Method for removing zearalenone from natural vitamin E and product obtained by said method
阅读说明：本技术 从天然维生素e中脱除玉米赤霉烯酮的方法与由所述方法得到的产品 (Method for removing zearalenone from natural vitamin E and product obtained by said method ) 是由 孟永宏 牛永洁 郭建琦 杨璐 于 2021-07-23 设计创作，主要内容包括：本发明涉及一种从天然维生素E中脱除玉米赤霉烯酮的方法与由其方法得到的纯维生素E产品。该脱除玉米赤霉烯酮方法包括亚胺二乙酸型螯合树脂预处理、装柱、吸附、淋洗与分离等步骤。本发明脱除玉米赤霉烯酮方法过程简单,未引入其他物质,不需要其他分离步骤,且不会对维生素E产品造成二次污染；与硅藻土蒙脱石等吸附剂相比,吸附效率高约80～90％,物料损失小。(The invention relates to a method for removing zearalenone from natural vitamin E and a pure vitamin E product obtained by the method. The method for removing zearalenone comprises the steps of imine diacetic acid type chelating resin pretreatment, column filling, adsorption, leaching, separation and the like. The method for removing zearalenone has simple process, does not introduce other substances, does not need other separation steps, and does not cause secondary pollution to vitamin E products; compared with adsorbents such as diatomite montmorillonite, the adsorption efficiency is about 80-90%, and the material loss is small.)
1. A method for removing zearalenone from natural vitamin E is characterized by comprising the following steps:
A. imine diacetic acid type chelating resin pretreatment
Soaking iminodiacetic acid type chelate resin in deionized water with the pH value of 4-10 for 3-5 hours at the room temperature of 20-30 ℃ to completely swell the chelate resin, then soaking the completely swelled chelate resin in saturated sulfate solution for 0.8-1.2 hours, washing with deionized water, and drying at the temperature of 35-45 ℃ to obtain modified chelate resin;
B. column mounting
Filling the modified chelate resin obtained in the step A into a chromatographic column, allowing deionized water to pass through a modified chelate resin bed at a flow rate of 0.6-0.8 times of the column volume per hour for washing, then emptying the deionized water, and then allowing an ethanol aqueous solution with the concentration of 95% by volume to pass through the modified chelate resin bed to remove the deionized water;
C. adsorption
According to the ratio of the natural vitamin E in grams to the ethanol water solution in milliliters of 1: 3-5, mixing natural vitamin E with 85-95% ethanol aqueous solution by volume to prepare vitamin E solution, and then allowing the vitamin E solution to pass through a modified chelating resin bed at a flow rate of 0.6-0.8 times of column volume per hour for adsorption until zearalenone is detected from the effluent liquid at the bottom of a chromatographic column;
D. leaching with water
According to the ratio of the modified chelating resin in grams to the ethanol aqueous solution in milliliters of 1: 1-3, leaching an ethanol water solution with the concentration of 90-98% by volume by using a modified chelating resin bed, and collecting leaching liquor containing vitamin E from the bottom of a chromatographic column;
E. separation of
D, carrying out decompression desolventizing on the leacheate containing the vitamin E obtained in the step D by using a single-effect concentrator, then carrying out film evaporation by using a film evaporator, and finally carrying out molecular distillation by using secondary molecular distillation equipment to obtain a pure vitamin E product.
2. The method for removing zearalenone according to claim 1, characterized in that in step a, the ratio of the chelating resin of iminodiacetic acid type in grams to deionized water in milliliters is 1: 5 to 10.
3. The method for removing zearalenone according to claim 1, characterized in that in step a, the ratio of the iminodiacetic acid-based chelating resin in grams to the saturated sulfate solution in milliliters is 1 to 3; the sulfate is sodium sulfate, potassium sulfate, ammonium sulfate, sodium bisulfate or potassium bisulfate.
4. The method for removing zearalenone according to claim 1, characterized in that in step a, the ratio of the soaked chelating resin in grams to the deionized water in milliliters is 2-4 times, and the washing is performed 2-4 times in the same manner.
5. The method of claim 1, wherein in step B, the column is a column having a height to diameter ratio of 1: 5-10 of cylindrical chromatographic column.
6. The method for removing zearalenone according to claim 1, characterized in that in step B, the ratio of the modified chelating resin in grams to the deionized water in milliliters is 1: 1-3; the volume ratio of the ethanol aqueous solution to the modified chelating resin bed is 1: 1 to 3.
7. The method for removing zearalenone according to claim 1, characterized in that in step C, the zearalenone content of natural vitamin E is 0.00001-0.0002% by weight.
8. The method for removing zearalenone according to claim 1, characterized in that in step D, the aqueous ethanol solution is rinsed through the bed of modified chelating resin at a flow rate of 0.6 to 0.8 column volumes per hour.
9. The method for removing zearalenone according to claim 1, characterized in that in step E, the reduced pressure desolventization is carried out at a temperature of 60 to 80 ℃ and a pressure of-0.06 MPa to-0.08 MPa; the thin film evaporation is carried out at the temperature of 110-130 ℃ and under the pressure of 80-100 MPa; the first stage molecular distillation is carried out at the temperature of 175-195 ℃ and the pressure of 5-10 MPa, and the second stage molecular distillation is carried out at the temperature of 210-240 ℃ and the pressure of 1-5 MPa.
