CN1718679A - Subcritical methanol phase solid acid alkali catalytic stearic exchange system method of bio-diesel oil - Google Patents
Subcritical methanol phase solid acid alkali catalytic stearic exchange system method of bio-diesel oil Download PDFInfo
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- CN1718679A CN1718679A CNA2005100126602A CN200510012660A CN1718679A CN 1718679 A CN1718679 A CN 1718679A CN A2005100126602 A CNA2005100126602 A CN A2005100126602A CN 200510012660 A CN200510012660 A CN 200510012660A CN 1718679 A CN1718679 A CN 1718679A
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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
A kind of subcritical methanol phase solid acid alkali catalytic stearic exchange system method of bio-diesel oil is that vegetables oil and methyl alcohol are added autoclave with the ratio of mol ratio 1: 3～60, the solid catalyst that adds oil quantity 2～10wt%, 130～180 ℃ of control reaction temperature, reaction pressure 1～8MPa, 5～50 minutes reaction times; The product that obtains after reaction finishes is centrifugal or filter to isolate catalyzer, reaction product standing demix, upper strata are methyl alcohol and fatty acid methyl ester admixture, and it is biofuel that distillating carbinol obtains fatty acid methyl ester, lower floor is the mixture of methyl alcohol and glycerine, and distillating carbinol obtains glycerine.Have temperature of reaction and pressure is low, facility investment is little, the advantage that the reaction times is short.
Description
Technical field
The present invention relates to the renewable energy source domain, belong to the green chemical industry process, is a kind of subcritical methanol phase solid acid alkali catalytic grease and methyl alcohol transesterify production method of bio-diesel oil.
Background technology
Biofuel is meant and comes from the material that biological product can be used as diesel-fuel, comprises fatty acid ester that the crackate of vegetable and animals oils or vegetable and animals oils and short chain alcohol transesterify obtain etc.That biofuel has is renewable, burning fully, little, the readily biodegradable of tail gas pollution, characteristics such as harmless.Biofuel research and use for the reply oil crisis, improve fuel safety, be that the transition etc. of fuel band after the petroleum resources exhaustion is significant.The application of biofuel at present mainly contains following four kinds of methods: directly mix use, microemulsified, pyrolysis, transesterify, ester-interchange method is that transesterification reaction is taken place for triglyceride level and low mass molecule alcohol (methyl alcohol or ethanol), generate fatty acid ester, can be separately or be mixed for the engine of any current version with ordinary diesel oil, need not change, be the main developing direction of biofuel.
Biodiesel manufacture is based on chemical method and biological process at present, promptly realize the transesterification reaction of triglyceride level and methyl alcohol by liquid soda acid homogeneous catalysis, as alkali lye catalysis grease and the methyl alcohol transesterify of ZL98811443.7 by potassium, the reaction process complexity, long reaction time, the separation problem that has catalyzer and saponification resultant, aftertreatment produces large amount of sewage.Problems such as pollution at the liquid acid alkaline catalysts, Cao Weiliang passes through solid acid alkali catalytic grease and methyl alcohol preparing biodiesel by ester exchange in the CN200410038292.4 application for patent, without sewage discharge, environmentally safe, but, add the catalyzer phase, interphase mass transfer difficulty in the reaction process because reactant methanol is insoluble with grease, thereby reaction process is longer, and the reaction times is 3～15 hours.Biological process is to utilize the biological enzyme transesterify, by biological enzyme grease and methyl alcohol transesterify, reaction conditions gentleness, environmental friendliness, reaction process are simple and easy to control, enzyme reuses or the like as ZL03119600.4, but speed of response is slow, methyl alcohol is toxic for biological enzyme, enzyme price height.
Supercritical methanol system methyl alcohol and grease dissolve each other, and have solved the interphase mass transfer problem, and transesterification reaction becomes homogeneous reaction from heterogeneous reaction, thereby speed of response significantly improves the reaction times shortening.Ayhan Demirbas etc. has carried out the research of supercritical methanol phase six vegetable oil and methyl alcohol ester-exchange reaction, temperature of reaction is above 240～300 ℃, methyl alcohol grease mol ratio surpasses under 40 the condition, the productive rate of fatty acid methyl ester has surpassed 90% (Energy Conversionand Management, 2002 (43): 2349～2356) during 5 minutes reaction times.The king of Wuhan Institute of Chemical Technology deposits the patent CN200410013430.3 that literary composition etc. is also declared relevant preparing biodiesel under supercritical condition in 2004, and at 220～400 ℃, 8～25MPa carries out transesterification reaction, 4～30 minutes reaction times.Supercritical methanol phase methyl alcohol and greasy transesterification reaction catalyst-free carry out but be reflected under the high-temperature and high-pressure conditions, and higher to equipment requirements, industrialization has difficulties.
