CN113025423A - Method for removing fatty acid by ionic liquid - Google Patents

Method for removing fatty acid by ionic liquid Download PDF

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CN113025423A
CN113025423A CN201911356486.1A CN201911356486A CN113025423A CN 113025423 A CN113025423 A CN 113025423A CN 201911356486 A CN201911356486 A CN 201911356486A CN 113025423 A CN113025423 A CN 113025423A
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oil
ion
ionic liquid
fat
cation
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赵格格
张海
徐学兵
姜元荣
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Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
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Wilmar Shanghai Biotechnology Research and Development Center Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/006—Refining fats or fatty oils by extraction
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/16—Refining fats or fatty oils by mechanical means

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Lubricants (AREA)

Abstract

The invention provides a method for reducing or removing free fatty acid and/or polycyclic aromatic hydrocarbon in grease, which comprises the step of contacting the grease with an ionic liquid or a solution thereof, wherein in the ionic liquid, a cation is selected from imidazolium ions, pyridinium ions, quaternary phosphonium cations, quaternary ammonium cations, benzimidazolium ions, pyrrolidinium ions and piperidinium ions, and an anion is benzoate. The invention also provides application of the ionic liquid in removing or reducing the content of free fatty acid and/or polycyclic aromatic hydrocarbon in grease.

Description

Method for removing fatty acid by ionic liquid
Technical Field
The present application relates to a method for removing fatty acids using an ionic liquid and to the use of the ionic liquid for removing fatty acids.
Background
Currently, the common grease deacidification methods in the grease processing industry mainly comprise chemical alkali refining deacidification and physical deacidification. Chemical alkali refining deacidification has the advantage of high product quality, but chemical alkali refining deacidification can cause a large amount of loss of nutrients. Physical deacidification often cannot ensure the production of high-quality oil, the pretreatment requirement on raw oil is strict, high temperature and high vacuum degree are required, side reactions such as polymerization and isomerization and harmful substances such as trans-fatty acid and chloropropanol are generated, and part of functional components are lost. The conventional organic solvent deacidification has the problems of solvent residue, incomplete deacidification, solvent volatilization and the like.
Rice bran oil (Rice bran oil, RBO) is prepared from fresh Rice bran, wherein vitamin E, sterol, oryzanol, etc. are helpful for absorption of nutrition of human body, and has effects of resisting oxidation, reducing blood lipid, cholesterol, etc. and promoting health. Under the influence of lipase, the acid value of the raw rice bran oil is very high, and the content of Free Fatty Acid (FFA) is generally over 10 percent, and some of the Free Fatty Acid (FFA) even reaches 20 percent. The consumption of alkali refining and deacidification is high, and the loss of functional components such as phytosterol, oryzanol, tocopherol and the like is serious; the physical deacidification also has the problem of partial sterol and oryzanol loss. Therefore, the development of an FFA removal method which has high deacidification efficiency, simple process and small influence on the content of substances such as sterol, oryzanol and the like is the target pursued by the rice bran oil refining process.
Polycyclic Aromatic Hydrocarbons (PAHs) generally refer to a class of compounds containing 2 or more benzene rings connected in a fused ring form, and are the first carcinogens and the most abundant carcinogens, and more than 400 carcinogenic Polycyclic Aromatic Hydrocarbons and derivatives thereof have been found. Polycyclic aromatic hydrocarbons are mostly insoluble in water, easily soluble in benzene aromatic solvents and slightly soluble in other solvents, and the polycyclic aromatic hydrocarbons are easily gathered in the grease due to the property. The plant oil itself contains little polycyclic aromatic hydrocarbon, but in the oil growth stage, atmospheric, water and soil pollution can cause polycyclic aromatic hydrocarbon to be absorbed by crops through root cortex and leaves. During the processing of the grease, the content of polycyclic aromatic hydrocarbon in the grease is greatly increased due to factors such as thermal processing treatment, processing aids, contact of packaging materials and the like. Therefore, the oil and fat refining process needs to be controlled and removed in a targeted manner.
