CN1904014A - Method of preparing fatty acid ester - Google Patents
Method of preparing fatty acid ester Download PDFInfo
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- CN1904014A CN1904014A CN 200510087070 CN200510087070A CN1904014A CN 1904014 A CN1904014 A CN 1904014A CN 200510087070 CN200510087070 CN 200510087070 CN 200510087070 A CN200510087070 A CN 200510087070A CN 1904014 A CN1904014 A CN 1904014A
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- oil
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Abstract
The present invention relates to a method for preparing aliphatic ester. Said method includes the following steps: mixing oil, monohydric alcohol with C1-C6 and alkaline compound, making them produced reaction at 200-300 deg.C and 5-12 MPa and separating aliphatic ester from the material obtained after reaction. The described alkaline compound is one or several kinds selected from hydroxide, alcoholate, oxide, carbonate, bicarbonate and C12-C24 fatty acid salt of IA and IIA elements in periodic table, and the added quantity of alkaline compound is 0.005-0.008% of oil weight.
Description
Invention field
The present invention relates to method by grease and monohydroxy-alcohol prepared in reaction fatty acid ester (being biofuel).
Background technology
Biofuel can be carried out transesterification reaction by grease and monohydroxy-alcohol and be made, and fatty acid ester is arranged in the reaction product, also has mono-glycerides, two sweet esters, glycerine, and unreacted pure and mild grease (being triglyceride level).In the prior art, the preparation method of biofuel can be divided into acid catalyzed process, base catalysis method, enzyme catalysis method and supercritical methanol technology.
It is raw material that CN1473907A adopts the tankage of vegetable oil refining and edible refiltered oil, catalyzer is inorganic and organic acid is composite forms by sulfuric acid, hydrochloric acid, tosic acid, Witco 1298 Soft Acid, naphthene sulfonic acid etc., produce through operations such as acidifying removal of impurities, continuously dehydrating, esterification, layering, underpressure distillation, the pressure of continous vacuum dehydration is 0.08～0.09Mpa, 60～95 ℃ of temperature, dewater to water-content below 0.2%, esterif iotacation step catalyzer add-on 1～3%, 60～80 ℃ of esterification temperatures, 6 hours reaction times.Reaction after product neutralization is earlier removed catalyzer, and then, layering removes and anhydrates, and the after product that anhydrates obtains biofuel through underpressure distillation.
Acid catalysis is compared existence with base catalysis problem is that speed of response is slow, has a large amount of spent acid and produces contaminate environment.
DE3444893 discloses a kind of method, use acid catalyst, normal pressure, 50～120 ℃, free fatty acids and alcohol are carried out esterification, oil plant is carried out pre-esterification treatment, under base metal catalysts, carry out transesterification reaction then, but the acid catalyst of leaving over will be neutralized by alkali, and the amount of base metal catalysts can increase.Adopt pre-esterification, make work flow elongated, facility investment, energy consumption significantly rises, and in addition, needs basic catalyst is removed from product, has a large amount of waste water to produce.Recovery glycerine difficulty.
CN1472280A discloses a kind of method, and as acyl acceptor, in the presence of biological enzyme, catalysis biological carries out transesterification reaction production biofuel with fatty acid ester.Adopt enzyme catalyst to exist deficiency to be: long reaction time, efficient are lower, and enzyme is more expensive, and in high purity methanol easy inactivation.
CN1111591C discloses the method for a kind of grease and monohydroxy-alcohol prepared in reaction fatty acid ester, this method comprises methyl alcohol reacted with grease and obtains fatty acid ester, at 270～280 ℃, under 11～12Mpa condition, the fatty acid methyl ester production rate is 55～60%, find out from this patent: the fatty acid methyl ester production rate is lower, and openly how mono-glycerides, two sweet esters, triglyceride level in the reacting coarse product is not handled.
Can find by above-mentioned prior art, adopt the middle and high platen press of successive to have the lower problem of fatty acid ester yield.In addition, aforesaid method does not add explanation to handling high acid value with the reaction effect that contains the unrefined oil of high unsaponifiables yet.
Summary of the invention
The invention provides a kind of method for preparing fatty acid ester, this method also can suppress the generation of burnt matter when obtaining high yield fatty acid ester.