Summary of the invention
The purpose of this invention is to provide the production method of bio-diesel oil that a kind of reaction times is short, reaction conditions is gentle.
Methyl alcohol and greasy supercritical phase behavioral study find that along with the variation of methyl alcohol and grease ratio, the stagnation point of system also changes, and table 1 dissolves each other a little and the critical point determination result for the methanol/soybean oil binary system.
Table 1 methanol/soybean oil binary system dissolves each other a little and critical point determination
| Methyl alcohol/grease (mole) | 268 | 217 | 161 | 108 | 54 |
| Dissolve each other temperature (℃) | 124.8 | 124.9 | 124.5 | 137.9 | 136.0 |
| Miscibility pressure (MPa) | 1.01 | 0.61 | 0.59 | 0.86 | 0.90 |
| Critical temperature (℃) | 248.3 | 249.6 | 251.6 | 271.7 | 314.0 |
| Emergent pressure (MPa) | 8.44 | 8.64 | 8.76 | 10.66 | 13.31 |
By table 1 as seen, the mass ratio of methyl alcohol and soybean oil from reduce to 54: 1 process at 268: 1, its mixture critical temperature has been raised to 314.0 ℃ from 248.3 ℃, emergent pressure also becomes 13.31Mpa from 8.67MPa, reduction along with quantity of methyl alcohol, critical temperature and emergent pressure are more and more higher, thereby mol ratio is that 40 o'clock supercritical methanol phase transesterification reaction temperature should be higher than 300 ℃ far away usually.Simultaneously, also find in the thermodynamic study process, methyl alcohol and grease dissolve each other in the time of 120～140 ℃, this moment, pressure also was no more than 1Mpa, reduction along with quantity of methyl alcohol, the temperature of dissolving each other and miscibility pressure slightly raise but well below stagnation point, this moment, then the interphase mass transfer problem obtained solution if carry out methyl alcohol and greasy transesterification reaction.
The present invention be with the low-temperature catalytic activity of solid acid-base and subcritical methyl alcohol mutually methyl alcohol combine with the greasy characteristic of dissolving each other, have complementary advantages, both solved the high pressure-temperature problem in the supercritical methanol phase non-catalytic reaction process, solve the interphase mass transfer problem that methyl alcohol and grease do not dissolve each other and brings in the popular response process again, under lower temperature conditions, finished methyl alcohol and greasy transesterification reaction faster.
Concrete operations step of the present invention is as follows: be raw material with the vegetables oil, carry out transesterification reaction at subcritical methyl alcohol by solid acid alkali catalytic methyl alcohol and grease and prepare biofuel that its concrete steps comprise:
(1), be that 1: 3～60 ratio adds autoclave with vegetables oil and methyl alcohol with mol ratio, add the solid catalyst of oil quantity 2～10wt%, 130～180 ℃ of control reaction temperature, reaction pressure 1～8MPa, 5～50 minutes reaction times;
(2), the product that after reaction finishes (1) is obtained is centrifugal or filter to isolate catalyzer, reaction product standing demix, upper strata are methyl alcohol and fatty acid methyl ester admixture, and it is biofuel that distillating carbinol obtains fatty acid methyl ester, lower floor is the mixture of methyl alcohol and glycerine, and distillating carbinol obtains glycerine.
Aforesaid vegetables oil is meant soybean oil, rapeseed oil, Rice pollard oil, Viscotrol C, peanut oil, Trisun Oil R 80 or various discarded edible oil.
Aforesaid solid catalyst is solid acid catalyst or solid base catalyst.
Aforesaid solid acid catalyst is SO
4-/ ZrO
2, SO
4-/ ZrO
2-TiO
2, ZrSO
4Or H type molecular sieve.