There are also studies exploring liquid-liquid extraction methods to separate fats and oils from polycyclic aromatic hydrocarbons at present: cyclohexane or n-hexane is used for dissolving oil and fat, and a mixed solution (aqueous diformylamide solution, aqueous sulfolane solution, caffeine-formic acid solution and the like) is used as an extracting agent. There are also studies using liquid-liquid distribution method to dissolve vegetable oil with n-heptane, then using dimethyl sulfoxide to extract polycyclic aromatic hydrocarbon therein for separation, then adding water into dimethyl sulfoxide phase to change the distribution coefficient of polycyclic aromatic hydrocarbon in two phases, and then back-extracting polycyclic aromatic hydrocarbon into cyclohexane. The method needs a large amount of organic solvent and needs multiple liquid-liquid distribution, and the operation is complex and time-consuming.
Ionic Liquids (ILs) are salts composed of organic cations and organic or inorganic anions, and have the excellent properties of low steam pressure, stable property, good solubility, adjustable structure, controllable hydrogen bond acidity and alkalinity and the like. Due to the unique properties of the ionic liquid, the ionic liquid is widely applied to the fields of catalysis, drug extraction, electrochemistry, gas separation, mineral extraction and the like, and is considered to be an environment-friendly green medium with great development potential.
The ionic liquid is almost immiscible with the grease, so that oil consumption can be greatly reduced in the application process, the density difference between the ionic liquid and the grease is large, and the grease and the ionic liquid can be separated by simple centrifugation. In addition, the ionic liquid after the target substances in the grease are removed can be recycled by adding a stripping agent. Therefore, the ionic liquid has great application potential in the grease processing process.
At present, few research reports are reported on the application of ionic liquid as a solvent in the grease processing process, wherein the research reports are applied to the deacidification process as follows:
CN 106833886a this patent uses crude soybean oil (AV 2.392) as raw material, deacidification temperature is 70 ℃, 1, 3-dimethyl imidazole dimethyl phosphate ([ mm ] [ DMP ]) as deacidification agent, when the mass ratio of crude soybean oil to [ mm ] [ DMP ] is 2:1, FFA removal rate is 64.97%, because one-time deacidification can not reach corresponding standard, it needs to extract [ mm ] [ DMP ] and [ mm ] [ DMP ] or methanol solution of 50% tetrabutyl phosphonium bromide ([ P4,4, 4] [ Br ]) for the second time, so as to reach deacidification efficiency of more than 85%. The deacidification efficiency of the selected [ Mmim ] [ DMP ] is low, so that the use amount of the ionic liquid is large.
Disclosure of Invention
In one aspect, the present application provides a method for removing free fatty acids and/or polycyclic aromatic hydrocarbons from a fat, comprising the step of contacting the fat with an ionic liquid or a solution thereof, wherein the cation of the ionic liquid is selected from the group consisting of imidazolium ion, pyridinium ion, quaternary phosphonium cation, quaternary ammonium cation, benzimidazolium ion, pyrrolidinium ion, and piperidinium ion, and the anion is benzoate.
The imidazolium ions are 1, 3-dialkyl imidazolium ions.
The pyridinium ion is an N-alkylpyridinium ion.
The pyrrolidinium ions are N, N-dialkyl pyrrolidinium ions.
The piperidinium ion is an N, N-dialkylpiperidinium ion.
The benzimidazolium ion is a 1, 3-dialkylbenzimidazolium ion.
The alkyl substituents on the cation of the ionic liquid are each independently C1-12 alkyl, or each independently C1-8 alkyl, or each independently C2-C6 alkyl.
In the contacting step, the oil and the ionic liquid are mixed at a mass ratio of 3:1 to 1:3, or at a mass ratio of 1.5:1 to 1: 1.5.
The working temperature in the contacting step is 30-180 ℃, or the temperature can be increased to 80-180 ℃, or the temperature can be increased to 100-160 ℃, or the temperature can be increased to 120-140 ℃. For example, in the contacting step, the temperature may be gradually raised to a desired temperature while stirring the mixture of the fat and the ionic liquid.
After raising the temperature to the desired temperature, the oil and fat are brought into sufficient contact with the ionic liquid or the solution thereof at a high shear rate of, for example, 1000 to 20000rpm, 5000 to 15000rpm, or 8000 to 15000 rpm. In addition, the shearing time can be 1-10 min or 2-5 min. Optionally, the contacting step further comprises stirring the mixture at constant temperature for 10-60 min or 20-40 min after shearing, for example, at the same temperature.
The method further comprises a centrifugation step, wherein the fully contacted mixture of the grease and the ionic liquid is centrifuged for 3-30 min or 8-15 min at a rotating speed of 3000-10000 rpm or 5000-8000 rpm.
