CN102839055B - Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil - Google Patents
Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil Download PDFInfo
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- CN102839055B CN102839055B CN201210047269.6A CN201210047269A CN102839055B CN 102839055 B CN102839055 B CN 102839055B CN 201210047269 A CN201210047269 A CN 201210047269A CN 102839055 B CN102839055 B CN 102839055B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention discloses a method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil, and belongs to the technical field of biodiesel oil. The method comprises the following steps of: performing ester exchange reaction on the natural oil and lower alcohol (containing 1 to 3 carbons), heating the fatty acid ester serving as an ester exchange product and dimaleate under the protection of nitrogen and in the presence of a cyclo-addition catalyst to the temperature of between 160 and 280 DEG C, and reacting for 3 to 12 hours; and cooling to the temperature of between 120 and 240 DEG C after reaction, vacuumizing, keeping the vacuum degree of over 750mmHg, and distilling under reduced pressure, wherein the distillate is the biodiesel oil (fatty acid ester) and the residue is the C22-cyclic fatty triacid ester. By utilizing the characteristics that the structure of the fatty acid ester has two or more double bonds, the C22-cyclic fatty triacid ester serving as a chemical product with high additional value is produced when the biodiesel oil is prepared, so that the production cost is reduced.
Description
Technical field
The invention belongs to technical field of biodiesel preparation, refer in particular to and utilize natural fats and oils co-producing biodiesel and C
22the method of-cycloaliphatic three acid esters.
Background technology
Along with the continuous consumption of petroleum resources and the enhancing day by day of people's environmental consciousness, the natural fats and oils of take is produced fuel and Chemicals become a kind of inevitable trend and direction as raw material part petroleum replacing.The subject matter of restricting current China Biodiesel is that production cost is higher, and wherein material cost accounts for 75%, and the profit that enterprise can create is very limited.With regard to existing market, natural fats and oils, cannot be as the normal raw material of producing of biofuel because its cost of material is higher than biofuel product price.Consider in natural fats and oils and contain a large amount of two keys, in mixed aliphatic ester prepared therefrom, contain a large amount of unsaturated fatty acid esters.If utilize these unsaturated fatty acid esters, in production biofuel, coproduction has the Chemicals compared with high added value, just can reduce costs, and allows production of biodiesel enterprise obtain good economic benefit.
Chinese patent 200410014887.6 carries out esterification by natural fats and oils and low-carbon alcohol (containing 1 ~ 3 carbon), esterification products fatty acid ester and fatty acid methyl ester blending polymerization containing two or above conjugated double bond, obtain biofuel (fatty acid ester) and dimeric acid methyl ester through underpressure distillation.Chinese patent CN101260311 B provides the another kind of method by animal-plant oil co-producing biodiesel and dimeric dibasic acid ester.First this patent carries out transesterification reaction by animal-plant oil and low-carbon alcohol (containing 1 ~ 3 carbon), then with urea adduct method, product is divided into polyunsaturated fatty acid ester and unsaturated fatty acid ester two portions; Then by unsaturated fatty acid ester polymerization, product obtains dimer (fatty acid) yl ester and fatty acid monomer ester through underpressure distillation separation; The fatty acid monomer ester polyunsaturated fatty acid ester that obtain separated with aforementioned urea inclusion method merged and be biofuel.Above-mentioned two patents, by coproduction dimeric dibasic acid ester, have all reduced the production cost of biofuel effectively.
Making full use of the feature that has two keys on natural acid ester structure, continue new the having compared with the Chemicals of high added value and applications well prospect of research and development, realize Poly-generation, is an important directions of Biodiesel development.
summary of the invention
The object of the invention is to provide a kind ofly take renewable resources natural fats and oils as raw material, co-producing biodiesel and C
22the method of-cycloaliphatic three acid esters.
The present invention takes following technological line co-producing biodiesel and C
22-cycloaliphatic three acid esters:
(1) transesterification reaction:
Natural fats and oils+low-carbon alcohol → mixed aliphatic ester+glycerine
(2) cycloaddition reaction:
Mixed aliphatic ester+maleic acid diester → C
22-cycloaliphatic three acid esters+biofuel.
The present invention takes following technical scheme: by natural fats and oils co-producing biodiesel and C
22the method of-cycloaliphatic three acid esters, according to following step, carry out:
(1) transesterification reaction: natural fats and oils is processed through decompression dehydration, the catalyzer that adds low-carbon alcohol and relative natural fats and oils quality 0.1% ~ 5% by oleyl alcohol mol ratio 1:3 ~ 1:10, at pressure, be that normal pressure ~ 10MPa, temperature of reaction are at room temperature ~ 300 ℃, reaction 0.1 ~ 8h, react complete, distill out unnecessary low-carbon alcohol, then cooling stratification; Isolate lower floor's byproduct glycerine, obtain mixed aliphatic ester;
(2) cycloaddition reaction: according to the content of linoleate in mixed aliphatic ester, by maleic acid diester/linoleate mol ratio=0.9 ~ 1.1, add maleic acid diester in mixed aliphatic ester; Then under nitrogen protection and the existence of cycloaddition catalyzer, be heated to 160 ~ 280 ℃, polyreaction 3 ~ 12 hours; React complete, cool to 120 ~ 240 ℃, vacuumize, keep vacuum tightness more than 750mmHg, to carry out underpressure distillation, distillate is biofuel (fatty acid ester), and still liquid is C
22-cycloaliphatic three acid esters.
