阅读说明：本技术 一种糖液脱色有机酸脱色取代活性炭的功能树脂 (Functional resin for decolorizing sugar liquor by organic acid instead of activated carbon ) 是由 蒋岳峰 钱平 包孝林 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种糖液脱色有机酸脱色取代活性炭的功能树脂,涉及树脂领域,由如下重量份数的原料制成：铵盐A、铵盐B、季铵化溶剂、回流溶剂、钠盐水溶液20份、十二烷基苯磺酸钠0.5份、三羟甲基丙烷三甲基丙烯酸酯0.5～1份、三甲基戊烷0.5～1份和偶氮二异丁腈0.5～1份,制备方法如下：S1、准备铵盐A、铵盐B、季铵化溶剂及回流溶剂,并配置水相及油相；S2、将水相与油相混合反应。本发明的糖液脱色有机酸脱色取代活性炭的功能树脂对于糖液有较好的脱色能力及经济效应,相对于市售的常用同类产品而言,特色能力相仿,但价格较低,具有极好的经济效应；本发明的糖液脱色有机酸脱色取代活性炭的功能树脂在脱色领域中,再生后的脱色率保存程度好。(The invention discloses a functional resin for decolorizing sugar liquor by organic acid instead of activated carbon, which relates to the field of resin and is prepared from the following raw materials in parts by weight: the preparation method comprises the following steps of preparing ammonium salt A, ammonium salt B, a quaternization solvent, a reflux solvent, 20 parts of sodium salt aqueous solution, 0.5 part of sodium dodecyl benzene sulfonate, 0.5-1 part of trimethylolpropane trimethacrylate, 0.5-1 part of trimethylpentane and 0.5-1 part of azobisisobutyronitrile, wherein the preparation method comprises the following steps: s1, preparing ammonium salt A, ammonium salt B, a quaternization solvent and a reflux solvent, and preparing a water phase and an oil phase; and S2, mixing the water phase with the oil phase for reaction. The functional resin for decoloring the sugar solution by using the organic acid instead of the activated carbon has better decoloring capacity and economic effect on the sugar solution, has similar characteristic capacity but lower price and has excellent economic effect compared with the common similar products sold in the market; the functional resin for decoloring the sugar solution by using the organic acid instead of the activated carbon has good decoloring rate and preservation degree after regeneration in the field of decoloring.)

1. A functional resin for decolorizing sugar liquor by organic acid instead of activated carbon is characterized by being prepared from the following raw materials in parts by weight:

ammonium salt A, ammonium salt B, quaternization solvent, reflux solvent, 20 parts of sodium salt aqueous solution, 0.5 part of sodium dodecyl benzene sulfonate, 0.5-1 part of trimethylolpropane trimethacrylate, 0.5-1 part of trimethylpentane and 0.5-1 part of azobisisobutyronitrile.

2. The functional resin for decolorizing the organic acid-substituted activated carbon in sugar solution according to claim 1, characterized in that: the preparation method of the functional resin for decolorizing sugar liquor by organic acid and replacing activated carbon comprises the following steps:

s1, preparing ammonium salt A, ammonium salt B, a quaternization solvent and a reflux solvent, and preparing a water phase and an oil phase;

s2, mixing the water phase and the oil phase for reaction, reacting at 60-100 ℃ for 1-12 hours, reacting at 90-140 ℃ for 1-12 hours, cooling to room temperature, and extracting to complete resin preparation;

s3, mixing resin, ammonium salt A and a quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1 (1-10), carrying out quaternization reaction, controlling the reaction time to be 6-72 h, controlling the stirring speed to be 100-1000 rpm, and controlling the reaction temperature to be 50-200 ℃;

s4, mixing the resin after the quaternization reaction, the ammonium salt B and the quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1 (1-10), carrying out the quaternization reaction for the second time, controlling the reaction time to be 6-72 h, controlling the stirring speed to be 100-1000 rpm, and controlling the reaction temperature to be 50-200 ℃;

s5, adding a refluxing solvent into the resin undergoing the second quaternization reaction to promote the completion of the resin preparation.

3. The functional resin for decolorizing the organic acid-substituted activated carbon in sugar solution according to claim 1, characterized in that: the chemical formula of the ammonium salt A is one or a combination of a formula (1) or a formula (2), and the number of main chain carbon atoms is 10-30.

4. The functional resin for decolorizing the organic acid-substituted activated carbon in sugar solution according to claim 1, characterized in that: the structural formula of the resin is shown as formula (5), and p is a repeating unit value, and the value range is 1000-2000.

5. The functional resin for decolorizing the organic acid-substituted activated carbon in sugar solution according to claim 1, characterized in that: the quaternization solvent is an isopropyl ketone solvent, and the chemical formula of the quaternization solvent is shown as a formula (6).

6. The functional resin for decolorizing the organic acid-substituted activated carbon in sugar solution according to claim 1, characterized in that: the reflux solvent is a mixed solvent of isopropanol and acetonitrile.