Aforesaid solid base catalyst is that solid base catalyst is ZnO, MgO, K
2CO
3/ Al
2O
3Or KF/Al
2O
3
The inventive method mainly contains following characteristics:
1, subcritical methyl alcohol phase methyl alcohol and grease dissolve each other, and have solved the interphase mass transfer problem, and the reaction times shortens greatly, has improved production capacity;
2, reduce temperature of reaction by solid acid alkali catalytic, solved the High Temperature High Pressure problem that supercritical methanol phase reaction process exists, reduced facility investment;
3, the pollution problem that brings of absence of liquid acid-base catalysis belongs to green environmental protection technique.
Embodiment
Embodiment 1:
(1), getting 90 milliliters of soybean oil adds autoclave, adding 9 gram K
2CO
3/ Al
2O
3Catalyzer, 140 ℃ of control reaction temperature, squeezing into methyl alcohol to system pressure by high pressure plunger pump is 2MPa, and add about 160 milliliters of methyl alcohol this moment, and mol ratio is about 1: 42,20 minutes reaction times;
(2), the product that after the reaction end (1) is obtained filters to isolate catalyzer, reaction product standing demix, upper strata are methyl alcohol and fatty acid methyl ester admixture, and it is biofuel that distillating carbinol obtains fatty acid methyl ester, lower floor is the mixture of methyl alcohol and glycerine, and distillating carbinol obtains glycerine.
Embodiment 2:
(1), getting 150 milliliters of rapeseed oils adds autoclave, adding 10 gram SO
4-/ ZrO
2-TiO
2Catalyzer, 150 ℃ of control reaction temperature, squeezing into methyl alcohol to system pressure by high pressure plunger pump is 3MPa, and add about 100 milliliters of methyl alcohol this moment, and mol ratio is about 1: 16,30 minutes reaction times;
(2), the product centrifugation that after the reaction end (1) is obtained goes out catalyzer, reaction product standing demix, upper strata are methyl alcohol and fatty acid methyl ester admixture, and it is biofuel that distillating carbinol obtains fatty acid methyl ester, lower floor is the mixture of methyl alcohol and glycerine, and distillating carbinol obtains glycerine.
Embodiment 3:
(1), getting 200 milliliters of peanut oil adds autoclave, adding 5 gram KF/Al
2O
3Catalyzer, 180 ℃ of control reaction temperature, squeezing into methyl alcohol to system pressure by high pressure plunger pump is 6Mpa, and add about 50 milliliters of methyl alcohol this moment, and mol ratio is about 1: 6,40 minutes reaction times;
(2), with embodiment 1.
Embodiment 4:
(1), get 180 milliliters of Rice pollard oils and add autoclaves, add 18 gram ZnO catalysts, 160 ℃ of control reaction temperature, squeezing into methyl alcohol to system pressure by high pressure plunger pump is 4Mpa, add about 70 milliliters of methyl alcohol this moment, mol ratio is about 1: 9,8 minutes reaction times;
(2), with embodiment 1.
Embodiment 5:
(1), getting 120 milliliters of Trisun Oil R 80s adds autoclave, adding 6 gram SO
4-/ ZrO
2Catalyzer, 150 ℃ of control reaction temperature, squeezing into methyl alcohol to system pressure by high pressure plunger pump is 7Mpa, and add about 130 milliliters of methyl alcohol this moment, and mol ratio is about 1: 26,50 minutes reaction times;
(2), with embodiment 1.
Claims (5)
1, a kind of subcritical methanol phase solid acid alkali catalytic stearic exchange system method of bio-diesel oil is characterized in that comprising the steps:
(1) vegetables oil and methyl alcohol are added autoclave with the ratio of mol ratio 1: 3～60, add the solid catalyst of oil quantity 2～10%, 130～180 ℃ of control reaction temperature, reaction pressure 1～8MPa, 5～50 minutes reaction times;
(2) product that after reaction finishes (1) is obtained is centrifugal or filter to isolate catalyzer, reaction product standing demix, upper strata are methyl alcohol and fatty acid methyl ester admixture, and it is biofuel that distillating carbinol obtains fatty acid methyl ester, lower floor is the mixture of methyl alcohol and glycerine, and distillating carbinol obtains glycerine.
2, the method for claim 1 is characterized in that described vegetables oil is soybean oil, rapeseed oil, Rice pollard oil, Viscotrol C, peanut oil, Trisun Oil R 80 or various discarded edible oil.
3, the method for claim 1 is characterized in that solid catalyst is solid acid catalyst or solid base catalyst.
4, method as claimed in claim 3 is characterized in that described solid acid catalyst is SO
4-/ ZrO
2, SO
4-/ ZrO
2-TiO
2, ZrSO
4Or H type molecular sieve.
