阅读说明：本技术 琥珀酸酯纤维素纤维及其制备方法和在食用油加工中的应用 (Succinate cellulose fiber, preparation method thereof and application thereof in processing edible oil ) 是由 韩立娟 刘琛 李楠楠 贺军波 齐玉堂 陈思瑶 于 2019-09-27 设计创作，主要内容包括：本发明公开一种琥珀酸酯纤维素纤维及其制备方法和在食用油加工中的应用,所述琥珀酸酯纤维素纤维的成分为醋酸羟丙基甲基纤维素琥珀酸酯。本发明以醋酸羟丙基甲基纤维素琥珀酸酯为原材料,通过纺丝制成琥珀酸酯纤维素纤维,具有良好的吸附性能,用作食用油脱除DBP的吸附剂时,显著提高了DBP的脱除率。(The invention discloses succinate cellulose fiber, a preparation method thereof and application thereof in processing edible oil. The invention takes the hydroxypropyl methyl cellulose acetate succinate as a raw material, and the succinate cellulose fiber is prepared by spinning, has good adsorption performance, and obviously improves the DBP removal rate when being used as an adsorbent for removing DBP from edible oil.)

1. The succinate cellulose fiber is characterized in that the succinate cellulose fiber is hydroxypropyl methyl cellulose acetate succinate.

2. The succinate cellulose fiber of claim 1, wherein the hydroxypropyl methyl cellulose acetate succinate has a weight average molecular weight of 20000 to 75000.

3. Cellulose succinate fibers according to claim 1 or 2, wherein said hydroxypropylmethylcellulose acetate succinate comprises 8% hydroxypropoxyl, 30% methoxyl, 16% succinyl and 8% acetyl.

4. A method for preparing succinate cellulose fibres according to any one of claims 1 to 3, comprising the following steps:

hydroxypropyl methyl cellulose acetate succinate is dissolved in an organic solvent to prepare a spinning solution, and then the succinate cellulose fiber is prepared by electrostatic spinning.

5. The method for producing succinate cellulose fibers according to claim 4, wherein the organic solvent is a mixed solvent of ethanol and dimethylacetamide, and the volume ratio of ethanol to dimethylacetamide in the mixed solvent is (1:2) to (1: 5).

6. The method for producing succinic acid ester cellulose fibers according to claim 4, wherein the mass concentration of the hydroxypropyl methyl cellulose acetate succinate in the spinning solution is 10 to 20%.

7. Use of succinate cellulosic fibers according to any of claims 1 to 6 for the processing of edible oils, comprising the following steps:

adding succinate cellulose fibers into edible oil to be degreased, heating and stirring to enable the succinate cellulose fibers to absorb dibutyl phthalate in the edible oil, and separating and removing the succinate cellulose fibers to obtain the degreased edible oil.

8. The use of succinate cellulose fibers in the processing of edible oil according to claim 7, wherein the step of adding succinate cellulose fibers to edible oil to be degreased, heating and stirring the mixture to enable the succinate cellulose fibers to adsorb dibutyl phthalate in the edible oil, and then separating and removing the succinate cellulose fibers to obtain the degreased edible oil comprises the specific steps of:

adding the succinate cellulose fiber into the edible oil to be degreased, heating to 110-140 ℃, stirring for 20-50 min, and then centrifuging to separate out the succinate cellulose fiber to obtain the degreased edible oil.

9. The use of succinate cellulose fibers according to claim 7 in the processing of edible oil, wherein the succinate cellulose fibers are added in an amount of 0.5-4% by mass of the edible oil.

Technical Field

The invention relates to the technical field of edible oil processing, in particular to succinate cellulose fibers, a preparation method thereof and application thereof in edible oil processing.

Background

Phthalates (PAEs) are a common class of environmental hormone compounds and have become one of the most common pollutants worldwide in recent years. To avoid this, china, the united states, japan, and the european union, etc. list them as "priority control contaminants" and limit their addition amount in food contact materials. It has been found that PAEs present in vegetable fats and oils are dimethyl phthalate (DMP), diethyl phthalate (DEP), Dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), di (2-ethyl) hexyl phthalate (Bis (2-ethylhexyl) phthalate, DEHP), and diisobutyl phthalate (DIBP), etc., as specified in the Ware-office supervision letters (2011) No. 551, phthalate esters DBP of 0.3mg/kg or less, DEHP of 1.5mg/kg or DINP of 9.0mg/kg in foods and food additives.

