CN105154240A - Method for producing environment-friendly fatty acid methyl ester with glycerol method - Google Patents
Method for producing environment-friendly fatty acid methyl ester with glycerol method Download PDFInfo
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- CN105154240A CN105154240A CN201510486430.3A CN201510486430A CN105154240A CN 105154240 A CN105154240 A CN 105154240A CN 201510486430 A CN201510486430 A CN 201510486430A CN 105154240 A CN105154240 A CN 105154240A
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- methyl ester
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Abstract
The invention discloses a method for producing environment-friendly fatty acid methyl ester with a glycerol method. According to the method, animal and vegetable oil or an oil byproduct and glycerol are taken as raw materials and have an esterification reaction at the reaction temperature of 160-230 DEG C, and glyceride is produced; the produced glyceride has a transesterification reaction with methyl alcohol under the catalysis of a basic catalyst, crude methyl ester and glycerol are produced, the glycerol and the crude methyl ester are obtained through layering and separation, the glycerol is recycled secondarily, reduced pressure distillation is performed on the crude methyl ester, and a required product, namely, the fatty acid methyl ester, is distilled. With the adoption of the method, the environment-friendly and harmless glycerol is taken as the raw material and can have the esterification reaction at the high temperature, and the fatty acid methyl ester is produced; no concentrated sulfuric acid catalyst is required in the whole production process, meanwhile, the usage amount of the methyl alcohol is greatly reduced, and environmental pollution and damage to health of workers are reduced.
Description
Technical field
The present invention relates to fatty acid methyl Lipase absobed field, be specifically related to a kind of method of glycerine method production environment-friendly type fatty acid methyl ester.
Background technology
Fatty acid methyl ester (also known as methyl esters, biofuel, Witconol 2301) is the basic raw material producing the kinds of surface promoting agents such as alkylol amide, methyl ester sulfonate, polyvalent alcohol ester type nonionogenic tenside, senior perfumed soap, and fatty alcohol obtained after high-pressure hydrogenation is again one of indispensable raw material manufacturing the tensio-active agents such as oxygen ethylene type nonionogenic tenside, ether alcohol sulfate (AES), aliphatic alcohol sulfate (K-12).Higher aliphatic acid methyl esters directly can be used as advanced lubrication oil additives, the additive of machining oil, cooling fluid, rolloff oil and boring wet goods finish in mechanical workout, additive in Rubber processing, also can directly as diesel-fuel or diesel oil additive, fatty acid methyl ester is also developed day by day in the application in other industry and field.
Under the effect of catalyzer, esterification is there is and obtains in the production method of existing biofuel mainly through lipid acid and short chain alcohol.It is as follows to there is shortcoming in it: the building-up process of fatty acid methyl ester adopts mostly carries out under an acidic catalyst catalysis from the Long carbon chain lipid acid of vegetable and animals oils and a large amount of methyl alcohol, and traditional production technique adopts dense H
2sO
4, the liquid catalyst such as tosic acid, though equipment is simple, reaction conditions is gentle, transformation efficiency is high, but refining step is many, production cost is high, produce a large amount of waste water, catalyst separating and reuse difficulty, and acid catalysis is because of severe corrosive enamel equipment, is unfavorable for scale operation.Meanwhile, the use of strong acid and a large amount of methyl alcohol causes very big destruction to environment, and the health for individual also causes great damage.
As patent 200710020352.3,201310725449.X all disclose with the homogeneous reaction process of strong acid (as the vitriol oil) catalysis pre-esterification, its speed of response is very fast, but there is etching apparatus, product postprocessing complex process, and produce a large amount of waste water, to environment.Patent CN1766040A selects lipase as catalyst for esterification reaction, lipase-catalyzed process environmental protection, and reaction terminates easily to be separated from product afterwards, but its catalytic efficiency is lower, and the susceptibility of enzyme environment to external world causes its easy inactivation.Patent CN200610083300 is then with ionic liquid-catalyzed esterification, and its reactive behavior is high, good stability, but after reaction, difficulty is separated with by-product glycerin, and reaction process needs certain pressure.
