阅读说明：本技术 一种分子蒸馏单硬脂酸甘油酯乳化剂及其制备方法 (Molecular distillation glycerin monostearate emulsifier and preparation method thereof ) 是由 陈清年 于 2020-05-09 设计创作，主要内容包括：本发明涉及一种分子蒸馏单硬脂酸甘油酯乳化剂及其制备方法,属于食品添加剂技术领域,分子蒸馏单硬脂酸甘油酯乳化剂包括以下重量份的组分：脱酸分子蒸馏单硬脂酸甘油酯180-240份,水520-600份,本发明的乳化剂具有降低分子蒸馏单硬脂酸甘油酯乳化剂的酸价,从而提高品质的效果。(The invention relates to a molecular distillation glycerin monostearate emulsifier and a preparation method thereof, belonging to the technical field of food additives, wherein the molecular distillation glycerin monostearate emulsifier comprises the following components in parts by weight: 180 portions of deacidified molecular distillation glycerin monostearate and 240 portions of water and 520 portions of water, the emulsifier of the invention has the effect of reducing the acid value of the molecular distillation glycerin monostearate emulsifier, thereby improving the quality.)

1. A molecular distillation glycerin monostearate emulsifier is characterized in that: the emulsifier comprises the following components in parts by weight: deacidifying molecular distillation glycerin monostearate 180-240 parts, water 520-600 parts;

the preparation method of deacidified molecular distillation glycerin monostearate comprises the following steps:

s1: dissolving tetrabutyl phosphonium bromide in methanol to obtain tetrabutyl phosphonium bromide solution, wherein the weight ratio of tetrabutyl phosphonium bromide to methanol is (0.8-1.2): 1;

s2: uniformly mixing tetrabutyl phosphonium bromide solution, 1-ethyl-3-methylimidazole dimethyl phosphate and 1-butyl-3-methylimidazole dinitrile amine salt to obtain a deacidification agent, wherein the weight ratio of the tetrabutyl phosphonium bromide solution to the 1-ethyl-3-methylimidazole dimethyl phosphate to the 1-butyl-3-methylimidazole dinitrile amine salt is (1-2): (0.5-1.5): (0.2-1.8);

s3: uniformly mixing the molecular distillation glyceryl monostearate and a deacidification agent, stirring and extracting at the temperature of 45-55 ℃ for 1-5 minutes, standing, and taking an upper layer liquid to obtain the deacidified molecular distillation glyceryl monostearate, wherein the weight ratio of the molecular distillation glyceryl monostearate to the deacidification agent is 1: (2.5-6.5).

2. A molecularly distilled glyceryl monostearate emulsifier according to claim 1, wherein: the emulsifier comprises the following components in parts by weight: 200 portions and 220 portions of deacidified molecular distillation glycerin monostearate and 580 portions of water.

3. A molecularly distilled glyceryl monostearate emulsifier according to claim 1, wherein: the preparation method of the deacidified molecular distillation glycerin monostearate comprises the following steps:

s1: dissolving tetrabutyl phosphonium bromide in methanol to obtain tetrabutyl phosphonium bromide solution, wherein the weight ratio of tetrabutyl phosphonium bromide to methanol is (0.95-1.05): 1;

s2: uniformly mixing tetrabutyl phosphonium bromide solution, 1-ethyl-3-methylimidazole dimethyl phosphate and 1-butyl-3-methylimidazole dinitrile amine salt to obtain a deacidification agent, wherein the weight ratio of tetrabutyl phosphonium bromide mixed solution to 1-ethyl-3-methylimidazole dimethyl phosphate to 1-butyl-3-methylimidazole dinitrile amine salt is (1.25-1.75): (0.8-1.2): (0.6-1.4);

s3: uniformly mixing the molecular distillation glyceryl monostearate and a deacidification agent, stirring and extracting at the temperature of 48-52 ℃ for 2-4 minutes, standing, and taking an upper layer liquid to obtain the deacidified molecular distillation glyceryl monostearate, wherein the weight ratio of the molecular distillation glyceryl monostearate to the deacidification agent is 1: (3.5-5.5).

4. A molecularly distilled glyceryl monostearate emulsifier according to claim 1, wherein: the emulsifier also comprises 30-31.6 parts of modified citrus peel adsorbent;

the preparation method of the modified citrus peel adsorbent comprises the following steps:

weighing citrus peel, putting the citrus peel into absolute ethyl alcohol, adding a sodium hydroxide solution with the concentration of 0.8-1.2mol/L, soaking the citrus peel at the temperature of 22-27 ℃ for 22-26h, then washing with water until the pH value is 10, drying at the temperature of 55-65 ℃, and then crushing to obtain the modified citrus peel adsorbent, wherein the weight ratio of the citrus peel to the absolute ethyl alcohol to the sodium hydroxide solution is (3-6): 1: (0.5-1.5).

