CN1580218A - Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material - Google Patents
Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material Download PDFInfo
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- CN1580218A CN1580218A CNA031355609A CN03135560A CN1580218A CN 1580218 A CN1580218 A CN 1580218A CN A031355609 A CNA031355609 A CN A031355609A CN 03135560 A CN03135560 A CN 03135560A CN 1580218 A CN1580218 A CN 1580218A
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- chain ester
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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
Abstract
The invention is a kind of continuous methods for producing short chain ester of aliphatic acid from fatty oil. It belongs to the field. The invention provides a new craft using atomizer-model esterifying technics and hypergravity circle alcoholysis technics to distill short chain ester of aliphatic acid from fatty oil. The approach follows this. 1, esterify continuously. Esterigy raw oil after add short chain alcohol and acidic catalyser in chamfer for esterigying. In this way, fatty acid short chain ester can be produced. 2, alcoholysis by two level hypergravity. Let fatty acid short chain ester which acid degree is below 1, pomade, glycerin and water pass through hypergravity machine. add short chain alcohol and alkali catalyst, alcoholysis in hypergravity circle, after this, do two level circled alcoholysising. 3, purification. Remove diethyl hydrine and alcohol from fatty acid short chain ester and mixture liquor containing sundries, the end product is produced. It can be replace diesel oil as fuel, named biologic diesel oil.
Description
Technical field:
The invention belongs to the method and technology field of preparation fatty acid short-chain ester from grease.
Background technology
Fatty acid short-chain ester is a kind of multiduty compound, can make fuel to replace diesel oil, is commonly called as biofuel, also can be as the raw material of making soap and washing composition.It can use the depleted grease to make raw material, has the low advantage of production cost, and the attention that is subjected to very much domestic and international scientific research and production unit is Development and Production competitively.Yet prior art is used traditional Processes and apparatus mostly, and production unit is huge, and investment cost is big, and energy consumption is big, the production cost height, and fail to realize the continuous production operation.For example Chinese invention patent ublic specification of application application number is the disclosed technology of 92114795.3 " a kind of process for production of methyl fatty acid ".
Summary of the invention
Technical problem to be solved provides a kind of method for preparing fatty acid short-chain ester with the animal-plant oil for the raw material continuous processing that adopts nozzle-type pre-esterification reactor and hypergravity rotation alcoholysis reaction technology.
The technical scheme that solves its technical problem comprises following production process of carrying out continuously:
A. continuously pre-esterification:
Pump up to 100 °-120 ℃ raw oil material heating and to enter the esterification groove through nozzle, be incorporated as heating to 70 ° ± 5 ℃ short chain alcohol gas and being an acidic catalyst of raw oil material weight 0.15-0.3% of raw oil material weight 20-30% at the nozzle place, in nozzle place and esterification groove, carry out pre-esterification treatment, under normal pressure and material self temperature, lipid acid in the grease and short chain alcohol reaction generate fatty acid short-chain ester and water; The mixed solution of the fatty acids short-chain ester in the esterification groove, grease, a small amount of glycerine and water not cracked ends pump pressurization returns esterification groove formation circulation through nozzle; The water that unreacted short chain alcohol and reaction generate in the esterification groove is discharged from the short chain alcohol gas relief outlet of esterification groove and is entered fractionator and isolate moisture, and short chain alcohol gas then promptly turns back to nozzle without condensation and enters in the esterification groove and recycle; When the acidity of material in the esterification groove during less than 1 (mgKOH/g), the mixed solution of the fatty acids short-chain ester in the part esterification groove, grease, a small amount of glycerine and water is pumped into the hypergravity rotatable reactor by the outlet of esterification tank liquid, enter next process; Simultaneously in the esterification groove, mend with pump to grease, short chain alcohol and an acidic catalyst of hypergravity rotatable reactor with the mixed solution equivalent weight that enters next process, react continuously to keep balance, the short chain alcohol of mending for mending the 20-30% of grease weight, institute's an acidic catalyst of mending is the 0.15-0.3% that benefit is gone into grease weight;
Short chain alcohol can be used methyl alcohol, ethanol, propyl alcohol, butanols.
An acidic catalyst can be used sulfuric acid, phosphoric acid, tosic acid, alkyl benzene sulphonate (ABS), methyl-hydrogen-sulfate monomethyl-sulfate, strongly-acid ion-exchange resin.