10. The pure vitamin E product obtained by the zearalenone removing process according to any one of claims 1 to 9, characterized in that its zearalenone content is 0.0000035% by weight or less.
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of food. More particularly, the present invention relates to a process for the removal of zearalenone from natural vitamin E and to the pure vitamin E product obtained by said process.
[ background of the invention ]
Zearalenone (ZEN ) also known as F-2 virus is a lactone compound of 2, 4-dihydroxy benzoic acid, and is a secondary metabolite of fusarium (including fusarium graminearum, fusarium trilobate, fusarium equiseti, fusarium oxysporum, fusarium moniliforme, and the like). Zearalenone is of great interest because of its frequent occurrence in cereals around the world and its high estrogenic activity. In addition to the pronounced estrogenic effects, zearalenone also exhibits immunotoxicity, genotoxicity, reproductive toxicity and carcinogenicity. Corn is the most vulnerable grain to zearalenone contamination.
The natural vitamin E product is derived from deodorized distillate generated in the refining process of soybean oil and corn oil, so the natural vitamin E product has the safety hazard of zearalenone. In recent years, the quality requirement of vitamin E products is higher and higher, and researches on removing zearalenone are more and more, mainly comprising a physical adsorption method, a chemical method and a biological method.
Physical adsorption method: at present, many researches show that montmorillonite, activated carbon, clinoptilolite, cholestyramine and the like all have certain adsorption capacity on mycotoxin, but the adsorbents generally have low adsorption efficiency and no selectivity; for example, CN 104961718B discloses a special device and a method for removing trace harmful impurity zearalenone in natural vitamin E, which comprises extracting natural vitamin E-petroleum ether solution with methanol-water solution, and adsorbing with montmorillonite or active carbon as adsorbent. The method has the advantages that the adsorption of the montmorillonite and the activated carbon is not selective, the yield of the vitamin E is reduced, the shutdown is needed for replacing the adsorbent when 30 tons of the vitamin E are treated, the efficiency is low, and the operation cost is high.
The chemical method comprises the following steps: generally, chemicals such as acid, alkali, oxidant and the like are used for degrading the structure of zearalenone, but the addition of the chemicals can cause certain damage to nutritional ingredients such as grains, feed or other foods and possibly generate new toxic compounds, so that the method is generally rarely used in the field of foods.
The biological method comprises the following steps: generally, the microorganisms or enzymes capable of degrading ZEN are obtained by screening and converted into nontoxic substances. The method has stronger specificity, but microorganisms or enzymes need actual temperature and pH value, and need inactivation and separation after treatment; for example, CN 107245369B discloses a method for producing vegetable oil without zearalenone by a bio-enzyme method, in which in the process of producing vegetable oil, bio-enzyme is added to treat the product oil under enzyme reaction conditions suitable for the stage of enzyme reaction using bio-enzyme, and after the enzyme reaction, separation is performed.
Therefore, in view of the technical defects of the prior art, the present inventors have completed the present invention by summarizing the prior art through a large number of experimental studies and analyses.
[ summary of the invention ]
[ problem to be solved ]
The invention aims to provide a method for removing zearalenone from natural vitamin E.
It is another object of the present invention to provide a pure vitamin E product resulting from the removal process.
[ solution ]
The invention is realized by the following technical scheme.
The invention relates to a method for removing zearalenone from natural vitamin E.
The method for removing zearalenone from natural vitamin E comprises the following steps:
A. imine diacetic acid type chelating resin pretreatment
Soaking iminodiacetic acid type chelating resin in deionized water with the pH value of 4-10 for 3-5 hours at the room temperature of 20-30 ℃ to completely swell the chelating resin, then soaking the completely swelled chelating resin in saturated sulfate solution for 0.8-1.2 hours, washing with deionized water, and drying at the temperature of 35-45 ℃ to obtain the modified chelating resin;
B. column mounting
Filling the modified chelate resin obtained in the step A into a chromatographic column, allowing deionized water to pass through a modified chelate resin bed at a flow rate of 0.6-0.8 times of the column volume per hour for washing, then emptying deionized water, and then allowing an ethanol aqueous solution with the concentration of 95% by volume to pass through the modified chelate resin bed to remove the deionized water in the modified chelate resin bed;
C. adsorption
According to the ratio of the natural vitamin E in grams to the ethanol water solution in milliliters of 1: 3-5, mixing natural vitamin E with 85-95% ethanol aqueous solution by volume to prepare vitamin E solution, and then allowing the vitamin E solution to pass through a modified chelating resin bed at a flow rate of 0.6-0.8 times of column volume per hour for adsorption until zearalenone is detected from the effluent liquid at the bottom of a chromatographic column;
D. leaching with water
According to the ratio of the modified chelating resin in grams to the ethanol aqueous solution in milliliters of 1: 1-3, leaching an ethanol water solution with the concentration of 90-98% by volume by using a modified chelating resin bed, and collecting leacheate containing vitamin E from the bottom of a chromatographic column;
E. separation of
D, carrying out decompression desolventizing on the leacheate containing the vitamin E obtained in the step D by using a single-effect concentrator, then carrying out film evaporation by using a film evaporator, and finally carrying out molecular distillation by using secondary molecular distillation equipment to obtain a pure vitamin E product.
According to a preferred embodiment of the invention, in step a, the ratio of chelating resin of iminodiacetic acid type in grams to deionised water in milliliters is 1: 5 to 10.