5. A molecularly distilled glyceryl monostearate emulsifier according to claim 4, wherein: the particle size of the modified citrus peel adsorbent is 80-120 meshes.

6. A molecularly distilled glyceryl monostearate emulsifier according to claim 4, wherein: the emulsifier also comprises 11-12.1 parts by weight of alkali microcrystalline cellulose powder;

the preparation method of the alkali microcrystalline cellulose powder comprises the following steps:

weighing microcrystalline fiber powder, putting the microcrystalline fiber powder into a sodium hydroxide solution with the concentration of 18-22mol/L, stirring for reaction for 85-95min, filtering and separating to obtain a precipitate, washing with 93-97% ethanol, drying, crushing, and sieving with a 50-70 mesh sieve to obtain alkaline microcrystalline cellulose powder, wherein the weight ratio of the microcrystalline fiber powder to the sodium hydroxide solution is 1: (33-37).

7. The molecularly distilled glyceryl monostearate emulsifier of claim 6, wherein: the weight ratio of the alkali microcrystalline cellulose powder to the modified citrus peel adsorbent is 1: (2.65-2.7).

8. The process for the preparation of a molecularly distilled glyceryl monostearate emulsifier according to any one of claims 1 to 7, wherein: uniformly mixing deacidified molecular distillation glycerin monostearate and water, heating to 65-70 ℃, uniformly stirring at the rotating speed of 1200-1250r/min, reacting for 2-3h, and cooling to 22-27 ℃ to obtain the molecular distillation glycerin monostearate emulsifier.

Technical Field

The invention relates to the technical field of food additives, in particular to a molecular distillation glycerin monostearate emulsifier and a preparation method thereof.

Background

The molecular distillation glyceryl monostearate is obtained by purifying crude ester, the crude ester is refined by three-stage distillation, other components in the crude ester are removed to the maximum extent, the molecular distillation glyceryl monostearate with the purity of over 90 percent is obtained, and the molecular distillation glyceryl monostearate has hydrophilic and lipophilic groups, so that the molecular distillation glyceryl monostearate has good emulsification, dispersion, stability and other effects, and is widely applied to industries such as food, cosmetics and the like as an emulsifier.

The acid value is a metering standard of the amount of free carboxylic acid in a compound or a mixture, free carboxylic acid can be decomposed under the action of factors such as moisture, temperature, light and the like in the process of long-term storage of the molecular distillation glyceryl monostearate emulsifier, so that the acid value of the molecular distillation glyceryl monostearate emulsifier is increased, and the stability of the molecular distillation glyceryl monostearate emulsifier is reduced due to the increase of the acid value of the molecular distillation glyceryl monostearate emulsifier, so that the quality is influenced, and therefore, the acid value can be used as an index of the deterioration degree of the oil ester.

Disclosure of Invention

The invention aims to provide a molecular distillation glycerin monostearate emulsifier, which has the effect of reducing the acid value of the molecular distillation glycerin monostearate emulsifier, thereby improving the quality;

the invention also aims to provide a preparation method of the molecular distillation glyceryl monostearate emulsifier, which has the effects of reducing the acid value of the molecular distillation glyceryl monostearate emulsifier, improving the quality and improving the preparation efficiency of the molecular distillation glyceryl monostearate emulsifier.

The above object of the present invention is achieved by the following technical solutions:

a molecular distillation glycerin monostearate emulsifier comprises the following components in parts by weight: deacidifying molecular distillation glycerin monostearate 180-240 parts, water 520-600 parts;

the preparation method of deacidified molecular distillation glycerin monostearate comprises the following steps:

s1: dissolving tetrabutyl phosphonium bromide in methanol to obtain tetrabutyl phosphonium bromide solution, wherein the weight ratio of tetrabutyl phosphonium bromide to methanol is (0.8-1.2): 1;

s2: uniformly mixing tetrabutyl phosphonium bromide solution, 1-ethyl-3-methylimidazole dimethyl phosphate and 1-butyl-3-methylimidazole dinitrile amine salt to obtain a deacidification agent, wherein the weight ratio of the tetrabutyl phosphonium bromide solution to the 1-ethyl-3-methylimidazole dimethyl phosphate to the 1-butyl-3-methylimidazole dinitrile amine salt is (1-2): (0.5-1.5): (0.2-1.8);

s3: uniformly mixing the molecular distillation glyceryl monostearate and a deacidification agent, stirring and extracting at the temperature of 45-55 ℃ for 1-5 minutes, standing, and taking an upper layer liquid to obtain the deacidified molecular distillation glyceryl monostearate, wherein the weight ratio of the molecular distillation glyceryl monostearate to the deacidification agent is 1: (2.5-6.5).

