CN1962823A - Method for synthesis of bio-diesel oil with monomer acids as main raw materials - Google Patents
Method for synthesis of bio-diesel oil with monomer acids as main raw materials Download PDFInfo
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- CN1962823A CN1962823A CNA2005100197909A CN200510019790A CN1962823A CN 1962823 A CN1962823 A CN 1962823A CN A2005100197909 A CNA2005100197909 A CN A2005100197909A CN 200510019790 A CN200510019790 A CN 200510019790A CN 1962823 A CN1962823 A CN 1962823A
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- methyl alcohol
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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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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesizing method of biological diesel based on monomer acid as main raw material, which comprises the following steps: putting monomer acid in the esterification autoclave to heat conductive oil as well as 8-15% solid acid catalyst; heating to 130-160 Deg C; adding carbinol with 0.4-0.6 times as monomer acid in the material tank for five times; sampling every 2-4h; detecting the acid value of material; stopping adding carbinol until the acid value is less than 1mgKOH/g; cooling the material under 80 Deg C; generating the product.
Description
Technical field
The present invention relates to a kind of is the method for main raw material biodiesel synthesis with the monomer acids, belongs to field of grease chemical technology.
Background technology
Biofuel mainly is to produce with chemical method, under inorganic acid or strong alkali catalyst and high temperature, carry out transesterification reaction with low-carbon alcohol such as animal-plant oil and methyl alcohol, ethanol, generate corresponding fatty acid methyl ester or ethyl ester, be drying to obtain biofuel through washing again.Methyl alcohol or ethanol can be recycled in process of production, can produce byproduct glycerine in the production process.With this technology biodiesel synthesis following shortcoming is arranged: complex process, need subsequent disposal such as washing, drying, increased production cost greatly.Recently, people begin one's study and use the biological enzyme biodiesel synthesis, promptly carry out transesterification reaction with animal grease and low-carbon alcohol by lipase, prepare corresponding fatty acid methyl ester and ethyl ester.The enzyme process biodiesel synthesis has that mild condition, pure consumption are little, the advantage of non-pollution discharge.But subject matter has at present: low to methyl alcohol and ethanol conversion, and generally only be 40%～60%, because lipase is effective to the esterification or the transesterificationization of long chain aliphatic alcohol at present, and low to transformation efficiencys such as short chain fatty alcohol such as methyl alcohol or ethanol.And short chain fatty alcohol has certain toxicity to enzyme, and shortened the work-ing life of enzyme.By-product glycerin and shipwreck not only product are formed and suppress, and glycerine are toxic to immobilized enzyme in recovery, also can make immobilized enzyme shortening in work-ing life.
At present, production biofuel starting material are animal-plant oil mostly both at home and abroad, for example disclosed Chinese patent application publication number CN1570029 " preparation method of bio-diesel oil " by natural fats and oils, this invention is raw material with the natural fats and oils, carry out transesterification with 1～3 carbon molecular weight under the mineral acid catalyst effect, this method need be through steps such as dehydration, dealcoholysis, separation of glycerin, distillation, process more complicated, energy consumption is also bigger, has increased production cost of products greatly.And directly be the relevant report of raw material production biofuel and few with lipid acid, for example disclosed Chinese patent application publication number CN1060089 " C
6～24Lipid acid semicontinuous formicester operation mode and optimization ", mention with C
6～24Saturated and unsaturated fatty acids is a raw material, be to carry out esterification with methyl alcohol under the condition of catalyzer at methyl-hydrogen-sulfate monomethyl-sulfate, this production method is comparatively simple, and the reaction times is shorter, but, bring bigger hidden danger to production safety because the used catalyst sulfuric acid hydrogen methyl esters of reaction belongs to highly toxic substance.The present invention is the synthetic production method of bio-diesel oil of main raw material with the monomer acids, does not meet similar report by retrieval.
Technology contents
By Oleum Gossypii semen or soya fatty acid through heat polymerization and the synthetic dimer (fatty acid) yl, except that producing dimeracid, trimer acid, also has the by product monomer acids, its content accounts for about 35%, monomer acids is to have neither part nor lot in the lipid acid of reaction in the raw material and produce isomerized lipid acid under clay catalyst and high temperature, and its classical group becomes 5～10% palmitinic acids, 45～60% oleic acid, 30～50% isomerization lipid acid.The present invention is the raw material production biofuel with the monomer acids, and monomer acids is the byproduct when synthesizing dimer (fatty acid) yl, obtains in the dimer (fatty acid) yl purification process.
Production Flow Chart and equipment with in the reaction kettle of the esterification 1 of heat-conducting oil heating, add solid acid catalyst with the monomer acids input as shown in drawings simultaneously.When treating that material is warming up to 130～160 ℃, methyl alcohol adds continuously from methanol feed jar 5.Sampling at regular intervals detects the material acid number in the reaction process, during less than 1mgKOH/g, stops to add methyl alcohol until the material acid number, and material is cooled to blowing below 80 ℃, promptly gets the biofuel finished product.