According to another preferred embodiment of the invention, in step a, the ratio of chelating resin of the iminodiacetic acid type in grams to saturated sulphate solution in milliliters is 1: 1-3; the sulfate is sodium sulfate, potassium sulfate, ammonium sulfate, sodium bisulfate or potassium bisulfate.
According to another preferred embodiment of the present invention, in the step a, the ratio of the soaking chelating resin in grams to the deionized water in milliliters is 2 to 4 times, and the washing is performed 2 to 4 times in the same manner.
According to another preferred embodiment of the invention, in step B, the chromatography column is a column having a height to diameter ratio of 1: 5-10 of cylindrical chromatographic column.
According to another preferred embodiment of the invention, in step B, the ratio of modified chelating resin in grams to deionized water in milliliters is 1: 1-3; the volume ratio of the ethanol aqueous solution to the modified chelating resin bed is 1: 1 to 3.
According to another preferred embodiment of the present invention, in step C, the zearalenone content of natural vitamin E is 0.00001-0.0002% by weight.
According to another preferred embodiment of the present invention, in step D, the aqueous ethanol solution is rinsed through the bed of modified chelating resin at a flow rate of 0.6 to 0.8 column volumes per hour.
According to another preferred embodiment of the invention, in step E, the reduced pressure desolventization is carried out at a temperature of 60 to 80 ℃ and a pressure of-0.06 MPa to-0.08 MPa; the thin film evaporation is carried out at the temperature of 110-130 ℃ and under the pressure of 80-100 MPa; the first molecular distillation is carried out at the temperature of 175-195 ℃ and the pressure of 5-10 MPa, and the second molecular distillation is carried out at the temperature of 210-240 ℃ and the pressure of 1-5 MPa.
The invention also relates to a pure vitamin E product obtained by the method for removing zearalenone, wherein the content of zearalenone is below 0.0000035 percent by weight.
The present invention will be described in more detail below.
The invention relates to a method for removing zearalenone from natural vitamin E.
In the following part of the present specification, the chelate resin, the iminodiacetic acid-type chelate resin and the modified iminodiacetic acid-type chelate resin should be understood to have the same meaning.
The method for removing zearalenone from natural vitamin E comprises the following steps:
A. imine diacetic acid type chelating resin pretreatment
Soaking iminodiacetic acid type chelating resin in deionized water with the pH value of 4-10 for 3-5 hours at the room temperature of 20-30 ℃ to completely swell the chelating resin, then soaking the completely swelled chelating resin in saturated sulfate solution for 0.8-1.2 hours, washing with deionized water, and drying at the temperature of 35-45 ℃ to obtain the modified chelating resin;
iminodiacetic acid-based chelate resins have high selective adsorption of heavy metals and are widely used in the technical fields of removal of heavy metals from table salts, purification of liquid medicines and the like. The iminodiacetic acid-based chelate resin used in the present invention is a product currently on the market, for example, a product sold under the trade name DIAION CR-11 by Mitsubishi chemical corporation.
In the present invention, the chelating resin of iminodiacetic acid type obtained from the market needs to be pretreated, and the main purpose of the chelating resin is to modify the resin, and the supported biological transition metal ions can form a complex with carbonyl in zearalenone.
First, the ratio of iminodiacetic acid-type chelating resin in grams to deionized water in milliliters was 1: 5-10, soaking the iminodiacetic acid type chelating resin in deionized water with the pH value of 4-10 for 3-5 hours at the room temperature of 20-30 ℃ to ensure that the chelating resin is completely swelled.
In the present invention, swelling of the iminodiacetic acid-based chelate resin is understood to mean a phenomenon in which the chelate resin swells when immersed in water due to water absorption. The main effect of fully swelling the chelating resin is to make the iminodiacetic acid active groups more easily ionizable.
The swelling of the iminodiacetic acid chelate resin was measured according to GB/T8331-2008 "method for measuring Wet apparent Density of ion exchange resin".
According to the present invention, when the pH, the soaking temperature and the time of deionized water are within the above ranges, if the ratio of the iminodiacetic acid-based chelate resin to deionized water is more than 1: 5, the resin is not sufficiently swelled; if the ratio of the imine diacetic acid type chelate resin to the deionized water is less than 1: 10 is not necessary; thus, the ratio of iminodiacetic acid-based chelating resin to deionized water was 1: 5 to 10 are appropriate, and preferably 1: 6-8;
similarly, if the soaking temperature is lower than 20 ℃, the mechanical strength of the resin is low when the ratio of the iminodiacetic acid type chelating resin to the deionized water and the pH value and the time of the deionized water are in the ranges; if the soaking temperature is higher than 30 ℃, the resin exchange capacity and the service life are influenced; therefore, the soaking temperature is suitably 20 to 30 ℃, preferably 22 to 28 ℃;
when the ratio of the iminodiacetic acid chelating resin to the deionized water and the pH value and the temperature of the deionized water are in the range, if the soaking time is shorter than 3 hours, the swelling is not complete; it is not necessary if the soaking time is longer than 5 hours; therefore, a soaking time of 3 to 5 hours is suitable, preferably 3.6 to 4.5 hours;
when the ratio of the iminodiacetic acid chelating resin to the deionized water, the soaking temperature and the soaking time are in the range, if the pH value of the deionized water is lower than 4, the next step of loading of transition metal is not facilitated; if the pH of the deionized water is higher than 10, the transition metal ions will react with OH-Carrying out reaction; therefore, the pH of the deionized water is reasonable to be 4-10, preferably 5-8;
then, soaking the fully swollen chelating resin in a saturated sulfate solution for 0.8 to 1.2 hours
The main effect of soaking the fully swollen chelating resin in a saturated sulfate solution is to enable metal ions in sulfate and active groups of the iminodiacetic acid type chelating resin to form a metal complex;
in this step, it is not preferable that the chelate resin is soaked in the saturated sulfate solution for a time exceeding the range, because a part of the active groups of the iminodiacetic acid-type chelate resin has not formed a complex with the metal ion for a short time and a long time is not necessary.