The method for preparing fatty acid ester provided by the invention comprises: make grease and C
1～C
6Monohydroxy-alcohol and basic cpd mix, and, react separating out fat acid esters from reacted material under pressure 5～12Mpa 200～300 ℃ of temperature of reaction.
Described grease comprises Vegetable oil lipoprotein and various animal grease, also comprises in addition from the oil plant in the materials such as microorganism, algae; Even also comprise frying oil, rotten waste oil etc.Vegetable oil lipoprotein such as soybean oil, rapeseed oil, peanut oil, wunflower seed oil, plam oil, Oleum Cocois and the material that contains fatty group (comprising the tall oil that produces in the paper-making process) that comes from fruit, stem, leaf, limb and the root of other various farm crop and wild plant.Animal grease such as lard, butter, sheep oil, fish oil etc.Stock oil can be the crude oil of the different acid numbers of various height, high-content unsaponifiables, adopts the inventive method stock oil can not carry out pre-treatment.
Described monohydroxy-alcohol is meant the unitary fatty alcohol of carbonatoms between 1～6, can be saturated alcohol or unsaturated alcohol.As methyl alcohol, ethanol, propyl alcohol, Virahol, vinyl carbinol, propyl carbinol and isomer thereof, amylalcohol and isomer thereof etc.Can use independent alcohol or their mixture.Particular methanol or ethanol.
Described basic cpd is selected from IA in the periodictable, the oxyhydroxide of IIA element, alcoholate, oxide compound, carbonate, supercarbonate, C
12～C
24Soap, preferred sodium, potassium, magnesium, calcium, the oxyhydroxide of barium, alcoholate, oxide compound, carbonate, supercarbonate, soap, more preferably following compound: the oxyhydroxide of sodium, potassium, magnesium, oxide compound, alcoholate, C
12～C
14Soap.The add-on of basic cpd is 0.005～0.08% of a grease weight, preferred 0.008～0.05%.
Specifically, method provided by the invention is to adopt fixed-bed reactor, grease and alcohol can offer reactor separately, or with offering reactor after their pre-mixings, before offering reactor, available preheater is with the material preheating, also can directly enter reactor, if raw material directly enters reactor, so, reactor had both played the effect of preheater, also played the effect of reactor.As adopt preheater, preheating together after can or mixing grease and alcohol difference preheating.
Temperature of reactor is 200～300 ℃, preferred 200～280 ℃, and pressure 5～12Mpa, best 6～10Mpa, pure and greasy mol ratio is 3～60: 1, preferred 4～12: 1, liquid hourly space velocity is 0.1～20h
-1, preferred 1～15h
-1
Temperature raises, and reaction conversion ratio is high more, because from the kinetics angle, temperature raises to help reacting and carries out, but when temperature was higher than 300 ℃, reaction product was black, had burnt matter to produce, simultaneously, also can cause glycerine to decompose, therefore, temperature of reactor is answered＜300 ℃, best 200～300 ℃.
Pressure is high more favourable more to reaction, but pressure is too high, makes the investment of device and process cost raising more, so, pressure 5～12Mpa, best 6～10Mpa.
Monohydroxy-alcohol and greasy mol ratio can in very large range change in the inventive method, and methyl alcohol shortens material residence time in reactor with the too high meeting of mol ratio of oil, and transformation efficiency descends.Plant energy consumption and process cost are increased, usage ratio of equipment is descended.So monohydroxy-alcohol and greasy mol ratio are 3～60: 1, are preferably 4～12: 1.
Because the add-on of basic cpd is less, can adopt the method for absorption, the reacting coarse product of outflow reactor is removed through adsorption tower.Avoided washing to produce the problem of waste water.
The stock oil that the inventive method is suitable for is very extensive, and acid number can change within a large range, for example 0～60mgKOH/g.Unsaponifiables can be less than 0.5g/100g oil, also can be up to 5～10g/100g oil.
The inventive method has solved the lower problem of fatty acid methyl ester yield in existing middle pressure, the moving method of high pressure continuous flow, the yield of fatty acid ester can reach 94～97%, and the color of reaction back oil plant is not compared intensification with stock oil, in reactor, do not find carbon distribution or burnt matter, in addition, also helping the product acid number reduces.
Embodiment
Further specify the present invention below by example, but the present invention is not limited to this.
