CN102226134A - Method for producing biodiesel by using waste oil - Google Patents
Method for producing biodiesel by using waste oil Download PDFInfo
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- CN102226134A CN102226134A CN201110123397XA CN201110123397A CN102226134A CN 102226134 A CN102226134 A CN 102226134A CN 201110123397X A CN201110123397X A CN 201110123397XA CN 201110123397 A CN201110123397 A CN 201110123397A CN 102226134 A CN102226134 A CN 102226134A
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- 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 by using waste oil. The method comprises the following steps that: (A) acid-containing oil raw materials and alcohol are subjected to a esterification and a ester exchange reaction to obtain a mixture of the biodiesel and crude glycerine, followed by a phase separation to obtain a mixing glycerin layer; (B) the mixing glycerin layer from the step (A) is subject to acidification, evaporation, recovery and separation to seperate methanol, then separating salt, aliphatic acid and methyl esters to obtain the crude glycerine; (C) the separated crude glycerine from the step (B) is added with aldehydes, ketones, acids or a mixture of the aldehydes, the ketones and the acids to carry out a reaction to obtain reaction products, followed by a centrifugation to separate salts to obtain products of glyceryl ketal (acetal), glycerin fatty acid ester and the like; (D) the mixing products of the glyceryl ketal (acetal) and the glycerin fatty acid ester are subjected to a rectification to separate the glyceryl ketal (acetal) and the glycerin fatty acid ester. According to the present invention, the reaction of the crude glycerine is adopted, such that a whole molecular utilization of the waste oil is improved. In addition, the products from the reaction of the crude glycerine are added to the biodiesel as pour point depressants for the biodiesel so as to eliminate pollution of the crude glycerine, reduce production cost, and protect environment.
Description
Technical field
The invention belongs to technical field of new energy production, relate to a kind of novel biofuel production technique particularly, the production biofuel and the glycerine that specially refer to waste oil molecule complete utilization utilize method.
Background technology
Biofuel is the mixture of fatty acid methyl ester, can obtain through transesterification reaction or esterification by animal-plant oil.Fatty acid methyl ester is very approaching with every index of petrifaction diesel on combustioncharacteristics.Therefore it can be separately or is blended in the diesel engine with petrifaction diesel and is used.Because the raw material of production biofuel comes from the animal or plant grease, so biofuel is undoubtedly a kind of reproducible resource.It with sun power, wind energy, tidal energy is called as 21 century that the renewable resources of development potentiality is arranged most.Compare with other 3 kinds of energy, biofuel has the advantage that easy deposit, source are influenced by natural cause at that time extensively and not.At present industrial often is the raw material production biofuel with the natural fats and oils.
A large amount of glycerine of by-product in the production of biodiesel process will produce very large impact to traditional glycerine manufacturing enterprise, because 10 tons of biofuel of every production just will produce 1 ton of glycerine.In recent years, along with the biofuel industry heats up gradually, will cause many traditional glycerine manufacturing enterprises to be forced to close.
The biofuel that waste oil is produced, because the raw material complexity, a large amount of polyunsaturated fatty acid esters is contained in the inside, causes its zero pour higher, is not suitable for using winter, has greatly limited the production and the use of biofuel.Glycerine run-of-the-mill as the biodiesel byproduct product is relatively poor, contains a large amount of inorganic salt, and it is big to obtain the high-purity glycerin facility investment with traditional treatment process, and operational path is long.
Summary of the invention
The purpose of this patent promptly is to utilize waste oil comprehensively, is raw material with the waste oil, and production biofuel and its glycerol derivative pour point depressant solve the condensation point problem of biofuel and the problem of complex utilization of by-product glycerin.
Technical scheme provided by the invention is as follows:
A kind of waste oil production method of bio-diesel oil may further comprise the steps:
(A) acid-containing oil raw material and alcohol are generated biofuel and raw glycerine mixture by the esterification transesterification reaction, utilizing is separated obtains mixing glycerin layer; Composition in this mixing glycerin layer comprises glycerine, methyl alcohol, catalyzer, fatty acid methyl ester etc.;
(B) the steps A gained is mixed the glycerin layer acidifying, evaporation is reclaimed and is isolated methyl alcohol, and separated salt and lipid acid and methyl esters obtain the mixture of raw glycerine;
(C) above-mentioned isolating raw glycerine layer is added aldehyde, ketone, acid or its mixture reaction; The reaction product centrifugation is gone out salt, promptly obtain products such as glycerol ketals (aldehyde), glycerol fatty acid ester;
(D) glycerol ketals (aldehyde), glycerol fatty acid ester are told in the mixing prod rectifying of glycerol ketals (aldehyde), glycerol fatty acid ester.