Prior art mainly adopts the vitriol oil as the catalyzer of esterification, and washing produces a large amount of sour water in the process.And rich vitriolated sour water is difficult to process, conduct oneself well if improper and put, serious harm will be caused to environment, and processing cost is high.Sulfuric acid is as a kind of strong acid simultaneously, all can cause serious acid etching loss to transport and water treating equipment.And using glycerine as raw material, without the need to catalyzer, only esterification at high temperature need can be there is, greatly reduce the usage quantity of methyl alcohol simultaneously, reduce the harm to human body.
In general, adopt glycerine as Material synthesis methyl esters, namely avoid the generation of sour water, also reduce the usage quantity of methyl alcohol, to environment and the person, all there is certain provide protection.
Summary of the invention
For solving the problems of the technologies described above, we have proposed a kind of glycerine that utilizes for the method for raw material production fatty acid methyl ester, using vegetable and animals oils or grease byproduct (carclazyte oil, lipid acid, acidification oil, waste cooking oil etc.) and glycerine as Material synthesis fatty acid methyl ester, the sour water, the problem of environmental pollution that produce in production process can be reduced, reduce methyl alcohol usage quantity to reduce the harm to human body simultaneously.
For achieving the above object, the technical solution used in the present invention is:
A method for glycerine method production environment-friendly type fatty acid methyl ester,
Step one: using through filtering, pretreated vegetable and animals oils of dewatering or grease byproduct and glycerine is as raw material, the mol ratio of vegetable and animals oils or grease byproduct and glycerine is 2.5-3.5: 1, carries out esterification and generate glyceryl ester under the temperature of reaction of 160-230 DEG C; After esterification 1-2 hour, leave standstill cooling, get upper liquid and detect acid value, when acid value≤8, then can carry out step 2 transesterification reaction, otherwise then continuation step one is reacted until acid value meets the demands;
Step 2: the methyl alcohol glyceryl ester generated in step one being added a certain amount of basic catalyst and 20%-30% carries out transesterification reaction, react 1-2 hour at the temperature of mechanical stirring and 40-70 DEG C after, obtain glycerine and thick methyl esters, continue to be warming up to 100-120 DEG C, methyl alcohol is steamed; Stratification, reclaims lower floor's glycerine; Then underpressure distillation, pressure be-0.08--0.10MPa, temperature steams desired product fatty acid methyl ester under being 180-260 DEG C of condition.
Preferably, a small amount of potassium hydroxide can be added in the esterification reaction process in step one and regulate pH value to 6-8 to promote that esterification is carried out.
Preferably, the add-on of the basic catalyst in step 2 adjusts according to the acid value of raw material vegetable and animals oils or grease byproduct: when acid value is less than 10, add the basic catalyst of mass ratio 0.3%, when acid value is at 10-80, add the basic catalyst of mass ratio 0.2%; When acid value is at 80-160, add the basic catalyst of 0.1%; When acid value is greater than 160, basic catalyst need not be added.
Preferably, basic catalyst is the alkoxide of sodium hydroxide, potassium hydroxide, carbonate, sodium and potassium.
Preferably, described grease byproduct is carclazyte oil, lipid acid, acidification oil or waste cooking oil.
Advantage of the present invention:
Embodiment
Below in conjunction with embodiment and embodiment, the present invention is further detailed explanation.
Embodiment 1:
Filtering and impurity removing is carried out to carclazyte oil, the pre-treatment such as dehydration are to remove throw out wherein and unnecessary moisture, take again mol ratio be the process of 3: 1 carclazyte oil and glycerine be placed in reactor, react under the hot conditions of mechanical stirring and 200-210 DEG C, a small amount of potassium hydroxide can be added and regulate pH value to 7.0-7.5 to promote that esterification is carried out, react after 1 hour, leave standstill cooling, get upper liquid and detect acid value, when acid value≤8, as then can second step transesterification reaction be carried out between 7-8, otherwise then continue the first step reaction until acid value meets the demands.