According to the invention, the ratio of the iminodiacetic acid-type chelating resin in grams to the saturated sulphate solution in milliliters is 1: 1-3; if the ratio of iminodiacetic acid-based chelating resin to saturated sulfate solution is greater than 1: 1, the amount of the sulfate solution is too small, and the resin particles cannot be completely soaked; if the ratio of iminodiacetic acid-based chelating resin to saturated sulfate solution is less than 1: 3 is not necessary; thus, the ratio of iminodiacetic acid-type chelating resin to saturated sulfate solution is 1: 1 to 3 are suitable, preferably 1: 1.5-2.5;
the sulfate used in the present invention is sodium sulfate, potassium sulfate, ammonium sulfate, sodium hydrogen sulfate or potassium hydrogen sulfate, which are all products currently sold in the market.
According to the present invention, the main effect of washing the chelate resin soaked in a saturated sulfate solution with deionized water is to wash away sulfate on the resin particles and metal ions that do not form a coordinate bond.
And during washing, the ratio of the soaking chelating resin in grams to the deionized water in milliliters is 2-4 times, and washing is carried out for 2-4 times in the same way.
Drying the washed chelate resin at 35-45 deg.C, detecting the water content of the chelate resin to be below 20% by weight by GB/T5757-2008 & lt method for measuring Water content of ion exchange resin & gt, performing conventional infrared spectroscopic analysis on the dried product, and obtaining an analysis result shown in figure 1, wherein the analysis result is 1384cm-1And 1615cm-1Nearby absorption peaks, indicating the effect of Me on O, such thatAsymmetric and symmetric telescopic vibration occurs; 619cm-1The nearby absorption peak is the vibration of chelate N-Me bond, and the dried chelate resin, i.e. the modified iminodiacetic acid type chelate resin, has the following chemical structural formula (I), wherein Me is transition metal ion:
B. column mounting
Filling the modified chelate resin obtained in the step A into a chromatographic column, allowing deionized water to pass through a modified chelate resin bed at a flow rate of 0.6-0.8 times of the column volume per hour for washing, then emptying deionized water, and then allowing an ethanol aqueous solution with the concentration of 95% by volume to pass through the modified chelate resin bed to remove the deionized water in the modified chelate resin bed;
according to the invention, the column is a column with a height to diameter ratio of 1: 5-10 of cylindrical chromatographic column.
Generally, screening the dried modified chelating resin obtained in the step A, and filling the chelating resin with the granularity of 20-40 meshes into the chromatographic column.
In this step, the main purpose of the washing by passing deionized water through the bed of modified chelating resin is to remove impurities in the resin interstices.
The ratio of modified chelating resin in grams to deionized water in milliliters is 1: 1 to 3, it is not preferable to exceed this range because too little water is used for the purpose of removing impurities, and too much water is not necessary;
according to the invention, the main purpose of passing a 95% by volume aqueous solution of ethanol through a bed of modified chelating resin is to remove deionized water from the column.
The volume ratio of the ethanol aqueous solution to the modified chelating resin bed is 1: 1 to 3, it is not preferable that the amount of the ethanol aqueous solution is too small to remove impurities, and it is not necessary to use too much water; .
C. Adsorption
According to the ratio of the natural vitamin E in grams to the ethanol water solution in milliliters of 1: 3-5, mixing natural vitamin E with 85-95% ethanol aqueous solution by volume to prepare vitamin E solution, and then allowing the vitamin E solution to pass through a modified chelating resin bed at a flow rate of 0.6-0.8 times of column volume per hour for adsorption until zearalenone is detected from the effluent liquid at the bottom of a chromatographic column;
the natural vitamin E used in the present invention is a product currently marketed, for example, by Greeney Biopsis, Fujian under the trade name vitamin E mixed tocopherol. According to the detection of a first standard analysis method of GB 5009.209-2016 (determination of zearalenone in national food safety standards), the content of zearalenone in the food is usually 0.00001-0.0002% by weight.
In the invention, if the ratio of the natural vitamin E to the 85-95% ethanol aqueous solution by volume is more than 1: 3, the vitamin E-ethanol solution is viscous and has poor fluidity; if the ratio of the natural vitamin E to the 85-95% ethanol aqueous solution by volume is less than 1: 5, the method is unnecessary, and the workload of subsequent desolventizing is increased; therefore, the ratio of the natural vitamin E to the 85-95% ethanol aqueous solution by volume is 1: 3 to 5 are appropriate, preferably 1: 3.6 to 4.2;
in the present invention, it is not feasible that the flow rate of the vitamin E solution through the modified chelate resin bed exceeds the range, because the zearalenone in vitamin E cannot be completely adsorbed by the resin at too fast a flow rate.
