CN1031070C - Producing technology for fathy acid alkyl ester - Google Patents
Producing technology for fathy acid alkyl ester Download PDFInfo
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- CN1031070C CN1031070C CN 89107686 CN89107686A CN1031070C CN 1031070 C CN1031070 C CN 1031070C CN 89107686 CN89107686 CN 89107686 CN 89107686 A CN89107686 A CN 89107686A CN 1031070 C CN1031070 C CN 1031070C
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- alkanol
- esterification
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Abstract
The present invention relates to a technology for producing fatty acid alkyl esters by taking natural grease containing free fatty acids as raw material. The technology comprises: 1. under the condition that an acid catalyst exists, natural grease reacts with C-[1]-C-[4] alkanol continuously passing through a reactor at a temperature above the boiling point of the alkanol until the acid value of the reaction compound is less than 1; 2. after alkanol and an alkali catalyst are added to the reaction compound, the reaction compound carries out an ester interchange reaction under counterflow conditions. The technology for producing fatty acid alkyl esters has the advantages of simple manufacturing process and convenient operation, and in addition, the yield can reach over 98%, and the acid value of adaptable grease as raw material can reach over 100; therefore, the present invention is a technology for producing fatty acid alkyl esters, which deserves to be popularized.
Description
The present invention relates to grease and produce the method for fatty acid alkyl ester, the natural fats and oils that is specifically related to contain free fatty acids is produced fatty acid alkyl ester through transesterify, particularly the method for fatty acid methyl ester.
As everyone knows, industrial widely used Fatty Alcohol(C12-C14 and C12-C18), fatty acid methyl ester sulfonate and alkylolamide, soap etc. are intermediate raw material mostly with the fatty acid methyl ester, so fatty acid methyl ester occupies considerable status in chemical industry.
Industrial often is the raw material production fatty acid methyl ester with the natural fats and oils, the production method that adopts has alkali refining one ester-interchange method both at home and abroad, the high pressure ester-interchange method, pre-esterification-ester-interchange method etc., because natural fats and oils nearly all contains the free fatty acids of a great deal of and (generally surpasses 3%, sometimes up to 50%), the existence of lipid acid is unfavorable for the carrying out of transesterify, alkali refining-ester-interchange method only is adapted to the low grease of fatty acid content, for the higher natural fats and oils raw material of fatty acid content, adopt alkali refining-ester-interchange method to produce fatty acid methyl ester, loss is big, and yield is low; The high pressure ester-interchange method is produced fatty acid methyl ester, acid value to raw material requires low, but the excess coefficient of methyl alcohol is too big, and high temperature (240 ℃), high pressure (100 crust), energy consumption is big, apparatus expensive, be difficult for generally promoting, DE3 in 1984,444,893 disclose the method that fatty acid methyl ester is produced in the pre-esterification of a kind of improved normal pressure-transesterify:
(1) in the presence of an acidic catalyst, normal pressure, 50-120 ℃, C
1-C
4Alkanol and lipid acid carry out pre-ester reaction,
(2) reaction mixture contains alcohol that catalyzer and partial reaction generate water mutually and oil phase static being divided into,
(3) with the water in glycerine and the carbinol mixture extraction oil phase,
(4) in the presence of basic catalyst, the oil phase after the extraction under normal pressure with C
1-C
3Alcohol carries out transesterification reaction.
This method solves acid greasy transesterify problem better, to answer mild condition, facility investment is little, and methyl alcohol and energy consumption are also little, and yield is also than higher, but owing to need carry out the separation and the recovery of alcohol, oil phase after the pre-esterification, and separation of oil subsequently extraction just carries out transesterify, the technical process complexity, and operation steps is many, therefore loss of material is big, and yield decreases.
The objective of the invention is to provides the production technique of the fatty acid alkyl ester that a kind of technical process is simple, easy to operate, low to the natural fats and oils specification of quality, yield is high at the foot of above-mentioned improved pre-esterification-ester-interchange method.
