阅读说明：本技术 一种应用松香基阴离子大孔吸附树脂去除糖浆中色素的方法 (Method for removing pigment in syrup by using rosin-based anion macroporous adsorption resin ) 是由 李文 鄂羽羽 雷福厚 李�浩 程格格 孙耀 谢文博 杨建林 丁猛 于 2019-10-29 设计创作，主要内容包括：本发明公开一种应用松香基阴离子大孔吸附树脂去除糖浆中色素的方法,属于糖浆的精制技术领域。本发明将松香基阴离子大孔吸附树脂加入糖浆中,采用静态吸附法,松香基阴离子大孔吸附树脂用量控制在0.01-0.5g·mL<Sup>-1</Sup>,温度为30-80℃,吸附时间为0.5-24h,对糖浆中的色素有较好的去除效果,对糖浆中色素的去除率可达到90％以上。吸附饱和后的松香基阴离子大孔吸附树脂经洗涤,再生,树脂可以重复使用,安全,环保,无毒,成本低,适合推广应用。(The invention discloses a method for removing pigment in syrup by using rosin-based anionic macroporous adsorption resin, belonging to the technical field of syrup refining. The invention adds rosin-based anion macroporous adsorption resin into syrup, adopts a static adsorption method, and controls the dosage of the rosin-based anion macroporous adsorption resin to be 0.01-0.5 g.mL ‑1 The temperature is 30-80 ℃, the adsorption time is 0.5-24h, the pigment in the syrup is well removed, and the removal rate of the pigment in the syrup can reach more than 90%. The rosin-based anion macroporous adsorption resin after saturated adsorption is washed and regenerated, and the resin can be reused, is safe, environment-friendly, non-toxic, low in cost and suitable for popularization and application.)

1. A method for removing pigment in syrup by using rosin-based anionic macroporous adsorption resin is characterized in that the method is to add the rosin-based anionic macroporous adsorption resin into the syrup and adopt a static adsorption method, and the dosage of the rosin-based anionic macroporous adsorption resin is controlled to be 0.01-0.5 g.mL^-1The temperature is 30-80 ℃, and the adsorption time is 0.5-24 h; the structural formula of the rosin-based anion macroporous adsorption resin is as follows:

wherein R is:

2. the method for removing pigment in syrup by using the rosinyl anion macroporous adsorption resin as claimed in claim 1, wherein the method is to add the rosinyl anion macroporous adsorption resin into the syrup by a static adsorption method, and the dosage of the rosinyl anion macroporous adsorption resin is controlled to be 0.1-0.3 g-mL^-1The temperature is 50-70 ℃, and the adsorption time is 5-10 h.

3. Use of rosin-based anions according to claim 2The method for removing pigment in syrup by using macroporous adsorption resin is characterized in that the method is that rosin-based anion macroporous adsorption resin is added into syrup, a static adsorption method is adopted, and the dosage of the rosin-based anion macroporous adsorption resin is controlled to be 0.2 g/mL^-1The temperature is 60 ℃, and the adsorption time is 6 h.

4. The method for removing pigment in syrup by using the rosin-based anionic macroporous adsorption resin as claimed in any one of claims 1 to 3, wherein the rosin-based anionic macroporous adsorption resin is a spherical porous material with an average pore diameter of 10 to 35nm and a specific surface area of 10 to 20m²/g。

5. The method for removing pigment in syrup by using the rosin-based anionic macroporous adsorption resin as claimed in any one of claims 1 to 3, wherein the removal rate of the rosin-based anionic macroporous adsorption resin on the pigment in the syrup is 80% or more.

Technical Field

The invention belongs to the technical field of syrup refining, and particularly relates to a method for removing pigment in syrup by using rosin-based anionic macroporous adsorption resin.

Background

In the production of sucrose, the color value of sugar is an important indicator. When the sugar juice is evaporated and concentrated at high temperature, reducing sugar and amino acid can continuously generate Maillard reaction to produce melanoidin pigment, so that the color value of the sugar juice is increased. The melanoidins produced remain in the crystals during sucrose crystallization, resulting in a higher color value of granulated sugar. Therefore, there is a need to remove melanoidin pigment from syrup.

