CN113122387A - Method for decoloring oil and removing plasticizer - Google Patents
Method for decoloring oil and removing plasticizer Download PDFInfo
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- CN113122387A CN113122387A CN201911390963.6A CN201911390963A CN113122387A CN 113122387 A CN113122387 A CN 113122387A CN 201911390963 A CN201911390963 A CN 201911390963A CN 113122387 A CN113122387 A CN 113122387A
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- polyethylene glycol
- oil
- grease
- phenyl ether
- triton
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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
- C11B3/10—Refining fats or fatty oils by adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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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
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
Abstract
The invention relates to a method for decolorizing oil and removing plasticizer, which comprises the step of contacting polyethylene glycol alkyl phenyl ether with oil. The method can decolorize the grease at low temperature and can remove the plasticizer in the grease; the shelf life of the grease is prolonged while the quality of the grease is maintained.
Description
Technical Field
The invention relates to a method for decoloring oil and removing a plasticizer.
Background
The adsorption decoloration can remove pigment in the grease, and can also remove other pollutants in the grease, but the adsorption decoloration is usually carried out at higher temperature.
At present, the grease decoloring process is usually carried out at about 100 ℃, and the high temperature can cause the peroxide value in the grease to be increased and destroy the quality of the grease, so that the decoloring at the low temperature can preserve nutrient substances in the grease, and the aims of improving the quality of the grease and prolonging the shelf life are particularly important.
Phthalate esters are a class of estrogen-like contaminants that interfere with secretion in humans. Among the phthalates, dimethyl phthalate (DMP), dibutyl phthalate (DBP) and di (2-ethylhexyl) phthalate (DEHP) are the three most common and commonly used phthalate plasticizers.
Dimethyl phthalate of the formula C10H10O4And has a molecular weight of 194. Dimethyl phthalate is a colorless, transparent and yellowish oily liquid, can be mixed with ethanol and ether organic solvents and is insoluble in water.
Dibutyl phthalate of the formula C16H22O4And the molecular weight is 278. Dibutyl phthalate is a colorless oily liquid, flammable, and aromatic in flavor. Can be mutually soluble with organic solvents such as ethanol, diethyl ether, acetone, benzene and the like, and has the solubility of 0.04 percent (25 ℃) in water.
Di (2-ethylhexyl) phthalate of formula C24H38O4And a molecular weight of 390. Di (2-ethylhexyl) phthalate is a colorless transparent liquid, has a special odor, is soluble in most organic solvents and hydrocarbons, and is slightly soluble in glycerol and ethylene glycol. Solubility in water<0.1%(25℃)。
The three plasticizers have good solubility in oil, and plastic containers used in oil transportation, plastic oil pipelines used in oil production, soil of raw material planting fields and the like all possibly cause the pollution of phthalate.
The phthalate substance can cause great harm to human body, and the maximum detection amount of di (2-ethylhexyl) phthalate (DEHP) and dibutyl phthalate (DBP) required in food and food additives is 1.5mg/kg and 0.3mg/kg respectively. The current reports on the removal of phthalate esters mostly focus on the removal of pollutants from environmental water, and the main methods are physical methods, such as removal by adsorption (Journal of Hazardous Materials 273(2014) 61-69); besides physical methods, chemical methods are also commonly used, and an oxidation method is generally used to remove the plasticizer (Applied Catalysis B: Environmental 174-175 (2015) 277-292) from the Environmental water. There are few reports about plasticizer removal from grease, and at present, the most effective way to remove plasticizer from grease is solvent extraction, which has high removal efficiency, but the solvent used in the removal process is too large, and at the same time, the solvent used for extraction is volatile, and a process of multiple extractions is required, so that the method is not suitable for large-scale industrial production, and therefore, there is a need to find a suitable substance that can be used in the conventional grease refining process to remove plasticizer from grease.
