CN100497526C - Method for synthesizing biologic diesel oil based on ion liquid - Google Patents
Method for synthesizing biologic diesel oil based on ion liquid Download PDFInfo
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- CN100497526C CN100497526C CNB2005100829720A CN200510082972A CN100497526C CN 100497526 C CN100497526 C CN 100497526C CN B2005100829720 A CNB2005100829720 A CN B2005100829720A CN 200510082972 A CN200510082972 A CN 200510082972A CN 100497526 C CN100497526 C CN 100497526C
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
A process based on ionic liquid for synthesizing biologic diesel oil features that the ionic liquid can be used as both catalyst and solvent, so speeding up the reaction. Said ionic liquid is prepared from the N or P contained compound (alkylimidazole, alkylpyredine, quaternary ammonium salt, etc) and the halide (or acidic salt) of metal or non-metal.
Description
Technical field:
The present invention relates to green, field of renewable energy technology, specifically refer to a kind of method based on ion liquid catalysis for preparing biodiesel oil.
Background technology:
Along with fossil resource peter out and worldwide environmental protection problem comes into one's own day by day, the reproducible energy and resource are all being sought by various countries.Because world's vehicle diesel oil trend is accelerated day by day, the diesel oil demand increases rapidly, biofuel (fatty acid methyl ester) as biomass energy, because it is wide, renewable to have raw material sources, have advantages such as the petrifaction diesel of being better than at aspects such as combustionproperty, pollutant emission, cetane value, therefore, be subjected to attention and the rapid exploitation and the utilization and extention of developed countries such as America and Europe very soon.
Biofuel was succeeded in developing in Germany in 1988, be as raw material with rapeseed oil, and formally put on market in 1989, use through 3 years proves, use the various performance performances of B30 biofuel (30% biofuel+70% petrifaction diesel) machine good, reduced poisonous, discharge of harmful gases significantly, Germany began to promote the use of biofuel in 1991.
The U.S. begins to use soybean oil as the raw material production biofuel nineteen ninety, and is classified as clean fuel by national energy administration, applies, and existing blending ratio is a biofuel 20%+ petrifaction diesel 80% (B20).
The production of biodiesel catalyst system therefor mainly is mineral alkali (as sodium hydroxide) and mineral acid (as the vitriol oil) at present.The use of these catalyzer has caused very big negative effect, and such as the corrodibility height, catalyzer is difficult recycles product aftertreatment complexity etc.It is imperative to design and develop new and effective clean catalysis agent and technology.
There is abundant raw material crop resource in China, but the research of biofuel is in the starting stage, has also carried out the research work of some biofuel for many years, has a long way to go but compare with western developed country.The Chinese government has formulated a series of policies and measure for the solution energy, resource, problem of environment, believes that one accelerates China's biofuel research steps surely.
Summary of the invention:
A kind of ionic liquid is as the method for synthesizing biologic diesel oil of catalyzer, be to use animal-plant oil and methyl alcohol as reactant, catalyzer is selected from the composite catalyst that a kind of or this ionic liquid in acidity or the basic imidazole class ionic liquid and other catalyzer form, wherein other catalyzer are selected from a kind of in acid or the alkali according to ion liquid acid-basicity, in the reaction pressure scope is 0.1-1MPa, temperature range is 303.15K-573.15K, reaction times 50min-20h, molar ratio of methanol to oil is 3:1-30:1, is used for catalytic transesterification and prepares biofuel.
The structural formula of used glyoxaline ion liquid catalyzer is A
+B
-:
Cation A
+Structural formula is
Substituent R in the formula
1, R
2Be selected from a kind of in alkane group, olefin group, aromatic hydrocarbon group, the heterocyclic group respectively, wherein R
1, R
2Substituent carbon number is between 1-18; Negatively charged ion B
-Be selected from HS0
4 -, OH
-, H
2PO
4 -In a kind of.
The alkali of forming composite catalyst with basic imidazole class ionic liquid is selected from a kind of in sodium hydroxide, yellow soda ash, salt of wormwood, sodium oxide, potassium oxide, sodium alkoxide, the potassium alcoholate.
The acid of forming composite catalyst with acid glyoxaline ion liquid is selected from the vitriol oil, strong phosphoric acid, toluenesulphonic acids, Witco 1298 Soft Acid, a kind of in the naphthene sulfonic acid.
In the composite catalyst, the mol ratio of ionic liquid and other catalyzer is 15:1-1:15.
Wherein catalyst levels is lower than 20% of raw materials quality.
Compare with traditional catalyzer, ionic liquid used in the present invention (or by its composite catalyst that constitutes) has the following advantages in the transesterify process:
1. can help the mixing of reactant simultaneously as reaction medium and catalyzer, quickening can be reacted;
2. ionic liquid has steam and forces down, characteristics such as cleaning, do not have in the use volatilization, pollution-free, corrodibility is low;
3. structure can design, and can synthesize different functionalized ion liquids as required;
4. after glycerine being isolated, the recyclable utilization of ionic liquid.