B. two-stage hypergravity rotation alcoholysis:
With the acidity that exports out by the esterification tank liquid among the operation a less than 1 fatty acids short-chain ester, grease, the mixed solution of a small amount of glycerine and water is incorporated as the basic catalyst of raw oil material weight 0.1-0.5%, from the liquid jet of hypergravity rotatable reactor axially enter rotating speed be in 600-900 rev/min the rotor under the rotor effect to the centrifugal direction high-speed motion, be incorporated as the short chain alcohol gas of raw oil material weight 20-30% simultaneously at the housing inlet of hypergravity rotatable reactor, at normal pressure and respectively participating under reactant self temperature, the grease and the basic catalyst of high-speed motion meet under gasiform short chain alcohol and the rotor effect, fully alcoholysis is carried out in reaction, generate fatty acid short-chain ester and glycerine, outlet by the hypergravity rotatable reactor is discharged, enter dish formula separator, be under 1000-7000 rev/min the high speed rotor effect at the rotating speed of dish formula separator, fatty acid short-chain ester and grease are separated with glycerine, and heavy glycerine is discharged from the separator bottom.Fatty acid short-chain ester that proportion is little and grease are then discharged from separator top, enter second stage hypergravity rotatable reactor, and add and participate in to react grease weight accordingly with the short chain alcohol gas and the basic catalyst of equal proportion, carry out second stage rotation alcoholysis reaction, fatty acid short-chain ester that reaction back is discharged by the outlet of hypergravity rotatable reactor and glycerine mixed solution enter dish formula separator isolate glycerine after, fatty acid short-chain ester and the mixed solution that still contains other compositions enter the next process purifying;
Basic catalyst can be used KOH, NaOH, CH
3ONa.
C. purifying:
The fatty acids short-chain ester that obtains in the b operation and unreacted short chain alcohol and micro-greasy mixed solution are pumped into vaporizer, under normal pressure, heat to 70-100 ℃, short chain alcohol evaporation is wherein reclaimed, with the salt solution washing doubly of the fatty acid short-chain ester of gained for its weight 0.2-1; Then, be decompressed to the 10-20KPa dehydration, the mixed fatty acid short-chain ester finished product that obtains conforming to quality requirements.
Beneficial effect: the present invention is applied to the preparation of fatty acid short-chain ester.Compared with the prior art, the present invention adopts nozzle material-feeding in pre-esterifying process, and the short chain alcohol of taking away water generation reaction promptly be can be recycled without the condensation supercharging, and employing is rotated alcoholysis in the hypergravity rotatable reactor.Its production unit uses huge reactor to change into by tradition and uses small-sized nozzle-type reactor and hypergravity rotatable reactor.And the participation reactant is met under the high-speed motion condition, make reaction process abundant, fast.Can save the writing investment, reduce energy expenditure, realize continuous production, reduce production costs, guarantee quality product.
Embodiment
Embodiment 1, and will heat to 100-110 ℃ of acid number is that the compound lard 5.0Kg of 20 (mgKOH/g) is together with heating to the methyl alcohol gas and the 98%H of 70 ° ± 5 ℃ 1kg methyl alcohol
2SO
4An acidic catalyst 0.01Kg pumps into the esterification groove through nozzle and carries out pre-esterification.After acidity is reduced to 1 (mgKOH/g), with material with contain the methanol solution 0.125Kg of NaOH20% and the methyl alcohol gas of 1Kg methyl alcohol adds hypergravity machine simultaneously, carry out alcoholysis reaction, isolate glycerine through separator, the fatty acid methyl ester of gained and grease added contain 20%NaOH methanol solution 0.04Kg, and the methyl alcohol gas of 0.5Kg methyl alcohol enters second stage hypergravity machine and carries out alcoholysis reaction, isolate glycerine, deviate from unreacted methanol, through washing, dehydration, get mixed methyl aliphatic ester 4.92Kg, yield is 98.4%, gets 80% raw glycerine 0.56Kg.
Embodiment 2, are 40 grease 10Kg with heating to 100-110 ℃ of acidity, add the methyl alcohol gas and the methyl-hydrogen-sulfate monomethyl-sulfate 0.02Kg of 2.2Kg methyl alcohol, pump into the esterification groove through nozzle and carry out pre-esterification treatment.When acidity is reduced to below 1, with material with contain 20%NaOH methanol solution 0.3Kg, the methyl alcohol gas of 2Kg methyl alcohol adds hypergravity machine simultaneously, carry out alcoholysis reaction, isolate glycerine through separator, the methyl alcohol gas that the fatty acid methyl ester of gained and grease are added 20% NaOH methanol solution 0.1Kg and 0.5Kg methyl alcohol enters second stage hypergravity machine and carries out alcoholysis reaction once more.Isolate glycerine, deviate from unreacted methanol, through washing, dewater mixed methyl aliphatic ester 9.8Kg, yield is 98%, 75% raw glycerine 1.03Kg.