Material after the first step reaction being terminated adds potassium hydroxide methanol solution, the add-on of methyl alcohol is 20% (mass ratio) of material, the add-on of potassium hydroxide, then according to the acid value of carclazyte oil, when acid value is less than 10, adds the potassium hydroxide of 0.3% (mass ratio); When acid value is at 10-80, add the potassium hydroxide of 0.2%; When acid value is at 80-160, add the potassium hydroxide of 0.1%; When acid value is greater than 160, potassium hydroxide need not be added; At the temperature of mechanical stirring and 60 DEG C, reaction is after 1.5 hours, continues to be warming up to about 110 DEG C, is steamed by methyl alcohol, stratification, and after being reclaimed by lower floor's glycerine, be-0.1MPa at pressure, temperature is 200-230 DEG C, can steam desired product fatty acid methyl ester.
Chemical equation:
Embodiment 2:
The pre-treatment such as filtering and impurity removing, dehydration is carried out to remove throw out wherein and unnecessary moisture to carclazyte oil, take again mol ratio be the process of 3: 1 carclazyte oil and glycerine be placed in reactor, react under the hot conditions of mechanical stirring and 190-200 DEG C, a little potassium hydroxide can be added and carry out adjustment about PH to 6.5-7 to promote that reaction is carried out, react after 2 hours, leave standstill cooling, get upper liquid and detect acid value, when acid value is between 5-6, then can carry out second step transesterification reaction, otherwise then continue the first step reaction until acid value meets the demands.
Material after the first step reaction being terminated adds sodium hydroxide, methanol solution, the add-on of methyl alcohol is 30% (mass ratio) of material, the add-on of sodium hydroxide, then according to the acid value of carclazyte oil, when acid value is less than 10, adds the sodium hydroxide of 0.3% (mass ratio), when acid value is at 10-80, add the sodium hydroxide of 0.2%, when acid value is at 80-160, add the sodium hydroxide of 0.1%, when acid value is greater than 160, sodium hydroxide need not be added; At the temperature of mechanical stirring and 50 DEG C, reaction is after 2 hours, continues to be warming up to 115-120 DEG C, is steamed by methyl alcohol, stratification, and after being reclaimed by lower floor's glycerine, be-0.1MPa at pressure, temperature is 210-220 DEG C, steams desired product fatty acid methyl ester.
Embodiment 2, compared with embodiment 1, the selection of material only changes catalyzer into sodium hydroxide by potassium hydroxide, and parameter makes suitable adjustment simultaneously.
Embodiment 3:
The pre-treatment such as filtering and impurity removing, dehydration is carried out to remove throw out wherein and unnecessary moisture to carclazyte oil, take again mol ratio be the process of 3.5: 1 carclazyte oil and glycerine be placed in reactor, react under the hot conditions of mechanical stirring and 190-200 DEG C, a little potassium hydroxide can be added and carry out adjustment about PH to 7.5 to promote that reaction is carried out, react after 2 hours, leave standstill cooling, get upper liquid and detect acid value, when acid value is less than 5-8, then can carry out second step transesterification reaction, otherwise then continue the first step reaction until acid value meets the demands.
Material after the first step reaction being terminated adds potassium hydroxide, methanol solution, the add-on of methyl alcohol is 25% (mass ratio) of material, the add-on of potassium hydroxide, then according to the acid value of carclazyte oil, when acid value is less than 10, adds the potassium hydroxide of 0.3%, when acid value is at 10-80, add the potassium hydroxide of 0.2%, when acid value is at 80-160, add the potassium hydroxide of 0.1%, when acid value is greater than 160, potassium hydroxide need not be added; At the temperature of mechanical stirring and 50 DEG C, reaction is after 2 hours, continues to be warming up to 110 DEG C, is steamed by methyl alcohol, stratification, and after being reclaimed by lower floor's glycerine, be-0.09MPa at pressure, temperature is 210-220 DEG C, can steam desired product fatty acid methyl ester.