For realizing purpose of the present invention, the production technique of fatty acid alkyl ester of the present invention may further comprise the steps:
(1) in the presence of an acidic catalyst, the natural fats and oils that contains free fatty acids is at normal pressure, and temperature is 80-160 ℃ of following and continuous C by reactor
1-C
4Reaction of alkanol, until the acid value of reaction mixture less than 1,
(2) through being cooled to 30-60 ℃ said mixture, at the C that adds capacity
1-C
4Behind alkyl alcohol and the adding carbon catalyzer, be warming up to 60-130 ℃, refluxed transesterify 30-70 minute down,
(3) purifying of the separation of reaction mixture and product.
The present invention adopts higher temperature of reaction to feed alkanol continuously, the method of the steam of unreacted alkanol of discharge section and water generation reaction is carried out pre-esterification reactor continuously, make water generation reaction be taken out of reaction system effectively, not only promoted the carrying out of pre-esterification and transesterification reaction, and the reaction mixture after the pre-esterification generally need not to separate and extract, can carry out transesterification reaction after the cooling, to the grey seed nucleolus oil of ropy grease such as mountain, be preferably in and steam the ester that has generated earlier after the pre-esterification and carry out transesterify again, not only technology is simple, easy to operate, and also low to the natural fats and oils specification of quality, yield is also than higher.
By method of the present invention, owing to adopt excessive C
1-C
4Alkanol is taken water generation reaction out of reaction system by reactor continuously, pre-esterification is carried out fully, so low to the crude quality requirement, the acid value of natural fats and oils (being the content of free fatty acids) can in very large range change, low crude oil of acid value such as Oleum Cocois, plam oil both can have been adapted to, lard, Tallow Inedible Grade also can adapt to higher crude oil of acid value such as thick cotton oil, fragrant fruit oil, even acid value is up to the grey seed nucleolus oil in 100 mountain, also be suitable raw material of the present invention, after the pre-esterification, acid value still can be less than 1.
C used in the present invention
1-C
4Alkanol comprises the alcohol that is used to dilute acid pre-esterification catalyst, adds the transesterify alcohol into reactor in the pre-esterification process after the alcohol of continuous feeding reactor and the pre-esterification, generally selects for use with a kind of alcohol, preferably selects methyl alcohol for use.
By method of the present invention; Can take totally continuous mode to carry out in the pre-esterification process; Also can adopt semicontinuous mode to carry out; Pre-esterification process of the present invention selects semicontinuous mode to carry out; The alcohol, oil mixture that contains acidic catalyst in the reactor is fixing phase; Liquid phase alcohol is mobile phase; Liquid phase alcohol enters through distributor with selected speed and is warming up to 85-160 ℃ reaction system; Distillate from the reactor mouth after unreacted alcohol and the water generation reaction vaporization; Cooling is reclaimed; The recovery methyl alcohol of dehydration to 98.599% can be recycled in pre-esterification
Pre-esterification catalyst of the present invention can be for example vitriol oil of nonvolatile mineral acid, phosphoric acid, or nonvolatile alkyl, phenyl or alkane phenylbenzimidazole sulfonic acid be tosic acid for example, toluenesulphonic acids and naphthene sulfonic acid etc., vitriol oil low price, aboundresources, it is top-priority esterifying catalyst, catalyst consumption is generally the heavy 0.1-4% of oil, be preferably the heavy 0.2-0.8% of oil, with the vitriol oil as catalyzer, preferably earlier with adding in the crude oil again after the alkanol dilution, also the vitriol oil dropwise can be added in the crude oil alcohol mixture to avoid carrying out excessive sulfonation reaction, dilution is generally 4.10% of former weight of oil with the alkanol amount.