Compare with traditional method, this synthetic method has simple, the environmental friendliness of technology, and catalyzer such as can reuse at advantage, is expected to become the cleaning procedure synthetic route that has competitive power.
Embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
The alkali ionic liquid catalytically synthesizing biological diesel oil
Used ionic liquid is [emim] OH
Reaction implementation method: 20g (about 0.023mol) soya-bean oil is joined in the there-necked flask of 50mL clean dried, normal pressure places 60 ℃ of oil bath preheatings, meanwhile with pure methyl alcohol of 4.4g anhydrous assay (approximately O.138mol) and 0.2g[emim] OH ionic liquid thorough mixing and in oil bath, joining rapidly in three mouthfuls of round-bottomed flasks behind the backflow preheat to 60 ℃, controlled temperature is at 60 ± 0.1 ℃, reaction 1h the results are shown in following table 1.
Table 1 NaOH compares with [emim] OH catalytic performance
Embodiment 2
Alkali ionic liquid and other alkali composite catalyzing biodiesel synthesis
Used ionic liquid is [emim] OH+NaOH
Reaction implementation method: 20g soya-bean oil is joined in the there-necked flask of 50mL clean dried, place 60 ℃ of oil bath preheatings, meanwhile with pure methyl alcohol of 4.4g anhydrous assay and 0.1g[emim] OH and 0.1g NaOH thorough mixing and in oil bath, join rapidly in three mouthfuls of round-bottomed flasks behind the backflow preheat to 60 ℃, controlled temperature is at 60 ± 0.1 ℃, reaction 50min the results are shown in following table 2.
Table 2 NaOH compares with [emim] OH+NaOH catalytic performance
Embodiment 3
The presence of acidic ionic liquid catalyst biodiesel synthesis
Ionic liquid is [bmim] HSO
4
Reaction implementation method: 20g soya-bean oil and the pure methyl alcohol of 10.72g anhydrous assay (about 0.46mol) are joined in the there-necked flask of 125mL clean dried, place 80 ℃ of oil bath preheatings, meanwhile with pure methyl alcohol of 4.0g anhydrous assay (reducing the ionic liquid viscosity) and 2g[bmim] HSO
4Thorough mixing and be preheated to 60 ℃ after join rapidly in three mouthfuls of round-bottomed flasks, controlled temperature is at 80 ± 0.1 ℃, reaction 20h the results are shown in following table 3.
The dense H of table 3
2SO
4With [bmim] HSO
4Catalytic performance relatively
Embodiment 4
Acidic ion liquid and other sour composite catalyzing biodiesel synthesis
Used catalyst system is [bmim] HSO
4+ H
2SO
4
Reaction implementation method: 20g (about 0.023mol) soya-bean oil and the pure methyl alcohol of 10.72g anhydrous assay (about 0.46mol) are joined in the there-necked flask of 125mL clean dried, place 80 ℃ of oil bath preheatings, meanwhile with pure methyl alcohol of 4.0g anhydrous assay (reducing the ionic liquid viscosity) and 2g[bmim] HSO
4Reach 0.2g vitriol oil thorough mixing and be preheated to 60.Join rapidly behind the C in three mouthfuls of round-bottomed flasks, controlled temperature is at 80 ± 0.1 ℃, and reaction 20h the results are shown in following table 4.
The dense H of table 4
2SO
4With [bmim] HSO
4+ H
2SO
4Catalytic performance relatively
Embodiment 5
The composite catalyst repeat performance of ionic liquid and formation thereof
Adopt soya-bean oil and methyl alcohol at temperature range 60-80 ℃, carry out the transesterify biodiesel synthesis under the reaction times 1-20h condition and understand the reusable possibility of composite catalyst of ionic liquid and formation thereof, after having reacted each time, after glycerine separated, under 100 ℃ of conditions, suitably water and the unreacted methanol (about 10-20min) in the decompression deionizing liquid fed in raw material once more and repeated transesterification reaction, the results are shown in following table.
Table 5[emim] OH reuses the influence of number of times to catalytic effect
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency/% | 94 | 84 | 78 | 70 |
Table 6[bmim] HSO
4Reuse the influence of number of times to catalytic effect
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency/% | 65 | 62 | 61.8 | 61 |
Table 7[emim] OH+NaOH reuses the influence of number of times to catalytic effect
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency/% | 95 | 90 | 85 | 80 |
Table 8[bmim] HSO
4+ H
2SO
4Reuse the influence of number of times to catalytic effect
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency/% | 75 | 73 | 70 | 69 |
Claims (6)
1. an ionic liquid is as the method for synthesizing biologic diesel oil of catalyzer, it is characterized in that using animal-plant oil and methyl alcohol as reactant, catalyzer is selected from the composite catalyst that a kind of or this ionic liquid in acidity or the basic imidazole class ionic liquid and other catalyzer form, wherein other catalyzer are selected from a kind of in acid or the alkali according to ion liquid acid-basicity, in the reaction pressure scope is 0.1-1MPa, temperature range is 303.15K-573.15K, reaction times 50min-20h, molar ratio of methanol to oil is 3:1-30:1, is used for catalytic transesterification and prepares biofuel.