Wherein described in step (1), natural fats and oils is Oleum Gossypii semen, rapeseed oil, soybean oil or waste animal and vegetable oil; Wherein low-carbon alcohol described in step (1), containing 1 ~ 3 carbon, is specially methyl alcohol, ethanol, Virahol;
Wherein the catalyzer described in step (1) is strong acid or highly basic; Described strong acid is wherein any such as 98% vitriol oil, anhydrous phosphoric acid, solid super-strong acid, and described highly basic is wherein any such as potassium hydroxide, sodium hydroxide, solid alkali (CaO or MgO).
Wherein the maleic acid diester described in step (2) is dimethyl maleate, ethyl maleate, dibutyl maleinate, Diisopentyl Maleate Using, dioctyl maleate.
Wherein the cycloaddition catalyzer described in step (2) is atlapulgite or iodine, and its add-on is equivalent to 0 ~ 3% of linoleate quality in mixed aliphatic ester.
The invention has the beneficial effects as follows:
The present invention directly uses natural fats and oils product of transesterification reaction fatty acid ester as biofuel, but utilizes the feature that has 2 and above pair keys in fatty acid ester structure, in preparation biofuel, and coproduction chemical products with high added-value C
22-cycloaliphatic three acid esters, thus production cost reduced; The present invention is according to linoleate content in mixed aliphatic ester, adjust the add-on of maleic acid diester, flexibly after gate ring addition reaction, in system, polyunsaturated fatty acid ester and unsaturated fatty acid ester are a suitable ratio, that is the prepared biofuel of the present invention has moderate iodine number; Biofuel prepared by the present invention is not containing glycerine, and the biofuel that routine techniques makes is at present containing more than 0.5% glycerine, therefore the present invention has improved the quality of obtained biofuel.
Embodiment
Embodiment 1
In 500mL four-hole boiling flask, 31 grams of 300 grams of Oleum Gossypii semens, the methyl alcohol (oleyl alcohol mol ratio is 1:3) that add drying to process, stirring heating reaches approximately 65 ℃ of left and right of methanol eddy temperature, adds 3 grams of solid alkali CaO, back flow reaction 3 hours.Reaction finishes, and distills out unnecessary methyl alcohol.Reacting liquor while hot is filtered, and isolates catalyzer, then filtrate is poured into standing stay-over demixion in separating funnel.Separate lower floor's byproduct glycerine, obtain 288 grams of fatty acid methyl esters.It is 96.5% that chromatogram detects fatty acid methyl ester.
By above-mentioned 288 grams of fatty acid methyl esters, (methyl linoleate mass content is 55.7%;); with 70.7 grams of dimethyl maleates (maleic acid diester/linoleate mol ratio=0.9); add in a three-necked flask with thermometer, agitator; add 0.3 gram of iodine; under nitrogen protection, be heated to 160 ℃, react 3 hours.Then underpressure distillation, obtains 156 grams of fatty acid esters (biofuel), C
22198 grams of the sour trimethyls of-cycloaliphatic three.
Embodiment 2
In the 500mL three-necked flask with vacuum dewatering plant, thermometer and reflux exchanger, add 300 grams of rapeseed oils, be heated to 120 ℃, decompression dehydration 1 ~ 2h, is cooled to 50 ℃, adds 150 grams of ethanol (oleyl alcohol mol ratio is 1:10), 2.5 grams of potassium hydroxide, after back flow reaction 5 hours, finish reaction, distill out unnecessary alcohol, be cooled to 50 ℃, then pour stratification in separating funnel into, separate lower floor's byproduct glycerine, obtain 298 grams of fatty-acid ethyl esters.It is 95.4% that chromatogram detects fatty-acid ethyl ester content.
By above-mentioned 298 grams of fatty-acid ethyl esters (methyl linoleate mass content is 23.5%) and 51.8 grams of dibutyl maleinates (maleic acid diester/linoleate mol ratio=1.0); add in a three-necked flask with thermometer, agitator; add 2 grams of atlapulgites; under nitrogen protection, be heated to 280 ℃, react 8 hours.Then underpressure distillation, obtains 238 grams of fatty-acid ethyl esters (biofuel), C
22105 grams of sour two fourth one ethyl esters of-cycloaliphatic three.
Embodiment 3
In the 500mL three-necked flask with vacuum dewatering plant, thermometer and reflux exchanger, add 300 grams of discarded edible oils, be heated to 120 ℃, decompression dehydration 1 ~ 2h, is cooled to 50 ℃, adds 83.5 grams of methyl alcohol (oleyl alcohol mol ratio is 1:8), 2.5 gram of 98% vitriol oil, after back flow reaction 5 hours, finish reaction, distill out unnecessary methyl alcohol, be cooled to 50 ℃, then pour stratification in separating funnel into, separate lower floor's byproduct glycerine, obtain 290 grams of fatty acid methyl esters.It is 94.4% that chromatogram detects fatty acid methyl ester.