Disclosure of Invention
The invention provides a method for decoloring and/or removing a plasticizer from grease, which comprises the step of contacting polyethylene glycol alkyl phenyl ether with the grease.
In one or more embodiments, the polyethylene glycol alkylphenyl ether has a degree of polymerization of the polyethylene glycol segment between 10 and 20.
In one or more embodiments, the polyethylene glycol alkylphenyl ether has an alkyl group that is branched or straight C6-20An alkyl group.
In one or more embodiments, the polyethylene glycol alkylphenyl ether has a polyethylene glycol segment ortho, meta, or para, preferably para, to the phenyl ring with the alkyl segment.
In one or more embodiments, the polyethylene glycol alkylphenyl ether is polyethylene glycol octylphenyl ether.
In one or more embodiments, the polyethylene glycol octylphenyl ether is selected from Triton X-100 and Triton X-114.
In one or more embodiments, the polyethylene glycol alkylphenyl ether is used in an amount of greater than 10% by weight of the oil, such as at least 20%, or at least 1 time by weight of the oil.
In one or more embodiments, the polyethylene glycol alkylphenyl ether is contacted with the oil for at least 30 minutes.
In one or more embodiments, the contacting is performed at a temperature ranging from room temperature to 200 ℃.
In one or more embodiments, the contacting is performed with agitation, preferably at a speed of 50 to 5000 rpm.
In one or more embodiments, after the contacting is complete, the oil is separated.
The invention also provides a method for refining the oil, which comprises the step of decolorizing the oil, and one or more of the steps of degumming, physical deacidification, alkali refining, water washing, drying, conventional decolorization, dewaxing and deodorization.
The invention also comprises the application of the polyethylene glycol alkyl phenyl ether in oil and fat decolorization and/or plasticizer removal, or the application in the preparation of a reagent for oil and fat decolorization and/or plasticizer removal.
In one or more embodiments, the polyethylene glycol alkylphenyl ether has a degree of polymerization of the polyethylene glycol segment between 10 and 20.
In one or more embodiments, the polyethylene glycol alkylphenyl ether has an alkyl group that is branched or straight C6-20An alkyl group.
In one or more embodiments, the polyethylene glycol alkylphenyl ether has a polyethylene glycol segment ortho, meta, or para, preferably para, to the phenyl ring with the alkyl segment.
In one or more embodiments, the polyethylene glycol alkylphenyl ether is polyethylene glycol octylphenyl ether.
In one or more embodiments, the polyethylene glycol octylphenyl ether is selected from Triton X-100 and Triton X-114.
Detailed Description
Various aspects of the invention are described in detail below. Unless otherwise specified, the various starting materials of the present invention may be obtained commercially or prepared according to conventional methods in the art. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, unless otherwise specified, the percentage means weight percentage, and the ratio is mass ratio.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention discovers that the oil can be decolorized at low temperature and the plasticizer in the oil can be removed by using the adsorbing material with the specific group; the shelf life of the grease is prolonged while the quality of the grease is maintained; in addition, the decoloring process at normal temperature can also reduce the energy consumption in the oil production process.
The adsorbing material used in the invention is polyethylene glycol alkyl phenyl ether. Preferably, in the polyethylene glycol alkylphenyl ether of the present invention, the polymerization degree of the polyethylene glycol segment is between 10 and 20. Preferably, the alkyl group in the polyethylene glycol alkylphenyl ether of the present invention is branched or straight chain C6-20Alkyl groups including, but not limited to, hexyl, heptyl, octyl, such as 1,1,3, 3-tetramethylbutyl, and the like, preferably straight or branched C6-12An alkyl group. In the polyethylene glycol alkyl phenyl ether of the present invention, the polyethylene glycol segment and the alkyl segment may be in the ortho-position, meta-position and para-position of the benzene ring, preferably in the para-position. In a preferred embodiment, the polyethylene glycol alkylphenyl ether used in the present invention is polyethylene glycol octylphenyl ether. Commercially available octyl phenyl ethers of polyethylene glycol, such as Triton X-100 and/or Triton X-114, may be used to practice the present invention.