7. The functional resin for decolorizing the organic acid-substituted activated carbon in sugar solution according to claim 1, characterized in that: the water phase preparation method comprises the step of mixing a sodium salt water solution and sodium dodecyl benzene sulfonate, wherein the sodium dodecyl benzene sulfonate accounts for 0.05-4% of the total amount.

8. The functional resin for decolorizing the organic acid-substituted activated carbon in sugar solution according to claim 1, characterized in that: the oil phase is prepared by mixing trimethylolpropane trimethacrylate, trimethylpentane and azobisisobutyronitrile.

Technical Field

The invention relates to the field of resin, in particular to functional resin for decoloring sugar liquor by organic acid instead of activated carbon.

Background

Ion exchange resins can be further classified into styrene resins and acrylic resins according to the types of the matrixes, the types of chemically active groups in the resins determine the main properties and types of the resins, and in practical use, the resins are often converted into other ion types for operation so as to meet various requirements.

The charcoal has low decolorizing power, is fine and sticky, is not easy to filter, leaves more residual acid, iron salt and calcium salt during carbon washing, seriously influences the quality and efficiency of sugar liquid production, and simultaneously has poor performance price ratio of other resin of the same type, so that the production cost cannot be reduced.

Disclosure of Invention

The invention aims to: in order to solve the problems of elimination of the existing sugar liquor decolorizing charcoal product and poor cost performance of the similar resin, a functional resin for decolorizing sugar liquor by organic acid instead of activated carbon is provided.

In order to achieve the purpose, the invention provides the following technical scheme: a functional resin for decolorizing sugar liquor by organic acid instead of activated carbon is prepared from the following raw materials in parts by weight: ammonium salt A, ammonium salt B, quaternization solvent, reflux solvent, 20 parts of sodium salt aqueous solution, 0.5 part of sodium dodecyl benzene sulfonate, 0.5-1 part of trimethylolpropane trimethacrylate, 0.5-1 part of trimethylpentane and 0.5-1 part of azobisisobutyric acid.

Preferably, the preparation method of the functional resin for decolorizing the sugar solution by using the organic acid and the substituted activated carbon comprises the following steps:

s1, preparing ammonium salt A, ammonium salt B, a quaternization solvent and a reflux solvent, and preparing a water phase and an oil phase;

s2, mixing the water phase and the oil phase for reaction, reacting at 60-100 ℃ for 1-12 hours, reacting at 90-140 ℃ for 1-12 hours, cooling to room temperature, and extracting to complete resin preparation;

s3, mixing resin, ammonium salt A and a quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1 (1-10), carrying out quaternization reaction, controlling the reaction time to be 6-72 h, controlling the stirring speed to be 100-1000 rpm, and controlling the reaction temperature to be 50-200 ℃;

s4, mixing the resin after the quaternization reaction, the ammonium salt B and the quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1 (1-10), carrying out the quaternization reaction for the second time, controlling the reaction time to be 6-72 h, controlling the stirring speed to be 100-1000 rpm, and controlling the reaction temperature to be 50-200 ℃;

s5, adding a refluxing solvent into the resin undergoing the second quaternization reaction to promote the completion of the resin preparation.

Preferably, the chemical formula of the ammonium salt A is one or a combination of formula (1) or formula (2), and the number of main chain carbon atoms is 10-30.

Preferably, the structural formula of the resin is shown as formula (5), and p is a repeating unit value and is in a range of 1000-2000.

Preferably, the quaternizing solvent is an isopropyl ketone solvent having the formula (6).

Preferably, the refluxing solvent is a mixed solvent of isopropanol and acetonitrile.

Preferably, the water phase preparation method is to mix the sodium salt water solution and sodium dodecyl benzene sulfonate, wherein the sodium dodecyl benzene sulfonate accounts for 0.05-4% of the total amount.

Preferably, the oil phase is trimethylolpropane trimethacrylate mixed with trimethylpentane and azobisisobutyronitrile.

Compared with the prior art, the invention has the beneficial effects that:

1. the functional resin for decoloring the sugar solution by using the organic acid instead of the activated carbon has better decoloring capacity and economic effect on the sugar solution, has similar characteristic capacity but lower price and has excellent economic effect compared with the common similar products sold in the market;

2. the functional resin for decoloring the sugar solution by using the organic acid instead of the activated carbon has better decoloring rate and preservation degree after regeneration in the field of decoloring.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

S1, same aqueous phase preparation method: 20 parts of sodium salt aqueous solution and 0.5 part of sodium dodecyl benzene sulfonate are mixed, wherein the sodium dodecyl benzene sulfonate accounts for 2.5 percent of the total amount.

S2, the same oil phase preparation method: 0.5 part of trimethylolpropane trimethacrylate is mixed with 0.5 part of trimethylpentane and 0.5 part of azobisisobutyronitrile.

S3, same refluxing solvent preparation: isopropanol and acetonitrile mixed solvent.

And S4, mixing the water phase and the oil phase for reaction, reacting at 70 ℃ for 11 hours, reacting at 120 ℃ for 10 hours, cooling to room temperature, and extracting to complete the resin preparation.