The methods commonly used in the sugar industry to remove melanoidin pigment at present mainly include:

1. heiguan, Liangxianhui, etc., the influence of clarification process conditions of a sulfurous method cane sugar factory on the phenol removal and decoloration effects of cane juice [ J ] food industry 2015, 112-115, wherein the sulfurous method is used for cane juice clarification.

2. Living, ceramic membrane filtration behavior mechanism and key problem study of sugarcane mixed juice clarification [ D ] university of cantonese, 2018: 116, 141, wherein use of ceramic membranes to remove pigments from syrups is mentioned.

3. Chinese patent 102020745B discloses a novel acrylic acid series decolorizing resin and a preparation method thereof, vinyl pyridine monomer and aliphatic unsaturated ester monomer are adopted, polyvinyl monomer is taken as cross-linking agent, suspension polymerization is carried out in the presence of pore-forming agent to obtain white spheres, the obtained white spheres and polyethylene polyamine are subjected to aminolysis reaction to introduce amido, the obtained amine spheres and monomer containing alcoholic hydroxyl are reacted under alkaline condition to obtain the acrylic acid series ion exchange decolorizing resin, and the resin has the properties of strong base resin containing pyridine group and weak base resin. However, the raw materials are mainly pyridine compounds, have certain carcinogenicity and potential food safety hazards, and are difficult to separate in food grade.

Luo J, Hang X, et al, refining sugar juice by an integrated Membrane process, Filtration behavor of polymeric Membrane at high brightness and [ J ] Journal of Membrane Science,2016,509:105 and 115, wherein the use of polymeric membranes to remove pigments from sugarcane juice is mentioned.

Although the membrane technology can retain nearly 100% of suspended impurities and most of pigments in the cane juice, the retention rate of the membrane technology to reducing sugar and amino acid in the cane juice is low, so that the reducing sugar and the amino acid continuously undergo Maillard reaction in the subsequent process of the cane juice, the color value of the cane juice is increased again, and in addition, the problems of membrane pollution, high production cost and the like are difficult to solve, so that the membrane technology is rarely used. Therefore, the macroporous adsorption resin method is gradually paid attention to in the sugar industry, and the macroporous adsorption resin method utilizes exchange groups and abundant pore structures of the resin for adsorption and exchange. However, at present, no adsorption resin which is safe and environment-friendly and has an obvious effect of removing pigments in syrup exists, so that an adsorption resin which is safer and environment-friendly and has better adsorption performance is needed to be found for removing the pigments in the syrup.

Disclosure of Invention

Aiming at the problems, the invention provides a method for removing pigment in syrup by using rosin-based anionic macroporous adsorption resin, which is safe and environment-friendly and has obvious effect of removing pigment in syrup.

The invention is realized by the following technical scheme:

a method for removing pigment from syrup by using rosin-based anionic macroporous adsorption resin comprises the steps of adding the rosin-based anionic macroporous adsorption resin into the syrup, and adopting a static adsorption method, wherein the dosage of the rosin-based anionic macroporous adsorption resin is controlled to be 0.01-0.5 g/mL^-1The temperature is 30-80 ℃, and the adsorption time is 0.5-24 h; the structural formula of the rosin-based anion macroporous adsorption resin is as follows:

wherein R is:

the static adsorption method is a method in which a certain amount of adsorbent and a certain amount of solution are brought into sufficient contact for a long time to reach equilibrium; the static adsorption method is a method for balancing a certain amount of rosin-based anion macroporous adsorption resin and a certain amount of syrup by fully contacting for a long time.

Preferably, the method adopts a static adsorption method by adding the rosin-based anion macroporous adsorption resin into the syrup, and the dosage of the rosin-based anion macroporous adsorption resin is controlled to be 0.1-0.3 g/mL^-1The temperature is 50-70 ℃, and the adsorption time is 5-10 h.

Preferably, the method adopts a static adsorption method by adding the rosin-based anion macroporous adsorption resin into the syrup, and the dosage of the rosin-based anion macroporous adsorption resin is controlled to be 0.2 g/mL^-1The temperature is 60 ℃, and the adsorption time is 6 h.