2. method according to claim 1, the structural formula of used glyoxaline ion liquid catalyzer are A
+B
-: cation A
+Structural formula is
Substituent R in the formula
1, R
2Be selected from a kind of in alkane group, olefin group, aromatic hydrocarbon group, the heterocyclic group respectively, wherein R
1, R
2Substituent carbon number is between 1-18; Negatively charged ion B
-Be selected from HSO
4 -, OH
-, H
2PO
4 -In a kind of.
3. method according to claim 1, the alkali of forming composite catalyst with basic imidazole class ionic liquid are selected from a kind of in sodium hydroxide, yellow soda ash, salt of wormwood, sodium oxide, potassium oxide, sodium alkoxide, the potassium alcoholate.
4. method according to claim 1, the acid of forming composite catalyst with acid glyoxaline ion liquid is selected from the vitriol oil, strong phosphoric acid, toluenesulphonic acids, Witco 1298 Soft Acid, a kind of in the naphthene sulfonic acid.
5. method according to claim 1, in the composite catalyst of composition, the mol ratio of ionic liquid and other catalyzer is 15:1-1:15.
6. method according to claim 1, catalyst levels is lower than 20% of raw materials quality.
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| CN100497526C true CN100497526C (en) | 2009-06-10 |
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Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0505064D0 (en) * | 2005-03-11 | 2005-04-20 | Univ Belfast | Production of bio-diesel |
| EP1878716A1 (en) * | 2006-07-14 | 2008-01-16 | Rohm and Haas Company | Method for transesterification of triglycerides |
| KR100746996B1 (en) | 2006-09-06 | 2007-08-08 | 인하대학교 산학협력단 | Method for production of biodiesel and glycerol using ionic liquids |
| JPWO2010061702A1 (en) * | 2008-11-28 | 2012-04-26 | 国立大学法人京都工芸繊維大学 | Method for producing fatty acid ester |
| CN101451072B (en) * | 2008-12-30 | 2012-12-05 | 广东工业大学 | Method for preparing biodiesel by sulfonic acid type ion liquid |
| CN101475825B (en) * | 2009-01-21 | 2013-11-20 | 王英国 | Method for preparing biodiesel by ester exchange |
| CN101851562B (en) * | 2010-07-05 | 2013-02-13 | 中国人民解放军后勤工程学院 | Technology for preparing biodiesel by food and beverage waste oil |
| CN102492558A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method of preparing biodiesel in ionic liquid |
| CN103160379A (en) * | 2011-12-09 | 2013-06-19 | 深圳市贝壳能源科技有限公司 | Method for producing biodiesel by virtue of high-acid-value oil raw material |
| CN102603451A (en) * | 2012-02-28 | 2012-07-25 | 南开大学 | Method for preparing diphenylethane catalyzed by mixed liquid of concentrated sulfuric acid and ion liquid |
| CN102911793B (en) * | 2012-10-04 | 2013-10-23 | 盐城师范学院 | Functionalized alkaline ionic liquid and application thereof in preparation of biodiesel |
| CN102876466B (en) * | 2012-10-05 | 2013-10-23 | 盐城师范学院 | Method for catalyzing ester exchange reaction with alkaline ionic liquid |
| CN102875471B (en) * | 2012-10-23 | 2016-05-04 | 吴峰 | A kind of alkaline compound ion liquid and biodiesel oil preparing process |
| CN103031217B (en) * | 2012-12-17 | 2014-06-18 | 常州大学 | Method for preparing biodiesel from waste fat oil in presence of catalyst such as pyrrolidone basic ionic liquid |
| CN103131540A (en) * | 2013-02-19 | 2013-06-05 | 华侨大学 | Method for preparing biodiesel based on ionic liquid catalyzing peracid value rice bran oil |
| CN103756791B (en) * | 2013-12-25 | 2015-08-19 | 郑州奇克生物科技有限公司 | The synthetic method of biofuel |
| CN104152276A (en) * | 2014-07-14 | 2014-11-19 | 石家庄新泰特种油有限公司 | Method for catalytic synthesis of monoglyceride from ionic liquid |
| CN104560409B (en) * | 2014-12-19 | 2017-05-24 | 中国科学院广州能源研究所 | Method for direct preparation of biodiesel by utilizing microalgae ultrasonic-assisted ionic liquid composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187309C (en) * | 2002-11-07 | 2005-02-02 | 华东师范大学 | Method of esterifying in ion liquid [Hmim]+ BF4- |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187309C (en) * | 2002-11-07 | 2005-02-02 | 华东师范大学 | Method of esterifying in ion liquid [Hmim]+ BF4- |
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