CN1594504A - Process for supercritical preparation of biologic diesel oil - Google Patents
Process for supercritical preparation of biologic diesel oil Download PDFInfo
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- CN1594504A CN1594504A CNA2004100134303A CN200410013430A CN1594504A CN 1594504 A CN1594504 A CN 1594504A CN A2004100134303 A CNA2004100134303 A CN A2004100134303A CN 200410013430 A CN200410013430 A CN 200410013430A CN 1594504 A CN1594504 A CN 1594504A
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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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- 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
- 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
The invention discloses a process for supercritical preparation of biologic diesel oil by using animal or plant oil, waste edible oil, oiling crop seeds as raw material through the steps of filtering, dewatering, esterification, ester interchange, filtering, steaming methanol and phase-splitting.
Description
Technical field
The present invention relates to a kind ofly prepare the technology of fatty acid methyl ester-biofuel, belong to field of grease chemical technology with vegetable and animals oils.
Background technology
At present, the hot technology of oil fuel is paid attention on the one hand in substituting, the energy in promptly non-petroleum chemistry source; Be what is called " regenerative raw materials " on the other hand, wherein vegetable and animals oils particularly.The vegetable and animals oils main component is a glycerin fatty acid ester, and it belongs to the biodegradable and the Environmental compatibility energy.But, because own physical and chemical performance (molecular weight is big, and low-temperature fluidity is poor, and high high-temp stability is poor) has limited its use on automobile.By chemical process, carry out modification, reduced cold filter clogging temperature, improved high-temperature stability, become so-called biofuel, so just make it can be used as the power fuel of automobile etc.But present biofuel is to use acid or alkali as a catalyst to make vegetables oil and methyl alcohol or ethanol carry out transesterification reaction.This method exists that complex process, pure consumption are big, product is difficult for recovery, shortcoming such as big for environment pollution because of using catalyzer, and be mixed with free lipid acid or water in the reactant, reaction is had very big impairment effect, and product must be washed, and can produce alkali waste in the washing process.
Material has three kinds of special states, i.e. gaseous state, liquid state and solid-state.When temperature surpasses critical temperature, material have by exert pressure also not can condensation liquid state, this state of material is exactly a supercritical state.
Be in postcritical fluid and have different character with liquid or gas.Under supercritical state, fluidic density and density of liquid are approaching, and the viscosity of fluidic viscosity and gas is close, and fluidic thermal conductivity and spread coefficient are between the thermal conductivity and spread coefficient of gas and liquid.Being in postcritical fluid, to be used as non-liquid solvent (or participating in reaction directly) extensive in Application in Chemistry, do not appear in the newspapers at home but directly it is applied on the biodiesel manufacture technology.
Related industries such as present catering trade, grocery trade all can produce a large amount of waste animal vegetable oils every day, these waste oil generally all contain a large amount of impurity, a part is recovered and is used to make soap, but also has quite a few directly to discharge without reclaiming and handling, thereby causes environmental pollution.Simultaneously, annual grain department also has a large amount of stock's oil plants to go bad because of long-term storage, and this part rotten oil does not find the extraordinary approach that utilizes at present yet.Therefore, how to make waste animal vegetable oil obtain fully, effectively utilize, reduce waste animal vegetable oil the pollution of environment such as waters and the injury of human body more and more are subjected to people's attention.Vast rural area has a large amount of waste mountain wastes idle, if be used for planting oil crops, can improve the rural environment resource, increases farmers' income.
The production of biofuel has very big economic benefit.And the social effect that use produced of biofuel can't be estimated especially, the exploitation of bioenergy is a strategic problem that solves the petroleum resources shortage problem, also being to solve the pollution problem that the very difficult exhaust gas emission that solves of oil fuel brings, is a major action of benefiting the nation and the people.
Summary of the invention
The objective of the invention is to provide a kind of supercritical preparation process of biofuel for the shortcoming that overcomes above-mentioned technology.Thisly produce the green energy resource novel process by renewable raw materials, environmental pollution, petroleum-based energy safety are significant.This technological reaction productive rate height, non-pollution discharge, raw material is renewable, aftertreatment is simple, generates green energy resource---biofuel by the Green Chemistry reaction.
For achieving the above object, technical scheme of the present invention is to realize like this.