By adopting the technical scheme, the deacidification agent is prepared by mixing 1-ethyl-3-methylimidazole dimethyl phosphate and 1-butyl-3-methylimidazole dinitrile amine salt with higher alkalinity and tetrabutyl phosphonium bromide with deacidification capacity, and is combined with free carboxylic acid in the molecular distillation glyceryl monostearate to achieve the effect of deacidifying the molecular distillation glyceryl monostearate, the number of the free carboxylic acid in the deacidification molecular distillation glyceryl monostearate is reduced, so that the acid value of the molecular distillation glyceryl monostearate emulsifier is reduced, and the stability and the quality of the molecular distillation glyceryl monostearate emulsifier are improved;

meanwhile, tetrabutyl phosphonium bromide, 1-ethyl-3-methylimidazole dimethyl phosphate and 1-butyl-3-methylimidazole dinitrile amine salt belong to ionic liquid, have broad-spectrum dissolving capacity, are not easy to volatilize, have good thermal stability, are non-toxic and tasteless, belong to a green reagent, and because the ionic liquids are insoluble in n-hexane, free carboxylic acid groups in the ionic liquid can be subjected to reverse extraction by using the n-hexane to obtain recovered ionic liquid, the recovered ionic liquid can be repeatedly used, and the cost is reduced;

because the tetrabutyl phosphonium bromide is powdery, the tetrabutyl phosphonium bromide is dissolved in the methanol, the methanol has the shortest alkyl chain and the highest polarity, and is a common reagent for extracting free carboxylic acid, and is mixed with the tetrabutyl phosphonium bromide to form a tetrabutyl phosphonium bromide solution, so that the tetrabutyl phosphonium bromide solution and the tetrabutyl phosphonium bromide can generate a synergistic effect, the number of free carboxylic acid is reduced to a greater extent, the acid value of the molecular distillation glycerin monostearate emulsifier is reduced, and the effect of improving the quality is achieved;

the three ionic liquids are matched and mixed according to a certain proportion for use, so that the reaction of combining the ionic liquid and the free carboxylic acid can be mutually promoted, the hydrogen bond acting force of combining the ionic liquid and the free carboxylic acid is improved, the combination is more completely stable, the number of the free carboxylic acid is reduced, the acid value of the molecular distillation glycerin monostearate emulsifier is reduced, the dosage of the ionic liquid can be reduced, a small dosage is used, a large effect is exerted, and the cost is reduced;

within a proper temperature range, the extraction temperature is increased, so that the viscosity of the deacidification agent is reduced, the mass transfer efficiency is improved, the extraction effect of the deacidification agent is improved, the number of free carboxylic acids is reduced, and the acid value of the molecular distillation glycerin monostearate emulsifier is reduced; if the temperature is continuously increased beyond the proper temperature range, the molecular distillation glycerin monostearate is promoted to be dissolved in the methanol, the extraction selectivity of the deacidification agent is reduced, and the extraction effect of the deacidification agent is reduced.

The present invention in a preferred example may be further configured to: the emulsifier comprises the following components in parts by weight: 200 portions and 220 portions of deacidified molecular distillation glycerin monostearate and 580 portions of water.

By adopting the technical scheme, the deacidified molecular distillation glyceryl monostearate and the water are mixed according to a proper part, and the dispersity of the deacidified molecular distillation glyceryl monostearate can be improved while the emulsifying capacity of the molecular distillation glyceryl monostearate emulsifier is not influenced, so that the molecular distillation glyceryl monostearate emulsifier can be better combined with used substances when in use.