According to research reports, PEAs in drinking water or sewage can be partially removed by using the solid adsorbent, for example, 94% of DBP in drinking water can be removed by using an activated carbon-attapulgite composite filter material, and the solid adsorbent also has a certain removing effect on DMP, DEP and DEHP in water. For removing PAEs in vegetable oil, the currently adopted method mainly adopts activated carbon adsorption, steam distillation or molecular distillation, wherein the steam distillation or molecular distillation method has high requirement on removal temperature, the equipment investment is high, the production cost is higher, and dangers such as chloropropanol and the like can be generated in the oil at high temperature; compared with steam distillation or molecular distillation, the activated carbon adsorption method has the advantages of simple method and low requirement on temperature. However, the existing activated carbon adsorption method has poor removal effect on DBP (DBP) of a plasticizer component with a larger molecular weight in vegetable oil, and cannot reach the national standard limit regulation.

Disclosure of Invention

The invention mainly aims to provide succinate cellulose fibers, a preparation method thereof and application thereof in edible oil processing, and aims to improve the DBP removal rate in the edible oil processing process.

In order to achieve the purpose, the succinate cellulose fiber comprises hydroxypropyl methyl cellulose acetate succinate as a component of the fiber derivative fiber.

Preferably, the weight average molecular weight of the hydroxypropyl methyl cellulose acetate succinate is 20000-75000.

Preferably, the hydroxypropyl methyl cellulose acetate succinate comprises 8% of hydroxypropoxyl, 30% of methoxyl, 16% of succinyl and 8% of acetyl.

In order to achieve the above object, the present invention also provides a method for preparing the succinate cellulose fiber, comprising the following steps:

hydroxypropyl methyl cellulose acetate succinate is dissolved in an organic solvent to prepare a spinning solution, and then the succinate cellulose fiber is prepared by electrostatic spinning.

Preferably, the organic solvent is a mixed solvent of ethanol and dimethylacetamide, and the volume ratio of ethanol to dimethylacetamide in the mixed solvent is (1:2) - (1: 5).

Preferably, the mass concentration of the hydroxypropyl methyl cellulose acetate succinate in the spinning solution is 10-20%.

The invention also provides the application of the succinate cellulose fiber in the processing of edible oil, which comprises the following steps:

adding succinate cellulose fibers into edible oil to be degreased, heating and stirring to enable the succinate cellulose fibers to absorb dibutyl phthalate in the edible oil, and separating and removing the succinate cellulose fibers to obtain the degreased edible oil.

Preferably, the method comprises the steps of adding succinate cellulose fibers into the edible oil to be degreased, heating and stirring to enable the succinate cellulose fibers to adsorb dibutyl phthalate in the edible oil, and then separating and removing the succinate cellulose fibers to obtain the degreased edible oil, and specifically comprises the following steps:

adding the succinate cellulose fiber into the edible oil to be degreased, heating to 110-140 ℃, stirring for 20-50 min, and then centrifuging to separate out the succinate cellulose fiber to obtain the degreased edible oil.

Preferably, the addition amount of the succinate cellulose fiber is 0.5-4% of the mass of the edible oil.

According to the technical scheme provided by the invention, hydroxypropyl methyl cellulose acetate succinate is used as a raw material, the fiber derivative fiber is prepared by spinning, the adsorption performance is good, and when the adsorbent is used as an adsorbent for removing DBP from edible oil, the DBP removal rate is obviously improved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.

Fig. 1 is an appearance view of edible oil with DBP removed according to application example 1 and comparative example 1.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The existing method for removing PAEs in edible oil by using activated carbon adsorption has the advantages of simple method and low requirement on temperature, but has poor removal effect on DBP (diethylene glycol monobutyl ether) serving as a plasticizer component with higher molecular weight in vegetable oil, and cannot reach the national standard limit regulation. In order to solve the problems, the invention provides succinate cellulose fibers, the components of the succinate cellulose fibers are cellulose derivatives, namely the succinate cellulose fibers are prepared from the cellulose derivatives serving as raw materials through spinning, the succinate cellulose fibers have good adsorption performance, and when the succinate cellulose fibers are used as an adsorbent for removing DBP from edible oil, the removal rate of the DBP is remarkably improved, wherein the cellulose derivatives are hydroxypropyl methyl cellulose succinate acetate. Hydroxypropyl methyl cellulose Acetate Succinate (HPMCAS) is a mixed ester of acetic acid and succinic acid of Hydroxypropyl methyl cellulose, is an enteric cellulose derivative material which is safe, nontoxic, good in biocompatibility and completely degradable in vivo, and is mainly applied to drug enteric coatings and related fields at present. In the technical scheme provided by the invention, the succinate cellulose fiber prepared by taking HPMCAS as the raw material has excellent adsorption performance, has obvious DBP removal effect on edible oil when being used for DBP removal treatment of the edible oil, is easy to completely separate from the edible oil after being used, and does not influence the color and luster of the edible oil.