Zearalenone detection from the column bottom effluent was performed according to the standard analytical method described above.
The modified chelate resin obtained in this adsorption step was subjected to conventional infrared spectroscopic analysis, the results of which are shown in FIG. 2 at 1162cm-1And 1074cm-1Two absorption peaks appear at the position, which are the absorption of the aromatic ester structure and are at 2780cm-1And 1980cm-1The obvious absorption peak is the infrared vibration of the alkyl group, 1937cm-1Stretching vibration of carbonyl group is adopted, and the stretching vibration all accord with the structure of zearalenone; 405 cm-1The absorption peak appeared here, which is ascribed to the vibration of the O-Me bond. As can be seen from the attached FIG. 2, the transition metal ion of the modified resin forms a complex with the carbonyl group on the benzene ring of zearalenone, which is specifically shown in the following chemical structural formula (II):
D. leaching with water
According to the ratio of the modified chelating resin in grams to the ethanol aqueous solution in milliliters of 1: 1-3, leaching an ethanol water solution with the concentration of 90-98% by volume by using a modified chelating resin bed, and collecting leacheate containing vitamin E from the bottom of a chromatographic column;
according to the invention, the essential function of the leaching is to leach the vitamin E in the resin gaps from the chromatographic column bed.
According to the invention, 90-98% by volume of an aqueous ethanol solution is rinsed through the bed of modified chelating resin at a flow rate of 0.6-0.8 times the column volume per hour.
In the present invention, it is not feasible that the rinsing flow rate exceeds the range, because the flow rate is too low, the rinsing effect is not good, the flow rate is too high, and the rinsing flow path is easy to cause local short circuit.
E. Separation of
D, carrying out decompression desolventizing on the leacheate containing the vitamin E obtained in the step D by using a single-effect concentrator, then carrying out film evaporation by using a film evaporator, and finally carrying out molecular distillation by using secondary molecular distillation equipment to obtain a pure vitamin E product.
According to the invention, the reduced pressure desolventization is understood to be reduced pressure distillation, the essential function of which is to remove ethanol from the eluate.
The decompression desolventizing is carried out at the temperature of 60-80 ℃ and under the pressure of-0.06 MPa-0.08 MPa;
in the invention, when the pressure of the reduced pressure desolventizing is-0.06 MPa to-0.08 MPa, if the temperature of the reduced pressure desolventizing is lower than 60 ℃, the evaporation capacity is small, and the desolventizing rate is slow; if the temperature of decompression desolventizing is higher than 80 ℃, the evaporation capacity is too large, the condensation is not thorough, and the solvent loss is large; therefore, the temperature of decompression desolventizing is reasonable to be 60-80 ℃, and is preferably 66-72 ℃;
when the temperature of the decompression desolventizing is 60-80 ℃, if the pressure of the decompression desolventizing is higher than-0.06 MPa, the evaporation temperature is high; if the pressure of the decompression desolventization is lower than-0.08 MPa, the decompression desolventization is unnecessary; therefore, it is preferable that the pressure for the pressure-reduced desolvation is-0.06 MPa to-0.08 MPa;
the reduced pressure desolventizing apparatus used in the present invention is a product currently marketed, for example, a reduced pressure desolventizing product sold as a list effect evaporator by the company Limited for mechanical manufacture of Saian tripod.
According to the invention, the thin film evaporation is understood to be the evaporation mode which is carried out by forming the feed liquid into a thin film, and the basic function of the evaporation mode is to remove residual micromolecule volatile components such as ethanol, water and the like in the vitamin E.
The thin film evaporation is carried out at the temperature of 110-130 ℃ and under the pressure of 80-100 MPa;
in the invention, when the evaporation pressure of the film is 80 Pa-100 MPa, if the evaporation temperature of the film is lower than 110 ℃, the volatile component can not be completely vaporized; if the temperature of the film evaporation is higher than 130 ℃, the temperature is too high, and the vitamin E product can be oxidized; therefore, the temperature of the film evaporation is suitably 110 to 130 ℃, preferably 116 to 124 ℃;
when the temperature of the film evaporation is 110-130 ℃, if the pressure of the film evaporation is lower than 80Pa, the vaporized volatile component can not be quickly introduced into a condenser for condensation; if the evaporation pressure of the film is higher than 100MPa, the film-forming material is influenced by descending of gravity; therefore, the pressure at which the film is evaporated is suitably 80Pa to 100 MPa;
the thin film evaporator used in the present invention is a product currently marketed, for example, by Wuxi and Xiang Biochemical Equipment Co., Ltd.
The product obtained by thin film evaporation requires a second molecular distillation, in which:
the primary and secondary molecular distillation mainly has the function of distilling out vitamin E products;
the pure vitamin E product meeting the requirements can be obtained through the secondary molecular distillation.
The first-stage molecular distillation is carried out at the temperature of 175-195 ℃ and under the pressure of 5 Pa-10 MPa.