Embodiment 1
Vegetables oil with acid number 1.4mgKOH/g is a raw material, at molar ratio of methanol to oil 5, liquid hourly space velocity 1.2h
-1Condition under, continuously be provided in the tubular reactor, adding weight is the NaOH of grease weight 0.01%, temperature is 260～270 ℃ in the reactor, pressure 8Mpa, grease reaction conversion ratio 100w%, fatty acid methyl ester yield 97 ± 1w%.
Embodiment 2
With acid number 1.2mgKOH/g vegetables oil is raw material, is 5 at molar ratio of methanol to oil, liquid hourly space velocity 7h
-1Condition under, continuously be provided in the tubular reactor, adding weight is the NaOH of grease weight 0.01%, temperature is 260～270 ℃ in the reactor, pressure 8Mpa, grease reaction conversion ratio 100w%, reacting coarse product steams fatty acid methyl ester through rectification under vacuum, fatty acid methyl ester yield 94w%.
Residue raffinate fatty acids methyl esters, mono-glycerides, two sweet esters can be used as raw material and are circulated to the reactor feed mouth at the bottom of the rectifying still, and are repeated use after fresh feed mixes.
Embodiment 3
With acid number 44mgKOH/g raw plant oil is raw material, at molar ratio of methanol to oil 5.2, liquid hourly space velocity 1.2h
-1Condition under, continuously be provided in the tubular reactor, adding weight is the NaOH of grease weight 0.01%, temperature is 260～270 ℃ in the reactor, pressure 8～9Mpa, grease reaction conversion ratio 100w%, the ester phase acid number 2.1mgKOH/g that reacting coarse product obtains through separation, reacting coarse product steams fatty acid methyl ester through rectification under vacuum, fatty acid methyl ester yield 95-96w%.
Residue raffinate fatty acids methyl esters, mono-glycerides, two sweet esters can be used as raw material and are circulated to the reactor feed mouth at the bottom of the rectifying still, and are repeated use after fresh feed mixes.
Embodiment 4
With acid number 1.4mgKOH/g vegetables oil is raw material, at molar ratio of methanol to oil 10, liquid hourly space velocity 13.5h
-1Condition under, continuously be provided in the tubular reactor, adding weight is the NaOH of grease weight 0.01%, temperature is 270～280 ℃ in the reactor, pressure 8～9Mpa, grease reaction conversion ratio 100w%, rectification under vacuum steams fatty acid methyl ester, fatty acid methyl ester yield 89w%.
Residue raffinate fatty acids methyl esters, mono-glycerides, two sweet esters at the bottom of the rectifying still, it can be used as raw material and is circulated to the reactor feed mouth, and is repeated use after fresh feed mixes.
Embodiment 5
With acid number 52mgKOH/g, the raw plant oil that contains unsaponifiables 4% is a raw material, at molar ratio of methanol to oil 12, liquid hourly space velocity 1.2h
-1Condition under, continuously be provided in the tubular reactor, adding weight is the Mg (OH) of grease weight 0.07%
2, temperature is 270～280 ℃ in the reactor, pressure 9～10Mpa, and reacting coarse product steams fatty acid methyl ester through rectification under vacuum, fatty acid methyl ester yield 87w%.
Residue raffinate fatty acids methyl esters, mono-glycerides, two sweet esters at the bottom of the rectifying still, it can be used as raw material and is circulated to the reactor feed mouth, and is repeated use after fresh feed mixes.
Embodiment 6
With acid number 39mgKOH/g raw plant oil is raw material, at molar ratio of methanol to oil 4.5, liquid hourly space velocity 1.2h
-1Condition under, continuously be provided in the tubular reactor, adding weight is the oleic sylvite of grease weight 0.07%, temperature is 260～270 ℃ in the reactor, pressure 8.5Mpa, reacting coarse product steams fatty acid methyl ester through rectification under vacuum, fatty acid methyl ester yield 86w%.
Residue raffinate fatty acids methyl esters, mono-glycerides, two sweet esters at the bottom of the rectifying still, it can be used as raw material and is circulated to the reactor feed mouth, and is repeated use after fresh feed mixes.
Embodiment 7
Raw plant oil with acid number 26mgKOH/g is a raw material, at molar ratio of methanol to oil 5, liquid hourly space velocity 2.4h
-1Condition under, continuously be provided in the tubular reactor, adding weight is the KOH of grease weight 0.01%, temperature is 260～270 ℃ in the reactor, pressure 9Mpa, reacting coarse product steams fatty acid methyl ester through rectification under vacuum, fatty acid methyl ester yield 89w%.