In the pre-esterification reactor process, continuous alkanol by reactor, be reaction be again to take water generation reaction the needs of reaction system out of by alkanol vaporization, therefore alkanol depends on the acid value size of crude oil and the size of pre-esterification reactor speed by the speed of reactor, the acid value of stock oil is high more, pre-esterification reactor speed is fast more, alkanol should be big more by the speed of reactor, too small alkanol feeding speed is unfavorable for that alcohol fully contacts with crude oil, the carrying out that is unfavorable for pre-esterification reactor, prolong the reaction times, equipment capacity reduces, excessive feeding speed, cause product to carry and increase the loss and the energy consumption of alkanol secretly, for example, the difference of the acid value of the based on crude of the present invention and feeding speed of the methyl alcohol selected for use is 0.20-0.60 gram methanol/gram oil, hour.
For alcohol is evenly contacted with crude oil in the reactor effectively, need usually contact with oil phase via the circle distributor of the perforate of equipment in reactor, cooperate stirring simultaneously, with the minimizing resistance to mass transfer.
The pressure of pre-esterification reactor is generally normal pressure, also can a little higher than normal pressure, and the said normal pressure of the present invention can be a little more than normal atmosphere.
The temperature of pre-esterification reactor is different with the alkanol of selecting for use, usually be controlled under the reflux temperature of alkanol and carry out, the present invention selects for use under far above the alkanol boiling point temperature of reaction 80-160 ℃ and carries out, for example, if select methyl alcohol for use, temperature of reaction is preferably in 90-100 ℃, the alkanol that higher top esterification reaction temperature not only can make reaction water be vaporized is effectively taken reaction system out of, but also can destroy the part detrimental impurity of the part of reaction system, thereby promote the carrying out of pre-esterification and transesterification reaction effectively; Under the higher temperature of reaction, carry out the part transesterification reaction in the time of pre-esterification, shortened the reaction times, improved throughput.
After pre-esterification reactor is finished, for example can adopt the reactor jacket water quench to 30-60 ℃, add transesterify with alkyl alcohol and basic catalyst, the disposable adding of the alkyl alcohol of adding, suitably excessive anhydrous alkyl alcohol helps the raising of ester exchange rate, be generally the 20-50% of crude oil, basic catalyst can be an alkali metal hydroxide, for example potassium hydroxide or sodium hydroxide, it also can be sodium methylate, the present invention selects for use sodium hydroxide or sodium methylate basic catalyst in the present invention also to be used for and an acidic catalyst and the residual free fatty acids of pre-esterification reactor, during described base catalysis dosage comprises and required amount and the heavy 0.12-0.5% of oil of an acidic catalyst and residual free fatty acids, be preferably 0.25% heavy catalyzer catalyzer of oil.
Transesterification reaction is carried out under reflux temperature (60-130 ℃), preferably earlier under stirring condition, refluxes, and react 20-50 minute, and complete for the separation that impels reaction mixture and transesterification reaction is preferably in and stops to stir down backflow 10-20 minute.
The separation of reaction mixture of the present invention comprises separating of separating of unreacted methanol and reaction product and product fatty acid alkyl ester and glycerine, can select for use arbitrarily existing isolation technique and step with unreacted alkyl alcohol, fatty acid alkyl ester and glycerine are separated from one another, the present invention at first adopts the method for progressively underpressure distillation, utilize the waste heat of reaction system that unreacted alkyl alcohol is steamed, in order to reduce the loss of alkyl alcohol, can adopt freezing method to reclaim alkyl alcohol in case of necessity, for the glycerine that steams alkyl alcohol is separated better with fatty acid alkyl ester, improve the yield of glycerine, the present invention can also add the water of the heavy 2-5% of oil, improve the flowability and the polarity of glycerin layer, improve the separating effect between glycerine and ester.
Can adopt the method for repeatedly washing to remove wherein impurity such as pigment with fatty acid alkyl ester after glycerin layer is separated, again the method for use-case such as normal pressure or vacuum distilling dewater thick alkyl ester.
