CN105111256A - Integrated extracting and purifying method for active ingredients of apple pomace - Google Patents

Abstract

Based on the fact of the apple industry and the agricultural production in China, the integrated extracting and purifying method for active ingredients of apple pomace, according to the social demands and the self-research conditions, positively responses to the national policy to call for the spread of a recycling economy development model of resource-product-waste-resource for the apple residue resource current situation, constructs a chain circuit economic structure, performs integrated extraction and purification of biological wax, pectin, microcrystalline cellulose, apple polysaccharide, apple acid, apple polyphenol, phloridzin and phloretin from the apple pomace, namely the apple functional components, and overcomes the shortcoming of ''selecting the general and discarding the essence'' of the traditional extraction.

Description

The integrated extracting and purifying method of apple residue effective constituent

Technical field

The present invention relates to the integrated extracting and purifying method of apple residue effective constituent.

Background technology

China is world's apple production first big country, planting scale and ultimate production account for 1/3 of the total production level of world's apple, Jin Nianlai China cultivated area of the apple more than 4,000 ten thousand mu, output reaches more than 3,000 ten thousand tons, account for the over half of world's gross production, outlet concentrated Succus Mali pumilae, more than 700,000 tons, accounts for more than 70% of world's concentrated apple slag volume of trade, all has obvious comparative advantages in all many-sides.The resources advantage of China's apple is processing concentrated Succus Mali pumilae to the main path that economic advantages transform, and annual production surpasses 800,000 tons, and accounting for nearly the last 1/2 of world's fruit juice concentrate ultimate production and volume of trade, occupies first place in the world in position.In recent years China steps larger paces in fruit preliminary working, the existing juice production enterprise in the whole nation surpasses 70, annual working ability surpasses 4,000,000 tons, and for the inferior fruit of numerous orchard workers have found outlet, its processing fent peel residue accounts for the 20-25% of amount of finish, peel residue moisture content 65-80%, carbohydrate 9-22%, robust fibre 4-10%, protein 11.8%, pectin substance 1.5-2.5% is of great value renewable resource.But compared with developed countries, the comprehensive utilization ratio of China's apple processing industry is also very low, and the recycling of apple residue is particularly outstanding, governs the development of China's Apple Industry to a certain extent.As apple production processing big country, China all can have more than 200 ten thousand tons of apple residues to produce every year, and except small part is used as except feed through roughing, major part abandons as waste and causes the serious wasting of resources and environmental pollution.Simple owing to processing, can only squeezing juice, many effective constituent compositions in apple are not used, and cause the wasting of resources, the useless pomace after squeezing the juice cannot process, and causes large-scale pollution.Domestic and international people in the industry evaluates domestic existing apple processing and deep processing is " get it general, abandon its elite ", and this not only wastes precious resource, also causes huge financial loss.Apple residue has the features such as cost is low, nutritious, harmful toxic matter content is low, can improve the additional output value, alleviate environmental pollution after deep processing, improves Business Economic Benefit, has very large development potentiality.Along with developing rapidly of fruit processing industry, the apple peel that regeneration is discarded in a large number has become a problem urgently studied.Apple peel regeneration approach, one is its chemical composition of extracting directly; Two is utilize its nutritive ingredient as substratum, through fermentable.In recent years, the and then inexhaustible expansion of China's cultivated area of the apple, apple production increases year by year, and apple processing also more and more receives the concern of people, has become investigation popular.

Carry out economical utilizing about apple research; for quickening apple residue commercial development paces, extend apple processing chain; increase apple processing enterprise profit; increase peasant economy income; be conducive to the level of comprehensive utilization greatly improving apple; protection of the environment; promote that Apple Industry changes to mass type and profit evaluation model; be conducive to the Sustainable development of Apple Industry; improve the added value of apple raw material; be conducive to increasing economic efficiency and ecological benefits, to creating policy civilized society, there is far-reaching realistic meaning and social effect.

1. apple wax apple wax is one deck wax being present in apple epidermis, in faint yellow, primarily of material compositions such as wax ester, hydrocarbon polymer, free fatty acidies, can be used for manufacturing special makeup, also may be used for food product pack, wax-pattern lubricant, rumbling compound etc.Experiment shows that the sealing process of apple wax to moisture of skin and the provide protection to protein are better than most plant and synthetic wax, and as beeswax, coffin palmitic acid wax, lanolin, this shows that apple wax is good skin care product and treatment.

Wang Youqiong; Duan Qiongfen; Zhao Hong etc. report in " green product-biological wax " animal wax and vegetable wax also known as be biological wax; majority is the nutrient reserve of bio secretion in external Protective substances or organism; do not contain hazardous substance; be a kind of green product of pure natural, be widely used in the aspects such as floor wax, automobile polish, medicine.Biological wax product is not only safeguard oneself healthy, or a kind of identity and status symbol.In daily life, play irreplaceable vital role, can be rated as the present that nature gives the portion preciousness of the mankind, compared with synthetic wax, prices are rather stiff for they.

2. apple pectin (Applepectin) molecular formula: C ₄₇h6 ₈o ₁₆, molecular weight: 889.0332, CASNo.124843-18-1, English name: 7, 11:11, 14:16, 19:20, 25:22, 25:26, 29-Hexaepoxy-12H-furo [3, 2-b] oxacyclotetratriacontin-22 (13H)-carboxylicacid, 2, 3, 3a, 5, 6, 7, 8, 9, 10, 14, 1516, 17, 18, 19, 20, 21, 23, 24, 26, 27, 28, 29, 30, 31, 35a-hexacosahydro-15-hydroxy-6, 16, 29, 31, 33-pentamethyl-5, 18-dioxo-2-[(2S, 3R, 4R)-tetrahydro-2, 3-dihydroxy-4-methyl-2H-pyran-2-yl]-, (2S, 3aR, 6R, 7S, 11R, 14S, 15S, 16R, 19R, 20R, 22S, 25S, 26R, 29R, 31R, 32E, 34, 35aR)-.Structural formula is as follows:

Pectin is a kind of poly-polysaccharide of acidity height be made up of galacturonic acid, semi-lactosi and pectinose etc. in plant, and be generally white to pale yellow powder, have water-soluble, molecular weight is about 5-30 ten thousand, is present in cell walls and the cell internal layer of plant.Pectin has good gelationization and stable emulsifying effect, has been widely used in food, medicine, daily use chemicals and textile industry.Food is done jelling agent, thickening material, stablizer, suspension agent, emulsifying agent, flavouring synergistic agent, to protection skin, prevents ultraviolet radiation, treatment wound, beautifying face and moistering lotion all deposits certain effect.Different vegetables, fruit mouthfeel is had any different, and the difference of the pectin content mainly contained by them and pectin molecule determines.Can be divided into homogeneity polysaccharide and mixed polysaccharide by the composition of pectin, the pectin of different sources, its ratio is also each variant.In natural pectin, the carboxyl of about 20-60% is esterified, and molecular weight is 2-4 ten thousand.Its extraction changes insoluble pectin in peel residue into soluble pectin, and soluble pectin is separated to liquid phase transfer.China starts pectin production and research from the beginning of the seventies, and within 1981, international food and agricultural organization is classified as the foodstuff additive not having every day intake to limit.Apple residue pectin content is at 10-15%.Utilize apple residue to extract pectin, only have Denmark CPKELCO and DENISCO company in the world, German H & F company, OBIPEKTINAG company of Switzerland and CARGILL company of the U.S..Although west pectin manufacturer adheres to technical monopoly and blockade policy always, there is lack of raw materials etc. puzzledly becomes clear day by day for the high and pomace pericarp of its factory building and ageing equipment, labor cost.At present, the 6-8 that can rise in value extract pectin from skin slag after doubly, greatly can improve the added value of apple raw material.The soluble pectin that acid system, cellulase, hemicellulase three kinds of methods are extracted glues, and molecular weight is respectively 292600,122400 and 165200Da.Gas-chromatography shows that apple pectin is made up of fructose, rhamnosyl, pectinose, wood sugar, seminose, glucose, Fucose and semi-lactosi.