The above-mentioned solid acid catalyst that adds can be with high temperature resistant macropore polystyrene storng-acid cation exchange resin, and its feeding quantity is 8～15% of a monomer acids feeding quantity; Total add-on of methyl alcohol is 0.4～0.6 times of monomer acids feeding quantity, and it is 2～4 hours that reaction process sampling detects material its timed interval of acid number, during less than 1mgKOH/g, stops to add methyl alcohol until the material acid number.
Water vapor that reaction process generates and excessive methanol gas directly enter methanol rectifying tower 2 and separate purification, the used filler of rectifying tower is a corrugated wire gauze packing, tower still steam heating, cat head methyl alcohol enters surge tank 4 after methanol condenser 3 condensations, the methyl alcohol part of surge tank 4 enters methanol feed jar 5, a part refluxes and reenters methanol rectifying tower 2, and the methanol purity of purifying through methanol rectifying tower is to be reused for the required methyl alcohol of reaction process greater than 98%.
The present invention's advantage compared with prior art: it is catalyzer that (1), the present invention adopt high temperature resistant macropore polystyrene storng-acid cation exchange resin, its maximum operation (service) temperature can reach 180 ℃, and have advantages such as corrodibility is low, nontoxic, greatly reduce service requirements, exempted subsequent processes such as washing required when being catalyzer, drying simultaneously with the vitriol oil to production unit.(2), adopt the production technique of reactive distillation can make full use of the heat that reaction process excessive methanol gas and water vapor are carried secretly, the energy consumption when having significantly reduced useless methanol purification.
Description of drawings
Accompanying drawing is a Production Flow Chart synoptic diagram of the present invention.
Numeral wherein:
The 1-reaction kettle of the esterification; The 2-methanol rectifying tower; The 3-methanol condenser; The 4-surge tank; 5-methanol feed jar.
Embodiment
Following embodiment is for content of the present invention is described, but is not to limit the scope of the invention by any way.
Embodiment 1:
The 400Kg monomer acids is dropped in the reactor 1, add the high temperature resistant macropore polystyrene of 32Kg strong acid cation exchange resin catalyst, when treating that material is warming up to 130 ℃, add methyl alcohol continuously, the add-on of methyl alcohol is 15Kg/ hour, reacts after 13 hours that to detect acid number be 0.90mgKOH/g, stops to add methyl alcohol, material is cooled to 80 ℃ of blowings, promptly gets the biofuel finished product.Water vapor and excessive methanol gas that reaction process generates enter methanol rectifying tower 2, separate purification, and the purity that records methyl alcohol is 98.8%
Embodiment 2:
The 400Kg monomer acids is dropped in the reactor, add the high temperature resistant macropore polystyrene of 32Kg strong acid cation exchange resin catalyst, when treating that material is warming up to 140 ℃, add methyl alcohol continuously, the add-on of methyl alcohol is 15Kg/ hour, reacts after 12 hours that to detect acid number be 0.81mgKOH/g, stops to add methyl alcohol, material is cooled to 80 ℃ of blowings, promptly gets the biofuel finished product.Water vapor that reaction process generates and excessive methanol gas enter methanol rectifying tower, separate purification, and the purity that records methyl alcohol is 98.7%.
Embodiment 3:
The 400Kg monomer acids is dropped in the reactor, add the high temperature resistant macropore polystyrene of 40Kg strong acid cation exchange resin catalyst, when treating that material is warming up to 140 ℃, add methyl alcohol continuously, the add-on of methyl alcohol is 15Kg/ hour, reacts after 11 hours that to detect acid number be 0.85mgKOH/g, stops to add methyl alcohol, material is cooled to 80 ℃ of blowings, promptly gets the biofuel finished product.Water vapor that reaction process generates and excessive methanol gas enter methanol rectifying tower, separate purification, and the purity that records methyl alcohol is 98.7%.
Embodiment 4:
The 400Kg monomer acids is dropped in the reactor, add the high temperature resistant macropore polystyrene of 40Kg strong acid cation exchange resin catalyst, when treating that material is warming up to 140 ℃, add methyl alcohol continuously, the add-on of methyl alcohol is 20Kg/ hour, reacts after 10.5 hours that to detect acid number be 0.9mgKOH/g, stops to add methyl alcohol, material is cooled to 80 ℃ of blowings, promptly gets the biofuel finished product.Water vapor that reaction process generates and excessive methanol gas enter methanol rectifying tower, separate purification, and the purity that records methyl alcohol is 98.1%.
