阅读说明：本技术 一种磷酸/过氧化氢溶液处理杜仲果壳提取杜仲胶的方法 (Method for extracting gutta-percha by treating eucommia ulmoides nutshells with phosphoric acid/hydrogen peroxide solution ) 是由 刘桂萍 方庆红 许振川 于 2019-10-11 设计创作，主要内容包括：一种磷酸/过氧化氢溶液处理杜仲果壳提取杜仲胶的方法。该方法将杜仲果壳机械碾压破碎,去除杜仲果壳边缘等非胶部分,筛上部分用磷酸/过氧化氢混合液加热处理去除果壳组织细胞中的木质素、半纤维素和其他可溶性成分,然后对处理后的原料用石油醚进行提取杜仲胶。筛下部分及经磷酸/过氧化氢处理后的滤液和提胶后的残渣可以用于制备饲料添加剂。本方法可以高效地提取杜仲果壳中的杜仲胶,工艺简单,耗时短；所用磷酸和过氧化氢无毒、无污染；提胶过程中产生的废渣、废液中含有杜仲果壳中的一些营养成分,可用于制备饲料添加剂,真正实现了杜仲资源的综合利用。(A method for extracting gutta Percha from Eucommiae cortex shell by phosphoric acid/hydrogen peroxide solution treatment is provided. The method comprises the steps of mechanically grinding and crushing eucommia ulmoides shells, removing non-glue parts such as edges of the eucommia ulmoides shells, heating the oversize parts by using a phosphoric acid/hydrogen peroxide mixed solution to remove lignin, hemicellulose and other soluble components in shell tissue cells, and extracting eucommia ulmoides glue from the treated raw materials by using petroleum ether. The sieved part, the filtrate after phosphoric acid/hydrogen peroxide treatment and the residue after gum extraction can be used for preparing feed additives. The method can efficiently extract the gutta-percha in the eucommia ulmoides nutshell, and has simple process and short time consumption; the used phosphoric acid and hydrogen peroxide are nontoxic and pollution-free; the waste residue and waste liquid generated in the process of extracting the gel contain some nutrient components in the eucommia ulmoides shell, can be used for preparing feed additives, and really realizes the comprehensive utilization of eucommia ulmoides resources.)

1. A method for extracting gutta-percha by treating eucommia ulmoides nutshells with phosphoric acid/hydrogen peroxide solution is characterized by comprising the following preparation processes:

(1) peeling kernels and crushing: shelling the eucommia key fruit with a sheller, collecting shells, mechanically grinding and crushing the shells into floccules, screening the floccules through a 20-mesh screen, removing non-glue parts such as the edges of the eucommia shells, and collecting the parts above the screen and below the screen for later use;

(2) oxidation and extraction: adding a phosphoric acid/hydrogen peroxide mixed solution into the oversize part according to a material-liquid ratio of 1: 8-10, heating to remove lignin, hemicellulose and other soluble components in eucommia ulmoides nutshell tissue cells, and filtering to obtain filter residues and filtrate for later use;

(3) rinsing and drying: washing the filter residue after the oxidation and extraction treatment in the step (2) to neutrality and drying at 50 ℃;

(4) extracting glue: adding the filter residue obtained in the step (3) into the mixture with the boiling range of 60⁰C~90⁰Heating the petroleum ether of C to extract the gutta-percha, filtering while the gutta-percha is hot to obtain filtrate and filter residue, and carrying out secondary gel extraction on the filter residue;

(5) freezing and separating gel: cooling the filtrate obtained in the step (4), freezing at-18-0 ℃ for 1-2 hours, and separating out white filamentous gutta-percha; filtering, drying to obtain gutta-percha, and using the filtrate (petroleum ether) for secondary extraction of the filter residue in the step (4);

(6) and (3) mixing the sieved part in the step (1), the filtrate in the step (2) and the filter residue obtained by secondary gel extraction to prepare the eucommia feed additive.

2. The method for extracting gutta-percha by treating eucommia ulmoides nutshell with phosphoric acid/hydrogen peroxide solution according to claim 1, wherein the concentration of phosphoric acid used in the step (2) is 3%, the concentration of hydrogen peroxide is 2% -3%, the volume ratio of the phosphoric acid to the hydrogen peroxide is 1: 2-4, the oxidation extraction temperature is 70%⁰C~ 80⁰And C, the treatment time is 1 hour.

3. The method for extracting gutta-percha by treating eucommia ulmoides oliv shells with phosphoric acid/hydrogen peroxide solution according to claim 1, wherein the ratio of the filter residue in the step (4) to the petroleum ether is 1: 30-50, and the extraction temperature is 80%⁰C ~85⁰C, extracting for 2 hours.

