on the 2-furan methyl ester fumarate and a-olefin to prepare 2-furan methyl ester polyfumarate synthetic oil. The bio-based polyester synthetic oil and the preparation method thereof have the advantages that the prepared polyester synthetic oil can be used as lubricant base oil, a lubricant viscosity index modifier, an environment-friendly anti-wear extreme-pressure reagent and a high-cleanliness fuel lubricating additive, so that the range of application is wide.
Description
Technical field
The invention belongs to bio-based synthetic oil field, be specifically related to a kind of agriculture and forestry organic waste material that utilizes for the technology of Material synthesis polyester oil.
Background technology
Polyester oil is relatively new gang's synthetic lubricant base oil, it is the multipolymer of alpha-olefin and unsaturated diester, its molecular structure feature is: being connected to, hydrocarbon skeleton is alternative hydrocarbon side chain and paired ester pendant groups, so have the features such as excellent oilness, viscosity-temperature characteristics, stability and sealing material consistency.Be mainly used in the field requiring high lubricity, viscosity-temperature characteristics and high performance-price ratio advantage can be shown, as the I. C. engine oil of all automobiles, gear oil and heavy loading metalworking fluid.
Summary of the invention
The object of this invention is to provide one and can be used as synthetic lubricant base oil, also can be used as lubricating oil viscosity index properties-correcting agent, environment-friendly type extreme pressure anti-wear additives, the preparation method of the biological poly Lipase absobed oil of fuel with high cleanness oiliness additive.
Biological poly Lipase absobed oil of the present invention, its molecular structure is:
R=C
mH
2m+1 (m≥1)
N=2-20, molecular mass is 700-7000
The preparation method of biological poly Lipase absobed oil of the present invention is as follows:
1) take furfural as raw material, hydrogen peroxide is oxygenant, and its mol ratio is: H
2o
2/ furfural=1.5-4/1, at V
2o
5on catalyzer, reaction obtains fumaric acid in atmospheric conditions; V
2o
5catalyst levels is the 1-5wt% of furfural, temperature of reaction 50 ~ 120 DEG C, and equation is as follows:
2)with furfuryl alcohol and fumaric acid for raw material, its mol ratio is: furfuryl alcohol/fumaric acid=1-4/1, is, under catalyzer condition of normal pressure, carry out esterification with ZSM-5 molecular sieve, obtained fumaric acid two furfuryl ester; Catalyst levels is the 2-10 wt % of fumaric acid, temperature of reaction 200 ~ 300 DEG C, and equation is as follows:
3) with fumaric acid two furfuryl ester and a-alkene for raw material, its mol ratio is: fumaric acid two furfuryl ester/a-alkene=1/1-10, add initiator diisopropyl peroxide two carbonic ether of fumaric acid two furfuryl ester quality 1 ~ 2%, temperature of reaction 70 ~ 150 DEG C, under pressure 0 ~ 10MPa condition, carry out polyreaction, obtained poly-fumaric acid two furfuryl Lipase absobed oil.
the indices of polyester ucon oil of the present invention is as following table:
Described furfural is that raw material hydrolysis is obtained with agriculture and forestry organic waste material;
Described furfuryl alcohol take agriculture and forestry organic waste material as raw material, obtains through hydrolysis, hydrogenation.
Described a-alkene be a kind of C=C double bond at the alkene of 1, comprise a-normal olefine: as ethene, propylene, 1-butylene, 1-amylene, 1-hexene etc.; A-branched-chain alkene, as 3-methyl-1-butene, 2,3-methyl-1-butene etc.
Described ZSM-5 molecular sieve is outsourcing, its production unit: Tianjin Nan Hua catalyzer company limited.
Advantage of the present invention is: take agriculture and forestry organic waste material as raw material, cost is low, abundant raw material source, environmental protection, obtained polyester synthetic oil, can be used as synthetic lubricant base oil, also can be used as lubricating oil viscosity index properties-correcting agent, environment-friendly type extreme pressure anti-wear additives, fuel with high cleanness oiliness additive, of many uses.
Embodiment
The present invention with agriculture and forestry organic waste materials such as agricultural crop straw, corn cob, scrub growth stump things for raw water solution obtains furfural.Furfural is through catalyzed oxidation fumaric acid; The furfuryl alcohol that fumaric acid and furfural hydrogenation obtain obtains fumaric acid two furfuryl ester through ZSM-5 catalytic esterification; Fumaric acid two furfuryl ester and a-olefinic polymerization system gather fumaric acid two furfuryl Lipase absobed oil.If pressure does not refer in particular in embodiments of the invention, be relative pressure.
embodiment 1
1, the preparation of fumaric acid:
The furfural produced with agriculture and forestry organic waste material, for raw material, is that (mol ratio is oxygenant: H with hydrogen peroxide
2o
2/ furfural=2/1), at V
2o
5on catalyzer (consumption is the 2wt% of furfural consumption), temperature of reaction 95 ~ 100 DEG C, under condition of normal pressure, reaction 30min, obtained fumaric acid, yield is 75%.