Yin Yongguang, Fan Xiangdong, Liu Fengxia etc. report the pectin being used for by high-voltage pulse electric field technology extracting in apple residue in " with high-voltage pulse electric field technology rapid extraction apple residue pectin ".The optimal processing parameter extracting apple residue pectin has been drawn by single factor experiment and orthogonal test, apple residue pectin yield is up to 14.12% Bai Lijuan, Li Xiangdong, Wang Xiaoying reports salting-out process and alcohol deposition method to the impact of apple residue pectin extraction in the comparative study of pectin method " 2 kinds extract from apple residue ", the yield that alcohol deposition method extracts pectin is 7.85%, and gained pectin purity is high, and color and luster is good, Functionality, quality and appealing design, the yield that salting-out process extracts pectin is 6.14%.Han Rui, Deng Hong, Zhou Wenshan etc. to report with XDA-7 macroporous resin as sorbent material in " research of apple residue pectin resin absorption static and dynamic Status decoloration process ", have studied the decoloration process of apple residue pectin, inquire under static and dynamic Status condition, XDA-7 type resin is to the adsorption bleaching ability of apple residue pectin, and experimental result shows: XDA-7 resin has good adsorption bleaching effect to pectin extracting soln, and rate of loss is lower, percent of decolourization is 36.17%, and rate of loss is 3.70%.Dynamic percent of decolourization is 61.66%, and rate of loss is 3.05%, and the pectin extracting soln decoloured under optimal dynamic processing condition is after alcohol precipitation and lyophilize, and its finished product color and luster meets QB2484-2000 standard.Peng Kai, Zhang Yan, king waits like brocade and report the impact of microwave drying pre-treatment on apple residue extraction pectin in " microwave drying pre-treatment is on the impact of apple residue extraction pectin ", microwave energy is larger, the fragmentation of apple residue weave construction is more serious, its rehydration ability is more weak, microwave drying pre-treatment can significantly improve pectin yield, about 50% is improve than contrast, but when microwave energy is greater than 8.3 × 10-2kWh, disadvantageous effect is had to pectin yield, microwave drying pre-treatment affects without significance pectin galacturonic acid content, but significantly improve the gamma value of pectin, limiting inherent viscosity and glutinous equal molecular mass.Li Pengliang, Liu Dunhua report and utilize orthogonal test to adopt acid to put forward the extraction process of method to apple residue pectin of saltouing and be studied in " optimization of apple residue pectin extraction ", and extraction yield can reach 17%.Xu Zengwei, Yue Tianli, Ma Huiling etc. report in " impact that different times apple residue is prepared apple pectin " have studied different times apple residue in pectin content, the change of pectin extraction rate and other index, compare artificial seasoning and seasoning two kinds of modes to the impact of pectin, and determine the changing conditions of pectin degree of gelation after saving for some time, result shows, apple residue pectin content keeps high level from August to November, September reaches maximum value, artificial seasoning is higher than natural drying condition pectin extraction rate, pectin degree of gelation after depositing for some time has decline in various degree.You Xinxia, Han Shuqin reports and has investigated 6 kinds of different resins to the decolorization of apple residue pectin extracting soln in " research that resin adsorption method decolours to apple residue pectin extracting soln ", have studied the impact of absorbing process condition on resin decolorization ability in detail, test-results shows, X-5 resin has good decolorizing effect to apple residue pectin extracting soln.Ren little Qing, Li Haibin report the optimised process adopting salting-out process and alcohol deposition method to extract pectin in " research of apple residue pectous extracting method condition ", are alcohol deposition method extraction pectin better from product yield and quality comparation.Wang Jiang wave, Xu Zengwei, Ma Huiling etc. report and choose pectous extracting method parameter with orthogonal test in " being prepared the technique of pectin oligosaccharide by apple residue ", by single factor test and response surface experiments, take output as the technique that index optimization polygalacturonase (EC232-883-6) is hydrolyzed apple pectin and prepares pectin oligosaccharide, prepare fine white powder apple pectin, yield 11%, its polygalacturonic acid content 84.3%, the yield relative to pomace of enzyme-squash techniqued oligose is 5.92%.Ma Huiling, Sheng Yibao, Zhang Liping etc. are reported as and adopt that high-temperature acid puies forward technique in " separation and purification of apple residue pectin polysaccharide and anti-oxidant activity are studied ", middle temperature acid is put forward technique and from apple residue, extracted 3 kinds of pectin polysaccharide half sterlings obtaining and high-temperature acid propose pectin sediment fraction and dissolving part, middle temperature acid and carry pectin and carry out wash-out with water, 0.1mol/LNaCl, 0.3mol/LNaCl successively through ion exchange column and obtain polysaccharide sterling.Old snow peak, Zhan Xueying, Yang great Qing reports that in " extracting process of pectin research in apple residue " acid solution is extracted, the method for alcohol precipitating produces high methoxyl pectin in order to take, inquire into sour kind to the impact of product yield, and be that representative have studied acid strength, solid-liquid ratio, acid extraction to the impact of product yield with hydrochloric acid, determine the optimum extraction condition of pectin from apple pomace.Qu Haoyang, red legend, Liu Chen etc. report the method adopting orthogonal test and response surface analysis in " ester effect assessment falls in the optimization of apple residue pectous extracting method and alkaline process ", optimize the processing condition extracting low-ester pectin.Result shows, the factor affecting high ester pectin yield is that solid-liquid ratio > extracts system pH > Extracting temperature > extraction time.The factor that methyl esters degree falls in base catalysed de-esterification affects low-ester pectin yield is system pH > treatment time > treatment temp.It is 38.26% that methyl esters degree pectin esterification degree falls in alkaline process, affects the factor of pectin esterification degree yield for being the system for handling pH value > treatment temp > treatment time.Liu Chao, Lee's samarium, Han Yuqian reports the ultrasonic-assisted extraction processing condition of pectin in " ultrasonic extraction apple pectin process optimization and gel property measure ", solid-liquid ratio, Extracting temperature, ultrasonic time, extracting solution pH are inquired into the impact of pectin from apple pomace extraction yield, and be evaluation index with extraction yield, Optimized Extraction Process, and gel property mensuration has been carried out to the pectin obtained.The extraction yield of apple residue pectin is 15.12%.Di Zheng, pay ability, Li Na etc. report Hydrochloric Acid Hydrolysis Method and cellulase in " characteristic research of Enzymatic Extraction apple peel pectin ", hemicellulase is to the extraction effect of apple peel pectin, High Performance Anion Exchange Chromatography Coupled with Pulsed Amperometric Detection is adopted to measure the monosaccharide component of soluble pectin, and by viscometer determining limiting viscosity, derivation viscosity-average molecular weight, the pectin of Enzymatic Extraction, than yield height 2-3 times of acidity extraction, and solvability is good, acid system, cellulase, the soluble pectin that hemicellulase three kinds of methods are extracted glues, molecular weight is respectively 292600, 122400 and 165200Da.Deng Hong, Song Jirong, Shi Hongbing reports the comparative study that employing five kinds of salt carry out pectin Precipitation in " salting-out process extracts the Study of operational conditions of pectin from apple residue ", the influence factors such as salt consumption, pH value, temperature, reaction times when saltouing are tested simultaneously, obtain the optimum process condition of salting-out process.Xu Wenxiu, the solid-liquid ratio that Gao Xia reports hydrolyzation system in " Optimized by Orthogonal Test extracts the technical study of pectin from apple pomace " has the greatest impact to pectin yield, next is pH value, extraction time, is finally Extracting temperature, and under optimum hydrolysising condition, pectin productive rate can reach 9.25%.Lu Huifang, fourth long river, Hou Lifen etc. report hot acid method and extract apple pectin in " the mensuration research of pectin from apple pomace extraction conditions and molecular mass thereof ", and its extraction conditions and molecular mass are studied, result shows, the pH of extraction system, Extracting temperature and the extraction yield of time to pectin all have considerable influence, and wherein pH value has the greatest impact, and the sticky equal molecular mass of pectin product is 89.7ku.Kong Zhen, Liu Zhongdong, old lance of starting reports the impact on yield of microwave radiation temperature, radiated time, pH value, addition of aluminum sulfate and liquid ratio in " microwave method extracts the research of pectin from apple residue ", by experiment of single factor and orthogonal experiment determination optimal processing parameter, and attributional analysis is carried out to the pectin extracted.Xu Wenxiu reports and adopts acid-hydrolysis method to extract pectin in " research of Extracted Pectin from Pomace by Acid Hydrolyzation ", inquire into sour kind, pH value, hydrolysis temperature and time, solid-liquid ratio to the impact of pectin extraction rate, determine in apple residue the optimum extraction condition extracting pectin.Xu Wenxiu, Ding Xueru reports and carries out orthogonal test to solid-liquid ratio, ultrasonic power, Extracting temperature, treatment time four influence factors in " technical study of ultrasonic extraction pectin from apple pomace ", obtain extracting pectin optimum process condition in apple residue, yield reaches 7.53%.Tian Yuxia, enemy agronomy, Deng Hong etc. report the impact on pectin yield of ultrasonic frequency, ultrasonic time, solid-liquid ratio, Extracting temperature and extracting liquid pH value in " ultrasonic-assisted extraction of pectin from apple pomace and characteristic research ", according to orthogonal test, obtain the suitableeest extraction conditions of pectin, yield brings up to 13.64% by 11.45%, and gas-chromatography shows that apple pectin is made up of fructose, rhamnosyl, pectinose, wood sugar, seminose, glucose, Fucose and semi-lactosi.Wang Xianqing, He Shuqing reports the different salt of employing 5 kinds as pectin precipitation agent in " extracting the research of pectin from apple residue ", by experiment, contrast the influence factors such as the amount of screening precipitation agent, pH value, temperature of reaction and reaction times, obtain the optimised process bar extracting pectin.Zhu Xiaohong, report in " extracting the research of process of pectin condition from apple residue " in grain husk and adopt that acid solution is extracted, the method for ethanol precipitating produces pectin, the factors such as acid strength, time, solid-liquid ratio, temperature of having investigated are on the impact of pectin output, by the extraction process of optimization of orthogonal test, under this condition, pectin yield is 13.7%.Chang great Wei, Zhang Shuan, Kong Lingzhi reports and adopts ultrasonic assistant acid solution to extract pectin in " research of ultrasonic-assisted extraction pectin from apple pomace ", different extraction agent, solid-liquid ratio, pH value, ultrasonic time, temperature, power is have studied on the impact of pectin yield by experiment of single factor and orthogonal experimental design etc., determine optimum process condition, under this optimal conditions, pectin yield can reach more than 13%.Yu Ting, Yao Li, the refined grade of sun reports in different acid solution the highest with the product yield of citric acid extraction in " different times apple residue extracts the characteristic research of high methoxyl pectin ", various conventional decoloring method is to the DeGrain of pectin decoloration, discovery is analyzed for raw material extracts pectin and carries out detection with the apple residue of different times, different dry drying method, the high methoxyl pectin yield that early stage pomace is extracted compared with the pomace in other each period is high, is the better raw material extracting high methoxyl pectin.Water is bright of heap of stone, nationality is kept tie, the method that Li Bo etc. report column chromatography in " macroporous resin to apple residue in the research that is separated with pectin of polyphenol " to apple residue in polyphenol be separated with pectin, result shows, the separating effect of XDA-5 type macroporous resin to polyphenol and pectin is best.The optimised process that Xu Bingshen, Ma Yingge report apple residue hydrolysis in " utilizing apple residue to produce the research of hydrolyzed pectin technique " to acidity, temperature, heat-up time three factors dictate higher.Deng Hong, Li Ping, Shi Hongbing reports the processing condition that the precipitator method extract pectin in " apple residue extracts the deposition condition research of pectin ", by the research to influence factors such as precipitation agent consumption, pH value, temperature of reaction and reaction times, obtains the optimum process condition extracting pectin.Li Tao reports and filters out the suitableeest extraction agent in " pectin from apple pomace Study on extraction ", ultrasonic assistant acid hydrolyzation is adopted to carry out the extraction of pectin from apple pomace material, with pectin productive rate for evaluation index designs single factor test and orthogonal test respectively, pectin productive rate can reach 13.12%.Zhao Jiang, Cheng Yanwei reports in " research of Optimized Hydrolysis Conditions of Pectin Extracted From Apple Pomace " to be affected pectin extraction yield in factors such as material-water ratio, pH value, extraction time and temperature, utilize optimization of orthogonal test extraction process, gained pectin purity reaches 85.67%.Liu Shaoyang, Ding Xiuling, Zeng Weili reports and adopts orthogonal on single factor experiment basis in " extracting the research of process of pectin condition from apple residue ", alcohol precipitation process is utilized to have studied solid-liquid ratio, pH value, pomace particle diameter, extraction temperature, extraction time to the impact of pectin extraction rate, result shows, it is not remarkable that different acid affects difference to pectin extraction rate, considers, select nitric acid to be that lixiviate acid is more applicable, pectin average recoveries is 12.45%.Ma Huiling, Yue Tianli, Zhang Cunli etc. report and select preparation LM pectin optimised process, product yield 18.8%-19.3% by one-factor experiment method in " being prepared the technical study of LM pectin, food fibre by apple residue ".It is the optimum process condition that raw material extracts pectin that Zang Yuhong reports with apple residue in " extracting the technical study of pectin from apple residue ", and optimum process condition, productive rate reaches 14.04%.Xu Jinrui, Liu Xinghua, Ren Yamei report and are studied the technique of saltouing of pectin from apple pomace in " technical study of saltouing of pectin from apple pomace ", and result shows: Tai-Ace S 150 is the salting-out agent of precipitated pectin the best.Protorosaur, Wang Xiaozheng, Lv little Ming report the optimum process condition that salting-out process extracts pectin in " extracting the technical study of pectin from apple residue ", and result shows, different acid is little on extraction yield impact, and common acid (example hydrochloric acid, sulfuric acid) can be selected to make hydrolytic reagent.The solid-liquid ratio that Xu Wenxiu, Gao Xia report hydrolyzation system in " Optimized by Orthogonal Test extracts the technical study of pectin from apple pomace " has the greatest impact to pectin yield, and being secondly pH value, extraction time, is finally Extracting temperature, pectin productive rate 9.25%.Liu Aihua, Xue Yongqiang, Shi Jianqing reports and adopts acid solution extraction in " extracting the research of process of pectin condition in wet pomace ", salt precipitation legal system gets pectin, by carrying out analyzing to the influence factor of acidolysis condition, salting-out condition and desalination condition and studying, obtain the optimum process condition and processing parameter that extract pectin, the quality extraction yield of pectin is about 1.5%.Tian Yuxia, Dong Jian, enemy agronomy etc. " are being studied apple pectin ultrafiltration process separation condition and the pectin of different molecular weight and the relation of its character, adopt 5 kinds of differences to dam the Ultra filtration membrane apple pectin of molecular weight (MWCO), the pectin of different molecular weight obtains good separation, and molecular weight is larger, its galacturonic acid content and gamma value are all higher, transmittance reduces, and meanwhile, the decolouring of ultrafiltration to liquid pectin has good action.The technique of the decoloration process reporting a kind of apple pectin in patent CN200510124554.3 and the apple pectin producing white fine powder, the method is improved the technique that classical acid carries alcohol deposition method production pectin, pretreatment operation condition before technique employing accurate control raw material abstraction, add acid extraction liquid removal of impurities desolventing technology link, the macroporous resin HP2MGL chromatographic adsorption post adopting Japan recently to research and develop carries out dynamichandling to acid extraction liquid, the clearance of aldehydes matter is made to reach more than 88%, the extracting solution of purification is again through concentrate drying, pulverize, obtain the pectin powder of off-white to paper white high-quality.A kind of production method of apple pectin is reported in patent CN200810141118.0.Comprise the broken pre-treatment of following Pericarpium Mali pumilae, hydrolysis extracted, filter, decolouring, filtrate are concentrated, alcohol precipitation, filter, dry, finished product, described filtrate is concentrated is with membrane concentration technology concentrated pectin solution under continuous charging and discharging circulation means.Report the production technique of low-methoxy apple pectin in patent CN200610044268.0, it comprises pomace cleaning, pectin extraction and remove pigment, pectinesterase enzymatic hydrolysis, alcohol settling, the operations such as finished product is made, dry finished product.Report the production technique of high molecular pectin in patent CN200610044267.6, comprise material choice, raw material cleans, hydrolysis, is separated concentrated, dry, and decolouring, cleaning, the operations such as vacuum-drying, secure satisfactory grades sub-pectin finished product.Report a kind of method extracting low-methoxy pectin from apple residue in patent CN201410074207.3, its extraction step is: water extraction under microwave-assisted, and acidifying is centrifugal, and clear liquid concentrates, obtain concentrated solution, decolouring, alkalization, concentrated, acidifying, alcohol precipitation, washing, is low-methoxy pectin.A kind of method extracting pectin from apple residue is reported in patent CN201110106218.1, apple tankage are carried out cleaning and pulverizing, mixes homogenate, press filtration, ultrafiltration, nanofiltration I, nanofiltration II, stir plastic, press filtration, distillation reuse, spraying dry and pulverizing and make sterling.A kind of extracting and developing method of pectin from apple pomace is reported in patent CN201010216203.6, apple residue is pulverized, dry after and water Hybrid Heating extract, obtain pectin crude extract, the centrifugation of pectin crude extract, obtain pectin supernatant liquor, gained supernatant liquor concentrating under reduced pressure, precipitates adding ethanol in concentrated solution, and namely precipitation solution centrifugation, alcohol wash, vacuum-drying are obtained pectin product after also pulverizing.Report a kind of method utilizing apple residue high-purity pectin in patent CN200610013391.6, apple residue be dry, pulverize, acid solution hydrolysis, filter, concentrated, precipitating, drying, pulverizing obtain pectin.Report a kind of production technique of pectin in patent CN201310239492.5, skin slag cleans and crush, and mixes by 1: 15 weight ratio with 60 DEG C ~ 70 DEG C water, stir and soak, squeezing, adds hydrochloric acid adjusted to ph, heat up, slowly stir, insulation, leave standstill, be separated pectin extraction liquid, after solution clarification, vacuum concentration, obtain fructose concentrating liquid, adopt vacuum dehydrating at lower temperature, obtain finished product.