By above-mentioned 290 grams of fatty acid methyl esters (methyl linoleate mass content is 47.2%); 174 grams of toxilic acid dibutyl esters (maleic acid diester/linoleate mol ratio=1.1); add in a three-necked flask with thermometer, agitator; add 0.5 gram of iodine; under nitrogen protection, be heated to 220 ℃, react 12 hours.Then underpressure distillation, obtains 190 grams of fatty acid methyl esters (biofuel), C
22265 grams of-cycloaliphatic three acid two pungent methyl esters.
Claims (1)
1. natural fats and oils co-producing biodiesel and C
22the method of-cycloaliphatic three acid esters, is characterized in that carrying out according to following step:
(1) transesterification reaction: natural fats and oils is processed through decompression dehydration, the catalyzer that adds low-carbon alcohol and relative natural fats and oils quality 0.1% ~ 5% by oleyl alcohol mol ratio 1:3 ~ 1:10, at pressure, be that normal pressure ~ 10MPa, temperature of reaction are at room temperature ~ 300 ℃, reaction 0.1 ~ 8h, react complete, distill out unnecessary low-carbon alcohol, then cooling stratification; Isolate lower floor's byproduct glycerine, obtain mixed aliphatic ester;
(2) cycloaddition reaction: according to the content of linoleate in mixed aliphatic ester, by maleic acid diester/linoleate mol ratio=0.9 ~ 1.1, add maleic acid diester in mixed aliphatic ester; Then under nitrogen protection and the existence of cycloaddition catalyzer, be heated to 160 ~ 280 ℃, polyreaction 3 ~ 12 hours; React complete, cool to 120 ~ 240 ℃, vacuumize, keep vacuum tightness more than 750mmHg, to carry out underpressure distillation, distillate is biofuel, and still liquid is C
22-cycloaliphatic three acid esters;
Wherein the cycloaddition catalyzer described in step (2) is atlapulgite or iodine, and what its add-on was equivalent to linoleate quality in mixed aliphatic ester is greater than 0 and be less than or equal to 3%;
Wherein described in step (1), natural fats and oils is Oleum Gossypii semen, rapeseed oil, soybean oil or waste animal and vegetable oil;
Wherein the maleic acid diester described in step (2) is dimethyl maleate, ethyl maleate, dibutyl maleinate, Diisopentyl Maleate Using or dioctyl maleate;
Wherein described in step (1), low-carbon alcohol is methyl alcohol, ethanol, Virahol;
Wherein the described catalyzer of step (1) be 98% vitriol oil, anhydrous phosphoric acid, solid super-strong acid any or be any in potassium hydroxide, sodium hydroxide, CaO or MgO.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210047269.6A CN102839055B (en) | 2012-02-28 | 2012-02-28 | Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210047269.6A CN102839055B (en) | 2012-02-28 | 2012-02-28 | Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil |
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| Publication Number | Publication Date |
|---|---|
| CN102839055A CN102839055A (en) | 2012-12-26 |
| CN102839055B true CN102839055B (en) | 2014-08-13 |
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| CN201210047269.6A Expired - Fee Related CN102839055B (en) | 2012-02-28 | 2012-02-28 | Method for producing biodiesel oil and C22-cyclic fatty triacid ester by using natural oil |
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| CN109576017B (en) * | 2017-09-28 | 2021-01-05 | 中国石油化工股份有限公司 | Method for preparing low-sulfur diesel lubricity improver under supercritical condition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944582A (en) * | 2006-10-19 | 2007-04-11 | 清华大学 | Method for producing biological diesel oil |
| CN1958748A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Fuel composition in use for internal-combustion engine |
| CN101260311A (en) * | 2008-04-29 | 2008-09-10 | 江苏工业学院 | Method for coproducing biological diesel oil and dimeric dibasic acid ester by using animals and plants grease |
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2012
- 2012-02-28 CN CN201210047269.6A patent/CN102839055B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958748A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Fuel composition in use for internal-combustion engine |
| CN1944582A (en) * | 2006-10-19 | 2007-04-11 | 清华大学 | Method for producing biological diesel oil |
| CN101260311A (en) * | 2008-04-29 | 2008-09-10 | 江苏工业学院 | Method for coproducing biological diesel oil and dimeric dibasic acid ester by using animals and plants grease |
Non-Patent Citations (4)
| Title |
|---|
| 吕涯等.生物柴油低温流动性能的研究.《上海化工》.2007,(第12期), |
| 张雅岸等.来自天然植物油的聚合物.《高分子通报》.2009,(第01期), |
| 来自天然植物油的聚合物;张雅岸等;《高分子通报》;20090115(第01期);全文 * |
| 生物柴油低温流动性能的研究;吕涯等;《上海化工》;20071215(第12期);全文 * |
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Address after: 213016 Baiyun District, Changzhou, Jiangsu Patentee after: Changzhou University Patentee after: Jiangsu Kate New Energy Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University Patentee before: Jiangsu Kate New Energy Co., Ltd. |
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