The oil and fat can be selected from vegetable oil and fat and animal oil and fat, especially liquid oil and fat at room temperature.
The ionic liquid or solution thereof may be contacted with the oil by any means, for example, by being added dropwise.
Examples of such ionic liquids include, but are not limited to, 1, 3-dimethylimidazole benzoate, 1-ethyl-3-methylimidazole benzoate, 1-methyl-3-ethylimidazole benzoate, 1-methyl-3-butylimidazole benzoate, 1-butyl-3-methylimidazole benzoate, 1-hexyl-3-methylimidazole benzoate, 1-octyl-3-methylimidazole benzoate, N-ethylpyridine benzoate, N-butylpyridine benzoate, N-propylpyridine benzoate, 1-methyl-3-butylbenzimidazole benzoate, N-butyl-N-methylpyrrolidine benzoate, N-butyl-N-methylpiperidine benzoate, tetrabutyl quaternary phosphonium benzoate, tetrabutyl quaternary ammonium benzoate.
The ionic liquid solution is an alcoholic solution of ionic liquid.
The alcoholic solution of the ionic liquid is methanol solution, ethanol solution or isopropanol solution of the ionic liquid.
The concentration of the ionic liquid in the alcoholic solution is 10-50%.
In a second aspect, the present application also provides a use of an ionic liquid or a solution thereof for removing free fatty acids and/or polycyclic aromatic hydrocarbons from oils and fats, wherein the cation in the ionic liquid is selected from imidazolium, pyridinium, quaternary phosphonium, quaternary ammonium, benzimidazolium, pyrrolidinium and piperidinium, and the anion is benzoate.
The imidazolium ions are 1, 3-dialkyl imidazolium ions.
The pyridinium ion is an N-alkylpyridinium ion.
The pyrrolidinium ions are N, N-dialkyl pyrrolidinium ions.
The piperidinium ion is an N, N-dialkylpiperidinium ion.
The benzimidazolium ion is a 1, 3-dialkylbenzimidazolium ion.
The polycyclic aromatic hydrocarbon is selected from naphthalene, acenaphthylene, fluorene,
Figure BDA0002336061790000041
Phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indene benzene (1,2,3-cd) pyrene, dibenzo (a, h) anthracene and benzo (g, h, i) perylene, more preferably selected from benzo (a) anthracene, anthracene,
Figure BDA0002336061790000042
Benzo (b) fluoranthene and benzo (a) pyrene.
The alkyl substituents on the cation of the ionic liquid are each independently C1-12 alkyl, or each independently C1-8 alkyl, or each independently C2-C6 alkyl.
In a third aspect, the present application also provides, inter alia, a method for processing an oil, comprising the step of contacting the oil with an ionic liquid or a solution thereof, wherein a cation in the ionic liquid is selected from an imidazolium ion, a pyridinium ion, a quaternary phosphonium cation, a quaternary ammonium cation, a benzimidazolium ion, a pyrrolidinium ion, and a piperidinium ion, and an anion is a benzoate.
The imidazolium ions are 1, 3-dialkyl imidazolium ions.
The pyridinium ion is an N-alkylpyridinium ion.
The pyrrolidinium ions are N, N-dialkyl pyrrolidinium ions.
The piperidinium ion is an N, N-dialkylpiperidinium ion.
The benzimidazolium ion is a 1, 3-dialkylbenzimidazolium ion.
The method further comprises one or more operations of degumming, dewaxing, deacidification, decoloration, deodorization, degreasing, fractionation, ester exchange and hydrogenation.
The oil is at least one selected from animal oil, vegetable oil and microbial oil.
The oil is any mixture of one or more than two of rice oil, sunflower seed oil, palm kernel oil, peanut oil, rapeseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow tree seed oil, almond oil, tung seed oil, rubber seed oil, rice bran oil, corn oil, wheat germ oil, sesame seed oil, castor bean oil, linseed oil, evening primrose seed oil, hazelnut oil, walnut oil, grape seed oil, linseed oil, glass chicory seed oil, sea buckthorn seed oil, tomato seed oil, pumpkin seed oil, macadamia nut oil, cocoa butter, beef tallow, mutton fat, lard, chicken oil, duck oil, seal oil, shrimp oil, fish oil and algae oil.