5, method as claimed in claim 3 is characterized in that described solid base catalyst is ZnO, MgO, K
2CO
3/ Al
2O
3Or KF/Al
2O
3
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100126602A CN100344732C (en) | 2005-07-06 | 2005-07-06 | Method of making biodiesel oil by subcritical methanol phase solid acid alkali catalytic oil fat ester exchange |
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| CNB2005100126602A CN100344732C (en) | 2005-07-06 | 2005-07-06 | Method of making biodiesel oil by subcritical methanol phase solid acid alkali catalytic oil fat ester exchange |
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|---|---|
| CN1718679A true CN1718679A (en) | 2006-01-11 |
| CN100344732C CN100344732C (en) | 2007-10-24 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100448946C (en) * | 2006-07-10 | 2009-01-07 | 中国科学院广州能源研究所 | Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor |
| CN101818083A (en) * | 2010-06-02 | 2010-09-01 | 天津大学 | Method for preparing biodiesel by using chenopodium glaucum linn |
| US7897798B2 (en) | 2006-08-04 | 2011-03-01 | Mcneff Research Consultants, Inc. | Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same |
| US7943791B2 (en) | 2007-09-28 | 2011-05-17 | Mcneff Research Consultants, Inc. | Methods and compositions for refining lipid feed stocks |
| US8017796B2 (en) | 2007-02-13 | 2011-09-13 | Mcneff Research Consultants, Inc. | Systems for selective removal of contaminants from a composition and methods of regenerating the same |
| CN102320924A (en) * | 2011-07-15 | 2012-01-18 | 潍坊市元利化工有限公司 | Method for preparing C16-18 alcohol from oil waste and soap waste |
| US8252949B2 (en) | 2007-06-11 | 2012-08-28 | Kao Corporation | Process for producing fatty acid esters |
| US8361174B2 (en) | 2008-10-07 | 2013-01-29 | Sartec Corporation | Catalysts, systems, and methods for producing fuels and fuel additives from polyols |
| US8445709B2 (en) | 2006-08-04 | 2013-05-21 | Mcneff Research Consultants, Inc. | Systems and methods for refining alkyl ester compositions |
| CN103343055A (en) * | 2013-06-24 | 2013-10-09 | 合肥工业大学 | Method for quality improvement of biological oil through catalytic esterification-deoxidize reforming in subcritical alcohol system |
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| US7897798B2 (en) | 2006-08-04 | 2011-03-01 | Mcneff Research Consultants, Inc. | Methods and apparatus for producing alkyl esters from lipid feed stocks and systems including same |
| US8445709B2 (en) | 2006-08-04 | 2013-05-21 | Mcneff Research Consultants, Inc. | Systems and methods for refining alkyl ester compositions |
| US8585976B2 (en) | 2007-02-13 | 2013-11-19 | Mcneff Research Consultants, Inc. | Devices for selective removal of contaminants from a composition |
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| US8361174B2 (en) | 2008-10-07 | 2013-01-29 | Sartec Corporation | Catalysts, systems, and methods for producing fuels and fuel additives from polyols |
| US9102877B2 (en) | 2008-11-12 | 2015-08-11 | Sartec Corporation | Systems and methods for producing fuels from biomass |
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| CN101818083A (en) * | 2010-06-02 | 2010-09-01 | 天津大学 | Method for preparing biodiesel by using chenopodium glaucum linn |
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| CN103343055A (en) * | 2013-06-24 | 2013-10-09 | 合肥工业大学 | Method for quality improvement of biological oil through catalytic esterification-deoxidize reforming in subcritical alcohol system |
| CN103894168A (en) * | 2014-04-18 | 2014-07-02 | 厦门大学 | Magnesium oxide solid base catalyst as well as preparation method and application thereof |
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Assignee: Shanxi SANHENG Chemical Technology Co Ltd Assignor: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2009.9.4 to 2014.12.29 Contract record no.: 2009990001288 Denomination of invention: Method of making biodiesel oil by subcritical methanol phase solid acid alkali catalytic oil fat ester exchange Granted publication date: 20071024 License type: Exclusive license Record date: 20091125 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.9.4 TO 2014.12.29; CHANGE OF CONTRACT Name of requester: SHANXI SANHENG CHEMICAL TECHNOLOGY CO., LTD. Effective date: 20091125 |
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