Equation is as follows:
2, the preparation of fumaric acid two furfuryl ester:
The furfuryl alcohol produced with agriculture and forestry organic waste material and fumaric acid are for raw material (mol ratio: furfuryl alcohol/fumaric acid=2/1), taking ZSM-5 molecular sieve as catalyzer (catalyst levels is the 4wt% of fumaric acid), temperature of reaction 245 ~ 255 DEG C, under condition of normal pressure, carry out esterification, obtained fumaric acid two furfuryl ester, yield is 47%.
Equation is as follows:
3, the preparation of poly-fumaric acid two furfuryl Lipase absobed oil:
With fumaric acid two furfuryl ester 1-butylene for raw material (mol ratio: fumaric acid two furfuryl ester/a-alkene=1/4), add initiator diisopropyl peroxide two carbonic ether of fumaric acid two furfuryl ester quality 2%, temperature of reaction 110 ~ 115 DEG C, under pressure 4-5MPa condition, carry out polyreaction, obtained poly-fumaric acid two furfuryl Lipase absobed oil, yield is 63%.
The indices of polyester ucon oil of the present invention is as following table:
| Project | Quality index | Product performance | Experimental technique |
| Density g/cm3 | 0.93~0.99 | 0.94 | ASTM D-1217 |
| Viscosity (100 DEG C) (mm2/s) | 15~700 | 632 | ASTM D-445 |
| Viscosity index | 140~200 | 184 | ASTM D-2270 |
| Pour point/DEG C | -28 ~ -10 | -12 | ASTM D-97 |
| Flash-point/DEG C | 250~280 | 266 | ASTM D-92 |
| Total acid value/(mgKOH/g) | 0.1~0.3 | 0.12 | ASTM D-974 |
| Thermal oxidation stability (200 DEG C, 12h, 15L air) viscosity increase/% | 90~110 | 102 | IP48 |
| Seal compatibility | Neutral | Neutral | CEC-L-39-X-95 |
| NOACK volatility/% | 2~3 | 2.4 | DIN51581 |
embodiment 2
1, the preparation of fumaric acid:
The furfural produced with agriculture and forestry organic waste material, for raw material, is that (mol ratio is oxygenant: H with hydrogen peroxide
2o
2/ furfural=2/1), at V
2o
5on catalyzer (consumption is the 2wt% of furfural consumption), temperature of reaction 65 ~ 70 DEG C, under condition of normal pressure, reaction 30min, obtained fumaric acid, yield is 45%.
Equation is as follows:
2, the preparation of fumaric acid two furfuryl ester:
The furfuryl alcohol produced with agriculture and forestry organic waste material and fumaric acid are for raw material (mol ratio: furfuryl alcohol/fumaric acid=2/1), taking ZSM-5 molecular sieve as catalyzer (catalyst levels is the 4wt% of fumaric acid), temperature of reaction 210 ~ 215 DEG C, under condition of normal pressure, carry out esterification, obtained fumaric acid two furfuryl ester, yield is 38%.
Equation is as follows:
3, the preparation of poly-fumaric acid two furfuryl Lipase absobed oil:
With fumaric acid two furfuryl ester 1-butylene for raw material (mol ratio: fumaric acid two furfuryl ester/a-alkene=1/4), add initiator diisopropyl peroxide two carbonic ether of fumaric acid two furfuryl ester quality 2%, temperature of reaction 75 ~ 80 DEG C, under pressure 4 ~ 5MPa condition, carry out polyreaction, obtained poly-fumaric acid two furfuryl Lipase absobed oil, yield is 39%.
The indices of polyester ucon oil of the present invention is as following table:
| Project | Quality index | Product performance | Experimental technique |
| Density g/cm3 | 0.93~0.99 | 0.93 | ASTM D-1217 |
| Viscosity (100 DEG C) (mm2/s) | 15~700 | 570 | ASTM D-445 |
| Viscosity index | 140~200 | 165 | ASTM D-2270 |
| Pour point/DEG C | -28 ~ -10 | -19 | ASTM D-97 |
| Flash-point/DEG C | 250~280 | 253 | ASTM D-92 |
| Total acid value/(mgKOH/g) | 0.1~0.3 | 0.16 | ASTM D-974 |
| Thermal oxidation stability (200 DEG C, 12h, 15L air) viscosity increase/% | 90~110 | 92 | IP48 |
| Seal compatibility | Neutral | Neutral | CEC-L-39-X-95 |
| NOACK volatility/% | 2~3 | 2.2 | DIN51581 |
embodiment 3
1, the preparation of fumaric acid:
The furfural produced with agriculture and forestry organic waste material, for raw material, is that (mol ratio is oxygenant: H with hydrogen peroxide
2o
2/ furfural=2/1), at V
2o
5on catalyzer (consumption is the 2wt% of furfural consumption), temperature of reaction 140 ~ 145 DEG C, under condition of normal pressure, reaction 30min, obtained fumaric acid, yield is 66%.