The method of the present invention comprises the step of contacting a polyethylene glycol alkylphenyl ether with a fat. In the present invention, the fat or oil may be any kind of fat or oil known in the art, particularly an edible oil, including animal fat or oil and vegetable fat or oil. Exemplary vegetable oils include, but are not limited to, rice oil, sunflower oil, palm kernel oil, peanut oil, rapeseed oil (also known as rapeseed oil), cottonseed oil, safflower oil, perilla oil, tea seed oil, palm fruit oil, coconut oil, olive oil, cocoa butter, Chinese tallow seed oil, almond oil, tung oil, rubber seed oil, rice bran oil, corn germ 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 seed oil, sea buckthorn seed oil, tomato seed oil, pumpkin seed oil, macadamia nut oil, cocoa butter, algae oil, and the like, or any mixture of two or more thereof. Exemplary animal fat and oil can be one or more of beef tallow, lard, mutton fat, chicken fat, fish oil, seal oil, whale oil, dolphin oil, oyster oil, etc., or any mixture thereof. The grease may be any grease that requires color and/or plasticizer removal. The grease may be crude oil, or grease subjected to one or more processes in a conventional grease refining process, and may be, for example, degummed oil, decolored oil, deodorized oil, or the like. In some embodiments, the oil or fat may be a refined oil, i.e., a finished oil.
In the process of the invention, the polyethylene glycol alkylphenyl ether is used in an amount of more than 10% by weight of the oil, for example at least 20%, or at least 1 time by weight of the oil. The present inventors have found that, when an oil or fat is treated with a polyethylene glycol alkyl phenyl ether having an oil weight of 1 time or more, 40% or more of a plasticizer in the oil or fat can be removed even at room temperature.
In the method of the present invention, the temperature of the system containing the polyethylene glycol alkylphenyl ether and the oil and fat during the contacting is usually in the range of room temperature to 200 ℃. As used herein, room temperature generally refers to room temperature above 20 deg.C, such as 20-35 deg.C. In some embodiments, the system temperature is preferably from 25 to 170 deg.C, more preferably from 25 to 135 deg.C. Different contact temperatures may be selected for different purposes. For example, in some embodiments, the contacting is carried out at a temperature of 20 to 50 ℃ for decolorization purposes, under which conditions a portion of the plasticizer can also be removed; in other embodiments, to achieve substantial or even complete plasticizer removal, the temperature of the system may be controlled to be relatively high, e.g., the temperature of the system may be at 120 ℃ to 170 ℃ at which dimethyl phthalate (DMP) may be substantially removed.
Accordingly, in some embodiments, the present invention provides a method for decolorizing fats and oils, comprising the step of contacting the fat and oil to be decolorized with the polyethylene glycol alkylphenyl ether described herein at room temperature. In other embodiments, the present invention provides a method for plasticizer removal from grease comprising the step of contacting grease with a polyethylene glycol alkyl phenyl ether as described herein at a temperature of 20 to 200 ℃. In other embodiments, the present invention provides a method for decolorizing and deplasticizing oils and fats, comprising the step of contacting the oil and fat to be decolorized with the polyethylene glycol alkyl phenyl ether described herein at 20-50 ℃.
The contacting may be achieved by stirring. The rotational speed of the stirring may be in the range of 50-5000 rpm. The contact time is at least 30 minutes. The rotating speed and the contact time can be adjusted according to different dosages of the polyethylene glycol alkyl phenyl ether so as to obtain the optimal decolorization and/or plasticizer removal effect. As demonstrated in the examples herein, polyethylene glycol alkylphenyl ether achieves essentially the greatest adsorption effect after a contact time of up to 4 hours. Therefore, the contact time can be controlled in the range of 30 minutes to 4 hours from the viewpoint of time cost.
