CN100451088C - Production process of biological diesel oil - Google Patents

Production process of biological diesel oil Download PDF

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Publication number
CN100451088C
CN100451088C CNB2006101634851A CN200610163485A CN100451088C CN 100451088 C CN100451088 C CN 100451088C CN B2006101634851 A CNB2006101634851 A CN B2006101634851A CN 200610163485 A CN200610163485 A CN 200610163485A CN 100451088 C CN100451088 C CN 100451088C
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acid
lipid acid
glycerine
aliphatic hydrocarbon
biofuel
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CN1970694A (en
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张以光
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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
    • 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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  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention discloses a making method of biological diesel, which is characterized by the following: proceeding ester-transmitting reaction for aminal and oil grease with some short-chain alcohol under catalyst; obtaining aliphatic acid methyl ester composition with C16 and C18; decomposing aliphatic acid methyl ester into aliphatic acid and carbinol; oxidizing easily under long time illumination; decarboxylating aliphatic acid to obtain aliphatic hydrocarbon with C15 and C17 catalyzed by quinoline and copper.

Description

A kind of preparation method of biofuel
Technical field
That the present invention relates to is a kind of preparation method of biofuel, especially a kind of from lipid acid decarboxylize generate aliphatic hydrocarbon and be prepared into method of bio-diesel oil.
Background technology
After last century, the eighties biofuel was succeeded in developing,, and make the technical study of biofuel and commercial applications in the ascendant because of its conservation of resources value, environment protection are worth and successful commercial value.Aspect technical study, at present, the preparation of biofuel has acid, base catalysis method, and enzyme catalysis method is arranged, the major technique key of these methods is that animal and plant grease and some short chain alcohol under the katalysis of catalyzer transesterification reaction are taken place, and the end product of these methods is to contain C 16And C 18Fatty acid methyl ester admixture, fatty acid methyl ester has the chemical property of general ester, as ester hydrolysis, ester alcoholysis etc., thereby fatty acid methyl ester can be generated lipid acid and methyl alcohol by airborne water molecules hydrolysis, under long illumination, fatty acid methyl ester is easily generated superoxide by airborne dioxygen oxidation, thereby causes the instability of biofuel quality.And in fact, the diesel oil of heating up in a steamer of oil is a class C 11-C 19Fat hydrocarbon mixture.And the technology of preparing of existing biofuel has exactly been ignored the existence of aliphatic hydrocarbon, has focused on the research and development of fatty acid methyl ester.Compare with fatty acid methyl ester, aliphatic hydrocarbon is more near the composition of heating up in a steamer of oil diesel oil, and meets international 0# diesel quality standard.The grease that in the seed of plant or fruit, extracts, the glycerin fatty acid ester that great majority are made up of 14-20 carbochain, these glycerin fatty acid esters are changed into the fat hydrocarbon material, then can prepare biofuel, Vegetable oil lipoprotein is a kind of recyclability resource, preparing biofuel thus has a extensive future, in this respect, existing research all is fruitful, yet also exist the space that to excavate, and the decarboxylation of fatty acids that will move, plant in the grease obtains method of bio-diesel oil, yet there are no relevant technology and discloses.
Summary of the invention
Purpose of the present invention just provides in a kind of driven, Vegetable oil lipoprotein and obtains method of bio-diesel oil through decarboxylation, overcome in the present technology deficiency that just obtains fatty acid methyl ester through catalysis process, these deficiencies comprise that the fatty acid methyl ester of gained is easy to hydrolysis and is easy to oxidation and makes biofuel quality instability.
The present invention is based on such principle: the animal and plant grease is under the catalysis of acid, and hydrolysis generates glycerine and lipid acid, and reaction formula is:
Figure C20061016348500041
R 1Represent C 18Aliphatic group, R 2Represent C 16Aliphatic group.
Above-mentioned reaction gained lipid acid heats in the organic solvent quinoline, and under the catalysis of cupric ion, the C-C bond rupture between carboxyl and the alkyl generates aliphatic hydrocarbon and emits carbonic acid gas again, and reaction formula is:
R represents C 16And C 18Aliphatic group.
Therefore, according to above-mentioned principle, for realizing purpose of the present invention, the present invention has taked such technical scheme: a kind of preparation method of biofuel is a feedstock production with the animal-plant oil, and described preparation method is:
(1) getting the animal and plant grease, to add weight ratio be 30-60%, and concentration is the sulfuric acid of 10-30%, reacts completely under 40-80 ℃ condition, obtains glycerine and lipid acid is standby;
(2) water gaging such as adding in above-mentioned glycerine and lipid acid, glycerine solution is soluble in water, and lipid acid floats on liquid level, separates also to reclaim glycerine, and the lipid acid of gained washes with water, is washed till PH=5-7, flush away free sulfuric acid then, it is standby to obtain purer lipid acid;
(3) add the organic solvent quinoline that accounts for fatty acid wt 30-70% in above-mentioned lipid acid, and add the copper powder catalysis of the 5-20% that accounts for fatty acid wt, reaction is 1-4 hour under 160-250 ℃ condition, obtains the aliphatic hydrocarbon mixed solution and emits carbonic acid gas;
(4) above-mentioned aliphatic hydrocarbon mixed solution is distilled, when boiling range is 160-250 ℃, obtain the organic solvent quinoline, when boiling range is 270-340 ℃, obtain aliphatic hydrocarbon biofuel of the present invention.
Take the present invention of above-mentioned measure, that produce is C 15And C 17Fat hydrocarbon mixture, the diesel oil main component of coming out with petroleum fractions is close, meets the quality standard of national 0# diesel oil, after testing, the biofuel that the present invention produces has following physical and chemical index: cetane value is not less than 50; Boiling range: 50% recovered temperature is not higher than 300 ℃, and 90% recovered temperature is not higher than 355 ℃, and 95% recovered temperature is not higher than 365 ℃; Condensation point: be not higher than 0 ℃; Flash-point: be not less than 60 ℃.The inventive method is scientific and reasonable, thereby the acidic hydrolysis yield of animals and plants fat reaches more than 95%, and the decarboxylation reaction yield has reached more than 89%.
Embodiment
Embodiment 1
(1) getting 10 kilograms of animal and plant greases, to add 5 kilograms of concentration be 30% sulphuric acid soln, reacts under 40 ℃ condition, and question response is complete, obtains glycerine and the lipid acid mixing solutions is standby, and this moment, yield was 95%;
(2) water gaging such as adding in the mixing solutions of above-mentioned glycerine and lipid acid, this moment, glycerine solution was soluble in water, and lipid acid floats on liquid level, separate the back and reclaim glycerine, the lipid acid of gained washes with water, is washed till PH=7, remove free sulfuric acid, it is standby to obtain purer lipid acid;
(3) add 4 kilograms of organic solvent quinoline in above-mentioned lipid acid, and add 1 kilogram of copper powder catalysis, reaction is 2 hours under 200 ℃ condition, obtains the aliphatic hydrocarbon mixed solution and emits carbonic acid gas, and this moment, yield was 89%.
(4) above-mentioned aliphatic hydrocarbon mixed solution is distilled, when boiling range is 160-250 ℃, reclaim and obtain the organic solvent quinoline, when boiling range is 270-340 ℃, obtain aliphatic hydrocarbon biofuel of the present invention.
Embodiment 2
(1) getting 10 kilograms of animal and plant greases, to add 5 kilograms of concentration be 10% sulphuric acid soln, reacts under 80 ℃ condition, and question response is complete, obtains glycerine and the lipid acid mixing solutions is standby, and this moment, reaction yield was 95%;
(2) water gaging such as adding in above-mentioned glycerine and lipid acid, glycerine solution is soluble in water, and lipid acid floats on liquid level, separates also to reclaim glycerine, and the lipid acid of gained washes with water, is washed till PH=5, flush away free sulfuric acid then, it is standby to obtain purer lipid acid;
(3) add 5 kilograms of organic solvent quinoline solution in above-mentioned lipid acid, and add 1 kilogram of copper powder catalysis, reaction is 2 hours under 200 ℃ condition, obtains the aliphatic hydrocarbon mixed solution and emits carbonic acid gas, and this moment, yield was 89%.
(4) above-mentioned aliphatic hydrocarbon mixed solution is distilled, when boiling range is 160-250 ℃, obtain the organic solvent quinoline, when boiling range is 270-340 ℃, obtain aliphatic hydrocarbon biofuel of the present invention.