The production technique of fatty acid alkyl ester of the present invention, reaction conditions gentleness, equipment are simple, investment is little.
The present invention, in the pre-esterification reactor process, adopted excessive alkyl alcohol continuously by answering device to force to take away the operational path of reaction water, promoted the carrying out of pre-esterification reactor, help greatly contained free fatty acids esterification in the natural fats and oils fully, guarantee the carrying out of transesterify, operational path of the present invention is lower to the specification of quality of crude oil simultaneously, and the crude oil acid value of permission can reach 100, adopts operational path of the present invention, after the pre-esterification, acid value is reduced to less than 1.
The present invention has got rid of the separation between alcohol, oil phase and the extraction process of recovery and oil phase, and it is short to have simplified technical process greatly, and is simple to operate and make things convenient for, and avoided pure separation of oil, reclaim and process such as oily extraction in loss of material.
The present invention selects higher pre-esterification reactor temperature for use, helps taking water generation reaction out of reaction system by the alkyl alcohol of reactor continuously, promotes the carrying out of pre-esterification and transesterification reaction; Under higher pre-esterification reactor temperature, part detrimental impurity in the reaction system can be destroyed, the carrying out that helps pre-esterification and transesterification reaction, and in pre-esterification reactor, also carried out part transesterification reaction (the about 30-50% of ester exchange rate), technology of the present invention is actually secondary transesterify process, so ester exchange rate is up to more than 99%, owing to carried out transesterification reaction simultaneously in the pre-esterification reactor process, shorten the reaction times greatly, improved throughput.
As seen the present invention and DE3,444,893 disclosed improved pre-esterification-ester-interchange methods are compared, not only technical process is short, (semicontinuous) simple to operation, crude oil wide adaptability, and because pre-esterification is complete, loss of material is few in the technological process, ester exchange rate is high, so the product yield is also high.
Example 1:
In 10001 enamel reaction stills that have stirring and methyl alcohol sparger, stirring down, the adding acid value is 9.57, the bonding glycerol content is the 1kg vitriol oil (96.0%) and the 20kg methanol mixture of 13.58% 500kg Oleum Cocois and preparation in advance, the reacting by heating mixture is during to 90-95 ℃, beginning feeds technical grade anhydrous methanol (water-content≤0.8%) with the speed of 130kg/hr through the methyl alcohol sparger, keep about 95 ℃ of temperature of reaction, part unreacted methanol steam distillates from reactor continuously, after cooled dehydrated, supply the usefulness of esterification, stop to feed methyl alcohol after one hour, reaction system is cooled to about 50 ℃, the acid value that records reaction system is 0.27, reclaims methyl alcohol 93kg altogether in the pre-esterification process.
Add 125kg methyl alcohol and 2.16kgNaOH (using the part dissolve with methanol), stir down and refluxed 40 minutes, stopped stirring and refluxing then 20 minutes, methyl alcohol 110kg is reclaimed in decompression down, adds 16kg water in system, tell glycerine 97.5kg, content 68.29%, the rate of recovery 37.91%, the thick methyl esters of telling after residual glycerine, catalyzer and methyl alcohol are removed in washing again through dewater methyl esters 490kg, record bonding glycerol content 0.16% according to a conventional method, acid value is 0.
As calculated: bonding glycerine release rate is 98.8%, and thick methyl esters is 98% to the stock oil yield.