React with supercritical lower alcohol with vegetable and animals oils, waste edible oil, sewer oil, oil crop seeds by using etc.Produce fatty acid methyl ester by technological processs such as esterification, transesterifys, may further comprise the steps:
(1) filters
(2) dehydration;
(3) esterification, transesterify;
(4) filter;
(5) steam methyl alcohol;
(6) phase-splitting;
Relevant processing condition in the above-mentioned technology:
1, edible oil, sewer oil filter and carry out under 10～40 ℃, continue 20～50 minutes;
2, waste edible oil, sewer oil dehydration are to carry out under 50～100 ℃ vacuum;
3, esterification, transesterify are carried out under 220～400 ℃, 8～25MPa, and used catalyzer is superpower solid acid, superpower solid alkali and metal oxide, and the reaction times is 4～30 minutes;
The consumption of low-carbon alcohol is 6～60 times of vegetable and animals oils amount of substance when 4, esterification, transesterify;
5, oil crop seeds by using filters down at 10～40 ℃, 30～60 minutes time length;
6, steam methyl alcohol and under 60～70 ℃, carry out 30～60 minutes time length.Methyl alcohol can be recycled;
7, phase-splitting is carried out under 20～60 ℃, 20～50 minutes time length.
8, low-carbon alcohol can be selected methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol and n-hexyl alcohol for use.
Raw material of the present invention is easy to get, implements easily, is not only applicable to prepare biofuel with vegetable and animals oils, also is applicable to preparation biofuel such as waste edible oil, sewer oil, oil crop seeds by using.The invention solves and adopt supercritical process by production biofuel such as vegetable and animals oils, waste edible oil, sewer oil, oil crop seeds by using, this biofuel is little than the tail gas pollution of petrifaction diesel, can effectively reduce " Greenhouse effect ".The biofuel supercritical preparation process has realistic meaning to environment protection, Oil Safety, increasing peasant income, ecological protection etc.
Embodiment
Embodiment one:
With 40g edible soybean oil and 100g methanol mixed, add in the high-temperature high-pressure reaction kettle, when being heated to 350 ℃, this moment, tensimeter showed that pressure is 10.4MPa, kept 20 minutes in this temperature then; High-temperature high-pressure reaction kettle is condensed water-cooled to room temperature; Methyl alcohol in the reaction is steamed only at 60～70 ℃, and methyl alcohol can be recycled; Carry out phase-splitting and handle under 30 ℃ condition, continue 30 minutes altogether, promptly generate 36.0g fatty acid methyl ester---biofuel, yield is 90%.Reaction in this example is the reaction that is under the super critical condition.
Embodiment two:
With edible rape seed oil of 60g and 140g methanol mixed, add in the high-temperature high-pressure reaction kettle, add the 2g catalyzer, when being heated to 320 ℃, this moment, tensimeter showed that pressure is 24MPa, kept 20 minutes in this temperature then; High-temperature high-pressure reaction kettle is condensed water-cooled to room temperature; Methyl alcohol in the reaction is steamed only at 60～70 ℃, and methyl alcohol can be recycled; Carry out phase-splitting and handle under 20 ℃ condition, continue 20 minutes altogether, promptly generate 57.2g fatty acid methyl ester---biofuel, yield is 95.3%.Reaction in this example is the reaction that is under the super critical condition.
Embodiment three:
With edible rape seed oil of 50g and 100g methanol mixed, add in the high-temperature high-pressure reaction kettle, when being heated to 250 ℃, this moment, tensimeter showed that pressure is 9.5MPa, kept 20 minutes in this temperature then; High-temperature high-pressure reaction kettle is condensed water-cooled to room temperature; Methyl alcohol in the reaction is steamed only at 60～70 ℃, and methyl alcohol can be recycled; Carry out phase-splitting and handle under 60 ℃ condition, continue 40 minutes altogether, promptly generate 46g fatty acid methyl ester---biofuel, yield is 92%.Reaction in this example is the reaction that is under the super critical condition.
Embodiment four:
Semen Brassicae campestris 50g and methyl alcohol 150g add in the high-temperature high-pressure reaction kettle, and when being heated to 320 ℃, this moment, tensimeter showed that pressure is 22.5MPa, kept 30 minutes in this temperature then; High-temperature high-pressure reaction kettle is condensed water-cooled to room temperature; Reacted coleseed is removed by filter under 25 ℃ of conditions, continue 40 minutes altogether; Methyl alcohol in the reaction is steamed only at 60～70 ℃, and methyl alcohol can be recycled; Carry out phase-splitting and handle under 20 ℃ condition, continue 20 minutes altogether, promptly generate 42g fatty acid methyl ester---biofuel, yield is 84%.Reaction in this example is the reaction that is under the super critical condition.