Embodiment 3, with heat to 100-110 ℃ of acidity less than 1 refining grease 15Kg, methanol solution 215 grams with containing 20%NaOH enter the esterification groove through nozzle and carry out pre-esterification treatment.When acidity is reduced to less than 0.5 the time, material and the methyl alcohol gas that contains 20%NaOH methanol solution 0.3Kg and 3Kg methyl alcohol are added hypergravity machine carry out alcoholysis reaction, after separator is isolated glycerine, the fatty acid methyl ester of gained and grease added 125g contains the methanol solution of 20%NaOH and the methyl alcohol gas of 1.5Kg methyl alcohol enters second stage hypergravity machine alcoholysis reaction once more, isolate glycerine, slough unreacted methanol, obtain mixed methyl aliphatic ester 14.8Kg through washing, dehydration, yield is 98.6%, gets 80% raw glycerine 1.86Kg.
Claims (1)
1, the method for preparing fatty acid short-chain ester with the animal-plant oil for the raw material continuous processing is characterized in that comprising following operation:
A. continuously pre-esterification:
Pump up to 100 °-120 ℃ raw oil material heating and to enter the esterification groove through nozzle, be incorporated as heating to 70 ° ± 5 ℃ short chain alcohol gas and being an acidic catalyst of raw oil material weight 0.15-0.3% of raw oil material weight 20-30% at the nozzle place, in nozzle place and esterification groove, carry out pre-esterification treatment, under normal pressure and material self temperature, lipid acid in the grease and short chain alcohol reaction generate fatty acid short-chain ester and water; The mixed solution of the fatty acids short-chain ester in the esterification groove, grease, a small amount of glycerine and water not cracked ends pump pressurization returns esterification groove formation circulation through nozzle; The water that unreacted short chain alcohol and reaction generate in the esterification groove is discharged from the short chain alcohol gas relief outlet of esterification groove and is entered fractionator and isolate moisture, and short chain alcohol gas then promptly turns back to nozzle without condensation and enters in the esterification groove and recycle; When the acidity of material in the esterification groove during less than 1 (mgKOH/g), the mixed solution of the fatty acids short-chain ester in the part esterification groove, grease, a small amount of glycerine and water is pumped into the hypergravity rotatable reactor by the outlet of esterification tank liquid, enter next process; Simultaneously in the esterification groove, mend with pump to grease, short chain alcohol and an acidic catalyst of hypergravity rotatable reactor with the mixed solution equivalent weight that enters next process, react continuously to keep balance, the short chain alcohol of mending for mending the 20-30% of grease weight, institute's an acidic catalyst of mending is the 0.15-0.3% that benefit is gone into grease weight;
B. two-stage hypergravity rotation alcoholysis:
With the acidity that exports out by the esterification tank liquid among the operation a less than 1 fatty acids short-chain ester, grease, the mixed solution of a small amount of glycerine and water is incorporated as the basic catalyst of raw oil material weight 0.1-0.5%, from the liquid jet of hypergravity rotatable reactor axially enter rotating speed be in 600-900 rev/min the rotor under the rotor effect to the centrifugal direction high-speed motion, be incorporated as the short chain alcohol gas of raw oil material weight 20-30% simultaneously at the housing inlet of hypergravity rotatable reactor, at normal pressure and respectively participating under reactant self temperature, the grease and the basic catalyst of high-speed motion meet under gasiform short chain alcohol and the rotor effect, fully alcoholysis is carried out in reaction, generate fatty acid short-chain ester and glycerine, outlet by the hypergravity rotatable reactor is discharged, enter dish formula separator, be under 1000-7000 rev/min the high speed rotor effect at the rotating speed of dish formula separator, fatty acid short-chain ester and grease are separated with glycerine, and heavy glycerine is discharged from the separator bottom.Fatty acid short-chain ester that proportion is little and grease are then discharged from separator top, enter second stage hypergravity rotatable reactor, and add and participate in to react grease weight accordingly with the short chain alcohol gas and the basic catalyst of equal proportion, carry out second stage rotation alcoholysis reaction, fatty acid short-chain ester that reaction back is discharged by the outlet of hypergravity rotatable reactor and glycerine mixed solution enter dish formula separator isolate glycerine after, fatty acid short-chain ester and the mixed solution that still contains other compositions enter the next process purifying;
