CN100577785C - Method of lowering acid value of oil and fat - Google Patents
Method of lowering acid value of oil and fat Download PDFInfo
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- CN100577785C CN100577785C CN200510087069A CN200510087069A CN100577785C CN 100577785 C CN100577785 C CN 100577785C CN 200510087069 A CN200510087069 A CN 200510087069A CN 200510087069 A CN200510087069 A CN 200510087069A CN 100577785 C CN100577785 C CN 100577785C
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Abstract
The present invention provides a method for reducing acid value of oil. Said method includes the following steps: making oil with high acid value and monohydric alcohol with C1-C6 produce reaction in fixed bed reactor under the condition of 170-280 deg.C and 5-12MPa, and collecting oil mixture whose acid value is reduced.
Description
Technical field
The present invention relates to a kind of method that reduces acid value of oil and fat.
Background technology
Biofuel can be carried out transesterification reaction by grease and monohydroxy-alcohol (generally being low-carbon alcohol, as the monohydroxy-alcohol of C1-C6) and be made.When grease and methyl alcohol carried out transesterification reaction, it was biofuel that fatty acid methyl ester is arranged in the reaction product, also had by products such as mono-glycerides, two sweet esters, glycerine in addition.
Needing to reduce acid number to raw material with preparing biological diesel fuel by high-acid-value grease as last handles, as adopt pre-esterification process, the DE3444893 method therefor is: (1) tosic acid, toluenesulphonic acids or sulfuric acid are catalyzer, normal pressure, 50～120 ℃, free fatty acids and alcohol are carried out esterification, oil plant is carried out pre-esterification treatment, (2) reaction mixture sat be divided into contain catalyzer and water alcohol mutually and oil phase.(3) water in the oil phase is removed with extracting process.(4) in the presence of basic catalyst, oil phase and alcohol after the extraction are carried out transesterification reaction.This processing step is many, long flow path, and loss of material is big.
It is catalyzer that CN1031070C adopts the vitriol oil, phosphoric acid or tosic acid, toluenesulphonic acids and naphthene sulfonic acid, with oil plant and pure under 80～160 ℃ of conditions, in the tank reactor that band stirs, carries out pre-esterification reactor.The reaction finish after, add pure and mild excess base, at first in and an acidic catalyst and residual free fatty acids, the residue alkali as catalyst for ester exchange reaction.
Adopt above-mentioned pre-esterification process, the acid catalyst of leaving over will be neutralized by alkali, and the consumption of base metal catalysts can increase, and work flow is longer, facility investment, and 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.
US2494366 adopts in the excess base and free fatty acids reduces acid number in the high-acid value grease, and carry out esterification reaction of organic acid, the soap that alkali and free fatty acids form is emitted free acid with the anti-neutralization of sulfuric acid after esterification, this part free acid carries out an esterification again under the acid catalysis effect, the finished product are through neutralization, filtration and rectifying obtain the methyl esters product, and this processing step is many, long flow path, loss of material is big, and inorganic wastes is many.
Find out by prior art: for the higher oil plant of acid number, as acid number greater than 1.0mgKOH/g, generally need carry out esterification treatment in advance to oil plant, free fatty acids is wherein become fatty acid methyl ester, this process is as adopting sulfuric acid etc. as catalyzer, seriously corroded can produce a large amount of spent acid, waste water; As to adopt solid acid be catalyzer, has the problem that catalyzer is more expensive, life cycle is short.As with in the alkali and free fatty acids also have same problem to exist.
Summary of the invention
The invention provides a kind of method that need not catalyzer and do not produce the reduction acid value of oil and fat of waste water, waste residue.
Method provided by the invention is: high-acid value grease and C1～C6 monohydroxy-alcohol are reacted in fixed-bed reactor, collect the rich mixture that acid number has reduced, wherein temperature of reactor is 170～280 ℃, best 200～235 ℃, pressure 5～12Mpa, best 6～10Mpa.
Specifically, can adopt tubular reactor by method provided by the invention, grease and alcohol can offer reactor separately, or offer reactor after they are given mixing, before offering reactor, available preheater is with the material preheating, also can directly enter reactor, like this, reactor had both played the effect of preheater, also played the effect of reactor.As adopt preheater, and can be with after grease and alcohol difference preheating or mixing, preheating together.
Described grease comprises Vegetable oil lipoprotein, also comprises 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.The acid number of stock oil can change within a large range, as 1～60mgKOH/g.Unsaponifiables also can change in 1～6g/100g oil scope.
Described monohydroxy-alcohol is meant the unitary fatty alcohol of C1～C6, 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.
Method rising temperature of reaction provided by the invention, reaction conversion ratio can improve, because from the kinetics angle, temperature raises to help reacting and carries out, but along with temperature raises, the reaction product color is dark more, is easy to generate burnt matter more, simultaneously, also can cause glycerine to decompose, therefore, temperature of reactor is 170～280 ℃, best 200～235 ℃.
Elevated pressures is to reacting favourable, but pressure is too high, and it is more that the investment of device and process cost are improved, so pressure is 5～12Mpa, best 6～10Mpa.
Liquid hourly space velocity can in very large range change, and higher liquid hourly space velocity can make equipment capacity increase, but liquid hourly space velocity is too high, and the reaction effect variation is so liquid hourly space velocity is generally 0.5～6h
-1, be preferably 0.5～4h
-1The time, reaction result is better.
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.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.