The present invention in a preferred example may be further configured to: the preparation method of the deacidified molecular distillation glycerin monostearate comprises the following steps:

s1: dissolving tetrabutyl phosphonium bromide in methanol to obtain tetrabutyl phosphonium bromide solution, wherein the weight ratio of tetrabutyl phosphonium bromide to methanol is (0.95-1.05): 1;

s2: uniformly mixing tetrabutyl phosphonium bromide solution, 1-ethyl-3-methylimidazole dimethyl phosphate and 1-butyl-3-methylimidazole dinitrile amine salt to obtain a deacidification agent, wherein the weight ratio of the tetrabutyl phosphonium bromide solution to the 1-ethyl-3-methylimidazole dimethyl phosphate to the 1-butyl-3-methylimidazole dinitrile amine salt is (1.25-1.75): (0.8-1.2): (0.6-1.4);

s3: uniformly mixing the molecular distillation glyceryl monostearate and a deacidification agent, stirring and extracting at the temperature of 48-52 ℃ for 2-4 minutes, standing, and taking an upper layer liquid to obtain the deacidified molecular distillation glyceryl monostearate, wherein the weight ratio of the molecular distillation glyceryl monostearate to the deacidification agent is 1: (3.5-5.5).

By adopting the technical scheme, the three ionic liquids are matched and mixed according to a certain proportion for use, the alkalinity of the ionic liquids can be utilized to mutually promote the reaction of the ionic liquids and the free carboxylic acid, the hydrogen bond acting force of the ionic liquids and the free carboxylic acid is improved, the number of the free carboxylic acids is reduced, the acid value of the molecular distillation glycerin monostearate emulsifier is reduced, the using amount of the ionic liquids can be reduced, the ionic liquids can be recovered for reuse after extraction is completed, and the cost is reduced; the proper extraction temperature is selected, so that the viscosity of the deacidification agent is reduced, the mass transfer efficiency is improved, the extraction effect of the deacidification agent is improved, the number of free carboxylic acids is reduced, the acid value of the molecular distillation glyceryl monostearate emulsifier is reduced, and the quality of the molecular distillation glyceryl monostearate emulsifier is improved.

The present invention in a preferred example may be further configured to: the emulsifier also comprises 30-31.6 parts of modified citrus peel adsorbent;

the preparation method of the modified citrus peel adsorbent comprises the following steps:

weighing citrus peel, putting the citrus peel into absolute ethyl alcohol, adding a sodium hydroxide solution with the concentration of 0.8-1.2mol/L, soaking the citrus peel at the temperature of 22-27 ℃ for 22-26h, then washing with water until the pH value is 10, drying at the temperature of 55-65 ℃, and then crushing to obtain the modified citrus peel adsorbent, wherein the weight ratio of the citrus peel to the absolute ethyl alcohol to the sodium hydroxide solution is (3-6): 1: (0.5-1.5).

By adopting the technical scheme, as the citrus peel contains cellulose, hemicellulose, lignin and other substances and has stronger adsorption capacity, the modified citrus peel adsorbent obtained after the citrus peel is soaked in the sodium hydroxide solution can adsorb and combine unbound free carboxylic acid remained in the deacidified molecular distillation glycerin monostearate, so that the free carboxylic acid in the deacidified molecular distillation glycerin monostearate is reduced, the acid value of the molecular distillation glycerin monostearate emulsifier is reduced, and the quality of the molecular distillation glycerin monostearate emulsifier is improved; if too much modified citrus peel adsorbent is added, the modified citrus peel adsorbent is in powder form, and the modified citrus peel adsorbent is too much added, so that the modified citrus peel adsorbent cannot be uniformly dispersed, and the acid value reducing capability of the modified citrus peel adsorbent is reduced.

The present invention in a preferred example may be further configured to: the particle size of the modified citrus peel adsorbent is 80-120 meshes.

Through adopting above-mentioned technical scheme, along with the particle diameter reduces in certain extent, can promote the structure of netted adsorption function such as cellulose, hemicellulose, lignin among the modified citrus peel adsorbent to open, make its ability that adsorbs free carboxylic acid improve, reach saturation when the adsorption efficiency of modified citrus peel adsorbent, continue to reduce the particle diameter again, not only can not improve adsorption efficiency, still can raise the cost, when the particle diameter of modified citrus peel adsorbent is too big, can make it can not disperse evenly, reduced its ability that reduces the acid value.

The present invention in a preferred example may be further configured to: the emulsifier also comprises 11-12.1 parts by weight of alkali microcrystalline cellulose powder;

the preparation method of the alkali microcrystalline cellulose powder comprises the following steps:

weighing microcrystalline cellulose powder, putting the microcrystalline cellulose powder into a sodium hydroxide solution with the concentration of 18-22mol/L, stirring for reaction for 85-95min, filtering and separating to obtain a precipitate, washing with 93-97% ethanol, drying, crushing, and sieving with a 50-70 mesh sieve to obtain the alkali microcrystalline cellulose powder, wherein the weight ratio of the microcrystalline cellulose powder to the sodium hydroxide solution is 1: (33-37).

