CN104450209A - Method for reducing acid value of crude rice bran oil through solid super acid catalysis - Google Patents
Method for reducing acid value of crude rice bran oil through solid super acid catalysis Download PDFInfo
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- CN104450209A CN104450209A CN201410716012.4A CN201410716012A CN104450209A CN 104450209 A CN104450209 A CN 104450209A CN 201410716012 A CN201410716012 A CN 201410716012A CN 104450209 A CN104450209 A CN 104450209A
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- oil
- crude oil
- acid
- catalyst
- rice pollard
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for reducing the acid value of crude rice bran oil through solid super acid catalysis. The method comprises the following steps: adding glycerinum and a solid super acid catalyst into crude rice bran oil with a high acid value, heating, stirring, vacuuming to remove water generated from reaction, after the reaction is completed, filtering and recycling the catalyst, thereby obtaining rice bran oil with a low acid value. The method disclosed by the invention is high in esterification rate, low in product acid value, simple in aftertreatment, free of environment pollution and very beneficial for industrialization production as loss caused by alkali refining physical refining is avoided.
Description
Technical field
The present invention relates to a kind of method that esterification process reduces fatty acid content in Rice pollard oil.
Background technology
Rice pollard oil is a kind of grease that the byproduct rice bran utilizing rice to process is produced.It is a kind of desirable edible vegetable oil, and oleic acid wherein and linolic acid ratio are roughly 1:1, and from the viewpoint of modern nutriology, the grease of this ratio has higher nutritive value, and after food, specific absorption can reach more than 90%.Also be conducive to the composition of human body containing abundant vitamin-E, sterol, thiaminogen etc. in Rice pollard oil, the beneficial effect such as the long-term edible cholesterol had in removing blood, reduction blood fat, promotion growth in humans growth, thus Rice pollard oil is the nutrient health oil of generally acknowledging both at home and abroad, just a kind of grease of great exploitation potential for its.Because manufacturing enterprise does not carry out glyceridase Passivation Treatment in time to Rice pollard oil raw materials for production rice bran, and rice bran storage time is long, reserve temperature is too high, under the effect of face glyceridase, the Rice bran crude oil acid number produced is general very high, even reach 30 ~ 50mgKOH/g, substantially exceed the national standard of the Rice bran crude oil of food oils, cannot for the production of edible oil.The process of deacidification value must be carried out to Rice pollard oil crude oil for this reason.
The method of current Rice pollard oil deacidification value mainly contains four kinds: alkali refining method, physical deacidification method, extraction process, esterification process.The depickling of chemistry alkali refining method is the industrial method the most generally used, and use alkali lye and free-fat acid-respons, free fatty acids (FFA) is with soap stock form precipitation, and soap stock removes through centrifugation.Alkali refining method effectively can remove the free fatty acids in Rice pollard oil, but neutral oil issues unboiled water solution in alkali effect, causes a large amount of neutral oil loss, and FFA content is higher, and oil consumption is larger, physical deacidification method is the lipid acid removed by the method for employing underpressure distillation in grease, and temperature, generally higher than 200 DEG C, requires the pre-treatment of stock oil relatively stricter, also can produce destruction, and part VE can be lost in lipid acid overhead product to grease, extraction process is that the lipid acid in grease extracts by extraction agent with alcohol such as methanol/ethanol, there is extraction not exclusively, and VE, thiaminogen Deng Cheng branch are extracted the problem causing nutrition leak, esterification process is a kind of many method of Recent study, mainly be reduced to fatty acid glyceryl ester by free lipid acid and glycerine or mono-glycerides esterification, effectively can avoid the loss of lipid acid, the catalyzer adopted mainly contains the liquid acid (vitriol oil, tosic acid), metallic zinc and compound (zinc oxide thereof, zinc chloride), tin protochloride etc., these Catalytic processes all also exist esterification reaction temperature high (180 ~ 220 DEG C), esterification is not thorough, reacted acid number is generally greater than 3mgKOH/g, and there is the problem of a large amount of mono-glycerides and two sweet esters, Rice pollard oil zero pour after esterification also can uprise, uncomfortable pleasant long-term edible.Solid super-strong acid is the solid acid that a kind of strength of acid is greater than 10000 times, 100% sulfuric acid, the appearance of solid super-strong acid overcomes the shortcoming of liquid acid, have easily be separated with liquid-phase reaction system, not etching apparatus, aftertreatment simple, seldom contaminate environment, selectivity advantages of higher, expand the range of application of the acid catalyzed reaction that thermodynamics may carry out.Adopt solid super-strong acid as catalyst glycerine and fatty acid esterification, can temperature of reaction be effectively reduced, improve esterification yield, and aftertreatment is simple, without the need to washing, do not produce problem of environmental pollution.