In the case of HPMCAS, it has a plurality of different molecular weights, and in the selection, if its molecular weight is too low, it is not easy to form a fiber by electrospinning, and if it is too high, it is difficult to dissolve HPMCAS, and the time required for dissolution is long, or a heat treatment is required in preparing the spinning solution, which is disadvantageous for the rapid preparation of the spinning solution. Therefore, in a preferred embodiment provided by the invention, the weight average molecular weight of the HPMCAS is 20000-75000, so that the HPMCAS is easy to form during spinning, and the spinning solution with the HPMCAS fully dissolved can be prepared quickly, and the process time is saved.

Further, the HPMCAS is preferably HPMCAS containing 8% of hydroxypropoxyl, 30% of methoxyl, 16% of succinyl and 8% of acetyl. Thus, the succinate cellulose fiber prepared by the HPMCAS containing the groups has higher DBP removal rate in the edible oil.

The succinate cellulose fiber can be prepared by an electrostatic spinning method which is conventional in the art, and in general, the electrostatic spinning process generally comprises dissolving a high molecular polymer in a solvent to prepare a spinning solution, and then preparing the fiber by electrostatic jet spinning. On the basis, the invention also provides a preparation method of the succinate cellulose fiber, and in one embodiment of the preparation method of the succinate cellulose fiber, the preparation method of the succinate cellulose fiber comprises the following steps: the HPMCAS is dissolved in an organic solvent to make a spinning solution, which is then electrospun to make succinate cellulose fibers.

In the process of preparing the HPMCAS into the spinning solution, there are various organic solvents used for dissolving the HPMCAS, for example, acetone, acetic acid, ethanol and the like, in this embodiment, the organic solvent is preferably a mixed solvent of ethanol and dimethylacetamide, and the volume ratio of ethanol and dimethylacetamide in the mixed solvent is (1:2) to (1: 5).

When HPMCAS is dissolved in a mixed solvent of ethanol and dimethylacetamide to prepare the spinning solution, if the concentration of HPMCAS in the prepared spinning solution is too low, the amount of HPMCAS contained in the extruded spinning solution at a fixed time and a fixed extrusion rate is too small, which is disadvantageous to the formation of fibers and reduces the efficiency of preparing fibers by electrospinning, whereas if the concentration of HPMCAS in the spinning solution is too high, which is not only disadvantageous to the sufficient dissolution of HPMCAS in the preparation but also causes poor fluidity due to too high viscosity of the prepared spinning solution, which is liable to cause disadvantages such as clogging of an extrusion die in electrospinning. Therefore, in the preferred embodiment, the mass concentration of the HPMCAS in the spinning solution is 10-20%, so that the spinning solution is easy to form during electrostatic spinning, the strength of the prepared fiber is high, the viscosity of the prepared spinning solution is proper, the flowability is good, and the problem that the extrusion die is blocked due to overhigh viscosity of the spinning solution is avoided.

Electrostatic spinning is a special existing fiber manufacturing process, polymer solution or melt is subjected to jet spinning in a strong electric field, liquid drops at a needle head are changed into a conical shape (namely, a Taylor cone) under the action of the electric field, fiber filaments are obtained by extending from the tip of the conical shape, and electrostatic spinning equipment in the prior art can be adopted. In this example, there is provided an electrospinning method of the succinate cellulose fibers, comprising the steps of: adding the spinning solution into an injector, extruding the spinning solution at a constant speed, and flying the spinning solution to a grounded aluminum collecting plate to prepare succinate cellulose fibers, wherein a metal needle at the front end of the injector is connected with a high-voltage electrostatic source with the voltage of 15-25 kV, and under the voltage condition, the spinning solution is extruded by the needle of the injector and then rapidly changed from spherical liquid drops into a conical shape, and a fiber filament is obtained by extending the conical tip; the constant rate is 0.8-1.2 mL/h, and the extrusion amount of the spinning solution is proper at the constant extrusion rate, so that the problem that the working efficiency of electrostatic spinning is reduced due to too small extrusion amount of the spinning solution can be avoided, and the problem that liquid drops extruded from an injector are easy to agglomerate when the extrusion amount of the spinning solution is too large can be avoided.