3. oxysuccinic acid oxysuccinic acid (malicacid) chemical name: 2-hydroxy-butanedioic acid, molecular formula: C ₄h ₆o ₅, molecular weight: 134.09, owing to there being a unsymmetrical carbon in molecule, oxysuccinic acid has L MALIC ACID, D-malic acid and DL-oxysuccinic acid 3 kinds of isomer.L MALIC ACID (L-Malicacid) molecular formula: C ₄h ₆o ₅, molecular weight: 134.08, CASNo.97-67-6, Chinese name: L-hydroxysuccinic acid, L-hydroxy succinic acid, oxysuccinic acid.English name: (2S)-2-Hydroxybutanedioicacid; (-)-Hydroxysuccinicacid; (-)-Malicacid; Appleacid; Hydroxysuccinnicacid (-); Butanedioicacid, hydroxy-, (2S)-; (-)-L-Malicacid; S-2-Hydroxybutanedioicacid; L-Malate; 124501-05-9; Butanedioicacid, hydroxy-, (S)-(9CI); L-Appleacid; L-MalicAcidAnd2-Ethyl-2-HydroxysuccinicAcid; 2-hydroxybutanedioicacid; L-MaleicAcid; Hydroxybutanedioicacid, (S)-; 84781-39-5; (S)-Malicacid; (S)-Malate; 498-37-3; (-)-1-Hydroxy-1,2-ethanedicarboxylicacid; S-(-)-Malicacid; L-(-)-Malicacid; L-2-Hydroxybutanedioicacid; 2-Hydroxybutanedioicacid, (S)-; 6294-10-6; MalicacidL-(-)-form.L MALIC ACID is colorless needle crystals, or white crystalline powder, odorless, be with irritant frank tart flavour, m.p.127-130 DEG C, specific rotatory power-2.3 ° (8.5 grams/100 ml water), soluble in water, methyl alcohol, acetone, dioxan, phenylethyl alcohol, be insoluble to ether, have water absorbability, the pH2.4 of 1% aqueous solution.Structural formula is as follows:

D-(+)-oxysuccinic acid (D (+)-Malicacid), molecular formula: C ₄h ₆o ₅, molecular weight: 134.09, CASNo.636-61-3.Chinese name: D-malic acid, D-toxilic acid, R-hydroxy-butanedioic acid, D (+)-oxysuccinic acid, D-(+)-oxysuccinic acid, (R)-hydroxy-butanedioic acid.English name: D (+)-Malic; D-Malicacid; D-Appleacid; 1 (+)-malicaci; (R)-Malicacid; D-Aepfelsaeure; (2R)-Malicacid; (+)-D-MalicD; D-(+)-Malicacid; D-(+)-Appleacid.D-type oxysuccinic acid m.p.101 DEG C, specific rotatory power+2.92 ° (methyl alcohol), water-soluble, methyl alcohol, ethanol, acetone, dioxan, be insoluble to benzene.Structural formula is as follows:

DL-oxysuccinic acid (DL-Malicacid), Chinese name: DL-hydroxy-butanedioic acid, CASNo.617-48-1, EINECSNo.210-514-9, molecular formula: C ₄h ₆o ₅, molecular weight: 134.09.Levo form and the dextrorotatory form of equivalent are mixed to get racemic modification, m.p.131-132 DEG C, and water-soluble, methyl alcohol, ethanol, dioxan, acetone, be insoluble to benzene.Structural formula is as follows:

Naturally occurring oxysuccinic acid is all L-type.At present, the production method of L MALIC ACID has extraction method, chemical synthesis, one-step fermentation, two-step fermenting, immobilized enzyme or cell conversion process.The fruit juice of immature apple, grape, peach etc. boils by extraction process, adds liming, generates calcium precipitation, and then treated generation dissociates oxysuccinic acid.L MALIC ACID is the important composition of straight juice, is the acid condiment of a new generation, is described as " optimal acid condiment " by organic sphere and nutrition circle.On world market, demand remains on the speed increment of average annual about 10%, and there are the U.S., Canada, Japan etc. in oxysuccinic acid major country of production of the world.