In the invention, when the pressure of the first-stage molecular distillation is 5 Pa-10 MPa, if the temperature of the first-stage molecular distillation is lower than 175 ℃, the vitamin E can not be vaporized or the vaporized vitamin E molecules are condensed when reaching a cold trap; if the temperature of the first-stage molecular distillation is higher than 195 ℃, the vaporization of the material liquid film is severe, and liquid splashes, so that the purity of the vitamin E product is influenced; therefore, the temperature of the first molecular distillation is suitably 175 to 195 ℃, preferably 180 to 190 ℃;
when the temperature of the first-stage molecular distillation is 175-195 ℃, the pressure of the first-stage molecular distillation is unnecessary to be lower than 5 Pa; if the pressure of the first-stage molecular distillation is higher than 10MPa, the vitamin E product is easy to oxidize; therefore, the pressure of the first molecular distillation is suitably from 5Pa to 10 MPa;
the second-stage molecular distillation is carried out at the temperature of 210-240 ℃ and under the pressure of 1 Pa-5 MPa.
In the invention, when the pressure of the second-stage molecular distillation is 1 Pa-5 MPa, if the temperature of the second-stage molecular distillation is lower than 210 ℃, a small amount of vitamin E cannot be vaporized and remains in the heavy phase, thus reducing the yield; if the temperature of the secondary molecular distillation is higher than 240 ℃, the vaporization of the material liquid film is severe, and liquid splashes, which affects the purity of the vitamin E product; therefore, the temperature of the second stage molecular distillation is suitably from 210 to 240 ℃, preferably from 220 to 230 ℃;
when the temperature of the second-stage molecular distillation is 210-240 ℃, the pressure of the second-stage molecular distillation is not necessary to be lower than 1 Pa; if the pressure of the second-stage molecular distillation is higher than 5MPa, a small amount of vitamin E cannot be vaporized and remains in the heavy phase, so that the yield is reduced; therefore, a pressure of 1Pa to 5MPa for the second stage of molecular distillation is suitable;
the secondary molecular distillation apparatus used in the present invention is a product currently marketed, for example, by Wuxi and Xiang Biochemical Equipment Co., Ltd. under the trade name of short path distiller.
The invention also relates to a pure vitamin E product obtained by the method for removing zearalenone, which is detected by the method for detecting zearalenone described above, and the content of the zearalenone is below 0.0000035% by weight.
[ advantageous effects ]
The invention has the following beneficial effects: compared with the prior art, the method has the advantages that,
1. the invention uses the modified resin to adsorb the zearalenone in the vitamin E, has simple process, does not introduce other substances, does not need other separation processes, and does not cause secondary pollution to the vitamin E product;
2. transition metal ions loaded on the modified resin can specifically form a complex with carbonyl in zearalenone, and compared with the in vitro adsorption effect [ J ] of montmorillonite on aflatoxin B _1(AFB _1) and Zearalenone (ZEN) of adsorbents such as diatomite montmorillonite (Chenguang, Xieling, Wangying, Liujiangjun, Liugui orchid, Liu Ailing. montmorillonite), the adsorption efficiency is about 80-90% higher, and the material loss is small.
[ description of the drawings ]
FIG. 1 is an infrared spectrum of a modified chelating resin;
FIG. 2 is an infrared spectrum of the modified chelate resin obtained in the adsorption step;
[ detailed description ] embodiments
The invention will be better understood from the following examples.
Example 1: removal of zearalenone from natural vitamin E
The implementation steps of this example are as follows:
A. imine diacetic acid type chelating resin pretreatment
At room temperature at a temperature of 26 ℃, the ratio of iminodiacetic acid-based chelating resin in grams to deionized water in milliliters is 1: soaking an iminodiacetic acid type chelate resin sold under the trade name DIAION CR-11 by Mitsubishi chemical corporation in deionized water at pH 8 for 3.6 hours to completely swell the chelate resin, then soaking the completely swollen chelate resin in a saturated sodium sulfate solution for 0.8 hour according to the ratio of iminodiacetic acid type chelate resin in grams to saturated sulfate solution in milliliters of 3.0, washing with deionized water according to the ratio of the chelate resin in grams to the deionized water in milliliters of 3, washing 2 times in the same manner, and drying at 35 ℃ to obtain a modified chelate resin;
B. column mounting
Filling the modified chelating resin obtained in the step A into a container with a height-to-diameter ratio of 1: 8, in a cylindrical chromatographic column, the ratio of the modified chelating resin in grams to the deionized water in milliliters is 1: 2.4, washing deionized water through the modified chelating resin bed at a flow rate of 0.7 column volumes per hour, then emptying the deionized water, and then mixing the ethanol water and the modified chelating resin bed according to the volume ratio of 1: 1.6, passing an ethanol aqueous solution with the concentration of 95 percent by volume through a modified chelating resin bed to remove deionized water;
C. adsorption
According to the ratio of the natural vitamin E in grams to the ethanol water solution in milliliters of 1: 3, mixing natural vitamin E with the zearalenone content of 0.00014 percent by weight with an ethanol aqueous solution with the concentration of 85 percent by volume to prepare a vitamin E solution, and then enabling the vitamin E solution to pass through a modified chelating resin bed at a flow rate of 0.8 times of the column volume per hour for adsorption until the zearalenone is detected from the effluent liquid at the bottom of a chromatographic column;
D. leaching with water
According to the ratio of the modified chelating resin in grams to the ethanol aqueous solution in milliliters of 1: 3.0, leaching the 95% ethanol aqueous solution with the concentration of 0.6 times of the column volume per hour through a modified chelating resin bed, and collecting the leacheate containing the vitamin E from the bottom of the chromatographic column;
E. separation of
D, carrying out decompression desolventizing on the leacheate containing the vitamin E obtained in the step D by using a single-effect concentrator which is manufactured by a Xian Ding machinery and sold by a commercial list effect evaporator under the conditions of 60 ℃ and-0.06 MPa of pressure, then carrying out thin film evaporation at a temperature of 130 ℃ and a pressure of 80MPa using a thin film evaporator sold under the trade name thin film evaporator by Stannless and Xiang Biochemical Equipment Co., Ltd, and finally carrying out primary molecular distillation at a temperature of 175 ℃ and a pressure of 5Pa using a two-stage molecular distillation apparatus sold under the trade name short path distiller by Stannless and Xiang Biochemical Equipment Co., Ltd, followed by secondary molecular distillation at a temperature of 220 ℃ and a pressure of 1MPa, the molecular distillation product is detected by the analysis method described in the specification of the application, and a pure vitamin E product with the zearalenone content of 0.0000031% by weight is obtained.