Claims (6)
1, a kind of is the method for main raw material biodiesel synthesis with the monomer acids, it is characterized in that: the monomer acids input is used in the reaction kettle of the esterification (1) of heat-conducting oil heating, add solid acid catalyst simultaneously, when treating that material is warming up to 130～160 ℃, methyl alcohol adds continuously from methanol feed jar (5); Sampling detects the material acid number in the reaction process, during less than 1mgKOH/g, stops to add methyl alcohol until the material acid number, and material is cooled to blowing below 80 ℃, promptly gets the biofuel finished product.
2, by the described method of claim 1, it is characterized in that: described solid acid catalyst is high temperature resistant macropore polystyrene storng-acid cation exchange resin, and its feeding quantity is 8～15% of a monomer acids feeding quantity.
3, by the described method of claim 1, it is characterized in that: total add-on of described methyl alcohol is 0.4～0.6 times of monomer acids feeding quantity.
4, by the described method of claim 1, it is characterized in that: it is 2～4 hours that described reaction process sampling detects material its timed interval of acid number.
5, by the described method of claim 1, it is characterized in that: described monomer acids is the byproduct when synthesizing dimer (fatty acid) yl, obtain in the dimer (fatty acid) yl purification process, its classical group becomes 5～10% palmitinic acids, 45～60% oleic acid, 30～50% isomerization lipid acid.
6, by the described method of claim 1, it is characterized in that: water vapor that reaction process generates and excessive methanol gas directly enter methanol rectifying tower (2) and separate purification, the used filler of rectifying tower is a corrugated wire gauze packing, tower still steam heating, cat head methyl alcohol enters surge tank (4) after methanol condenser (3) condensation, the methyl alcohol part of surge tank (4) enters methanol feed jar (5), a part refluxes and reenters methanol rectifying tower (2), and the methanol purity of purifying through methanol rectifying tower is to be reused for the required methyl alcohol of reaction process greater than 98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100197909A CN100424152C (en) | 2005-11-09 | 2005-11-09 | Method for synthesis of bio-diesel oil with monomer acids as main raw materials |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100197909A CN100424152C (en) | 2005-11-09 | 2005-11-09 | Method for synthesis of bio-diesel oil with monomer acids as main raw materials |
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| Publication Number | Publication Date |
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| CN1962823A true CN1962823A (en) | 2007-05-16 |
| CN100424152C CN100424152C (en) | 2008-10-08 |
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| CNB2005100197909A Expired - Fee Related CN100424152C (en) | 2005-11-09 | 2005-11-09 | Method for synthesis of bio-diesel oil with monomer acids as main raw materials |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465058A (en) * | 2010-11-04 | 2012-05-23 | 朱建军 | Production process for preparing biodiesel |
| CN102533309A (en) * | 2012-01-18 | 2012-07-04 | 浙江工业大学 | Biodiesel rectifying tower provided with multiple vaporization layers |
| CN102847612A (en) * | 2012-03-23 | 2013-01-02 | 太原理工大学 | Biodiesel for coal flotation and preparation method of biodiesel |
| CN104120038A (en) * | 2013-04-25 | 2014-10-29 | 中国石油化工股份有限公司 | Method for reducing oil acid value |
| CN104164304A (en) * | 2014-08-22 | 2014-11-26 | 北京科技大学 | Novel method for preparing biodiesel under catalysis of modified resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI324592B (en) * | 2002-11-28 | 2010-05-11 | Sulzer Chemtech Ag | A method for the esterification of a fatty acid |
| CN1580218A (en) * | 2003-08-06 | 2005-02-16 | 重庆正和生物能源有限公司 | Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material |
-
2005
- 2005-11-09 CN CNB2005100197909A patent/CN100424152C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465058A (en) * | 2010-11-04 | 2012-05-23 | 朱建军 | Production process for preparing biodiesel |
| CN102533309A (en) * | 2012-01-18 | 2012-07-04 | 浙江工业大学 | Biodiesel rectifying tower provided with multiple vaporization layers |
| CN102847612A (en) * | 2012-03-23 | 2013-01-02 | 太原理工大学 | Biodiesel for coal flotation and preparation method of biodiesel |
| CN104120038A (en) * | 2013-04-25 | 2014-10-29 | 中国石油化工股份有限公司 | Method for reducing oil acid value |
| CN104164304A (en) * | 2014-08-22 | 2014-11-26 | 北京科技大学 | Novel method for preparing biodiesel under catalysis of modified resin |
| CN104164304B (en) * | 2014-08-22 | 2016-08-10 | 北京科技大学 | A kind of modified resin catalysis prepares the new method of biodiesel |
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| CN100424152C (en) | 2008-10-08 |
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Owner name: FUJIAN ZHONGDE ENERGY CO., LTD. Free format text: FORMER OWNER: FUJIAN ZHONGDE TECHNOLOGY STOCK CO., LTD. Effective date: 20110524 |
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