The function of L MALIC ACID: 1. L MALIC ACID can make pectin produce gelation, therefore can be used for making fruitcake, the jam of jelly gel state and puree etc., oxysuccinic acid sterilizing ability in acid condition but larger than neutrallty condition more than 100 times, can also promote the thermally denature of protein; 2. oxysuccinic acid can reduce pH value, produces sequestering action, to suppress the vigor of phenol oxygenase, prevents brown stain, for reodorant, can remove fish raw meat, body odor and for Food storage; 3. L MALIC ACID can strengthen the ventilation property of dough, elasticity and toughness, also can bleach flour, improve the cohesive action of protein, L MALIC ACID can be used for making saline taste food, reduce salt consumption, as the color preserving agent of food, L MALIC ACID has good resistance of oxidation, adds food antioxidant and can delay oxidation, Shelf-life, the color, smell and taste of maintenance food and nutritive value.4. L MALIC ACID sodium salt is the active drug for the treatment of hepatic insufficiency particularly vascular hypertension, and L MALIC ACID potassium is that good potassium supplements medicine, treatment oedema, hypertension and fat generation disease etc.; 5. L MALIC ACID can be used for, in pharmaceutical preparation, tablet, syrup, can also allocating in amino acid solution, can significantly improve amino acid whose specific absorption; 6. L-apple may be used for various diseases such as treatment hepatopathy, anaemia, hypoimmunity, uremia, hypertension, liver failure etc., and can alleviate cancer therapy drug to Normocellular toxic action, also for the preparation of with synthesis wormer, anticalculus agent etc.; 7. L MALIC ACID can also as industrial cleaning agent, resin curing agent, synthetic materials softening agent, fodder additives etc.; 8. L MALIC ACID zinc is used for as antibacterial full of stains or spots dose and anti-calculus agent in toothpaste, synthetic perfume formula etc.; 9. the cutin that the removal of L MALIC ACID gentleness is always useless unnecessary, strengthens skin metabolism, effectively subtracts light wrinkle and pore shrinkage water of compacting, and has conditioning skin fat secretion, strengthens effect of pore fineness; 10. chemical industry application can be used as one of the synthesis material of scale remover, white dyes, and add in shellac varnish or other varnish, can prevent lacquer painting skinning, the alkyd resin produced with this kind of acid and Synolac are the plastics having special purpose.L MALIC ACID is the tricarboxylic cycle important intermediate of body, and protein, lipid, carbohydrate etc. are last all will through tricarboxylic cycle oxidation energy supply, and this is the final step of conversion process, is also an of paramount importance step, whether is normally related to human physiological functions.

4. the macromolecular polysaccharide that is made up of glucose of apple fibre element (Appledietaryfiber), water insoluble and common organic solvents alcohol, ether, acetone, benzene etc., be also insoluble in dilute alkaline soln, can be dissolved in cuprammonium Cu (NH ₃) ₄(OH) ₂solution and copper second two ammonium [NH ₂cH ₂cH ₂nH ₂] Cu (OH) ₂solution etc., can be dissolved in Schwitzer reagent or the vitriol oil.Mierocrystalline cellulose and water react oxo bridge and fragment into short chain molecule, until become glucose.Mierocrystalline cellulose and oxygenant react and generate the different material of a series of and original cellulosic structure.The basic ring of cellulose macromolecule is the polysaccharide that D-Glucose forms with β-Isosorbide-5-Nitrae glycosidic link, its chemical constitution carbon containing 44.44%, hydrogen 6.17%, oxygen 49.39%.Alpha-cellulose is crystallinity Mierocrystalline cellulose, β-cellulose, gamma cellulose contain various polyose, and a part for primitive fiber is decomposed due to the effect of cellulase, becomes solubility, Mierocrystalline cellulose dewaters and coking when being heated to about 150 DEG C, and Mierocrystalline cellulose is soft is rigidity.Before Mierocrystalline cellulose chemical industry starts from more than 160 year, be that polymer chemistry is born and the main study subject of development, the achievement in research of cellulose and its derivates be the foundation of Polymer Physics and chemistry subject, development and abundant made major contribution.

Food fibre has the effect of balance postprandial blood sugar, regulating blood glucose levels, treatment diabetes.Food fibre can be combined with cholic acid and excrete, and impels cholesterol to transform to cholic acid, prevents the generation of these carcinogenic substances.Food fibre can sodium ion in enteron aisle, potassium ion exchange, and reduces the natrium/kalium in blood, plays hypotensive effect.After food fibre water suction, intestinal contents volume is increased, can intestines peristalsis be promoted, increase faecal volume, shorten emptying time, reduce the chance that in food, carcinogens contacts with colon.Play the effect treated constipation; Food fibre produces the growing multiplication of butyric acid inhibition tumor cell, controls the expression of oncogene.Food fibre urgees the secretion increasing saliva and Digestive system, plays filling effect, is combined with partial fatty acid, can not be absorbed stomach.

Microcrystalline Cellulose (MicrocrystallineCellulose) molecular formula: C ₁₂h ₂₂o ₁₁, molecular weight: 342.2965.CASNo.9004-34-6；12656-52-9；152231-69-1；209533-95-9；39394-43-9；51395-76-7；58968-67-5；61991-21-7；61991-22-8；67016-75-5；67016-76-6；68073-05-2；70225-79-5；74623-16-8；75398-83-3；77907-70-1；84503-75-3；89468-66-6；9006-02-4；9012-19-5；9037-50-7；9076-30-6；99331-82-5。The Mierocrystalline cellulose of a kind of purifying, part depolymerization, white, odorless, tasteless, the crystalline powder be made up of small porous particle.Be widely used in the industries such as pharmacy, makeup, food, different particle size and water content have different characteristic sum ranges of application.English name: alpha-Cellulose; AvicelPH101 (R); AvicelPH102; AvicelPH105 (R); Avicel (R); AvicelSF; Cellulose; AvicelPH-200; AvicelPH-101; 4-O-[(1S)-hexopyranosyl]-D-glycero-hexopyranose.Structural formula is as follows:

This product can be used for anticaking agent, emulsifying agent, dispersion agent, tamanori, tablet agent and texturizers etc.Also can be used for thermo-stabilizer and quick-drying carrier.Also can be used as food fibre to be applied in the foods of special nutrients such as low in calories and lower fat.Color brightens, soft fabric, removal particulate fouling, and it is to cellulosic fibre, as effective in clothing that is cotton and cotton blended product.