Preferably, the rosin-based anion macroporous adsorption resin is a spherical porous material, the average pore diameter of the rosin-based anion macroporous adsorption resin is 10-35nm, and the specific surface area of the rosin-based anion macroporous adsorption resin is 10-20m²/g。

The rosin-based anion macroporous adsorption resin is prepared by adopting the patent technology 'rosin-based anion macroporous adsorption resin and a preparation method thereof' which is applied by the applicant on the same day.

The rosin-based anion macroporous adsorption resin has a removal rate of more than 80% to pigment in syrup.

The rosin-based anion macroporous adsorption resin can be repeatedly used, and comprises the following steps: washing the rosin-based anionic macroporous adsorption resin which is adsorbed and saturated in the syrup by using water to remove residual syrup and impurities, then converting the resin into an anionic type by using a 2% NaOH solution, and washing the rosin-based anionic macroporous adsorption resin by using water until the rosin-based anionic macroporous adsorption resin is close to neutral.

The adsorption and regeneration principle of the rosin-based anion macroporous adsorption resin is as follows:

(1) the adsorption process of the resin is as follows:

R(OH^-)+R₁ ^-→R₂R₁ ^-+OH^-；

(2) the regeneration process of the resin comprises the following steps: r₂R₁ ^-+OH^-→R(OH^-)+R₁ ^-(ii) a Wherein R is₁ ^-Representing negatively charged pigment molecules.

The resin adsorption process mainly comprises the following steps: functional group-N on resin⁺(CH₃)₃OH^-With pigment molecules R₁ ^-Ion exchange takes place. After the resin is adsorbed and saturated, the resin is converted into anion by using 0.01-5% NaOH solution, and can be recycled.

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

(1) the rosin-based anion macroporous adsorption resin is a polyester polymer material synthesized by taking rosin as a raw material, has the performance of complete biodegradation, is green and environment-friendly in the process of removing pigments in syrup, has the characteristic of no toxicity, and is suitable for being used in syrup; and the mechanical strength is high, the pressure resistance is strong, the cost is low, and the application prospect is good.

(2) The rosin-based anion macroporous adsorption resin applied by the invention has a good removal effect on pigments in syrup, and the removal rate of the pigments in the syrup is more than 80%. The rosin-based anion macroporous adsorption resin after saturated adsorption can be reused after being washed and regenerated, the adsorption capacity of the rosin-based anion macroporous adsorption resin on pigment in syrup can still reach more than 56% after 10 times of repeated use, and the application prospect is good.

(3) When the adding amount of the rosin-based anion macroporous adsorption resin is controlled to be 0.1-0.3 g/mL^-1The temperature is 50-70 ℃, the adsorption time is 5-10h, the removal effect on the pigment in the syrup is good, and the removal rate can reach more than 90%; particularly when the adding amount of the rosin-based anion macroporous adsorption resin is controlled to be 0.2 g/mL^-1The temperature is 60 ℃, the adsorption time is 6h, and the adsorption time is 6h for syrupThe pigment removal effect is best, and the removal rate can reach 92.25%.

Drawings

FIG. 1 is a graph showing the result of the reusability of rosin-based anionic macroporous adsorbent resin for removing pigments from syrup in example 9 of the present invention;

FIG. 2 is a graph showing the effect of the rosin-based anionic macroporous adsorbent resin on the dynamic adsorption performance of syrup for removing pigments in the syrup according to example 10 of the present invention.

Detailed Description

The present invention will be described in further detail with reference to the following description of specific embodiments and accompanying drawings, but the present invention is not limited thereto.

The structural formula of the rosin-based anion macroporous adsorption resin used in the invention is as follows:

wherein R is:

the average pore diameter of the rosin-based anion macroporous adsorption resin is 10-35nm, and the specific surface area is 10-20m²(ii) in terms of/g. The rosin-based terpolymer is prepared by a patent technology of a rosin-based terpolymer and a preparation method thereof which is disclosed by the applicant on the same day.