In a fourth aspect, the present application also provides, inter alia, a fat produced by the method of the first aspect of the present invention or the method of the third aspect of the present invention.
In the fifth aspect, the present application also specifically provides an oil or fat composition containing the oil or fat of the fourth aspect of the present invention.
Detailed Description
In one aspect, the present application provides a method for removing free fatty acids and/or polycyclic aromatic hydrocarbons from a fat, comprising the step of contacting the fat with an ionic liquid or a solution thereof, wherein the cation of the ionic liquid is selected from the group consisting of imidazolium ion, pyridinium ion, quaternary phosphonium cation, quaternary ammonium cation, benzimidazolium ion, pyrrolidinium ion, and piperidinium ion, and the anion is benzoate.
In some embodiments, the imidazolium ion is a 1, 3-dialkyl imidazolium ion.
In some embodiments, the pyridinium ion is an N-alkyl pyridinium ion.
In some embodiments, the pyrrolidinium ion is an N, N-dialkyl pyrrolidinium ion.
In some embodiments, the piperidinium ion is an N, N-dialkylpiperidinium ion.
In some embodiments, the benzimidazolium ion is a 1, 3-dialkylbenzimidazolium ion.
In some embodiments, the alkyl substituents on the cation of the ionic liquid may be the same or different from each other.
In some embodiments, the alkyl substituents on the cation of the ionic liquid may each independently be a straight or branched chain C1-C12Alkyl radicals, e.g. straight or branched C1-C8Alkyl or straight or branched C2-C6Alkyl or straight or branched C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11Or C12An alkyl group. Straight or branched C1-C12Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like.
Examples of suitable cations include, but are not limited to: 1, 3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1-methyl-3-butylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-hexyl-3-methylimidazolium ion, 1-octyl-3-methylimidazolium ion, N-ethylpyridinium ion, N-butylpyridinium ion, N-propylpyridinium ion, 1-methyl-3-butylbenzimidazolium ion, N-butyl-N-methylpyrrolidinium ion, N-butyl-N-methylpiperidinium ion, tetrabutylphosphonium ion, tetrabutylquaternary ammonium ion.
The term "remove" as used herein means to remove all or part of it. Thus, the term "removing free fatty acids from fats and oils" refers to removing free fatty acids in whole or in part (i.e., reducing the amount of free fatty acids); "removing polycyclic aromatic hydrocarbons from grease" refers to the removal of polycyclic aromatic hydrocarbons, either in whole or in part (i.e., reducing the amount of polycyclic aromatic hydrocarbons).
In some embodiments, the oil or fat may be at least one of an animal oil, a vegetable oil, a microbial oil.
In some embodiments, the oil may be rice oil, sunflower oil, palm kernel oil, peanut oil, rapeseed oil, cottonseed oil, safflower oil, perilla oil, tea seed oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, tung oil, rubber seed oil, rice bran oil, corn oil, wheat germ oil, sesame seed oil, castor bean oil, linseed oil, evening primrose seed oil, hazelnut oil, walnut oil, grape seed oil, linseed oil, glass endive oil, sea buckthorn seed oil, tomato seed oil, pumpkin seed oil, macadamia nut oil, cocoa butter and algae oil, beef tallow, mutton fat, lard, chicken oil, duck oil, seal oil, shrimp oil, fish oil, algae oil, or any mixture of two or more of these oils.
In some embodiments, the skilled person can generally select the specific contacting process according to actual needs, and accordingly select the specific ionic liquid amount, contacting temperature, contacting time, stirring time, centrifugation speed, centrifugation time, etc.
In some embodiments, the lipid is contacted with the ionic liquid or solution thereof sufficiently. For example, a grease is added to the ionic liquid of the present application, optionally heated to, e.g., 30-180 ℃. If the fat or oil is not liquid at ordinary temperature, it is heated at least to a temperature at which it is liquid.
In some embodiments, the mixture of the grease and ionic liquid is then maintained at this temperature for sufficient contact by high speed shearing in a high speed shear.