Technical Field

The invention relates to a method for extracting gutta-percha, in particular to a method for extracting gutta-percha by treating eucommia ulmoides shells with phosphoric acid/hydrogen peroxide solution.

Background

Eucommia ulmoides (eucommia ulmoides)Eucommia ulmoidc.s) Is a eucommia plant, is a unique rare medicinal material and woody oil plant in China. Eucommia bark is treasure throughout the body, and the bark, flower, fruit, leaf and the like have high edible and medicinal values. At present, eucommia seed oil and eucommia male flower are used as new resource food raw materials and are approved by the nation, and eucommia leaves are also approved to be listed as medicine of the nationFood homology directory ". In addition, eucommia ulmoides can enhance the immunity of poultry and livestock and improve the characteristics of meat quality and flavor, and realizes nonreactive cultivation, and eucommia ulmoides is listed in feed additive variety catalog (2013) by Ministry of agriculture in 2013. Meanwhile, eucommia ulmoides is a high-quality glue source tree species next to the Brazilian rubber tree. The root, stem, leaf, pericarp and other parts of eucommia ulmoides contain eucommia ulmoides rubber, wherein the gel content of the pericarp is 15% -18%. There are various methods for extracting gutta-percha from leaves, skins and fruits, such as alkaline leaching, solvent method, microbial fermentation or enzymolysis. Wherein, the alkaline leaching method is to use an alkaline hydrolysis method to destroy lignin of cell walls so as to expose the cellosilk. Chinese patent application CN86100216 discloses a method for extracting gutta-percha from folium Eucommiae or cortex Eucommiae, which comprises washing folium Eucommiae or cortex Eucommiae, fermenting, steaming with NaOH water solution, rinsing, crushing with hydraulic breaker, and sieving and rinsing to obtain gutta-percha. The alkaline leaching method consumes large amount of NaOH, which causes high cost and environmental pollution, and the gutta percha silk has large loss and low yield. The solvent method can adopt different organic solvents to extract the gutta-percha, and improves the dissolution and the dispersibility of the gutta-percha in the solvent by utilizing the solubility of the organic solvents to the gutta-percha, so that the gutta-percha penetrates through a cell wall fiber layer and diffuses into the solvent to be dissolved out. Chinese patent application CN92114760.0 discloses a method for extracting gutta-percha, which comprises grinding the non-gel-containing components on the surface of the leaves of eucommia ulmoides by a roller method to expose the gel-containing tissues in the leaves, achieving the purpose of enriching the gel-containing tissues, collecting the effective gel-containing parts by a sieve, extracting crude gel by organic solvents (toluene, benzene, dichloroethane, petroleum ether), and purifying by common organic solvents (alcohol, ketone, ether, aldehyde, ester). Chinese patent application CN200610051265.X discloses a method for extracting gutta-percha by solvent circulation, which takes petroleum ether with the boiling range temperature of 60-900C as a solvent to extract the gutta-percha from eucommia leaves or eucommia bark. The solvent method has the advantages of high purity of the gutta-percha, but also has the defects that the moistening and swelling effect of the organic solvent on cell walls is limited, the cell walls can obstruct the leaching of the gutta-percha, the dissolution of the gutta-percha is reduced, and the adopted organic solvent has toxicity, harm to human bodies, poor safety and the like. The microbial fermentation or enzymolysis method isThe cellulose of the cell wall is degraded, so that the cell wall is loosened, thereby being beneficial to dissolving out the gutta percha. Chinese patent application CN 201O 10252992.9 discloses a method for extracting gutta-percha from the sprouting branch bark of a eucommia ulmoides leaf forest, wherein trichoderma viride obtained by screening humus in a eucommia ulmoides forest area is utilized to ferment eucommia ulmoides bark under the optimal culture condition, and then a high-pressure water gun is utilized to wash and remove impurities to obtain the gutta-percha. Chinese patent application CN201210307947.8 discloses a method for extracting gutta-percha by enzymolysis, which comprises performing enzymolysis on one of eucommia bark, eucommia leaf or eucommia wing peel with complex enzyme of cellulase, pectinase and protease, filtering the mixture after enzymolysis, and extracting gutta-percha. Although the microbial fermentation method or the enzymolysis method does not adopt toxic organic solvents, the method also has the defects of long fermentation time and high cost. Because the traditional alkaline leaching method, the traditional solvent method and the traditional microbial fermentation or enzymolysis method are not satisfactory, the methods are improved by various colleges, scientific research institutions and enterprises at present, so that the use amount of an organic solvent is reduced, the fermentation time is shortened, and the like, so that the yield of the gutta percha is improved, the cost is reduced, and the environment is protected. The hydrogen peroxide can be decomposed into hydroperoxide anions (HOO) by heating⁻) Hydroxyl radical (HO. cndot.) and superoxide anion radical (O)₂ ⁻Cndot.). It has been reported that aryl ether linkages, lignin rings, alkenyl groups, carbonyl compounds and other linkages can be generated from HOO by decomposition of hydrogen peroxide⁻(Strong nucleophiles) and HO, O²⁻(active radical) cleavage. Thus, part of the lignin may follow H₂O₂And is degraded. On the other hand, hemicellulose may be more easily destroyed during acidic pretreatment. Therefore, the eucommia ulmoides nutshell can be treated by using the mixed liquid of phosphoric acid and hydrogen peroxide, so that components such as lignin, hemicellulose and the like in the eucommia ulmoides histocyte structure are removed, the cell wall structure is damaged, and the dissolution of gutta-percha is facilitated. Meanwhile, the leaves, the bark and the fruits of eucommia ulmoides oliv also contain rich nutrient components besides the gutta percha, and the green and environment-friendly gutta percha extraction process can utilize waste residues and waste liquid generated in the gum extraction process, such as production of eucommia ulmoides oliv feed additives, addition of concentrated feed or green mixingThe stored feed is fermented together to prepare antibiotic-free feed and the like, so that the waste of eucommia ulmoides resources is avoided, and the comprehensive utilization of the eucommia ulmoides resources is realized.