Equation is as follows:
2, the preparation of fumaric acid two furfuryl ester:
The furfuryl alcohol produced with agriculture and forestry organic waste material and fumaric acid are for raw material (mol ratio: furfuryl alcohol/fumaric acid=2/1), taking ZSM-5 molecular sieve as catalyzer (catalyst levels is the 4wt% of fumaric acid), temperature of reaction 280 ~ 285 DEG C, under condition of normal pressure, carry out esterification, obtained fumaric acid two furfuryl ester, yield is 42%.
Equation is as follows:
3, the preparation of poly-fumaric acid two furfuryl Lipase absobed oil:
With fumaric acid two furfuryl ester 1-butylene for raw material (mol ratio: fumaric acid two furfuryl ester/a-alkene=1/4), add initiator diisopropyl peroxide two carbonic ether of fumaric acid two furfuryl ester quality 2%, temperature of reaction 110 ~ 115 DEG C, under pressure 0.5 ~ 0.6MPa condition, carry out polyreaction, obtained poly-fumaric acid two furfuryl Lipase absobed oil, yield is 58%.
The indices of polyester ucon oil of the present invention is as following table:
| Project | Quality index | Product performance | Experimental technique |
| Density g/cm3 | 0.93~0.99 | 0.96 | ASTM D-1217 |
| Viscosity (100 DEG C) (mm2/s) | 15~700 | 620 | ASTM D-445 |
| Viscosity index | 140~200 | 170 | ASTM D-2270 |
| Pour point/DEG C | -28 ~ -10 | -16 | ASTM D-97 |
| Flash-point/DEG C | 250~280 | 264 | ASTM D-92 |
| Total acid value/(mgKOH/g) | 0.1~0.3 | 0.13 | ASTM D-974 |
| Thermal oxidation stability (200 DEG C, 12h, 15L air) viscosity increase/% | 90~110 | 102 | IP48 |
| Seal compatibility | Neutral | Neutral | CEC-L-39-X-95 |
| NOACK volatility/% | 2~3 | 2.4 | DIN51581 |
Claims (3)
1. a preparation method for biological poly Lipase absobed oil, is characterized in that: the molecular structure of described biological poly Lipase absobed oil is:
R=C
mH
2m+1，m≥1；
N=2-20, molecular mass is 700-7000;
Processing step is as follows:
1) take furfural as raw material, hydrogen peroxide is oxygenant, and its mol ratio is: H
2o
2/ furfural=1.5-4/1, at V
2o
5on catalyzer, reaction obtains fumaric acid in atmospheric conditions; V
2o
5catalyst levels is the 1-5wt% of furfural, temperature of reaction 50 ~ 120 DEG C;
2)with furfuryl alcohol and fumaric acid for raw material, its mol ratio is: furfuryl alcohol/fumaric acid=1-4/1, is, under catalyzer condition of normal pressure, carry out esterification with ZSM-5 molecular sieve, obtained fumaric acid two furfuryl ester; Catalyst levels is the 2-10 wt % of fumaric acid, temperature of reaction 200 ~ 300 DEG C;
3) with fumaric acid two furfuryl ester and a-alkene for raw material, its mol ratio is: fumaric acid two furfuryl ester/a-alkene=1/1-10, add initiator diisopropyl peroxide two carbonic ether of fumaric acid two furfuryl ester quality 1 ~ 2%, temperature of reaction 70 ~ 150 DEG C, under pressure 0 ~ 10MPa condition, carry out polyreaction, obtained poly-fumaric acid two furfuryl Lipase absobed oil.
2. the preparation method of biological poly Lipase absobed oil according to claim 1, is characterized in that: described furfural is that raw material hydrolysis is obtained with agriculture and forestry organic waste material.