Adopt the inventive method, reduce the reaction of acid number and can carry out, make material be not easy to take place to go bad, the material processing power is increased decrease machining cost in bigger air speed or under than the demulcent condition.Carry out pre-treatment for high-acid-value material, can effectively reduce the acid number of raw material, make follow-up transesterification reaction after, the acid number of the biofuel that obtains reaches the requirement of 0.8mgKOH/g oil (U.S.'s biofuel standard) easily, need not carry out the follow-up acid number that falls and handle.
Embodiment
Further specify the present invention below by example, but the present invention is not limited to this.
Embodiment 1
With the raw plant oil of acid number 28mgKOH/g with liquid hourly space velocity 4.6h
-1, molar ratio of methanol to oil 5 is provided in the tubular reactor, temperature is 280 ℃ in the reactor, pressure 10Mpa, the ester phase acid number 4.9mgKOH/g that reacting coarse product obtains through separation.
Embodiment 2
With the raw plant oil of acid number 28mgKOH/g with liquid hourly space velocity 1.2h
-1, molar ratio of methanol to oil 5 is provided in the tubular reactor, temperature is 235 ℃ in the reactor, pressure 8Mpa, the ester phase acid number 4.0mgKOH/g that reacting coarse product obtains through separation.
Embodiment 3
With the raw plant oil of acid number 28mgKOH/g with liquid hourly space velocity 1.2h
-1, molar ratio of methanol to oil 12 is provided in the tubular reactor, temperature is 220～225 ℃ in the reactor, pressure 8.5Mpa, the ester phase acid number 5.1mgKOH/g that reacting coarse product obtains through separation.
Embodiment 4
With the raw plant oil of acid number 28mgKOH/g with liquid hourly space velocity 0.6h
-1, molar ratio of methanol to oil 10 is provided in the tubular reactor, and temperature is 210～215 ℃ in the reactor, pressure 9Mpa, the ester phase acid number 3.2mgKOH/g that reacting coarse product obtains through separation.
Embodiment 5
With the raw plant oil of acid number 52mgKOH/g with liquid hourly space velocity 0.6h
-1, molar ratio of methanol to oil 12 is provided in the tubular reactor, and temperature is 215～220 ℃ in the reactor, pressure 10Mpa, the ester phase acid number 5.9mgKOH/g that reacting coarse product obtains through separation.
Embodiment 6
With the ester of acid number 4mgKOH/g among the embodiment 2 with liquid hourly space velocity 1.2h
-1, raw polyol mol ratio 5 is provided in the tubular reactor, and temperature is 270～280 ℃ in the reactor, pressure 8～9Mpa, reacting coarse product obtains fatty acid methyl ester acid number 0.8mgKOH/g through separation.
Claims (8)
1. method that reduces acid value of oil and fat comprises: with grease and C1～C6 monohydroxy-alcohol in fixed-bed reactor in 170～235 ℃ of temperature, pressure 5～12Mpa, monohydroxy-alcohol and greasy mol ratio 3～60: 1, liquid hourly space velocity 0.5～6h
-1Condition under react, collect the rich mixture that acid number has reduced.
2. in accordance with the method for claim 1, it is characterized in that described fixed-bed reactor are tubular reactors.
3. in accordance with the method for claim 1, it is characterized in that described greasy acid number is 1～60mgKOH/g.
4. in accordance with the method for claim 1, it is characterized in that described monohydroxy-alcohol is methyl alcohol or ethanol.
5. in accordance with the method for claim 1, it is characterized in that temperature of reaction is 200～235 ℃.
6. in accordance with the method for claim 1, it is characterized in that pressure is 6～10Mpa.
7. in accordance with the method for claim 1, it is characterized in that monohydroxy-alcohol and greasy mol ratio are 4～12: 1.
8. in accordance with the method for claim 1, it is characterized in that liquid hourly space velocity is 0.5～4h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510087069A CN100577785C (en) | 2005-07-26 | 2005-07-26 | Method of lowering acid value of oil and fat |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510087069A CN100577785C (en) | 2005-07-26 | 2005-07-26 | Method of lowering acid value of oil and fat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1904013A CN1904013A (en) | 2007-01-31 |
| CN100577785C true CN100577785C (en) | 2010-01-06 |
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| CN200510087069A Active CN100577785C (en) | 2005-07-26 | 2005-07-26 | Method of lowering acid value of oil and fat |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329695B (en) * | 2007-12-28 | 2015-05-20 | 中国石油化工股份有限公司 | Method for lowering acid value of oil material |
| CN101289627B (en) * | 2008-06-10 | 2011-07-27 | 河南星火生物能源有限公司 | Process for reducing acid value of biodiesel |
| CN101760225B (en) * | 2008-12-25 | 2013-09-04 | 中国石油化工股份有限公司 | Method for reduction of acid value of biodiesel |
| CN102559393B (en) * | 2010-12-23 | 2015-02-25 | 中国石油化工股份有限公司 | Method for preparing biodiesel with low acid value |
| CN103013676B (en) * | 2011-09-20 | 2014-12-03 | 中国石油化工股份有限公司 | Method for reducing biodiesel crude product acid value, and biodiesel preparation method |
| CN103173281B (en) * | 2011-12-21 | 2014-12-31 | 中国石油化工股份有限公司 | Method for reducing acid value of biodiesel crude product and preparation method of biodiesel |
| CN114453022A (en) * | 2022-01-23 | 2022-05-10 | 大连医诺生物股份有限公司 | Acid catalyst for reducing acid value of high-acid-value oil, preparation method, recovery method and application thereof |
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