In preferred embodiment of the present invention, in the acidifying of the described mixture glycerin layer of step B, used acid is protonic acid, comprises sulfuric acid, hydrochloric acid, phosphoric acid, organic acid.
In preferred embodiment of the present invention, the described catalyzer that adds in isolating raw glycerine layer of step C comprises mineral acid, organic acid or its mixture.
In preferred embodiment of the present invention, the described aldehyde that adds in isolating raw glycerine layer of step C comprises polyoxymethylene, acetaldehyde, propionic aldehyde, butyraldehyde or its mixture; Ketone comprises acetone, butanone, pimelinketone or its mixture; Acid comprises formic acid, acetate, longer chain fatty acid or its mixture.
In preferred embodiment of the present invention, the reaction times of step C is 3～10h, and temperature of reaction is 20～110 ℃.
In preferred embodiment of the present invention, the mode of rectification under vacuum is adopted in the described separation of step D.
Foregoing a kind of waste oil production method of bio-diesel oil, also comprise step (E): glycerol ketals (aldehyde), glycerol fatty acid ester join and cook pour point depressant in the biofuel.
Foregoing a kind of waste oil production method of bio-diesel oil, by volume, in the biofuel, glycerol ketals (aldehyde), glycerol fatty acid ester add-on are 1%-15%.
In preferred embodiment of the present invention, glycerol ketals (aldehyde), glycerol fatty acid ester join and cook pour point depressant in the biofuel, and its glycerol ketals (aldehyde) is 0.01--100 with the volume ratio of glycerol fatty acid ester.
From foregoing description as can be known, the present invention is directed to the biofuel of waste oil production and the characteristics of glycerine, the process pre-treatment of waste oil, esterification, transesterify production biofuel.Utilize the back raw glycerine that is separated to prepare glyceryl ester, glycerol ketals, glycerol acetonide ketone ester and product distillation, product purification etc. then.Byproduct crude glycerin with biofuel is further produced glyceryl acetate as raw material, and series product such as glycerol ketals (aldehyde) and glycerol ketals fatty acid ester, glycerine uncle butyl ether are cooked the pour point depressant of biofuel.By the raw glycerine reaction is utilized, help the full molecule utilization of waste oil, add the pour point depressant of doing biofuel in the biofuel to, can eliminate the pollution of raw glycerine, help reducing production costs the protection environment.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
With reference to figure 1, Fig. 1 is a process flow diagram of the present invention.
Embodiment one
In reactor, add and contain sour waste oil 1000Kg, acid number 115, after esterification, transesterify, phase-splitting obtains the raw glycerine layer.The raw glycerine layer is adjusted pH value to acid with sulfuric acid, separates upper strata lipid acid and methyl esters and lower floor's salt, obtains raw glycerine.Add acetone 50Kg in the raw glycerine, tosic acid 1Kg backflow stirring reaction 5 hours is rapidly heated to 100 degree, logical acetone gas reaction 2 hours.The centrifugal desalination of gained mixture.Rectifying separation obtains 65 kilograms in glycerol acetonide acetone.
Embodiment two
In reactor, add and contain sour waste oil 1000Kg, acid number 120, after esterification, transesterify, phase-splitting obtains the raw glycerine layer.The raw glycerine layer is adjusted pH value to acid with sulfuric acid, separates upper strata lipid acid and methyl esters and lower floor's salt, obtains raw glycerine.Add acetone 45Kg in the raw glycerine, sulfuric acid 1Kg backflow stirring reaction 6 hours is rapidly heated to 100 degree, logical acetone gas reaction 2 hours.The centrifugal desalination of gained mixture.Rectifying separation obtains 61 kilograms in glycerol acetonide acetone.