Claims (1)

1, a kind of preparation method of biofuel is that raw material is prepared with the animal and plant grease, it is characterized in that described preparation method is:
(1) getting the animal and plant grease, to add weight ratio be 30-60%, and concentration is the sulfuric acid of 10-30%, reacts completely under 40-80 ℃ condition, obtains glycerine and lipid acid is standby;
(2) water gaging such as adding in above-mentioned glycerine and lipid acid, glycerine solution is soluble in water, and lipid acid floats on liquid level, separates also to reclaim glycerine, and the lipid acid of gained washes with water, is washed till PH=5-7, flush away free sulfuric acid then, it is standby to obtain purer lipid acid;
(3) add the organic solvent quinoline that accounts for fatty acid wt 30-70% in above-mentioned lipid acid, and add the copper powder catalysis of the 5-20% that accounts for fatty acid wt, reaction is 1-4 hour under 160-250 ℃ condition, obtains the aliphatic hydrocarbon mixed solution and emits carbonic acid gas;
(4) above-mentioned aliphatic hydrocarbon mixed solution is distilled, when boiling range is 160-250 ℃, obtain the organic solvent quinoline, when boiling range is 270-340 ℃, obtain the aliphatic hydrocarbon biofuel.
CNB2006101634851A 2006-12-07 2006-12-07 Production process of biological diesel oil Expired - Fee Related CN100451088C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870927B (en) * 2010-06-25 2012-09-05 昆明理工大学 Method and device for preparing fatty acid methyl ester from oil residue
CN102477357A (en) * 2010-11-25 2012-05-30 中国石油化工股份有限公司 Method for preparing biodiesel
CN103408415A (en) * 2013-07-22 2013-11-27 张家港保税区超威电化技术服务有限公司 Synthesis method of capacitance grade 2-sebacate
CN103436371B (en) * 2013-08-27 2015-02-25 龚伟 Novel technology for preparing biodiesel by virtue of low-temperature enzyme fermentation method
CN103436369B (en) * 2013-09-04 2015-04-29 西安石油大学 Method for synchronously preparing biodiesel and glycerol carbonate under acceleration action of methanol
CN104479767A (en) * 2014-11-25 2015-04-01 重庆太鲁科技发展有限公司 Diesel engine fuel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1793288A (en) * 2006-01-09 2006-06-28 赵金玉 Esterification catalyst for preparing biological diesel oil by animal plant lipid and application method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1793288A (en) * 2006-01-09 2006-06-28 赵金玉 Esterification catalyst for preparing biological diesel oil by animal plant lipid and application method

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
生物柴油的生产技术. 梁斌.化工进展，第24卷第6期. 2005
生物柴油的生产技术. 梁斌.化工进展，第24卷第6期. 2005 *
生物柴油的研究与进展. 徐桂转等.华中农业大学学报，第24卷第6期. 2005
生物柴油的研究与进展. 徐桂转等.华中农业大学学报，第24卷第6期. 2005 *

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