Example 2: removal of zearalenone from natural vitamin E
The implementation steps of this example are as follows:
A. imine diacetic acid type chelating resin pretreatment
At room temperature at a temperature of 20 ℃, the ratio of iminodiacetic acid-based chelating resin in grams to deionized water in milliliters is 1: soaking an iminodiacetic acid type chelate resin sold under the trade name DIAION CR-11 by Mitsubishi chemical corporation in deionized water at pH 6 for 4.4 hours to completely swell the chelate resin, then soaking the completely swollen chelate resin in a saturated potassium sulfate solution at a ratio of iminodiacetic acid type chelate resin in grams to saturated sulfate solution in milliliters of 1.0 for 1.0 hour, then washing with deionized water at a ratio of soaking chelate resin in grams to deionized water in milliliters of 2, washing 3 times in the same manner, and drying at a temperature of 38 ℃ to obtain a modified chelate resin;
B. column mounting
Filling the modified chelating resin obtained in the step A into a container with a height-to-diameter ratio of 1: 5, in a cylindrical chromatographic column, the ratio of the modified chelating resin in grams to the deionized water in milliliters is 1: 1.0, washing deionized water through the modified chelate resin bed at a flow rate of 0.6 column volumes per hour, then emptying the deionized water, and then mixing the ethanol water and the modified chelate resin bed according to a volume ratio of 1: 2.4, passing the ethanol aqueous solution with the concentration of 95 percent by volume through a modified chelating resin bed to remove deionized water;
C. adsorption
According to the ratio of the natural vitamin E in grams to the ethanol water solution in milliliters of 1: mixing natural vitamin E with zearalenone content of 0.00001% by weight with an ethanol aqueous solution with the concentration of 90% by volume to prepare a vitamin E solution, and then allowing the vitamin E solution to pass through a modified chelating resin bed at a flow rate of 0.7 times of column volume per hour for adsorption until zearalenone is detected from the effluent liquid at the bottom of a chromatographic column;
D. leaching with water
According to the ratio of the modified chelating resin in grams to the ethanol aqueous solution in milliliters of 1: 1.6, leaching 90 percent ethanol water solution with the concentration of 0.7 times of the column volume per hour through a modified chelating resin bed, and collecting leaching solution containing vitamin E from the bottom of a chromatographic column;
E. separation of
D, carrying out decompression desolventizing on the leacheate containing the vitamin E obtained in the step D by using a single-effect concentrator which is manufactured by a Xian Ding machinery and sold by a commercial list effect evaporator under the conditions of the temperature of 74 ℃ and the pressure of-0.08 MPa, then carrying out thin film evaporation at a temperature of 110 ℃ and a pressure of 90MPa using a thin film evaporator sold under the trade name thin film evaporator by Stannless and Xiang Biochemical Equipment Co., Ltd, and finally carrying out primary molecular distillation at a temperature of 182 ℃ and a pressure of 100Pa using a two-stage molecular distillation apparatus sold under the trade name short path distiller by Stannless and Xiang Biochemical Equipment Co., Ltd, followed by secondary molecular distillation at a temperature of 210 ℃ and a pressure of 5MPa, the molecular distillation product is detected by the analysis method described in the specification of the application, and the pure vitamin E product with the zearalenone content of 0.0000028% by weight is obtained.