In some embodiments, after the shearing is completed, the mixture may be stirred at the same temperature for a period of time, such as 10-60 min. After the constant-temperature stirring is finished, cooling the mixture to room temperature or to a temperature still keeping liquid state, and centrifuging for 3-30 min at the rotating speed of 3000-10000 rpm by a centrifuge. After centrifugation, a separation occurs due to the immiscibility of the fat and oil with the ionic liquid, wherein the fat layer is freed from free fatty acids and/or polycyclic aromatic hydrocarbons and the ionic liquid layer contains extracted free fatty acids and/or polycyclic aromatic hydrocarbons. After the ionic liquid containing the free fatty acid and/or the polycyclic aromatic hydrocarbon is treated, the free fatty acid and/or the polycyclic aromatic hydrocarbon can be removed and recycled.
In some embodiments of the method, the fat is contacted with the ionic liquid at a mass ratio of 3:1 to 1:3 or at a mass ratio of 1.5:1 to 1:1.5 to obtain a mixture.
In some embodiments of the process, the fat and the ionic liquid may be contacted at a temperature of from 30 to 180 ℃, optionally heating the mixture, for example to a temperature of from 80 to 100 ℃, 80 to 130 ℃ or 80 to 180 ℃. At least the temperature is such that the fat and the ionic liquid are mixed in the liquid phase.
In the high-speed shearing machine, the shearing speed can be 1000-20000 rpm, 5000-15000 rpm or 8000-15000 rpm; and/or the shearing time of the high-speed shearing can be 1-10 min or 2-5 min.
In the process of stirring at constant temperature, the stirring time can be 10-60 min or 20-40 min.
The mixture of the grease and the ionic liquid can be separated at the rotating speed of 3000-10000 rpm or 5000-8000 rpm. The centrifugation time can be 3-30 min or 8-15 min.
It should be understood that features, characteristics, components or steps described in a particular aspect, embodiment or example of the present application may be applied to any other aspect, embodiment or example described herein unless incompatible therewith.
The above disclosure generally describes the present application, which is further exemplified by the following examples. These examples are described merely to illustrate the present application and do not limit the scope of the present application. Although specific terms and values are employed herein, they are to be understood as exemplary and not limiting the scope of the application.
Examples
All ionic liquids in the examples were obtained from Shanghai Chengjie chemical Co., Ltd
Parallel reactors are available from Radleys, Inc. of UK
The degummed rice bran oil and crude soybean oil are provided by Yihai (Tazhou) grain and oil industries, Inc
The method for measuring the acid value in the grease refers to the measurement of the acid value in GB5009.229-2016 food;
the determination method of polycyclic aromatic hydrocarbon in oil refers to 'Zhengzhu, Zhangliu, Wangjun, etc.. pollution condition of EU15+1PAHs in edible vegetable oil and influence of refining process on the content thereof [ J ] Chinese oil, 2016(12): 76-80.';
the method for measuring the total sterol in the oil refers to' GB/T25223-;
the method for measuring the oryzanol in the oil refers to the ultraviolet spectrophotometry of Liudeng, east China, for measuring the oryzanol content in the rice bran oil-Liudeng [ J ], the science and technology and the economy of grains, 2016,41(6): 40-43.
Calculation method of deacidification rate
Deacidification rate (%) - (AV)0-AV1)/AV0×100％
AV0、AV1Acid value before and after deacidification
The first embodiment is as follows:
taking about 3 parts of degummed rice bran oil of about 5g, respectively adding 5g of ionic liquid 1-butyl-3-methylimidazole benzoate ([ Bmim ] [ BA ]), 1-hexyl-3-methylimidazole benzoate ([ Hmim ] [ BA ]), and 1-octyl-3-methylimidazole benzoate ([ Omim ] [ BA ]), respectively shearing for 3min by adopting a high-speed shearing mode of 3000rpm, magnetically stirring for 30min at 80 ℃ in a parallel reactor, centrifuging for 3min at a rotating speed of 5000rpm, cooling to room temperature, and separating and measuring the acid value, polycyclic aromatic hydrocarbon, total sterol and oryzanol content of the upper layer oil phase.
Figure BDA0002336061790000091
Example two
Taking about 4 parts of 5g of soybean crude oil, and respectively adding 15g of ionic liquid 1-butyl-3-methylimidazol benzoate ([ Bmim)][BA]) N-butylpyridinobenzoate ([ Bpy ]][BA]) 1-methyl-3-butylbenzimidazole benzoate ([ Bmbim [ ]][BA]) N-butyl-N-methylpyrrolidine benzoate ([ PP ]1,4][BA]) Tetrabutylphosphonium benzoate ([ P ]4,4,4,4][BA]) And tetrabutylammonium benzoate ([ N ]4,4,4,4][BA]) Respectively shearing for 3min in 10000rpm high speed shearing mode in parallel reactorMagnetically stirring at 180 deg.C for 30min, centrifuging at 8000rpm for 3min, cooling to room temperature, and separating to determine acid value, polycyclic aromatic hydrocarbon, total sterol and oryzanol content of upper layer oil phase.