Summary of the invention
The object of the invention is the deficiency for above-mentioned deacidifying process, provide a kind of esterifying efficiency high, product yield is high, and aftertreatment is simple, does not produce environmental pollution, is more suitable for the method for the Rice pollard oil deacidification value of industrial application.The method of a kind of solid superacid as catalyst Rice pollard oil crude oil deacidification value of the present invention, is made up of following steps:
The Rice pollard oil crude oil that 100g comes unstuck is added in 250ml there-necked flask, add the glycerine of theoretical amount, the pulverulent solids super acidic catalyst of quality of crude oil 1 ~ 3%, under the condition of vacuum tightness 0.085 ~ 0.095Mpa, be stirred and heated to 120 ~ 160 DEG C, react 4 ~ 6 hours, then to lower the temperature filtration, obtain low-acid value rice bran oil, measure acid number by GB/T5530-1985 method, reusable three times of catalyzer.
Further, the solid super-strong acid wherein described in step is SO
4 2-/ M
xo
yclass solid super-strong acid, M
xo
yrefer to ZrO
2, TiO
2, SnO
2, Al
2o
3or its mixture.
Further, the Heating temperature wherein described in step is 120 ~ 160 DEG C.
Further, the consumption of the catalyzer wherein described in step is quality of crude oil 1 ~ 3%.
Further, the add-on of the glycerine wherein described in step is theoretical amount.
Further, the reaction times wherein described in step is 4 ~ 6 hours.
Beneficial effect: the method for a kind of solid superacid as catalyst Rice pollard oil crude oil deacidification value of the present invention, esterification temperature is low is 120-160 DEG C, esterification is thorough, after esterification deacidification, acid number is below 0.5mgKOH/g, after esterification, the mass yield of grease is greater than 100%, aftertreatment is simple, does not produce environmental pollution.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
embodiment 1:
In 250ml there-necked flask, add 100g acid number is the Rice pollard oil crude oil that the decolouring of 44mgKOH/g is come unstuck, add the glycerine of theoretical amount, the pulverulent solids super acidic catalyst of quality of crude oil 3%, under the condition of vacuum tightness 0.085 ~ 0.095Mpa, be stirred and heated to 120 DEG C, react 4 hours, then to lower the temperature filtration, obtain low-acid value rice bran oil, measure acid number by GB/T5530-1985 method, reusable three times of catalyzer.
The acid number of gained rice finished product oil extracted from rice husks is 0.4mgKOH/g, and mass yield is 107%.
embodiment 2:
In 250ml there-necked flask, add 100g acid number is the Rice pollard oil crude oil that the decolouring of 35mgKOH/g is come unstuck, add the glycerine of theoretical amount, the pulverulent solids super acidic catalyst of quality of crude oil 2%, under the condition of vacuum tightness 0.085 ~ 0.095Mpa, be stirred and heated to 140 DEG C, react 6 hours, then to lower the temperature filtration, obtain low-acid value rice bran oil, measure acid number by GB/T5530-1985 method, reusable three times of catalyzer.
The acid number of gained rice finished product oil extracted from rice husks is 0.5mgKOH/g, and mass yield is 105%.
embodiment 3:
In 250ml there-necked flask, add 100g acid number is the Rice pollard oil crude oil that the decolouring of 13mgKOH/g is come unstuck, add the glycerine of theoretical amount, the pulverulent solids super acidic catalyst of quality of crude oil 1%, under the condition of vacuum tightness 0.085 ~ 0.095Mpa, be stirred and heated to 160 DEG C, react 6 hours, then to lower the temperature filtration, obtain low-acid value rice bran oil, measure acid number by GB/T5530-1985 method, reusable three times of catalyzer.
The acid number of gained rice finished product oil extracted from rice husks is 0.2mgKOH/g, and mass yield is 101%.
Patent of the present invention is including but not limited to above-mentioned specific examples, and all deformation designs based on this patent are all in the protection domain of this patent.
Claims (6)
1., by a method for solid superacid as catalyst Rice pollard oil crude oil deacidification value, comprise the following steps:
The Rice pollard oil crude oil that 100g comes unstuck is added in 250ml there-necked flask, add the glycerine of theoretical amount, the pulverulent solids super acidic catalyst of quality of crude oil 1 ~ 3%, under the condition of vacuum tightness 0.085 ~ 0.095Mpa, be stirred and heated to 120 DEG C ~ 160 DEG C, react 4 ~ 6 hours, then to lower the temperature filtration, obtain low-acid value rice bran oil, measure acid number by GB/T5530-1985 method, reusable three times of catalyzer.