Zhang Wenhui report in " pomace dietary fibers research " fermentation method produce pomace dietary fibers processing condition, produce pomace dietary fibers color and luster protection be studied; testing and analysis has been carried out to the swelling property of the moiety of food fibre, dryness factor and food fibre, retention ability; by the mensuration to pomace dietary fibers dryness factor; in the known apple residue fermented, more than 80% is moisture and volatile matter, and pomace dietary fibers only accounts for about 18.70%.Fu Chengcheng, Guo Yurong, Dong Shouli etc. report the increase along with apple residue powder content in " development of pomace dietary fibers bread and the mensuration of texture characteristic thereof ", and the specific volume of bread and hardness reduce, and water-retentivity and elasticity increase.When apple ground-slag addition is 5%, bread is best.Ge Bangguo, Wu Maoyu, in " study on the modification of pomace dietary fibers ", chemical method and Physical is reported on the impact of dietary fiber modification with method great waves etc., show that physical method has good modification to food fibre, wherein after extrusion process, the content of apple residue SDF rises to 12.68% by 8.45%, after micronizing process, the retention ability of pomace dietary fibers improves 9.9%, and bulging force improves 9.8%.Liu Suwen, waits upon friend's treasured, and Li Hanchen etc. report and microwave heating technique is applied to H in " the processing parameter research of pomace dietary fibers microwave-assisted decolouring " ₂o ₂in decoloration process, adopt response phase method to draw optimal conditions, recording the whiteness after decolouring with colour-difference meter is 57.34%, and before decolouring, raw material whiteness is 27.54%, decolorizing effect is remarkable, and scanning electron microscope and X-ray diffraction analysis show that the microstructure of microwave to apple residue fiber surface has destruction.Liu Suwen, Guo Shuo, Liu Chang etc. report the processing condition that Microwave Irradiation Assisted Chemical method extracts soluble dietary fibre in " microwave radiation exaraction apple residue soluble dietary fibre ", and soluble dietary fibre yield is 20.98%.It is 19.84% that microwave-acid system prepares soluble dietary fibre yield under the optimum process condition of soluble dietary fibre.Li Rui, old snow peak, fiber crops pendant reports and is applied in decoloration process by ultrasonic technology in " the processing parameter research of pomace dietary fibers ultrasonic assistant decolouring ", draws by single factor test and orthogonal test the optimum process condition that pomace dietary fibers decolours.Old snow peak, Wu Liping reports and utilizes H in " research of Decoloration of Dietary Fiber from Apple Pomace " ₂o ₂apple residue is decoloured, obtains best decoloration process condition.Ge Bangguo, Wu Maoyu, Li Li etc. report and carry combined techniques with water extraction alkali and extract food fibre in apple residue in " extraction of pomace dietary fibers and decolouring ", and insoluble dietary fibre is 59.04%, and soluble dietary fibre content is 9.83%.Wherein alcohol ammonia process to the best decolorization condition of water-soluble dietary fibre is: the consumption 65%, material liquid pH 7-8 of dehydrated alcohol.Insoluble dietary fibre H ₂o ₂decolouring top condition is: the H of 4% ₂o ₂, pH=8,40 DEG C, soak 3h.Chai Lihong, Wang Yuan, Zuo Lin etc. report and adopt bulgaricus ccm and thermophilus streptococcus mixed strains to ferment in " fermentation method prepares the technical study of pomace dietary fibers ", the impacts of each factor on food fibre output and characteristic thereof such as inoculum size, fermentation time, leavening temperature are studied, along with the decline of food fibre output, its retention ability and swelling property are tending towards increasing.Gao Yue, Zhang Ying, Lu Qi etc. report immersion method in " water-bath and ultrasonic method prepare the research of apple residue soluble dietary fibre and performance thereof " and ultrasonic method prepares apple residue soluble dietary fibre, the yield that immersion method prepares the solvable food fibre of apple residue is 12.76%, and the yield that ultrasonic method prepares the solvable food fibre of apple residue is 14.14%.Ding Chenyang, Han Shunyu, it is discoloring agent that Sheng Wenjun etc. report with hydrogen peroxide in " optimization of apple residue insoluble dietary fibre decoloration process ", adopt response surface analysis, preliminary study is carried out to the decolouring of apple residue insoluble dietary fibre, its performance of Simultaneously test, apple residue insoluble dietary fibre decolorizing effect is best, after decolouring, water insoluble dietary fiber retention ability and swelling property all increase, and are respectively 1802.96% and 13.73mL/g.Wang Jing, He Xiaoling report the technique that microbe fermentation method extracts soluble dietary fibre from apple residue in " fermentation method produces the soluble dietary fibre in apple residue ", and the content preparing soluble dietary fibre can reach 24.11%.Song Jirong, Xu Kangzhen, Huang Jie etc. report the extraction process utilizing experiment of single factor and orthogonal experiment to have studied soluble dietary fibre and insoluble dietary fibre in " utilizing apple residue to prepare the technical study of food fibre ", the optimum process condition extracting soluble dietary fibre A is granularity 40 order, 0.3% hydrochloric acid soln, liquid ratio 15:1 (ml/g), temperature 80 DEG C time, optimum process condition when being 8%NaOH solution, liquid ratio 8: 1 (ml/g), temperature 90 DEG C of reaction 2.0h, soluble dietary fibre B, reaction 3.0h.Ding Chenyang, Han Shunyu, Sheng Wenjun etc. report and adopt acid-hydrolysis method to extract soluble dietary fibre from apple residue in " Response Surface Method optimizes apple residue soluble dietary fibre extraction process ", by response surface design analysis, investigate hydrochloric acid massfraction, solid-liquid ratio, extraction time, extraction temperature to the impact of soluble dietary fibre extraction yield, the extraction yield of soluble dietary fibre can reach 17.68%.Xue Zhanfeng, Guo Yurong, Fu Chengcheng etc. report and extract the processing condition of apple grunt dregs diet fibre and the physico-chemical property of water-soluble dietary fibre and water insoluble dietary fiber with hemicellulose enzyme process in " hemicellulose enzyme process is to the extraction of apple grunt dregs diet fibre ".Shi Hongbing, Song Jirong, Huang Jie etc. report and take chemical process to prepare soluble dietary fibre in " apple residue prepares the technical study of soluble dietary fibre ", have studied the impact on quality product and yield such as reaction solution concentration, liquid ratio, temperature of reaction and time, prepare that quality is high, the soluble dietary fibre of stable performance, obtained best processing condition.Peng Zhangpu, Gong Weizhong, Xu Yan etc. report and have employed acidity and alkaline extraction method prepares soluble dietary fibre from apple residue in " research of apple residue soluble dietary fibre extraction process ", orthogonal experimental design is utilized to determine optimal extract process, extracting extraction yield under the optimised process of acid-soluble food fibre is 17.49%, and under the optimum process condition of base-soluble dietary fiber, extraction yield can reach 16.93%.Report in Li Pengliang, Liu Dunhua etc. " optimization of apple residue pectin extraction " and adopt acid to put forward the extraction process of method to apple residue pectin of saltouing and be studied.Utilized orthogonal test to draw to extract the optimum process condition of apple residue pectin, its extraction yield can reach 17%.Huang Qun, Yang Wangen, Yu Ji reports on single factor experiment basis in " process optimization of ultrasonic assistant alkalinity extraction seed of bark of eucommia dregs of rice soluble dietary fibre ", choose solid-liquid ratio, ultrasonic time, Extracting temperature be influence factor, with soluble dietary fibre yield for response value, application Box-Behnken test design founding mathematical models, carry out response surface analysis, soluble dietary fibre yield reaches 22.92%.Old snow peak, Li Ruicen, Liu Ning reports and utilizes ultrasonic wave added hydrogen peroxide for decoloration technology to carry out desolventing technology to apple dietary fiber in " research of ultrasonic wave added hydrogen peroxide for decoloration apple dietary fiber ", the whiteness of the rear food fibre of decolouring is determined by spectral photometric colour measuring meter, have studied hydrogen peroxide concentration, concentration of lye, solid-liquid ratio, bleaching time and ultrasonic frequency are on the impact of decolorizing effect, by single factor test and orthogonal test, obtain best decolorization condition, after recording decolouring, the L value of food fibre reaches 80.79, its retention ability, bulging force, hold oily power and be respectively 13.29g/g, 15.10mL/g, 2.89g/g.Li Ruicen, old snow peak, Wu Fengling reports and utilizes ultrasonic wave added ozone decolorization technology to carry out desolventing technology to it in " the ultrasonic wave added ozone decolorization technique of apple dietary fiber ", by single factor experiment and orthogonal test, obtain best decoloration process condition, determine the L value of the rear food fibre of decolouring, can 80.11 be reached.Fiber crops are worn, old snow peak, Li Rui is at " in extruding apple residue the enzyme modification Study of operational conditions of food fibre " " in report and utilize cellulase to carry out modification to food fibre, to improve the content of soluble dietary fibre, thus improve the functional of product, by single factor test and orthogonal test determination optimum process condition, in apple residue, the stripping quantity of SDF is 26.79%.