S5, mixing the resin, the ammonium salt A and the quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1:3, carrying out quaternization reaction, controlling the reaction time to be 48h, controlling the stirring speed to be 900rpm, and controlling the reaction temperature to be 160 ℃.

S6, adding a refluxing solvent into the resin undergoing the second quaternization reaction to promote the completion of the resin preparation.

Example 2

S1, same aqueous phase preparation method: 20 parts of sodium salt aqueous solution and 0.5 part of sodium dodecyl benzene sulfonate are mixed, wherein the sodium dodecyl benzene sulfonate accounts for 2.5 percent of the total amount.

S2, the same oil phase preparation method: 0.5 part of trimethylolpropane trimethacrylate is mixed with 0.5 part of trimethylpentane and 0.5 part of azobisisobutyronitrile.

S3, same refluxing solvent preparation: isopropanol and acetonitrile mixed solvent.

And S4, mixing the water phase and the oil phase for reaction, reacting at 70 ℃ for 2 hours, reacting at 120 ℃ for 10 hours, cooling to room temperature, and extracting to complete the resin preparation.

S5, mixing the resin, the ammonium salt A and the quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1:3, carrying out quaternization reaction, controlling the reaction time to be 48h, controlling the stirring speed to be 900rpm, and controlling the reaction temperature to be 160 ℃.

S6, adding a refluxing solvent into the resin undergoing the second quaternization reaction to promote the completion of the resin preparation.

Example 3

S1, same aqueous phase preparation method: 20 parts of sodium salt aqueous solution and 0.5 part of sodium dodecyl benzene sulfonate are mixed, wherein the sodium dodecyl benzene sulfonate accounts for 2.5 percent of the total amount.

S2, the same oil phase preparation method: 0.5 part of trimethylolpropane trimethacrylate is mixed with 0.5 part of trimethylpentane and 0.5 part of azobisisobutyronitrile.

S3, same refluxing solvent preparation: isopropanol and acetonitrile mixed solvent.

And S4, mixing the water phase and the oil phase for reaction, reacting at 90 ℃ for 10 hours, then reacting at 100 ℃ for 10 hours, cooling to room temperature, and extracting to complete the resin preparation.

S5, mixing the resin, the ammonium salt A and the quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1:3, carrying out quaternization reaction, controlling the reaction time to be 48h, controlling the stirring speed to be 900rpm, and controlling the reaction temperature to be 160 ℃.

S6, adding a refluxing solvent into the resin undergoing the second quaternization reaction to promote the completion of the resin preparation.

Example 4

S1, same aqueous phase preparation method: 20 parts of sodium salt aqueous solution and 0.5 part of sodium dodecyl benzene sulfonate are mixed, wherein the sodium dodecyl benzene sulfonate accounts for 2.5 percent of the total amount.

S2, the same oil phase preparation method: 0.5 part of trimethylolpropane trimethacrylate is mixed with 0.5 part of trimethylpentane and 0.5 part of azobisisobutyronitrile.

S3, same refluxing solvent preparation: isopropanol and acetonitrile mixed solvent.

And S4, mixing the water phase and the oil phase for reaction, reacting at 70 ℃ for 10 hours, reacting at 120 ℃ for 10 hours, cooling to room temperature, and extracting to complete the resin preparation.

S5, mixing the resin, the ammonium salt A and the quaternization solvent, wherein the ratio of the resin to the ammonium salt A is 1:3, carrying out quaternization reaction, controlling the reaction time to be 48h, controlling the stirring speed to be 200rpm, and controlling the reaction temperature to be 160 ℃.

S6, adding a refluxing solvent into the resin undergoing the second quaternization reaction to promote the completion of the resin preparation.

Example 5

The same sugar solution was thoroughly mixed and then divided into 6 portions on average, and the respective resins obtained in examples 1, 2, 3 and 4 of the present invention were decolorized, and the decolorization ratios were measured with reference to commercially available resins D319 and DM-301 and activated carbon, and the results are shown in Table 1.

Table 1 comparison of the resins from examples 1, 2, 3 and 4 with commercially available resins and activated carbon results:

as can be seen from Table 1, the decolorization effect of the resins prepared in examples 1 and 3 of the present invention on sugar solution is similar to that of commercial resins D318, DM-301 and AB-8, and the decolorization rates are all over 91%, the decolorization rate of the resin prepared in example 1 of the present invention on sugar solution after primary regeneration is still over 91%, the decolorization rate after secondary regeneration is still over 90%, while the decolorization rate of the activated carbon is highest in the primary use, the decolorization rate after the primary regeneration is only 80.3 percent and is far lower than that of the products in examples 1 and 3 and the products sold in the market, and the decolorization rate after the secondary regeneration is far lower than that of all resin products, thus, the resin prepared in example 1 of the present invention has decolorization ability similar to commercial resin, but has good reproducibility, long service life, and good economic effect, compared with the active carbon, the material can be repeatedly used, saves cost, protects the environment and can replace the active carbon product.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.