Embodiment three
In reactor, add and contain sour waste oil 1000Kg, acid number 120, after esterification, transesterify, phase-splitting obtains crude fatty acid methyl ester and raw glycerine layer.Crude fatty acid methyl ester obtains 1007 kilograms of biofuel through the tower fractionation of vacuum.The raw glycerine layer is adjusted pH value to acid with sulfuric acid, separates upper strata lipid acid and methyl esters and lower floor's salt, obtains raw glycerine.Add propionic aldehyde 45Kg in the raw glycerine, sulfuric acid 1Kg backflow stirring reaction 6 hours is rapidly heated to 100 degree logical propionic aldehyde gas reaction 2 hours.The centrifugal desalination of gained mixture.The rectification under vacuum separation obtains 61 kilograms of glycerol acetonide propionic aldehyde.In the biofuel of 61 kilograms of whole adding gained of this glycerol acetonide propionic aldehyde.
Embodiment four
In reactor, add and contain sour waste oil 1000Kg, acid number 120, after esterification, transesterify, phase-splitting obtains crude fatty acid methyl ester and raw glycerine layer.Crude fatty acid methyl ester obtains 1007 kilograms of biofuel through the tower fractionation of vacuum; The raw glycerine layer is adjusted pH value to acid with sulfuric acid, separates upper strata lipid acid and methyl esters and lower floor's salt, obtains raw glycerine.Add acetate 45Kg in the raw glycerine, sulfuric acid 1Kg backflow stirring reaction 6 hours is rapidly heated to 100 degree logical acetate gas reaction 2 hours.The centrifugal desalination of gained mixture.Rectifying separation obtains 61 kilograms of glycerol acetonide acetate.This glycerol acetonide acetate all adds in the biofuel of gained.
Above-mentioned only is specific embodiments of the invention, but design concept of the present invention is not limited thereto, and allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Claims (9)
1. waste oil production method of bio-diesel oil may further comprise the steps:
(A) acid-containing oil raw material and alcohol are generated biofuel and raw glycerine mixture by the esterification transesterification reaction, utilizing is separated obtains mixing glycerin layer;
(B) the steps A gained is mixed the glycerin layer acidifying, evaporation is reclaimed and is isolated methyl alcohol, and separated salt and lipid acid and methyl esters obtain the mixture of raw glycerine;
(C) above-mentioned isolating raw glycerine layer is added aldehyde, ketone, acid or its mixture reaction; The reaction product centrifugation is gone out salt, promptly obtain products such as glycerol ketals (aldehyde), glycerol fatty acid ester;
(D) glycerol ketals (aldehyde), glycerol fatty acid ester are told in the mixing prod rectifying of glycerol ketals (aldehyde), glycerol fatty acid ester.
2. a kind of waste oil production method of bio-diesel oil according to claim 1 is characterized in that: in the acidifying of the described mixture glycerin layer of step B, used acid is protonic acid, comprises sulfuric acid, hydrochloric acid, phosphoric acid, organic acid.
3. a kind of waste oil production method of bio-diesel oil according to claim 1 is characterized in that: the described catalyzer that adds in isolating raw glycerine layer of step C comprises mineral acid, organic acid or its mixture.
4. a kind of waste oil production method of bio-diesel oil according to claim 1 is characterized in that: the described aldehyde that adds in isolating raw glycerine layer of step C comprises polyoxymethylene, acetaldehyde, propionic aldehyde, butyraldehyde or its mixture; Ketone comprises acetone, butanone, pimelinketone or its mixture; Acid comprises formic acid, acetate, longer chain fatty acid or its mixture.
5. a kind of waste oil production method of bio-diesel oil according to claim 1, it is characterized in that: the reaction times of step C is 3～10h, temperature of reaction is 20～110 ℃.
6. a kind of waste oil production method of bio-diesel oil according to claim 1 is characterized in that: the mode of rectification under vacuum is adopted in the described separation of step D.
7. according to each described a kind of waste oil production method of bio-diesel oil of claim 1 to 6, it is characterized in that: also comprise step (E): glycerol ketals (aldehyde), glycerol fatty acid ester join and cook pour point depressant in the biofuel.
8. a kind of waste oil production method of bio-diesel oil according to claim 7 is characterized in that: by volume, in the biofuel, the add-on of glycerol ketals (aldehyde), glycerol fatty acid ester is 1%-15%.