Embodiment five:
Waste edible oil 50g and methyl alcohol 120g that purifying treatment is crossed mix, and when being heated to 300 ℃, this moment, tensimeter showed that pressure is 13.5MPa, kept 15 minutes in this temperature then; High-temperature high-pressure reaction kettle is condensed water-cooled to room temperature; Methyl alcohol in the reaction is steamed only at 60～70 ℃, and methyl alcohol can be recycled; Carry out phase-splitting and handle under 60 ℃ condition, continue 30 minutes altogether, promptly generate 44.8g fatty acid methyl ester---biofuel, yield is near 90%.Reaction in this example is the reaction that is under the super critical condition.
Claims (10)
1, biofuel supercritical preparation process, it is characterized in that being raw material with vegetable and animals oils, waste edible oil, sewer oil, oil crop seeds by using etc., the solid catalyst effect is following or do not need any catalyzer, reacts with supercritical lower alcohol, may further comprise the steps:
(1) filters
(2) dehydration;
(3) esterification, transesterify;
(4) filter;
(5) steam methyl alcohol;
(6) phase-splitting.
2, biofuel supercritical preparation process according to claim 1 is characterized in that low-carbon alcohol can select methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, Pentyl alcohol and n-hexyl alcohol for use.
3, biofuel supercritical preparation process according to claim 1 is characterized in that it is to carry out that waste edible oil, sewer oil filter, and continues 20～50 minutes under 10～40 ℃.
4, biofuel supercritical preparation process according to claim 1 is characterized in that waste edible oil, sewer oil dehydration are to carry out under 50～100 ℃ vacuum.
5, biofuel supercritical preparation process according to claim 1 is characterized in that esterification, transesterify are to carry out under 220～400 ℃, 8～25Mpa condition, the reaction times is 4～30 minutes.
6, biofuel supercritical preparation process according to claim 1 is characterized in that catalyzer can select superpower solid acid, superpower solid alkali and metal oxide for use.
7, biofuel supercritical preparation process according to claim 1, the consumption of low-carbon alcohol is 6～60 times of vegetable and animals oils amount of substance when it is characterized in that esterification, transesterify.
8, biofuel supercritical preparation process according to claim 1 is characterized in that oil crop seeds by using filters 30～60 minutes time length down at 10～40 ℃.
9, biofuel supercritical preparation process according to claim 1 is characterized in that steaming methyl alcohol and carries out under 60～70 ℃, 30～60 minutes time length.
10, biofuel supercritical preparation process according to claim 1 is characterized in that phase-splitting carries out 20～50 minutes time length under 20～60 ℃.
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| CNA2004100134303A CN1594504A (en) | 2004-07-08 | 2004-07-08 | Process for supercritical preparation of biologic diesel oil |
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| CNA2004100134303A CN1594504A (en) | 2004-07-08 | 2004-07-08 | Process for supercritical preparation of biologic diesel oil |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335595C (en) * | 2005-09-09 | 2007-09-05 | 清华大学 | Continuous biological diesel oil preparing process |
| CN100344732C (en) * | 2005-07-06 | 2007-10-24 | 中国科学院山西煤炭化学研究所 | Method of making biodiesel oil by subcritical methanol phase solid acid alkali catalytic oil fat ester exchange |
| CN100441666C (en) * | 2006-09-01 | 2008-12-10 | 周斌 | Method of obtaining high quality biologic diesel oil |
| CN101331209A (en) * | 2005-11-18 | 2008-12-24 | 卢敏正 | A method for producing biodiesel using supercritical alcohols |
| CN100465249C (en) * | 2006-12-28 | 2009-03-04 | 浙江大学 | Method for preparing biodiesel oil |
| CN101550349A (en) * | 2008-03-31 | 2009-10-07 | 西安市宝润实业发展有限公司 | Method for preparing biodiesel by supercritical technology |
| CN1900224B (en) * | 2005-06-15 | 2010-05-12 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN101818102A (en) * | 2010-04-30 | 2010-09-01 | 大连理工大学 | Method for preparing biodiesel by catalytic intensification of supercritical methanol |
| CN101838591A (en) * | 2010-05-07 | 2010-09-22 | 厦门大学 | Catalytic esterification method of oil with high acid value |