After the contact, the adsorbent and impurities adsorbed by the adsorbent, such as plasticizer and pigment, can be removed by centrifugation to obtain oil. The contacting and separating steps described above may be performed one or more times until the desired effect is achieved. In a preferred embodiment, the contacting step is performed following a small number of passes.
In some embodiments, the present invention provides a method of refining fats and oils, comprising a step of decolorizing fats and oils as described herein and one or more steps selected from degumming, physical deacidification, caustic refining, water washing, drying, conventional decolorization, dewaxing, and deodorization. It is to be understood that one or more of the degumming, deacidification, dewaxing and deodorization may be omitted depending on the actual production conditions and the purpose of the production. The technological conditions of degumming, physical deacidification, alkali refining, water washing, drying, conventional decolorization, dewaxing and deodorization can be the conventional technological conditions in the field, and are adjusted according to the actual production conditions.
Exemplary degumming includes filtering the crude oil to remove solid impurities and adding a degumming medium to degum the crude oil. The degumming medium may be a degumming medium conventional in the art, such as citric acid solution, phosphoric acid solution and degumming enzyme. When using degumming enzymes such as PLA1 phospholipase, the reaction system is generally at 45-80 deg.C, pH 5-6, and time 2-6 h. The degumming medium is not less than 0.05 wt% of the weight of the crude oil, and is usually not more than 2 wt% of the weight of the crude oil. When an acid is used, the concentration of the acid is not less than 5 wt%, usually not more than 80 wt%, for example, it may be in the range of 5 to 65 wt%, 10 to 60 wt%, 20 to 50 wt%, based on the total weight of the solution. Water may be added simultaneously, usually in an amount of not less than 0.5% by weight based on the weight of the crude oil; typically, the amount of water used in a single degumming step is not more than 30 wt% of the oil weight, e.g. in the range of 0.5 to 20 wt%, 0.5 to 10 wt%, 5 to 25 wt%, excluding the water in the degumming medium. And separating the colloid after the reaction is finished to obtain the degummed oil.
The degumming is followed by deacidification, the main purpose of which is to remove free fatty acids from the crude oil and to remove some impurities such as pigments, phospholipids, hydrocarbons and mucilage. Physical deacidification methods may be used for deacidification. For example, the degummed oil may be treated at a pressure of 0.02 to 0.6kPa and a temperature of 180 ℃ and 250 ℃ to obtain a deacidified oil. Alternatively, deacidification may be carried out by an alkali refining process. For example, adding a proper amount of alkali liquor into the degummed oil at 80-90 ℃ for reaction for 10-60 minutes. Usually, the amount of alkali added is 7.13X 10-4×MOilX AV x (1+ excess alkali), the excess alkali can be 0-20%, the alkali liquor amount is alkali adding amount/alkali liquor concentration, wherein, MOilOil weight, AV acid number. And centrifuging after the reaction is finished to obtain the neutralized oil.
The deacidified oil can be dewaxed. If the deacidification is performed by alkali refining, the deacidified oil (neutralized oil) can be dried in water before the fat is dewaxed to remove soap, so as to obtain the soaped oil. For example, the neutralized oil can be heated to 80-90 deg.C, washed with hot water at a weight of less than 5 wt% (e.g., 1-3 wt%) of the oil, centrifuged, and vacuum dried at 90-120 deg.C to obtain the desaponified oil.
An exemplary dewaxing process includes pumping deacidified oil or soaped oil into a crystal growing tank, controlling the temperature to 50-60 ℃, standing for 10-60min, and then cooling and crystallizing. Reducing the temperature to 2-6 ℃ within 10-60 hours, then growing the crystal at the temperature for 6-10 hours, and filtering after the crystal growth is finished.