In this embodiment, the syringe is preferably a glass syringe, which facilitates observing the consumption of the spinning solution in the syringe at any time, the prepared spinning solution is added into the glass syringe and then extruded at a constant rate, a metal needle at the front end of the syringe is connected with a high-voltage electrostatic power source, after the high voltage is started, the spinning solution is continuously stretched in the process of flying to a grounded aluminum collecting plate under the action of the electrostatic field force, and meanwhile, the solvent in the spinning solution is rapidly volatilized in the process, so that the succinate cellulose fiber is prepared. The voltage of the high-voltage electrostatic source can be any voltage value of 15-25 kV, and is preferably 20 kV; the constant rate of the spinning solution extrusion can be any rate value in the range of 0.8-1.2 mL/h, and is preferably 1 mL/h.

The invention further provides an application of the succinate cellulose fiber in processing edible oil, wherein the succinate cellulose fiber is used as an adsorbent to remove a high molecular weight phthalate plasticizer DBP in the edible oil, and the application comprises the following steps: adding succinate cellulose fibers into edible oil to be degreased, heating and stirring to enable the succinate cellulose fibers to adsorb DBP in the edible oil, and separating and removing the succinate cellulose fibers to obtain the degreased edible oil. When the method is used for industrial production, equipment such as a reaction tank and the like is used for heating and stirring so that the succinic acid ester cellulose fibers completely adsorb DBP in the edible oil, and then an adsorbent (i.e. succinic acid ester cellulose fibers) in the edible oil is separated by a conventional solid-liquid separation method such as filtration, centrifugation and the like, so that the edible oil with DBP removed can be obtained.

When the cellulose derivative is used as an adsorbent to remove DBP in the edible oil, the heating and stirring temperature and time have certain influence on the DBP adsorption effect, the heating temperature is too low, the succinate cellulose fiber has poor adsorption on DBP, the time required for achieving a good adsorption effect is too long, the heating temperature is too high, and the negative influence is easily caused on the quality of the edible oil, so that the heating temperature is reduced as much as possible on the basis of achieving a good adsorption effect. In a preferred embodiment of the method for applying the succinate cellulose fiber to remove DBP from edible oil provided by the invention, the method comprises the following steps: adding the succinate cellulose fiber into the edible oil to be degreased, heating to 110-140 ℃, stirring for 20-50 min, and then centrifuging to separate out the succinate cellulose fiber to obtain the degreased edible oil. Stirring for 20-50 min at the temperature of 110-140 ℃, so that the DBP removal rate in the edible oil can reach 52.2-60.9%, and performing solid-liquid separation in a centrifugal mode, wherein the solid-liquid separation rate is higher and the operation is simple and convenient. In this embodiment, in a specific operation, the edible oil is centrifuged at 400 to 500rpm for 25 to 35min to completely separate the adsorbent from the edible oil, so as to obtain the purified oil.

When the cellulose derivative is used as an adsorbent for removing DBP in the edible oil, the addition amount of the cellulose derivative is too low to achieve the effect of effectively removing DBP, on the basis that DBP can be effectively removed, if the addition amount is too low, the adsorbent is unnecessary and wasted, and after adsorption is finished, the addition amount is too much to facilitate thorough separation from the edible oil. In the preferred embodiment, the addition amount of the succinate cellulose fiber is 0.5-4% of the edible oil, and within the addition range, the cellulose derivative can play a good role in removing DBP in the edible oil, is easy to separate from the edible oil, and can be completely separated and removed by only one-time centrifugal treatment.

The method for removing DBP in the edible oil has the advantages of high DBP removal rate, simple process, low requirement on equipment, lower operation temperature and capability of avoiding the problem of generating hazards in the edible oil due to high temperature.

The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.