| WO2010148652A1 (en) | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Diesel composition and process for improving oxidation stability of biodiesel |
| CN101225323B (en) * | 2008-02-03 | 2011-09-14 | 大连理工大学 | Method for preparing biodiesel from raw material by overcritical extraction-transesterification coupling process |
| CN101486953B (en) * | 2009-02-19 | 2012-08-08 | 山东科技大学 | Supercritical esterification modification process for bio-oil |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| TWI421335B (en) * | 2010-01-19 | 2014-01-01 | Metal Ind Res & Dev Ct | Continuous system and method for producing biomass diesel |
| TWI421336B (en) * | 2009-12-10 | 2014-01-01 | Metal Ind Res & Dev Ct | Continuous system and method for producing biomass diesel |
| CN104629914A (en) * | 2015-02-04 | 2015-05-20 | 大连理工大学 | Supercritical methanol extraction reaction coupling method for preparing biodiesel oil and coproducing regenerated carclazyte by using waste carclazyte |
| CN105062696A (en) * | 2015-04-16 | 2015-11-18 | 彭才文 | Single-tower countercurrent supercritical non-catalytic continuous esterification process method |
| CN108219979A (en) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | Supercritical extraction biodiesel synthesis |
| CN108728249A (en) * | 2018-06-15 | 2018-11-02 | 成都恒润高新科技股份有限公司 | A method of preparing biodiesel using swill |
| CN110423649A (en) * | 2019-07-15 | 2019-11-08 | 西安理工大学 | The overcritical heterogeneous catalysis preparation system of biodiesel |
-
2004
- 2004-07-08 CN CNA2004100134303A patent/CN1594504A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900224B (en) * | 2005-06-15 | 2010-05-12 | 中国石油化工股份有限公司 | Process for preparing biological diesel oil |
| CN100344732C (en) * | 2005-07-06 | 2007-10-24 | 中国科学院山西煤炭化学研究所 | Method of making biodiesel oil by subcritical methanol phase solid acid alkali catalytic oil fat ester exchange |
| CN100335595C (en) * | 2005-09-09 | 2007-09-05 | 清华大学 | Continuous biological diesel oil preparing process |
| CN101331209A (en) * | 2005-11-18 | 2008-12-24 | 卢敏正 | A method for producing biodiesel using supercritical alcohols |
| CN100441666C (en) * | 2006-09-01 | 2008-12-10 | 周斌 | Method of obtaining high quality biologic diesel oil |
| CN100465249C (en) * | 2006-12-28 | 2009-03-04 | 浙江大学 | Method for preparing biodiesel oil |
| CN101225323B (en) * | 2008-02-03 | 2011-09-14 | 大连理工大学 | Method for preparing biodiesel from raw material by overcritical extraction-transesterification coupling process |
| CN101550349A (en) * | 2008-03-31 | 2009-10-07 | 西安市宝润实业发展有限公司 | Method for preparing biodiesel by supercritical technology |
| CN101486953B (en) * | 2009-02-19 | 2012-08-08 | 山东科技大学 | Supercritical esterification modification process for bio-oil |
| WO2010148652A1 (en) | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Diesel composition and process for improving oxidation stability of biodiesel |
| TWI421336B (en) * | 2009-12-10 | 2014-01-01 | Metal Ind Res & Dev Ct | Continuous system and method for producing biomass diesel |
| TWI421335B (en) * | 2010-01-19 | 2014-01-01 | Metal Ind Res & Dev Ct | Continuous system and method for producing biomass diesel |
| CN101818102A (en) * | 2010-04-30 | 2010-09-01 | 大连理工大学 | Method for preparing biodiesel by catalytic intensification of supercritical methanol |
| CN101838591B (en) * | 2010-05-07 | 2013-08-21 | 厦门大学 | Catalytic esterification method of oil with high acid value |
| CN101838591A (en) * | 2010-05-07 | 2010-09-22 | 厦门大学 | Catalytic esterification method of oil with high acid value |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| CN102965203B (en) * | 2012-10-31 | 2014-06-25 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| CN104629914A (en) * | 2015-02-04 | 2015-05-20 | 大连理工大学 | Supercritical methanol extraction reaction coupling method for preparing biodiesel oil and coproducing regenerated carclazyte by using waste carclazyte |
| CN105062696A (en) * | 2015-04-16 | 2015-11-18 | 彭才文 | Single-tower countercurrent supercritical non-catalytic continuous esterification process method |
| CN108219979A (en) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | Supercritical extraction biodiesel synthesis |
| CN108728249A (en) * | 2018-06-15 | 2018-11-02 | 成都恒润高新科技股份有限公司 | A method of preparing biodiesel using swill |
| CN110423649A (en) * | 2019-07-15 | 2019-11-08 | 西安理工大学 | The overcritical heterogeneous catalysis preparation system of biodiesel |
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