3. the preparation method of biological poly Lipase absobed oil according to claim 1, is characterized in that: described furfuryl alcohol take agriculture and forestry organic waste material as raw material, and hydrolysis, hydrogenation obtain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210486521.3A CN102977244B (en) | 2012-11-26 | 2012-11-26 | Bio-based polyester synthetic oil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210486521.3A CN102977244B (en) | 2012-11-26 | 2012-11-26 | Bio-based polyester synthetic oil and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102977244A CN102977244A (en) | 2013-03-20 |
| CN102977244B true CN102977244B (en) | 2015-06-24 |
Family
ID=47851619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210486521.3A Active CN102977244B (en) | 2012-11-26 | 2012-11-26 | Bio-based polyester synthetic oil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102977244B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9321714B1 (en) | 2014-12-05 | 2016-04-26 | Uop Llc | Processes and catalysts for conversion of 2,5-dimethylfuran derivatives to terephthalate |
| WO2020130802A1 (en) | 2018-12-21 | 2020-06-25 | Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno | Oxidative preparation of maleic acid |
| CN115124494A (en) * | 2021-03-26 | 2022-09-30 | 中国科学院宁波材料技术与工程研究所 | 2, 5-tetrahydrofuran dimethanol sulfate ester compound and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200522A (en) * | 2007-11-26 | 2008-06-18 | 内蒙古金骄特种新材料有限公司 | Polyester oil and preparation method thereof |
| CN101899145B (en) * | 2010-07-28 | 2012-07-11 | 江南大学 | Preparation method of 2, 5-furan diformyl polyester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2994048B2 (en) * | 1990-12-18 | 1999-12-27 | 旭電化工業株式会社 | Thermochromic material |
-
2012
- 2012-11-26 CN CN201210486521.3A patent/CN102977244B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200522A (en) * | 2007-11-26 | 2008-06-18 | 内蒙古金骄特种新材料有限公司 | Polyester oil and preparation method thereof |
| CN101899145B (en) * | 2010-07-28 | 2012-07-11 | 江南大学 | Preparation method of 2, 5-furan diformyl polyester |
Non-Patent Citations (1)
| Title |
|---|
| Furfuryl ester of some dicarboxylic acids;W. R. EDWARDS et al.;《Journal of the American Chemical Society》;19541020;第76卷;5150-5152 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102977244A (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Singh et al. | Sustainability of a non-edible vegetable oil based bio-lubricant for automotive applications: A review | |
| US8188019B2 (en) | Biolubricant esters from the alcohols of unsaturated fatty acids | |
| US8273694B2 (en) | Synthetic compositions obtained from algae | |
| JP5536057B2 (en) | Conversion of vegetable oil to base oil and transportation fuel | |
| JP5580822B2 (en) | Conversion of vegetable oil to base oil and transportation fuel | |
| CN102977244B (en) | Bio-based polyester synthetic oil and preparation method thereof | |
| US8772555B2 (en) | Conversion of vegetable oils to base oils and transportation fuels | |
| CN105176641A (en) | Tractor three-purpose lubricating oil composition and preparation method of tractor three-purpose lubricating oil composition | |
| JP2005537383A5 (en) | ||
| CN103396865A (en) | Environment-friendly high-wear-resistance lubricating oil and preparation method thereof | |
| US20120102828A1 (en) | Fuel and base oil blendstocks from a single feedstock | |
| JPH0245678B2 (en) | ||
| Chang et al. | Palm oil derived trimethylolpropane triesters synthetic lubricants and usage in industrial metalworking fluid | |
| Barbera et al. | Recent developments in synthesizing biolubricants—a review | |
| JP2023159211A (en) | Synthetic fluids with improved biodegradability | |
| Khan et al. | A comparative physicochemical property assessment and techno-economic analysis of biolubricants produced using chemical modification and additive-based routes | |
| CN102796589A (en) | Environment-friendly synthesized lubricant and preparation method thereof | |
| CN108795996A (en) | A method of preparing polyol ester using levulic acid | |
| CN104152212A (en) | Lubricant and preparation method thereof | |
| CN109504515B (en) | Energy-saving environment-friendly agricultural machine oil and preparation method thereof | |
| US20120028863A1 (en) | Application-specific finished lubricant compositions comprising a bio-derived ester component and methods of making same | |
| CN101899355A (en) | Lubricating oil composite with oxidation resistance and preparation method thereof | |
| Ali et al. | Rheological review on potential of bio-lubricants | |
| CN115746896B (en) | Synthesis method of alkane bio-based lubricating oil base oil | |
| CN103571593B (en) | All-purpose lubricant for combined forest harvester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 014060 Wanshuiquan, Rare Earth High-tech Zone, Baotou City, Inner Mongolia Autonomous Region Patentee after: Pretty Oriental Bio Fuel Group Limited Address before: 014030 Jinjiao Industrial Park, Binhe New Area, Baotou Rare Earth High-tech Zone, Inner Mongolia Autonomous Region Patentee before: Jinjiao Special New Materials (Group) Co., Ltd. |