Disclosure of Invention

The invention aims to provide a method for extracting gutta-percha by treating eucommia ulmoides shells with a phosphoric acid/hydrogen peroxide solution.

The purpose of the invention is realized by the following technical scheme:

a method for extracting gutta-percha by treating eucommia ulmoides nutshell with phosphoric acid/hydrogen peroxide solution comprises the following preparation processes:

(1) peeling kernels and crushing: shelling the eucommia key fruit with a sheller, collecting shells, mechanically grinding and crushing the shells into floccules, screening the floccules through a 20-mesh screen, removing non-glue parts such as the edges of the eucommia shells, and collecting the parts above the screen and below the screen for later use;

(2) oxidation and extraction: adding a phosphoric acid/hydrogen peroxide mixed solution into the oversize part according to a material-liquid ratio of 1: 8-10, heating to remove lignin, hemicellulose and other soluble components in eucommia ulmoides nutshell tissue cells, and filtering to obtain filter residues and filtrate for later use;

(3) rinsing and drying: washing the filter residue after the oxidation and extraction treatment in the step (2) to neutrality and drying at 50 ℃;

(4) extracting glue: adding the filter residue obtained in the step (3) into the mixture with the boiling range of 60⁰C~90⁰Heating the petroleum ether of C to extract the gutta-percha, filtering while the gutta-percha is hot to obtain filtrate and filter residue, and carrying out secondary gel extraction on the filter residue;

(5) freezing and separating gel: cooling the filtrate obtained in the step (4), freezing at-18-0 ℃ for 1-2 hours, and separating out white filamentous gutta-percha; filtering, drying to obtain gutta-percha, and using the filtrate (petroleum ether) for secondary extraction of the filter residue in the step (4);

(6) and (3) mixing the sieved part in the step (1), the filtrate in the step (2) and the filter residue obtained by secondary gel extraction to prepare the eucommia feed additive.

The method for extracting gutta-percha by treating eucommia ulmoides shells with phosphoric acid/hydrogen peroxide solution comprises the following steps of (2) using 3% of phosphoric acid and 2% -3% of hydrogen peroxide according to the volume ratio of 1: 2-4, and oxidizing and extracting at the temperature of 70%⁰C~ 80⁰And C, the treatment time is 1 hour.

The method for extracting gutta-percha by treating eucommia ulmoides nutshells with phosphoric acid/hydrogen peroxide solution comprises the step (4) of mixing filter residue with petroleum ether according to the material-liquid ratio of 1: 30-50, and the extraction temperature is 80⁰C ~85⁰C, extracting for 2 hours.

The invention has the advantages and effects that:

according to the invention, the eucommia ulmoides nutshell is treated by using the mixed liquid of phosphoric acid and hydrogen peroxide, so that components such as lignin, hemicellulose and the like in the eucommia ulmoides tissue cell structure can be well removed, the cell wall structure is damaged, and the dissolution of gutta percha is facilitated. The method can efficiently extract the gutta-percha in the eucommia ulmoides nutshell, and has simple process and short time consumption; the used phosphoric acid and hydrogen peroxide are nontoxic and pollution-free; the waste residue and waste liquid generated in the process of extracting the gel contain some nutrient components in the eucommia ulmoides shell, can be used for preparing feed additives, and really realizes the comprehensive utilization of eucommia ulmoides resources.

Detailed Description

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

The crushed and crushed eucommia ulmoides shell is from biological limited.