In the present invention, the conventional decoloring method includes a step of decoloring with a conventional decoloring agent under a conventional decoloring condition. Conventional decolorizing agents include, but are not limited to, kieselguhr, activated clay, activated carbon, zeolites, attapulgite, diatomaceous earth, silica gel, and the like, as are well known in the art. . The decolorizing temperature can be 100-120 ℃, preferably 105-115 ℃; the addition amount of the decolorizing agent can be 0.5-5% of the grease mass, and is preferably 1-5%. The degree of vacuum for the decolorization can be 20 to 100mbar, preferably 30 to 50 mbar. The decolorization time may be 20-120min, preferably 30-120 min.
Exemplary deodorization methods are conventional deodorization methods in the art, and specific procedures are well known to those skilled in the art, such as but not limited to methods in beret oil chemistry and technology (vol. sixth). In one embodiment of the invention, the deodorization is: introducing nitrogen or steam (preferably high-heat steam) as deodorizing medium, deodorizing at 235-260 deg.C for 40-90 min under vacuum degree of not higher than 25 mBar.
The invention also provides the use of a polyethylene glycol alkyl phenyl ether as described herein for fat decolorization and/or plasticizer removal, or for the preparation of an agent for fat decolorization and/or plasticizer removal.
Compared with the prior art, the invention can decolorize at normal temperature, can reduce the energy consumption of factories, reserve beneficial components in the grease, prolong the shelf life of the grease, remove the plasticizer in the grease, simplify the production process flow and finally improve the quality of the grease.
The present invention will be illustrated below by way of specific examples. It is to be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The raw materials adopt a mode of adding DMP, DBP and DEHP reversely, and the addition amount of the DMP and the DBP is about 10 ppm. In addition to the back-added product oil, the oils used in the benzene invention also include oils that are taken on-line at the factory with an out-of-specification plasticizer level (DEHP level of 5-10 ppm). After reverse addition, the content of DMP, DBP and DEHP in the raw material is detected, and the detection method is disclosed in the reference document: (GB 5009.271-2016). The color and luster determination refers to the color and luster determination method of GB/T22460-2008 luvibond.
The first embodiment is as follows: effect of different adsorption temperatures on DMP, DBP and DEHP removal
Taking refined soybean oil, and adsorbing the plasticizer in the oil by using Triton X-100 at room temperature, 135 ℃ and 170 ℃. Vacuumizing at 135 ℃ and 170 ℃ without vacuumizing at room temperature, adding 20 percent of Triton X-100 by weight of the grease, stirring, keeping the temperature and the stirring speed for 1 hour, and then centrifuging the system to obtain the plasticizer-removed clear oil.
The removal rate of plasticizer from grease by Triton X-100 at different temperatures is shown in Table 1.
TABLE 1
DMP | DBP | DEHP | |
At room temperature | 30.70% | 20.70% | 19.05% |
135℃ | 82.80% | 24.52% | 22.91% |
170℃ | 100% | 18.98% | 17.66% |
Example two: effect of different isomeric Polyethyleneglycol octyl phenyl ethers on DMP, DBP and DEHP removal
Taking refined soybean oil, and adsorbing the plasticizer in the oil and fat by using Triton X-100 and Triton X-114 at room temperature. And (3) vacuumizing at room temperature, adding 20% of Triton X-100 and Triton X-114 by weight of the grease, stirring, keeping the temperature and the stirring speed for 1 hour, and then centrifuging the system to obtain the plasticizer-removed clear oil.
The removal efficiency of three plasticizers from grease at room temperature by Triton X-100 and Triton X-114, which are two octyl phenyl ethers of polyethylene glycol, is shown in Table 2.
TABLE 2
DMP | DBP | DEHP | |
Triton X-100 | 30.70% | 20.70% | 19.05% |
Triton X-114 | 19.36% | 18.36% | 22.65% |
Example three: decolorization of grease by Triton
Refined soybean oil was decolorized using Triton X-100 and Triton X-100, the amounts of Triton X-100 and Triton X-100 being 20% of the oil weight, respectively. Stirring for 1h at room temperature and 170 ℃ (vacuumizing), and centrifuging the system to obtain clear oil. The color of the grease was measured and the results are shown in Table 3.