Example 3: removal of zearalenone from natural vitamin E
The implementation steps of this example are as follows:
A. imine diacetic acid type chelating resin pretreatment
At room temperature, at a temperature of 24 ℃, the ratio of the iminodiacetic acid-based chelating resin in grams to the deionised water in milliliters is 1: 5, immersing an iminodiacetic acid type chelate resin sold under the trade name DIAION CR-11 by Mitsubishi chemical corporation in deionized water at pH 10 for 3.0 hours to completely swell the chelate resin, then immersing the completely swollen chelate resin in a saturated ammonium sulfate solution at a ratio of iminodiacetic acid type chelate resin in grams to saturated sulfate solution in milliliters of 1.6 for 1.2 hours, then washing with deionized water at a ratio of immersion chelate resin in grams to deionized water in milliliters of 4, washing 3 times in the same manner, and drying at a temperature of 42 ℃ to obtain a modified chelate resin;
B. column mounting
Filling the modified chelating resin obtained in the step A into a container with a height-to-diameter ratio of 1: 7 in a cylindrical chromatographic column, the ratio of modified chelating resin in grams to deionized water in milliliters is 1: 1.6, washing deionized water through the modified chelate resin bed at a flow rate of 0.8 column volumes per hour, then emptying the deionized water, and then mixing the ethanol water and the modified chelate resin bed according to a volume ratio of 1: 3.0, passing the ethanol aqueous solution with the concentration of 95 percent by volume through a modified chelating resin bed to remove deionized water;
C. adsorption
According to the ratio of the natural vitamin E in grams to the ethanol water solution in milliliters of 1: mixing natural vitamin E with zearalenone content of 0.00007% by weight with 95% ethanol aqueous solution by volume to prepare a vitamin E solution, and then allowing the vitamin E solution to pass through a modified chelating resin bed at a flow rate of 0.6 times of column volume per hour for adsorption until zearalenone is detected from effluent liquid at the bottom of a chromatographic column;
D. leaching with water
According to the ratio of the modified chelating resin in grams to the ethanol aqueous solution in milliliters of 1: 2.4, leaching the 95 percent ethanol water solution with the concentration of 0.8 times of the column volume per hour through a modified chelating resin bed, and collecting leaching solution containing vitamin E from the bottom of the chromatographic column;
E. separation of
D, carrying out decompression desolventizing on the leacheate containing the vitamin E obtained in the step D by using a single-effect concentrator which is manufactured by a Xian Ding machinery and sold by a commercial list effect evaporator under the conditions of 66 ℃ and-0.06 MPa of pressure, then thin film evaporation was carried out at a temperature of 116 ℃ and a pressure of 100MPa using a thin film evaporator sold under the trade name of tin-free and Xiang Biochemical Equipment Co., Ltd, and finally first molecular distillation was carried out at a temperature of 195 ℃ and a pressure of 1MPa using a secondary molecular distillation apparatus sold under the trade name of short path distiller by tin-free and Xiang Biochemical Equipment Co., Ltd, followed by second molecular distillation at a temperature of 230 ℃ and a pressure of 1Pa, the molecular distillation product is detected by the analysis method described in the specification of the application, and the pure vitamin E product with zearalenone content of below 0.0000030% by weight is obtained.
Example 4: removal of zearalenone from natural vitamin E
The implementation steps of this example are as follows:
A. imine diacetic acid type chelating resin pretreatment
At room temperature, at a temperature of 30 ℃, the ratio of iminodiacetic acid-type chelating resin in grams to deionized water in milliliters is 1: immersing a chelating resin of iminodiacetic acid type sold under the trade name DIAION CR-11 by Mitsubishi chemical corporation in deionized water at pH 4 for 5.0 hours to completely swell the chelating resin, then immersing the completely swollen chelating resin in a saturated potassium bisulfate solution for 1.0 hour in a ratio of the chelating resin of iminodiacetic acid type in grams to the saturated sulfate solution in milliliters of 2.4, then washing the immersed chelating resin in deionized water at a ratio of the chelating resin in grams to the deionized water in milliliters of 3, washing 4 times in the same manner, and drying at a temperature of 45 ℃ to obtain a modified chelating resin;
B. column mounting
Filling the modified chelating resin obtained in the step A into a container with a height-to-diameter ratio of 1: 10, in a cylindrical chromatographic column, the ratio of the modified chelating resin in grams to the deionized water in milliliters is 1: 3.0, washing deionized water through the modified chelating resin bed at a flow rate of 0.7 column volumes per hour, then emptying the deionized water, and then mixing the ethanol water and the modified chelating resin bed according to the volume ratio of 1: 1.0, passing an ethanol aqueous solution with the concentration of 95 percent by volume through a modified chelating resin bed to remove deionized water;
C. adsorption
According to the ratio of the natural vitamin E in grams to the ethanol water solution in milliliters of 1: mixing natural vitamin E with zearalenone content of 0.00020% by weight with an ethanol aqueous solution with the concentration of 90% by volume to prepare a vitamin E solution, and then allowing the vitamin E solution to pass through a modified chelating resin bed at a flow rate of 0.7 times of the column volume per hour for adsorption until zearalenone is detected from the effluent liquid at the bottom of a chromatographic column;
D. leaching with water
According to the ratio of the modified chelating resin in grams to the ethanol aqueous solution in milliliters of 1: 1.0, leaching 98 percent ethanol water solution with the concentration of 0.7 times of the column volume per hour through a modified chelating resin bed, and collecting leaching solution containing vitamin E from the bottom of a chromatographic column;
E. separation of
D, carrying out decompression desolventizing on the leacheate containing the vitamin E obtained in the step D by using a single-effect concentrator which is manufactured by a Xian Ding machinery and sold by a commercial list effect evaporator under the conditions of the temperature of 80 ℃ and the pressure of-0.08 MPa, then carrying out thin film evaporation at a temperature of 125 ℃ and a pressure of 90MPa using a thin film evaporator sold under the trade name thin film evaporator by Stannless and Xiang Biochemical Equipment Co., Ltd, and finally carrying out primary molecular distillation at a temperature of 188 ℃ and a pressure of 10MPa using a two-stage molecular distillation apparatus sold under the trade name short path distiller by Stannless and Xiang Biochemical Equipment Co., Ltd, followed by secondary molecular distillation at a temperature of 240 ℃ and a pressure of 100Pa, the molecular distillation product is detected by the analysis method described in the specification of the application, and the pure vitamin E product with the zearalenone content of 0.0000028% by weight is obtained.