Figure BDA0002336061790000092
Figure BDA0002336061790000101
Example three:
taking about 2 g of soybean crude oil, respectively adding 10g of methanol solution (the mass ratio of ionic liquid to methanol is 1:1) of ionic liquid 1-butyl-3-methylimidazolium benzoate ([ Bmim ] [ BA ]) and 10g of methanol solution (the mass ratio of ionic liquid to methanol is 1:1) of ionic liquid N-butylpyridinium benzoate ([ Bpy ] [ BA ]), respectively shearing for 3min in a 10000rpm high-speed shearing mode, magnetically stirring for 30min at 30 ℃ in a parallel reactor, centrifuging for 3min at 8000rpm, cooling to room temperature, and separating and measuring the acid value, polycyclic aromatic hydrocarbon and total sterol content of the upper layer grease phase.
Figure BDA0002336061790000102
Comparative example one:
taking 3 parts of 5g rice bran crude oil, and adding 1-ethyl-3-methylimidazol diethyl phosphate salt [ Emim ] according to the mass ratio of 1:1 respectively][DEP]And 1, 3-dimethylimidazole dimethyl phosphate [ Mmim [ ]][DEP]And 1-butyl-3-methylimidazolidineamine ([ Bmim)][N(CN)2]) Preheating the mixed solution in 70 ℃ water bath for 45min, magnetically stirring in a parallel reactor at 70 ℃ for 30min, centrifuging at 5000rpm for 3min, cooling to room temperature, collecting an upper oil sample, and detecting the acid value, polycyclic aromatic hydrocarbon, total sterol and oryzanol content of the oil sample.
Figure BDA0002336061790000111
Comparative example two:
deacidifying by a conventional alkali refining method: taking about 20g of degummed rice bran oil, adopting 20% NaOH solution and 0.5% of excessive alkali, magnetically stirring for 10min at constant temperature of 30 ℃ in a parallel reactor, dropwise adding the NaOH solution, reducing the stirring speed, heating to 60 ℃, centrifuging for 3min at the rotating speed of 5000rpm, and measuring the acid value, polycyclic aromatic hydrocarbon, total sterol and oryzanol content of the upper layer grease phase.
Figure BDA0002336061790000112
Comparative example three:
eight parts of degummed rice bran oil of about 5g are taken, 5g of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim ] [ BF4]), N-butylpyridinium tetrafluoroborate ([ BPy ] [ BF4]), 1-butyl-3-methylimidazolium hexafluorophosphate ([ Bmim ] [ PF6]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([ Bmim ] [ OTf ]), 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide ([ Bmim ] [ NTf2]), tetrabutylphosphonium bis (trifluoromethanesulfonyl) imide ([ P4,4,4,4] [ NTf2]), N-butylpyridinium bis (trifluoromethanesulfonyl) imide ([ Bpy ] [ NTf2]) is respectively added dropwise into each part of degummed rice bran oil, and 3min is sheared in a high-speed manner of 3000rpm, magnetically stirring at 80 deg.C for 30min in a parallel reactor, centrifuging at 5000rpm for 3min, cooling to room temperature, and separating to determine acid value, polycyclic aromatic hydrocarbon, total sterol and oryzanol content of upper layer oil phase.
The results are as follows:
Figure BDA0002336061790000121
it is to be understood that while the application is illustrated in certain forms, it is not limited to what has been shown and described herein. It will be apparent to those skilled in the art that various changes can be made without departing from the scope of the application. Such variations are within the scope of the claims of this application.

Claims (10)

1. A method for removing free fatty acids and/or polycyclic aromatic hydrocarbons from fats and oils, comprising the step of contacting the fats and oils with an ionic liquid or a solution thereof, wherein the cation of the ionic liquid is selected from the group consisting of imidazolium ion, pyridinium ion, quaternary phosphonium cation, quaternary ammonium cation, benzimidazolium ion, pyrrolidinium ion and piperidinium ion, and the anion is benzoate.