Oleum Cocois with different acid values is a raw material, adopts same steps as, condition gained to the results are shown in Table 1.(table 1 is seen the literary composition back)
Example 2:
Identical with example 1 step, 200g lard (acid value 11.8, bonding glycerol content 10.42%) and the vitriol oil of the 0.4g of preformulation (38%) and 10ml carbinol mixture add in the reactor, when being heated to 95 ℃, beginning feeds methyl alcohol with the speed of 36.8g/hr, stops heating after 1 hour, stir and logical methyl alcohol, cooling reaction system to 50 ℃ records reaction mixture acid value 0.35, adds 61.4g methyl alcohol and 0.74gNaOH.In 72 ℃ of backflows 40 minutes, stop to stir down and refluxed 20 minutes under stirring, steam methyl alcohol under the decompression, tell thick methyl esters 19.8g, washing dehydration back methyl alcohol ester 197g records acid value 0.02, bonding glycerol content 0.12%, the release rate that draws bonding glycerine as calculated reaches 98.9%, and the methyl esters yield is 98.5.
Example 3:
Identical with example 1 step, 200g Oleum Cocois (acid value 10.7, bonding glycerol content 13.42%) and the tosic acid of 0.4g (moisture 9.5%) and 10ml methanol mixture in reactor, when reacting by heating system to 110 ℃, begin to feed methyl alcohol with the speed of 39.5g/hr, stop after 1 hour stirring and logical methyl alcohol and cooling reaction system to 40 ℃, recording the reaction system acid value is 0.27, add 47.4g methyl alcohol and 0.65gNaOH, 72 ℃ of following stirring and refluxing 40 minutes, stop to stir down and refluxed 20 minutes, steam methyl alcohol under the decompression then, tell thick methyl esters 199.5g, record acid value 0.07, bonding glycerol content 0.10%, the release rate that draws bonding glycerine as calculated reaches 99%, and thick methyl esters yield is 99.75%.
Example 4:
This embodiment carries out pre-esterification reactor with the methyl alcohol that reclaims after the transesterify, operational condition is stated identical with last example, pre-esterification afterreaction system acid value is 0.48, the thick methyl esters that transesterify is told is heavy 19.4g after the washing dehydration, record acid value 0.15, bonding glycerol content 0.17%, bonding glycerine release rate is 98.7% as calculated, thick methyl esters yield is 98.7%.
Example 5:
This example just changes in alcohol as reactant, the mixture of 200g Oleum Cocois and 1g toluenesulphonic acids (moisture 9.5%) and 10ml propyl carbinol is joined in the reactor, begin when being heated to 150 ℃ to feed just in alcohol, speed is 50g/hr, stop logical propyl carbinol and stirring after 1 hour, cooling reaction system to 50 ℃, recording acid value is 0.49, add 84g propyl carbinol and 0.83gNaOH, refluxed 40 minutes down in 125 ℃, stop then stirring down and refluxed 20 minutes, steam propyl carbinol under the decompression, get slightly positive butyl ester 235g after the separation.Record bonding glycerol content 0.2%, bonding glycerine release rate reaches 98% as calculated, and positive butyl ester yield is 117.5%.
Example 6:
Mountain grey seed benevolence oil, acid value 61, unsaponifiables 5.63%, total fatty acid content 83.32%, should oil 3000g and the 90g vitriol oil (98%) and 130g methyl alcohol add in the reactor, when being heated to 95 ℃, begin to feed methyl alcohol with 1343g/hr speed, subsequently temperature rise to 105 ℃ about 1 hour, reduce to 95 ℃ then gradually, react after 1.5 hours, the methyl alcohol of reaction system is reclaimed in decompression down, washes reaction mixture with water to neutral, the decompression of dehydration back steams established methyl esters, steam the 2095g methyl esters 278 ℃ the time under 45mmHg, yield reaches 69.83%, after the cooling system resistates 860g acid value 0.48, add 204g methyl alcohol and 5.1g sodium hydroxide, carry out transesterify under stirring, get the 540g methyl esters, the thick methyl esters acid value 0.75 of gained after distillation is refining, total methyl esters is 2635g, convert for the lipid acid yield be 98.3%.
By table and the result of embodiment as can be seen, the present invention compares the bonding glycerine release rate high about 2% of document record, the yield high approximately 2% of thick methyl esters, and for acid value up to 61 mountain grey seed benevolence oil, also achieve satisfactory results, industrially promote the use of production technique of the present invention, can bring considerable economic.