Reporting a kind of in patent CN201110175428.6 take apple residue as the method that soluble dietary fibre prepared by raw material, apple residue is placed in loft drier and dries, and then add water stirring, carry out expanded with bulking machine, the apple residue after expanded is pulverized, apple residue is soluble in water, add amylase and papoid, soak, heated and boiled, filter, 95% ethanolic soln in filtrate, leave standstill, suction filtration, soluble cellulose is dry.Apple filter residue adds water, and adds cellulase degradation, heated and boiled, and enzymolysis solution is centrifugal, gets supernatant liquor, adds 95% ethanolic soln alcohol precipitation, suction filtration, dry, finally obtained soluble dietary fibre.A kind of method taking apple residue as raw material and prepare high refining food fibre is reported in patent CN03143271.9, add water former for apple slag mixing, enter high shearing mixing emulsor and carry out emulsification pretreatment, homogenization treatment is carried out with superhigh-voltage homogenizing machine, by centrifugal for the material after homogeneous, products therefrom lyophilize.The method of preparing apple dietary fiber by ultrasonic emulsification is reported in patent CN200810158957.3, taking apple peel as raw material makes through processing steps such as rubbing, defibrination, ultrasonic emulsification, homogeneous, centrifuge dehydration, vacuum-dryings, and the present invention makes that its technique is simple, product yield is high, production cost is low, be conducive to absorption of human body, its raw material availability is high, technique is simply convenient to suitability for industrialized production due to mechanical effects such as the physical action of hyperacoustic cavatition and heating and defibrination homogeneous.A kind of preparation method of apple residue Microcrystalline Cellulose is reported in patent CN201410197597.3, by swelling for apple residue hydrochloric acid soln, solute is centrifugal after constant temperature process at 77 ~ 79 DEG C of temperature, obtain supernatant liquor and throw out respectively, supernatant liquor is separated obtains crude pectin through concentrating under reduced pressure, dehydrated alcohol precipitation, spraying dry successively.Throw out is washed to pH value neutrality, then distilled water is added, 70 ~ 80 DEG C of constant temperature process after ice acetic acid and Textone, obtain filter residue after draining solution, be washed to pH value neutrality, swelling with sodium hydroxide solution, obtain solute, centrifugal after isothermal holding at 88 DEG C ~ 92 DEG C temperature, obtain supernatant liquor and throw out, supernatant liquor successively through concentrating under reduced pressure, dehydrated alcohol precipitation, be dried to constant weight after pulverize obtain hemicellulose.Precipitate dissolves adds heat decoloring, swelling, obtains solute, centrifugal after process at 79 DEG C ~ 81 DEG C temperature, dry, obtains water-insoluble apple residue Mierocrystalline cellulose.In water-insoluble apple residue Mierocrystalline cellulose, adding distil water is swelling, dropwise adds the glacial acetic acid solution that pH value is 2.0 ~ 2.8, makes its pH value to 4.1 ~ 5.0, add cellulose complex enzyme, and insulation enzymolysis, centrifuge dehydration, drying and crushing, obtains finished product Microcrystalline Cellulose.Report a kind of extraction process of non-pectin soluble pomace dietary fibers in patent CN200810139768.1, apple residue adds pomace NaOH solution, extracts 2.5h at 80 DEG C, alkali extract is carried out micronizing by colloidal mill,, through separating centrifuge centrifugation, collect supernatant liquor, vacuum concentration, with ethanol, enriched material is precipitated, and clean, dry, grinding, obtains soluble pomace dietary fibers.

5. apple polysaccharide polysaccharide (polysaccharide) is formed by multiple monosaccharide molecule condensation, dehydration, be molecule complex structure and huge glucide, the sugar chain combined by glycosidic link, at least will more than 10 monose composition polymerization sugar polymeric carbohydrate, available general formula (C ₆h ₁₀o ₅) n represents.Polysaccharide is not a kind of pure chemical substance, but the mixture of the different material of the polymerization degree.Polyose is generally water insoluble, without sweet taste, can not form crystallization, without reductibility and mutarotation.Polysaccharide is also glucosides, so can be hydrolyzed, obtains monose.

polysaccharide

Polysaccharide is extremely wide in distributed in nature, and structure unit is monose, relative molecular mass from several ten thousand to several ten million.Common glycosidic bond have α-Isosorbide-5-Nitrae-, β-Isosorbide-5-Nitrae-and α-1,6-glycosidic bond.Can be linked to be straight chain, also can form side chain, straight chain is generally linked to be with α-Isosorbide-5-Nitrae-glycosidic bond and β-Isosorbide-5-Nitrae-glycosidic bond; The tie point of side chain medium chain and chain is often α-1,6-glycosidic bond.What be made up of the monose of a type has glucose, mannosans, Polygalactan etc., and the mixed polysaccharide be made up of the monose of more than two kinds has the glycosamine dextran etc. of aminosugar, with regard to molecular weight, has from 0.5 ten thousand molecular to the polysaccharide more than 106.The short chain fewer than 10 be called oligosaccharides, what oligosaccharides combined protein and lipid also belongs to complex polysaccharide.By a kind of polysaccharide of monosaccharide molecule condensation, be called homogeneity polysaccharide.Glycogen glycogen and amylopectin similar, just branch degree is higher, every 4 glucosyl residue Bian Youyige branches.Structure is tightr, and cellulosic structure many β-D-Glucose molecule is connected with β-(1-4) glycosidic link and forms straight chain.By the polysaccharide of different monosaccharide molecule condensations, be called heterogeneity polysaccharide.Be made up of the repetition disaccharide series containing osamine some unhomogeneity polysaccharide, be called glycosaminoglycan, also known as mucopolysaccharide, glycosaminoglycan etc.

Marvin's is outstanding, Guo Yurong, in " application quadratic regression rotating orthogonal unitized design extracts the technical study of hydrosoluble apple polysaccharide ", certainly report the impact of water-soluble polysaccharide extraction yield in adopting orthogonally rotational combination design technique study Extracting temperature, extraction time, solid-liquid ratio on apple residue Wei, determine the more excellent extraction scope of apple polysaccharide, apple polysaccharide extraction yield is 14.94%.Su Yuqi, Ma Huiling, Luo Yaohong etc. report and adopt the multistage extraction method that alkali is carried, single-stage extraction method and the Ge Fa combination proposed with enzyme is proposed in acid to extract apple polysaccharide respectively from apple residue in " technology optimization that apple polysaccharide extracts ", the processing parameter of each extracting method is optimized by orthogonal experiment etc., adopt Optimization Technology to carry out grading extraction to apple polysaccharide, result is all higher than the polysaccharide yield of each one-step extraction.Zhang Liping, Sheng Yibao, it is that raw material therefrom extracts polysaccharide that Ma Huiling etc. report with apple residue in " screening of apple polysaccharide removal of impurities decoloration process ", and carries out deproteinated and desolventing technology to polysaccharide, and result shows, TCA method precipitates twice deproteinated best results, deproteinizing rate reaches 23.87%, and polysaccharide loss rate is only 0.40%, decolours then best with the effect of dialysis method, polysaccharide is canescence, and polysaccharide liquid transmittance improves 20.70%.Li Jinyun, Guo Yurong, Dong Shouli etc. report and adopt quadratic regression rotation combination design method to extract polysaccharide from cold broken apple peel in " in cold broken apple peel polysaccharide extracting process optimization and impurity-removing method research ", have studied Extracting temperature, extraction time, solid-liquid ratio, extraction time to the impact of Polyose extraction effect, determine the optimum extraction scope of cold broken apple peel polysaccharide.Experimental result shows, the primary and secondary order affecting cold broken apple peel polysaccharide extract rate Three factors is: Extracting temperature > extraction time > solid-liquid ratio, apple peel polysaccharide maximum extracted rate 11.28%.Employing HC1 method can by removal of protein in polysaccharide 80.2%, and polysaccharide loss rate is 9.7%, and dialysis method is best to polysaccharide decolorizing effect, and after dialysis, transmittance can reach 65.9%, and improve 23.5%, polysaccharide loss rate is only 31.7%.Liu Donglian, Zhao Liguo report in the technique study of total polysaccharides " in the ultrasonic-assisted extraction apple " ultrasonic technique on apple in the impact of total polysaccharides extraction effect, and orthogonal experiment is devised on the basis of experiment of single factor, determine the optimum extraction process of total polysaccharides in supersound extraction apple, apple polysaccharide extraction yield is up to more than 55%.Li Jinyun, Guo Yurong reports and adopts orthogonal experiment design method to extract polysaccharide from cold broken apple peel in the process optimization of polysaccharide " in the cold broken apple peel of ultrasound assisted extraction ", have studied supersound extraction power, Extracting temperature, extraction time, solid-liquid ratio to the impact of Polyose extraction effect, determine the best of breed of cold broken apple peel polysaccharide, maximum extracted rate 9.53%.Ma Huiling, Sheng Yibao, Zhang Lipings etc. report and adopt that high-temperature acid puies forward technique, middle temperature acid is put forward technique from apple residue, extracted 3 kinds of pectin polysaccharide half sterlings obtained in " separation and purification of apple residue pectin polysaccharide and anti-oxidant activity are studied ", and namely high-temperature acid is proposed pectin sediment fraction and dissolving part, middle temperature acid and carried pectin and carry out wash-out with water, 0.1mol/LNaCl, 0.3mol/LNaCl successively through ion exchange column and obtain polysaccharide sterling.Report the method extracting apple polysaccharide from fruit juice concentrate production process in patent CN200510017665.4, belong to apple polysaccharide extractive technique field.Apple polysaccharide is extracted in the dense poly-liquid of the membrane filtration that this method is formed from concentrated Succus Mali pumilae production process.The dense poly-liquid of available membrane filtration is analysed through alcohol, water-soluble impurity elimination, again alcohol are analysed and obtained; Or analyse with the dense poly-liquid of membrane filtration obtain through caustic soda salinization, hydrochloric acid neutralization, alcohol; Or with the dense poly-liquid of membrane filtration analyse through trichoroacetic acid(TCA) process, alcohol, again alcohol analyse and obtain.