C. purifying:
The fatty acids short-chain ester that obtains in the b operation and unreacted short chain alcohol and micro-greasy mixed solution are pumped into vaporizer, under normal pressure, heat to 70-100 ℃, short chain alcohol evaporation is wherein reclaimed, with the salt solution washing doubly of the fatty acid short-chain ester of gained for its weight 0.2-1; Then, be decompressed to the 10-20KPa dehydration, the mixed fatty acid short-chain ester finished product that obtains conforming to quality requirements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031355609A CN1580218A (en) | 2003-08-06 | 2003-08-06 | Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material |
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| CNA031355609A CN1580218A (en) | 2003-08-06 | 2003-08-06 | Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material |
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| CN1580218A true CN1580218A (en) | 2005-02-16 |
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| CNA031355609A Pending CN1580218A (en) | 2003-08-06 | 2003-08-06 | Method for preparing short-chain aliphatic ester by continuous process using animal-plant oil as raw material |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328353C (en) * | 2005-02-03 | 2007-07-25 | 云南师范大学 | Technology of preparing biological diesel oil from animal and vegetable oil |
| CN100390251C (en) * | 2006-04-05 | 2008-05-28 | 贵州大学 | Preparation of curcas biological diesel oil by solid phase catalytic method |
| CN100424152C (en) * | 2005-11-09 | 2008-10-08 | 福建中德科技股份有限公司 | Method for synthesis of bio-diesel oil with monomer acids as main raw materials |
| CN1984983B (en) * | 2004-07-13 | 2010-06-09 | 株式会社雷沃国际 | Process for producing fatty acid alkyl ester |
| CN1974724B (en) * | 2006-12-04 | 2010-09-29 | 李燕丽 | High efficiency preparation process of biological diesel oil |
| CN1923990B (en) * | 2005-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Process for preparing fatty acid ester |
| CN102086320A (en) * | 2009-12-08 | 2011-06-08 | 谢丹青 | Printing ink cleaning solvent and preparation method thereof |
| US8299281B2 (en) | 2009-03-27 | 2012-10-30 | Exxonmobil Research And Engineering Company | Process for making triglyceride plasticizer from crude glycerol |
| CN106337069A (en) * | 2015-07-13 | 2017-01-18 | 清华大学 | Fatty acid short chain ester two-step preparation technology |
| CN110218574A (en) * | 2019-06-03 | 2019-09-10 | 北京凯瑞英科技有限公司 | By the method for methyl-hydrogen-sulfate monomethyl-sulfate catalysis for preparing biodiesel oil |
-
2003
- 2003-08-06 CN CNA031355609A patent/CN1580218A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1984983B (en) * | 2004-07-13 | 2010-06-09 | 株式会社雷沃国际 | Process for producing fatty acid alkyl ester |
| CN1328353C (en) * | 2005-02-03 | 2007-07-25 | 云南师范大学 | Technology of preparing biological diesel oil from animal and vegetable oil |
| CN1923990B (en) * | 2005-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Process for preparing fatty acid ester |
| CN100424152C (en) * | 2005-11-09 | 2008-10-08 | 福建中德科技股份有限公司 | Method for synthesis of bio-diesel oil with monomer acids as main raw materials |
| CN100390251C (en) * | 2006-04-05 | 2008-05-28 | 贵州大学 | Preparation of curcas biological diesel oil by solid phase catalytic method |
| CN1974724B (en) * | 2006-12-04 | 2010-09-29 | 李燕丽 | High efficiency preparation process of biological diesel oil |
| US8299281B2 (en) | 2009-03-27 | 2012-10-30 | Exxonmobil Research And Engineering Company | Process for making triglyceride plasticizer from crude glycerol |
| CN102086320A (en) * | 2009-12-08 | 2011-06-08 | 谢丹青 | Printing ink cleaning solvent and preparation method thereof |
| CN102086320B (en) * | 2009-12-08 | 2014-02-19 | 谢丹青 | Printing ink cleaning solvent and preparation method thereof |
| CN106337069A (en) * | 2015-07-13 | 2017-01-18 | 清华大学 | Fatty acid short chain ester two-step preparation technology |
| CN110218574A (en) * | 2019-06-03 | 2019-09-10 | 北京凯瑞英科技有限公司 | By the method for methyl-hydrogen-sulfate monomethyl-sulfate catalysis for preparing biodiesel oil |
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