By adopting the technical scheme, the microcrystalline cellulose is a powdery substance obtained by hydrolyzing natural fibers to the limit polymerization degree, has low polymerization degree, large specific surface area and good adsorbability, and is mixed with a sodium hydroxide solution to obtain the alkali microcrystalline cellulose, wherein inorganic alkali and cellulose alkali in the alkali microcrystalline cellulose can adsorb and combine unbound free carboxylic acid remained in deacidified molecular distilled glyceryl monostearate, so that the free carboxylic acid in deacidified molecular distilled glyceryl monostearate is reduced, the acid value of the molecular distilled glyceryl monostearate emulsifier is reduced, and the quality of the molecular distilled glyceryl monostearate emulsifier is improved; when the adsorption capacity of the alkali microcrystalline cellulose reaches saturation, the addition amount of the alkali microcrystalline cellulose is continuously increased, so that the adsorption capacity is not improved, and the cost is also increased.

The present invention in a preferred example may be further configured to: the weight ratio of the alkali microcrystalline cellulose powder to the modified citrus peel adsorbent is 1: (2.65-2.7).

By adopting the technical scheme, the alkaline microcrystalline cellulose powder and the modified citrus peel adsorbent belong to natural substances, and free carboxylic acid is adsorbed by cellulose and inorganic base contained in the alkaline microcrystalline cellulose powder and the modified citrus peel adsorbent, so that the acid value of the emulsifier is reduced, the alkaline microcrystalline cellulose powder and the modified citrus peel adsorbent are mixed and matched according to a proportion to be used, a synergistic effect can be achieved, the addition amount of the alkaline microcrystalline cellulose powder and the acid value of the emulsifier can be reduced, the adsorption capacity is enhanced, the acid value reduction capacity of the emulsifier is enhanced, and the possibility of impurities in the emulsifier is reduced.

The second purpose of the invention is to provide a preparation method of the molecular distillation glycerin monostearate emulsifier, which is realized by the following technical scheme:

uniformly mixing deacidified molecular distillation glycerin monostearate and water, heating to 65-70 ℃, uniformly stirring at the rotating speed of 1200-1250r/min, reacting for 2-3h, and cooling to 22-27 ℃ to obtain the molecular distillation glycerin monostearate emulsifier.

By adopting the technical scheme, the temperature is increased, the neutralization reaction speed of cellulose, inorganic base and the like in the alkali microcrystalline cellulose powder and the modified citrus peel adsorbent and free carboxylic acid in deacidified molecular distillation glycerin monostearate can be increased, the acid value reduction capability is enhanced, the quality of the molecular distillation glycerin monostearate emulsifier is improved, and when the temperature is too high, the molecular movement speed in the solution is increased, the desorption effect is generated, and the total amount of adsorbed free carboxylic acid is reduced; meanwhile, the reaction time is controlled, so that the reaction of cellulose, inorganic base and the like with free carboxylic acid is more thorough, but when the reaction reaches a saturated state, the reaction time is continuously increased, the capability of reducing the acid value cannot be improved, and the preparation efficiency of the molecular distillation glycerin monostearate emulsifier is reduced.

In conclusion, the beneficial technical effects of the invention are as follows:

1. the alkalinity of the ionic liquid in the deacidification agent is utilized to be combined with free carboxylic acid in the molecular distillation glycerin monostearate, so that the acid value of the molecular distillation glycerin monostearate emulsifier is reduced, and the quality of the molecular distillation glycerin monostearate emulsifier is improved;

2. the modified citrus peel adsorbent and the alkaline microcrystalline cellulose powder are added according to a certain proportion to further adsorb and deacidify free carboxylic acid in the molecular distillation glyceryl monostearate, so that the effects of reducing the acid value of the molecular distillation glyceryl monostearate emulsifier and improving the quality of the molecular distillation glyceryl monostearate emulsifier are achieved;

3. by controlling the proportion of tetrabutyl phosphonium bromide, 1-ethyl-3-methylimidazole dimethyl phosphate and 1-butyl-3-methylimidazole dinitrile amine salt and controlling the addition amount of the modified citrus peel adsorbent and the alkaline microcrystalline cellulose powder, the effect of reducing the acid value of the molecular distillation glycerin monostearate emulsifier and reducing the cost is achieved;

4. the preparation temperature and the reaction time of the molecular distillation glyceryl monostearate emulsifier are controlled, so that the effect of improving the preparation efficiency while reducing the acid value of the molecular distillation glyceryl monostearate emulsifier is achieved.

Detailed Description

The present invention will be described in further detail with reference to examples.