Embodiment 4:
The pre-treatment such as filtering and impurity removing, dehydration is carried out to remove throw out wherein and unnecessary moisture to carclazyte oil, take again mol ratio be the process of 2.8: 1 carclazyte oil and glycerine be placed in reactor, react under the hot conditions of mechanical stirring and 220 DEG C, a little potassium hydroxide can be added and carry out adjustment about PH to 6.5 to promote that reaction is carried out, react after 2 hours, leave standstill cooling, get upper liquid and detect acid value, when acid value is less than 5-8, then can carry out second step transesterification reaction, otherwise then continue the first step reaction until acid value meets the demands.
Material after the first step reaction being terminated adds potassium hydroxide, methanol solution, the add-on of methyl alcohol is 28% (mass ratio) of material, the add-on of potassium hydroxide, then according to the acid value of carclazyte oil, when acid value is less than 10, adds the potassium hydroxide of 0.3% (mass ratio), when acid value is at 10-80, add the potassium hydroxide of 0.2%, when acid value is at 80-160, add the potassium hydroxide of 0.1%, when acid value is greater than 160, potassium hydroxide need not be added; At the temperature of mechanical stirring and 50 DEG C, reaction is after 2 hours, continues to be warming up to 110 DEG C, is steamed by methyl alcohol, stratification, and after being reclaimed by lower floor's glycerine, be-0.08MPa at pressure, temperature is about 215 DEG C, steams desired product fatty acid methyl ester.
Embodiment 5:
The pre-treatment such as filtering and impurity removing, dehydration is carried out to remove throw out wherein and unnecessary moisture to waste cooking oil, take waste cooking oil that mol ratio is the process of 2.5: 1 again and glycerine is placed in reactor, react under the hot conditions of mechanical stirring and 190-200 DEG C, a little potassium hydroxide can be added and carry out adjustment about PH to 6.5 to promote that reaction is carried out, react after 2 hours, leave standstill cooling, get upper liquid and detect acid value, when acid value is less than 5-8, then can carry out second step transesterification reaction, otherwise then continue the first step reaction until acid value meets the demands.
Material after the first step reaction being terminated adds potassium hydroxide, methanol solution, the add-on of methyl alcohol is 28% (mass ratio) of material, the add-on of potassium hydroxide, then according to the acid value of waste cooking oil, when acid value is less than 10, adds the potassium hydroxide of 0.3% (mass ratio), when acid value is at 10-80, add the potassium hydroxide of 0.2%, when acid value is at 80-160, add the potassium hydroxide of 0.1%, when acid value is greater than 160, potassium hydroxide need not be added; At the temperature of mechanical stirring and 50 DEG C, reaction is after 2 hours, continues to be warming up to 110 DEG C, is steamed by methyl alcohol, stratification, and after being reclaimed by lower floor's glycerine, be-0.08MPa at pressure, temperature is about 215 DEG C, steams desired product fatty acid methyl ester.
Embodiment 6:
To lipid acid, acidification oil carries out filtering and impurity removing, the pre-treatment such as dehydration are to remove throw out wherein and unnecessary moisture, take acidification oil that mol ratio is the process of 3: 1 again and glycerine is placed in reactor, react under the hot conditions of mechanical stirring and 210 DEG C, a little potassium hydroxide can be added and carry out adjustment about PH to 6.5-7 to promote that reaction is carried out, react after 2 hours, leave standstill cooling, get upper liquid and detect acid value, when acid value is between 5-6, then second step transesterification reaction can be carried out, otherwise then continue the first step reaction until acid value meets the demands.