TABLE 3
R | Y | |
Blank sample | 17.8 | 22.0 |
Triton X-100, Room temperature | 11.6 | 70.0 |
Triton X-100,170℃ | 20.0 | 40.0 |
And (4) conclusion: as can be seen from table 3, Triton X-100 decolorizes fats and oils at room temperature, but does not decolorize fats and oils at high temperature, and combined with the previous results, decolorization and removal of plasticizers from fats and oils are also possible.
Example four: a great amount of Triton is added to remove the plasticizer in the grease
Refined soybean oil was subjected to plasticizer removal using Triton X-100 and Triton X-114, respectively, which were the same weight as the oil. Stirring for 1h at room temperature, and then centrifuging the system to obtain the plasticizer-removed clear oil. The plasticizer removal effect is shown in table 4.
TABLE 4
DBP | DEHP | |
Triton X-100 | 53.4% | 44.2% |
Triton X-114 | 52.3% | 43.5% |
And (4) conclusion: as is clear from Table 4, Triton X-100 and Triton X-114 removed 40% or more of the plasticizer from the fat and oil at room temperature when added in large amounts.
Example five: triton removes plasticizer in grease under long-time adsorption condition
And (3) taking refined soybean oil, and respectively using Triton X-100 and Triton X-100 to remove plasticizers in the oil, wherein the using amounts of the Triton X-100 and the Triton X-100 are respectively 20% of the oil weight. Stirring for 4 hours at room temperature, and then centrifuging the system to obtain the plasticizer-removed clear oil. The removal rate of the plasticizer from the fat and oil is shown in Table 5.
TABLE 5
DBP | DEHP | |
Triton X-100 | 19.76% | 20.13% |
Triton X-114 | 20.22% | 23.05% |
And (4) conclusion: as is clear from Table 5, the effect of Triton X-100 and Triton X-114 on the removal of plasticizers from fats and oils during long-term (4 hours) adsorption was close to that of short-term adsorption.
Example six: removing plasticizer from peanut oil by using Triton
Taking peanut oil, and respectively using Triton X-100 and Triton X-100 to remove plasticizers in grease, wherein the use amounts of the Triton X-100 and the Triton X-100 are respectively 20% of the weight of the oil. Stirring for 1h at room temperature, and then centrifuging the system to obtain the plasticizer-removed clear oil. The plasticizer removal rate from the oil and fat is shown in Table 6.
TABLE 6
DBP | DEHP | |
Triton X-100 | 24.54% | 23.78% |
Triton X-114 | 19.44% | 25.76% |
And (4) conclusion: as is clear from Table 6, the effect of Triton X-100 and Triton X-114 on the removal of plasticizers from oils and fats during the treatment of peanut oil is close to the effect of short-time adsorption.
Comparative example one: substances with phthalate structures adsorb plasticizer in grease
Adsorbing plasticizer in oil and fat by using hydroxypropyl methyl cellulose phthalate (HPMCP), adding HPMCP accounting for 10 percent of the weight of the oil into the oil and fat at 100 ℃ and 135 ℃ respectively, adsorbing for 2 hours under vacuum condition, and performing suction filtration to obtain clear oil without the plasticizer. The plasticizer removal rate of the fat and oil is shown in table 7.
TABLE 7
DMP | DBP | DEHP | |
HPMCP-100℃ | 17.09% | 0% | 0% |
HPMCP-135℃ | 67.82% | 0.29% | 0% |
And (4) conclusion: the adsorbing material containing the phthalate group only has a certain removal effect on the small molecular plasticizer DMP in the grease at high temperature, and has almost no effect on the large molecular plasticizers DBP and DEHP. And the effect of removing DMP is not as good as that of polyethylene glycol octyl phenyl ether.