2. the method for a kind of solid superacid as catalyst Rice pollard oil crude oil deacidification value as claimed in claim 1, is characterized in that solid super-strong acid is SO
4 2-/ M
xo
yclass solid super-strong acid, M
xo
yrefer to ZrO
2, TiO
2, SnO
2, Al
2o
3or its mixture.
3. the method for a kind of solid superacid as catalyst Rice pollard oil crude oil deacidification value as claimed in claim 1, is characterized in that Heating temperature is 120 ~ 160 DEG C.
4. the method for a kind of solid superacid as catalyst Rice pollard oil crude oil deacidification value as claimed in claim 1, is characterized in that the consumption of catalyzer is quality of crude oil 1 ~ 3%.
5. the method for a kind of solid superacid as catalyst Rice pollard oil crude oil deacidification value as claimed in claim 1, is characterized in that the add-on of glycerine is theoretical amount, namely in crude oil lipid acid molar weight 1/3.
6. the method for a kind of solid superacid as catalyst Rice pollard oil crude oil deacidification value as claimed in claim 1, is characterized in that the reaction times is 4 ~ 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410716012.4A CN104450209A (en) | 2014-12-02 | 2014-12-02 | Method for reducing acid value of crude rice bran oil through solid super acid catalysis |
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| CN201410716012.4A CN104450209A (en) | 2014-12-02 | 2014-12-02 | Method for reducing acid value of crude rice bran oil through solid super acid catalysis |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239667A (en) * | 2016-12-27 | 2018-07-03 | 丰益(上海)生物技术研发中心有限公司 | A kind of detection method of phospholipase C vigor |
| WO2020074435A1 (en) | 2018-10-10 | 2020-04-16 | Basf Se | Method of producing biodiesel |
| CN111454770A (en) * | 2020-02-12 | 2020-07-28 | 常州市金坛区维格生物科技有限公司 | Method for reducing acid of waste oil by glycerol method |
| WO2021204610A1 (en) | 2020-04-07 | 2021-10-14 | Basf Se | Energy efficient biodiesel production from natural or industrial waste oil |
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| CN101319167A (en) * | 2008-06-13 | 2008-12-10 | 合肥工业大学 | High-acid value rice bran oil esterification depickling process |
| CN102294252A (en) * | 2011-07-18 | 2011-12-28 | 李搏 | Production method of solid super acidic catalyst S04<2->/Sb-SnO2 |
| CN102453613A (en) * | 2010-10-14 | 2012-05-16 | 姚昂 | Method for producing diesel oil by esterification deacidification of rice bran oil |
| CN102453607A (en) * | 2010-10-22 | 2012-05-16 | 徐传仁 | Rice bran oil refining method |
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2014
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| CN101319167A (en) * | 2008-06-13 | 2008-12-10 | 合肥工业大学 | High-acid value rice bran oil esterification depickling process |
| CN102453613A (en) * | 2010-10-14 | 2012-05-16 | 姚昂 | Method for producing diesel oil by esterification deacidification of rice bran oil |
| CN102453607A (en) * | 2010-10-22 | 2012-05-16 | 徐传仁 | Rice bran oil refining method |
| CN102294252A (en) * | 2011-07-18 | 2011-12-28 | 李搏 | Production method of solid super acidic catalyst S04<2->/Sb-SnO2 |
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| 张秋云等: "制备生物柴油的固体酸催化剂研究进展", 《化工进展》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239667A (en) * | 2016-12-27 | 2018-07-03 | 丰益(上海)生物技术研发中心有限公司 | A kind of detection method of phospholipase C vigor |
| CN108239667B (en) * | 2016-12-27 | 2022-08-12 | 丰益(上海)生物技术研发中心有限公司 | Detection method for activity of phospholipase C |
| WO2020074435A1 (en) | 2018-10-10 | 2020-04-16 | Basf Se | Method of producing biodiesel |
| CN111454770A (en) * | 2020-02-12 | 2020-07-28 | 常州市金坛区维格生物科技有限公司 | Method for reducing acid of waste oil by glycerol method |
| WO2021204610A1 (en) | 2020-04-07 | 2021-10-14 | Basf Se | Energy efficient biodiesel production from natural or industrial waste oil |
| US12031107B2 (en) | 2020-04-07 | 2024-07-09 | Basf Se | Energy efficient biodiesel production from natural or industrial waste oil |
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Application publication date: 20150325 |