Residue raffinate fatty acids methyl esters, mono-glycerides, two sweet esters can be used as raw material and are circulated to the reactor feed mouth at the bottom of the rectifying still, and are repeated use after fresh feed mixes.
Comparative Examples 1
With acid number 1.4mgKOH/g vegetables oil is raw material, molar ratio of methanol to oil 10, liquid hourly space velocity 1.2h
-1Condition under, continuously be provided in the tubular reactor, temperature is 280 ℃ in the reactor, pressure 10Mpa, the crude product after the oil plant transesterification reaction steams fatty acid methyl ester through rectification under vacuum, fatty acid methyl ester yield 47w%.
Claims (8)
1. method for preparing fatty acid ester, comprise: grease is mixed with C1～C6 monohydroxy-alcohol and basic cpd, 200～300 ℃ of temperature, react under pressure 5～12Mpa, separating out fat acid esters from reacted material, described basic cpd are selected from IA in the periodictable, the oxyhydroxide of IIA element, alcoholate, oxide compound, carbonate, supercarbonate, C
12～
24In the soap one or more, the add-on of basic cpd are 0.005～0.08% of grease weight.
2. in accordance with the method for claim 1, it is characterized in that described monohydroxy-alcohol is methyl alcohol or ethanol.
3. in accordance with the method for claim 1, it is characterized in that described basic cpd is oxyhydroxide, alcoholate, oxide compound, carbonate, supercarbonate or the C of sodium, potassium, magnesium, calcium, barium
12～C
24Soap.
4. according to claim 1 or 3 described methods, it is characterized in that described basic cpd is oxyhydroxide, alcoholate, oxide compound or the C of sodium, potassium, magnesium
12～C
24Soap.
5. in accordance with the method for claim 1, it is characterized in that the add-on of basic cpd is 0.008～0.05% of a grease weight.
6. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 240～280 ℃, pressure 6～10Mpa.
7. in accordance with the method for claim 1, it is characterized in that pure and greasy mol ratio is 3～60: 1, liquid hourly space velocity is 0.1～20h
-1
8. in accordance with the method for claim 7, it is characterized in that pure and greasy mol ratio is 4～12: 1, liquid hourly space velocity is 1～15h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100870706A CN100548963C (en) | 2005-07-26 | 2005-07-26 | A kind of method for preparing fatty acid ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100870706A CN100548963C (en) | 2005-07-26 | 2005-07-26 | A kind of method for preparing fatty acid ester |
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| CN1904014A true CN1904014A (en) | 2007-01-31 |
| CN100548963C CN100548963C (en) | 2009-10-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450897A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for producing triacetin |
| CN102234567A (en) * | 2011-05-27 | 2011-11-09 | 江苏恒顺达生物能源有限公司 | Method for lowering acid value of biodiesel |
| CN102807922A (en) * | 2011-05-31 | 2012-12-05 | 中国石油化工股份有限公司 | Preparation method for fatty acid ester |
| CN105647655A (en) * | 2014-11-26 | 2016-06-08 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN107794124A (en) * | 2017-11-29 | 2018-03-13 | 广西丰泰能源科技有限公司 | The method that catalysis prepares bio-fuel |
-
2005
- 2005-07-26 CN CNB2005100870706A patent/CN100548963C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450897A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Method for producing triacetin |
| CN101450897B (en) * | 2007-11-28 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing triacetin |
| CN102234567A (en) * | 2011-05-27 | 2011-11-09 | 江苏恒顺达生物能源有限公司 | Method for lowering acid value of biodiesel |
| CN102807922A (en) * | 2011-05-31 | 2012-12-05 | 中国石油化工股份有限公司 | Preparation method for fatty acid ester |
| CN105647655A (en) * | 2014-11-26 | 2016-06-08 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN105647655B (en) * | 2014-11-26 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN107794124A (en) * | 2017-11-29 | 2018-03-13 | 广西丰泰能源科技有限公司 | The method that catalysis prepares bio-fuel |
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| Publication number | Publication date |
|---|---|
| CN100548963C (en) | 2009-10-14 |
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