Comparative example two: polyethylene glycol adsorbs plasticizer in oil
Weighing 5.0g PEG1000 in a 150mL beaker, adding 20g water, heating to dissolve, adding 100g soybean oil containing DEHP, shearing at 13000rpm for 2min, taking out 50g, centrifuging at 3000rpm for 10min, and analyzing. The plasticizer removal rate from the fat and oil is shown in table 8 below.
TABLE 8
DMP | DBP | DEHP | |
PEG | 0.75% | 0% | 0% |
And (4) conclusion: polyethylene glycol does not remove plasticizers from oils and fats.
Comparative example three: polystyrene adsorbs plasticizer in grease
Weighing a certain amount of polystyrene resin, and soaking in 95% ethanol for three days. After three days, the ethanol was removed by suction filtration, and the treated resin was placed in a fume hood and air-dried for use.
In the adsorption experiment, the addition amount of the polystyrene resin is 20 percent of the weight of the oil, the adsorption temperature is 170 ℃, and the time is 2 hours. The plasticizer removal rates from the oils and fats are shown in table 9 below:
TABLE 9
DMP | DBP | DEHP | |
Adsorption with 20% polystyrene resin | NA | 28.24% | 8.83% |
And (4) conclusion: although the polystyrene resin contains a large amount of benzene ring groups, the removal effect of the polystyrene resin on DEHP in the grease is only about 8%.
Comparative example four: ethanol decolorizing plasticizer
Performing plasticizer removal experiment by using ethanol with the weight of 50% of that of the oil, performing ultrasonic treatment for 30min at room temperature, standing until the mixture is layered, and removing the ethanol to obtain the clear oil. The plasticizer removal rates from the oils and fats are shown in table 10 below:
watch 10
DMP | DBP | DEHP | |
Extraction with 50% ethanol | 53.80% | 27.04% | 10.55% |
And (4) conclusion: when the using amount of the ethanol is 50% of the weight of the oil, the ethanol can remove more than 50% of DMP in the grease, the removal rate of DBP is close to 30%, but the removal rate of DEHP is only about 10%. Meanwhile, ethanol has strong volatility and is difficult to fall to the ground industrially.
Performing decolorization experiment with 50% ethanol, ultrasonic treating at room temperature for 30min, standing for layering, and removing ethanol to obtain clear oil. The plasticizer removal rates from the fats and oils are shown in Table 11 below.
TABLE 11
R | Y | |
Blank sample | 17.8 | 22.0 |
Ethanol at room temperature | 17.6 | 22.3 |
And (4) conclusion: the ethanol has no decolorization effect and can only remove the plasticizer from the grease.
Comparative example five: plasticizer in grease removed by Triton aqueous solution
Adding triton X-100 in an amount of 1 wt% and H in an amount of 20 wt% to the oil2O; in another set of experiments, after the oil is stirred at room temperature, NaCl is added into a mixture added with water, ultrasonic separation is carried out, and the upper half part of the oil is taken; the mixture without water was centrifuged to obtain the upper half of the oil, and the plasticizer content and the color degree of the oil were measured, respectively, and the results of the plasticizer content in the oil are shown in table 12 below:
TABLE 12
ND means not detected
And (4) conclusion: after the triton aqueous solution is added into the oil, the mixture is stirred and then centrifuged, and the plasticizer content in the obtained oil is not reduced, which proves that the triton aqueous solution has no function of removing the plasticizer in the oil.
The results of the color test are shown in table 13 below:
watch 13
R | Y | |
Oil and fat | 17.8 | 22.0 |
Grease + triton + water | 17.5 | 23.3 |
And (4) conclusion: the triton aqueous solution also has no decolorizing effect on oil.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, which is defined broadly in the claims, and any other technical entity or method implemented by others, if it is exactly the same as or equivalent to the definition of the claims, will be considered to be covered by the claims.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above disclosure, and equivalents may fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for decolorizing and/or removing plasticizers from fats and oils, comprising the step of contacting a polyethylene glycol alkyl phenyl ether with a fat and oil.