Table 1
| Experiment numbers | The crude oil acid value | Acid value after the esterification | Crude oil bonding glycerol content (%) | Thick methyl esters bonding glycerol content (%) | The glycerine release rate | Thick methyl esters yield |
| ????1 | ?9.57 | ????0.27 | ????13.58 | ????0.16 | ?98.8 | ?98 |
| ????2 | ?6.7 | ????0.23 | ????13.98 | ????0.11 | ?99.2 | ?99.2 |
| ????3 | ?10.4 | ????0.27 | ????13.42 | ????0.08 | ?99.4 | ?99.3 |
| ????4 | ?12.1 | ????0.24 | ????13.62 | ????0.12 | ?99.1 | ?99.8 |
| ????* | ?15.1 | ????0.4 ????0.8 | ????13.2 | ????0.4 ????0.5 | ?＜＝97 | ?97 |
* be the embodiment data of documents DE3444.893
Claims (2)
1. a natural fats and oils that contains free fatty acids is the method for raw material production fatty acid alkyl ester, may further comprise the steps:
(1) in the presence of an acidic catalyst, the natural fats and oils that contains free fatty acids is at normal pressure, and temperature is 80-160 ℃ and passes through reactor down and continuously that speed is 0.20-0.60 gram/gram crude oil.Hour C
1-C
4Reaction of alkanol, until the acid value of reaction mixture less than 1,
(2) through being cooled to 30-60 ℃ above-mentioned reaction mixture, at the C that adds capacity
1-C
4Alkanol and add basic catalyst after, be warming up to 60-130 ℃, refluxed transesterify 30-70 minute down,
(3) purifying of the separation of reaction mixture and product.
2. the production method of fatty acid alkyl ester as claimed in claim 1 is characterized in that described C
1-C
4Alkanol is a methyl alcohol, and the temperature of reaction of step (1) is 90-100 ℃, and described an acidic catalyst is the vitriol oil, and described basic catalyst is sodium hydroxide or sodium methylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89107686 CN1031070C (en) | 1989-09-30 | 1989-09-30 | Producing technology for fathy acid alkyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89107686 CN1031070C (en) | 1989-09-30 | 1989-09-30 | Producing technology for fathy acid alkyl ester |
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| Publication Number | Publication Date |
|---|---|
| CN1050556A CN1050556A (en) | 1991-04-10 |
| CN1031070C true CN1031070C (en) | 1996-02-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89107686 Expired - Fee Related CN1031070C (en) | 1989-09-30 | 1989-09-30 | Producing technology for fathy acid alkyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031070C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186834B (en) * | 2007-12-24 | 2012-05-23 | 钱生球 | Method for preparing biological diesel oil from rubber seed oil |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091464C (en) * | 1999-11-25 | 2002-09-25 | 中国科学院新疆化学研究所 | Synthesis of modified black grass seed oil |
| US7943792B2 (en) * | 2007-04-02 | 2011-05-17 | Inventure Chemical Inc. | Production of biodiesel, cellulosic sugars, and peptides from the simultaneous esterification and alcoholysis/hydrolysis of materials with oil-containing substituents including phospholipids and peptidic content |
| CN102465058A (en) * | 2010-11-04 | 2012-05-23 | 朱建军 | Production process for preparing biodiesel |
| KR20160047771A (en) | 2014-10-23 | 2016-05-03 | 에스케이이노베이션 주식회사 | Lube base oil and method for preparing the same |
-
1989
- 1989-09-30 CN CN 89107686 patent/CN1031070C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186834B (en) * | 2007-12-24 | 2012-05-23 | 钱生球 | Method for preparing biological diesel oil from rubber seed oil |
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| Publication number | Publication date |
|---|---|
| CN1050556A (en) | 1991-04-10 |
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