Material after the first step reaction being terminated adds sodium hydroxide, methanol solution, the add-on of methyl alcohol is 30% (mass ratio) of material, the add-on of sodium hydroxide then adjusts according to the acid value of lipid acid, acidification oil, when acid value is less than 10, adds the sodium hydroxide of 0.3% (mass ratio), when acid value is at 10-80, add the sodium hydroxide of 0.2%, when acid value is at 80-160, add the sodium hydroxide of 0.1%, when acid value is greater than 160, sodium hydroxide need not be added; At the temperature of mechanical stirring and 50 DEG C, reaction is after 2 hours, continues to be warming up to 115-120 DEG C, is steamed by methyl alcohol, stratification, and after being reclaimed by lower floor's glycerine, be-0.1MPa at pressure, temperature is 210-220 DEG C, steams desired product fatty acid methyl ester.
Above-described is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (5)
1. a method for glycerine method production environment-friendly type fatty acid methyl ester, is characterized in that,
Step one: using through filtering, pretreated vegetable and animals oils of dewatering or grease byproduct and glycerine is as raw material, the mol ratio of vegetable and animals oils or grease byproduct and glycerine is 2.5-3.5:1, carries out esterification and generate glyceryl ester under the temperature of reaction of 160-230 DEG C; After esterification 1-2 hour, leave standstill cooling, get upper liquid and detect acid value, when acid value≤8, then can carry out step 2 transesterification reaction, otherwise then continuation step one is reacted until acid value meets the demands;
Step 2: the methyl alcohol glyceryl ester generated in step one being added a certain amount of basic catalyst and 20%-30% carries out transesterification reaction, react 1-2 hour at the temperature of mechanical stirring and 40-70 DEG C after, obtain glycerine and thick methyl esters, continue to be warming up to 100-120 DEG C, methyl alcohol is steamed; Stratification, reclaims lower floor's glycerine; Then underpressure distillation, pressure be-0.08--0.10MPa, temperature steams desired product fatty acid methyl ester under being 180-260 DEG C of condition.
2. the method for a kind of glycerine method production environment-friendly type fatty acid methyl ester according to claim 1, is characterized in that, can add a small amount of potassium hydroxide and regulate pH value to 6-8 to promote that esterification is carried out in the esterification reaction process in step one.
3. the method for a kind of glycerine method production environment-friendly type fatty acid methyl ester according to claim 1 and 2, it is characterized in that, the add-on of the basic catalyst in step 2 adjusts according to the acid value of raw material vegetable and animals oils or grease byproduct: when acid value is less than 10, add the basic catalyst of mass ratio 0.3%, when acid value is at 10-80, add the basic catalyst of mass ratio 0.2%; When acid value is at 80-160, add the basic catalyst of 0.1%; When acid value is greater than 160, basic catalyst need not be added.
4. the method for a kind of glycerine method production environment-friendly type fatty acid methyl ester according to claim 3, it is characterized in that, basic catalyst is the alkoxide of sodium hydroxide, potassium hydroxide, carbonate, sodium and potassium.
5. the method for a kind of glycerine method production environment-friendly type fatty acid methyl ester according to claim 1, it is characterized in that, described grease byproduct is carclazyte oil, lipid acid, acidification oil or waste cooking oil.
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Cited By (4)
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| CN106675789A (en) * | 2017-01-24 | 2017-05-17 | 江苏悦达卡特新能源有限公司 | Method for preparing biodiesel with low sulfur content from gutter oil |
| CN106966895A (en) * | 2017-03-27 | 2017-07-21 | 北京恩泽福莱科技有限公司 | A kind of synthetic method of fragrant low carbon acid methyl esters |
| CN112159730A (en) * | 2020-09-09 | 2021-01-01 | 湖北天基生物能源科技发展有限公司 | Method for treating esterified oil |
| CN113831243A (en) * | 2021-09-15 | 2021-12-24 | 常州市金坛区维格生物科技有限公司 | Method for purifying methyl oleate by cyclic elution mode |
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Application publication date: 20151216 |