2. The method for decolorizing and/or removing plasticizers from fats and oils according to claim 1, wherein the polyethylene glycol alkyl phenyl ether has one or more of the following characteristics:
(1) the polymerization degree of the polyethylene glycol chain segment in the polyethylene glycol alkyl phenyl ether is between 10 and 20;
(2) the alkyl in the polyethylene glycol alkyl phenyl ether is branched chain or straight chain C6-20An alkyl group; and
(3) in the polyethylene glycol alkyl phenyl ether, the polyethylene glycol chain segment and the alkyl chain segment are in ortho-position, meta-position or para-position on the benzene ring, and preferably in para-position.
3. The method for decoloring and/or removing a plasticizer from fats and oils according to claim 1, wherein the polyethylene glycol alkyl phenyl ether is polyethylene glycol octyl phenyl ether, preferably Triton X-100 and/or Triton X-114.
4. The method for decolorizing and/or removing plasticizers from fats and oils according to claim 1, characterized in that it comprises one or more of the following features:
(1) the polyethylene glycol alkylphenyl ether is used in an amount of 10% or more, for example at least 20%, or at least 1 time, by weight of the oil;
(2) the contact time of the polyethylene glycol alkyl phenyl ether and the grease is at least 30 minutes;
(3) said contacting is carried out at a temperature in the range of 20 to 200 ℃;
(4) the contacting is carried out with stirring, preferably at a speed of 50-5000 rpm; and
(5) after the contact is finished, grease is obtained by separation.
5. The method for decoloring and/or deplasticizing fats and oils according to claim 4, characterized in that the contacting is performed at a temperature ranging from 20 to 50 ℃, or at room temperature, or at a temperature ranging from 120 ℃ to 170 ℃.
6. A method for refining oils and fats, comprising a step of decoloring and one or more steps selected from degumming, physical deacidification, alkali refining, water washing, drying, conventional decoloring, dewaxing and deodorization, wherein the decoloring comprises a step of contacting a polyethylene glycol alkylphenyl ether with oils and fats at a temperature of 20 to 50 ℃.
7. The method of claim 6, wherein the polyethylene glycol alkylphenyl ether has one or more of the following characteristics:
(1) the polymerization degree of the polyethylene glycol chain segment in the polyethylene glycol alkyl phenyl ether is between 10 and 20;
(2) the alkyl in the polyethylene glycol alkyl phenyl ether is branched chain or straight chain C6-20An alkyl group; and
(3) in the polyethylene glycol alkyl phenyl ether, the polyethylene glycol chain segment and the alkyl chain segment are in ortho-position, meta-position or para-position on the benzene ring, and preferably in para-position.
8. The method according to claim 6, wherein the polyethylene glycol alkylphenyl ether is polyethylene glycol octylphenyl ether, preferably Triton X-100 and/or Triton X-114.
9. The method of claim 6, wherein the method comprises one or more of the following features:
(1) the polyethylene glycol alkylphenyl ether is used in an amount of 10% or more, for example at least 20%, or at least 1 time, by weight of the oil;
(2) the contact time of the polyethylene glycol alkyl phenyl ether and the grease is at least 30 minutes;
(3) the contacting is carried out with stirring, preferably at a speed of 50-5000 rpm;
(4) after the contact is finished, separating to obtain decolorized grease; and
(5) the conventional decoloring step is to decolor the grease by using a decoloring agent.
10. The application of polyethylene glycol alkyl phenyl ether in oil decolorization and/or plasticizer removal or the application in preparing a reagent for oil decolorization and/or plasticizer removal; preferably, the polyethylene glycol alkylphenyl ether is as claimed in claim 2 or 3.
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