2. The process according to claim 1, wherein the imidazolium ion is a 1, 3-dialkylimidazolium ion, and/or the pyridinium ion is an N-alkylpyridinium ion, and/or the pyrrolidinium ion is an N, N-dialkylpyrrolidinium ion, and/or the piperidinium ion is an N, N-dialkylpiperidinium ion, and/or the benzimidazolium ion is a 1, 3-dialkylbenzimidazolium ion; preferably, the alkyl substituents on the cation are each independently C1-12 alkyl, more preferably each independently C1-8 alkyl, and most preferably each independently C2-C6 alkyl.
3. The method according to claim 1 or 2, wherein in the contacting step, the oil and fat are mixed with the ionic liquid at a mass ratio of 3:1 to 1:3 or at a mass ratio of 1.5:1 to 1: 1.5.
4. The process according to any one of claims 1 to 3, wherein the temperature in the contacting step is from 30 to 180 ℃, preferably from 80 to 160 ℃, more preferably from 120 to 140 ℃.
5. The method according to any one of claims 1 to 4, wherein the contacting step comprises sufficiently contacting the oil and the ionic liquid or the solution thereof at a shear rate of 1000 to 20000rpm or 5000 to 15000rpm or 8000 to 15000 rpm; optionally, the shearing time is 1-10 min or 2-5 min; optionally, the contacting step further comprises stirring at the same temperature for 10-60 min or 20-40 min after shearing.
6. The method according to any one of claims 1 to 5, further comprising a centrifugation step, wherein the contacted oil and the ionic liquid or the solution thereof are centrifuged at a rotation speed of 3000 to 10000rpm or 5000 to 8000rpm for 3 to 30min or 8 to 15 min.
7. Use of an ionic liquid or a solution thereof for removing free fatty acids and/or polycyclic aromatic hydrocarbons from a fat or oil, wherein the cation in the ionic liquid is selected from imidazolium, pyridinium, quaternary phosphonium, quaternary ammonium, benzimidazolium, pyrrolidinium, and piperidinium, and the anion is benzoate; preferably, the imidazolium ion is a 1, 3-dialkyl imidazolium ion, and/or the pyridinium ion is an N-alkyl pyridinium ion, and/or the pyrrolidinium ion is an N, N-dialkyl pyrrolidinium ion, and/or the piperidinium ion is an N, N-dialkyl piperidinium ion, and/or the benzimidazolium ion is a 1, 3-dialkyl benzimidazolium ion; more preferably, the alkyl substituents on the cation are each independently C1-12 alkyl, preferably each independently C1-8 alkyl, more preferably each independently C2-C6 alkyl.
8. A method for processing a fat, comprising the step of contacting the fat with an ionic liquid or a solution thereof, wherein a cation in the ionic liquid is selected from an imidazolium ion, a pyridinium ion, a quaternary phosphonium cation, a quaternary ammonium cation, a benzimidazolium ion, a pyrrolidinium ion, and a piperidinium ion, and an anion is a benzoate;
optionally, the method further comprises one or more operations of degumming, dewaxing, deacidifying, decolorizing, deodorizing, degreasing, fractionation, transesterification, hydrogenation; and/or
Preferably, the oil is at least one selected from animal oil, vegetable oil and microbial oil; and/or
Preferably, the oil is any mixture of one or more of rice oil, sunflower seed oil, palm kernel oil, peanut oil, rapeseed oil, cottonseed oil, safflower seed oil, perilla seed oil, tea seed oil, palm fruit oil, coconut oil, olive oil, cocoa bean oil, Chinese tallow seed oil, almond oil, tung oil, rubber seed oil, rice bran oil, corn oil, wheat germ oil, sesame seed oil, castor bean oil, linseed oil, evening primrose seed oil, hazelnut oil, walnut oil, grape seed oil, linseed oil, glass endive oil, sea buckthorn seed oil, tomato seed oil, pumpkin seed oil, macadamia nut oil, cocoa butter, beef tallow, mutton fat, lard, chicken oil, duck oil, seal oil, shrimp oil, fish oil and algae oil.
9. An oil or fat produced by the method according to any one of claims 1 to 6 or the method according to claim 8.
10. An oil or fat composition comprising the oil or fat according to claim 9.
CN201911356486.1A 2019-12-25 2019-12-25 Method for removing fatty acid by ionic liquid Pending CN113025423A (en)

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