9. a kind of waste oil production method of bio-diesel oil according to claim 7, it is characterized in that: glycerol ketals (aldehyde), glycerol fatty acid ester join and cook pour point depressant in the biofuel, and its glycerol ketals (aldehyde) is 0.01--100 with the volume ratio of glycerol fatty acid ester.
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| CN201110123397XA CN102226134A (en) | 2011-05-12 | 2011-05-12 | Method for producing biodiesel by using waste oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504891A (en) * | 2011-11-02 | 2012-06-20 | 南京工业大学 | Preparation method of glyceryl biofuel additive |
| CN103834477A (en) * | 2014-03-14 | 2014-06-04 | 河南久大实业有限公司 | Production method of glycerin fuel |
| CN109111423A (en) * | 2018-05-24 | 2019-01-01 | 安徽科技学院 | A kind of method that crude glycerine recycling prepares solketal |
| CN109456838A (en) * | 2018-10-19 | 2019-03-12 | 中国科学院山西煤炭化学研究所 | A method of producing biodiesel and triacetyl glycerine |
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| EP1331260A2 (en) * | 2002-01-18 | 2003-07-30 | Industrial Management S.A. | Procedure to obtain biodiesel fuel with improved properties at low temperature |
| CN101033407A (en) * | 2007-04-18 | 2007-09-12 | 武安市正和生物能源有限公司 | Production process of biological diesel oil |
| CN101343550A (en) * | 2007-07-10 | 2009-01-14 | 张国滨 | Production process of biological diesel oil |
| CN101880603A (en) * | 2010-07-01 | 2010-11-10 | 云南铭惠石化有限公司 | Method for preparing low condensation point biodiesel from high acid value oil |
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2011
- 2011-05-12 CN CN201110123397XA patent/CN102226134A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1331260A2 (en) * | 2002-01-18 | 2003-07-30 | Industrial Management S.A. | Procedure to obtain biodiesel fuel with improved properties at low temperature |
| CN101033407A (en) * | 2007-04-18 | 2007-09-12 | 武安市正和生物能源有限公司 | Production process of biological diesel oil |
| CN101343550A (en) * | 2007-07-10 | 2009-01-14 | 张国滨 | Production process of biological diesel oil |
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Non-Patent Citations (1)
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| 陈水根: "高酸价油脂制备生物柴油及甘油精制技术的研究", 《中国优秀硕士学位论文全文数据库工业科技Ⅰ辑》, no. 4, 15 April 2009 (2009-04-15) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504891A (en) * | 2011-11-02 | 2012-06-20 | 南京工业大学 | Preparation method of glyceryl biofuel additive |
| CN103834477A (en) * | 2014-03-14 | 2014-06-04 | 河南久大实业有限公司 | Production method of glycerin fuel |
| CN103834477B (en) * | 2014-03-14 | 2016-06-01 | 河南久大实业有限公司 | The production method of a kind of glycerine fuel |
| CN109111423A (en) * | 2018-05-24 | 2019-01-01 | 安徽科技学院 | A kind of method that crude glycerine recycling prepares solketal |
| CN109456838A (en) * | 2018-10-19 | 2019-03-12 | 中国科学院山西煤炭化学研究所 | A method of producing biodiesel and triacetyl glycerine |
| CN109456838B (en) * | 2018-10-19 | 2021-05-11 | 中国科学院山西煤炭化学研究所 | Method for producing biodiesel and glycerol triacetate |
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Owner name: ZHONG CHUANXUE Free format text: FORMER OWNER: FUJIAN ZHANGZHOU DINGNENG BIOTECHNOLOGY CO., LTD. Effective date: 20111108 Owner name: FUJIAN ZHANGZHOU DINGNENG BIOTECHNOLOGY CO., LTD. |
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Effective date of registration: 20111108 Address after: 450000 Henan Province, Zhengzhou City Traffic Road 27 Hengye District No. 41 Building No. three hospital unit Applicant after: Zhong Chuanxue Co-applicant after: Fujian Zhangzhou Dingneng Biotechnology Co., Ltd. Address before: 363000, Fujian, Zhangzhou Province town of Pinghe County Comprehensive Industrial Zone Applicant before: Fujian Zhangzhou Dingneng Biotechnology Co., Ltd. |
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Application publication date: 20111026 |