6. apple polyphenol apple polyphenol is the common name of contained polyatomic phenol material in apple, it is the general name that in apple, there is phenyl ring and be combined with multiple hydroxy chemical structural material, mainly comprise flavan-3-alcohol class, flavonoid drugs, hydroxy-benzoic acid class, dihydrochalcone, the large class of anthocyanin class etc. five, apple polyphenol sterling is khaki powder, slightly apple local flavor, slightly bitter taste, soluble in water and ethanol, in apple, the composition of polyphenol substance and content are often because of kind, ripening degree, planting conditions and holding conditions and time, organize interior different sites and there is larger difference, prematurity apple is compared with transparent apple, the polyphenol content of crude fruit is 10 times of mellow fruit, although it becomes to be grouped into similar, but component content there is very big difference, in transparent apple, polyphenol is mainly chlorogenic acid, catechin and pycnogenols etc., then dihydrochalcone mostly is in prematurity apple, the compounds such as quercetin.Therefore extraction apple polyphenol adopts crude fruit to be advisable, containing chlorogenic acid, catechin, l-Epicatechol, apple condensed tannin, phlorrhizen, Phloretin, anthocyanidin etc. in thick apple polyphenol.Wherein apple condensed tannin accounts for the half of polyphenol total content.

1. due to apple polyphenol have anti-oxidant, scavenging free radicals, smelly eliminating, fresh-keeping, protect fragrant, protect look, prevent the effects such as vitamin loss, the functions such as Food Quality deterioration can be prevented, the natural antioxidants that can be used as a kind of high-efficiency low-toxicity is applied in foodstuffs industry, can be used for aquatic products processing, meat product processing, bread, cake, grease, the processing and manufacturing of oleaginous food and refreshment drink etc., its quality product and quality guaranteed period can be significantly improved, extend the storage period of food, improve the quality of food, increase the added value of food.2. because apple polyphenol has plurality of health care functions, as preventing dental caries, preventing hypertension, antitumor, anti-mutation, obstruction ultraviolet radiation absorption, anti-ageing, the physiological functions such as plurality of health care functions such as radioprotective, antianaphylaxis, muscle strength reinforcing, therefore can be used for the manufacture of protective foods and makeup.3. apple polyphenol has bacteriostasis efficacy, to restraining effect such as genus bacillus, intestinal bacteria, pseudomonass, has the effect of good suppression halitosis, can be applicable in the production of chewing gum, the existing corresponding product listing of Japan.4. after apple polyphenol utilizes phenolic hydroxyl group to be connected with the amide group in protein by hydrogen bond, can be used as the finings of drinks and beverage, gelatin, tannin can be made to form mixture and aggregate and precipitate, trap simultaneously and remove other suspended solidss.5. apple polyphenol has good convergency and sticking power; the synthesis of collagen can be safeguarded, suppress elastoser, assist the former albumen of body protecting glue and improve skin elasticity; thus avoid or reduce the generation of wrinkle; keep skin fine and smooth; be added in makeup, body lotion, hair dye, toothpaste, deodorant etc. and make activeconstituents, play anti-oxidant, anti-ageing, radioprotective, brighten and the multiple original effects such as moisturizing.6. the molecule that apple polyphenol is connected to polymkeric substance has the character of polyphenol, as polyphenol antibiotic filter screen absorbent resin grafting polyphenol, make anti-biotic material, have wide market at the antibiosis of diaper product.Apple polyphenol goods have been widely applied to the fields such as food, medicine, daily chemicals.

Jin Ying, Sun Aidong report by research AB-8 macroporous resin to the characterization of adsorption of apple polyphenol in " research of Purification of Apple Polyphenol by Resin Adsorption ", and find out the condition being suitable for apple polyphenol separation and purification, apple polyphenol purity can reach 39.98%.Jin Ying, Sun Aidong, Hu Xiaodan etc. report the research of apple polyphenol ultrasonic extraction condition in " ultrasonic extraction of apple polyphenol and Study on antioxidation ", establish the optimal processing parameter of extraction, and the in vitro anti-oxidation of apple polyphenol is studied, adopt DPPH method and DRI method to have studied the inhibition of apple polyphenol to DPPH free radical and .OH free radical, result shows, ethanol can be used as the optimum Extraction solvent of apple polyphenol.Wang Zhenyu, Liu Chunping reports the technique of AB-8 type resin separation purification apple polyphenol in " macroporous resin AB-8 is to the separation and purification of apple polyphenol ", by the research to purifying influence factor, determine that ethanol sedimentation is the best impurity-removing method of apple polyphenol crude extract, obtain the apple polyphenol purified that purity is 79.5%.Ai Zhilu, Guo Juan, Wang Yuhong etc. report the microwave extraction technique adopting secondary universal rotary combination design to have studied apple polyphenol in apple residue in the technical study of apple polyphenol " in the microwave radiation exaraction apple residue ", result shows, ethanol consumption has pole remarkably influenced to polyphenol yield, the mutual item of power, alcohol concn and extraction time and power has remarkably influenced to polyphenol yield, and extraction time does not make significant difference to polyphenol yield, apparently higher than backflow and ultrasonic extraction yield.Luan Yan, nationality is kept tie, Jiang Hui etc. in " research of apple polyphenol leach extraction method ", report organic solvent extraction and ultrasonic-leaching method two kinds of methods are extracting the similarities and differences in polyphenol from apple powder, influence factor mainly comprises Extraction solvent, temperature, time, solid-liquid ratio, extraction time, result shows, under same extraction conditions, ultrasonic-leaching yield is far above organic solvent lixiviate yield.Wei Fuxiang, Qu Enchao are at " supercritical CO ₂the technical study of extracting apple polyphenol from apple residue " in report by single factor test and orthogonal experiment research, to supercritical CO ₂the technique of extracting apple polyphenol is optimized design, experimental result shows: each factor on the primary and secondary order that apple polyphenol yield affects is: extraction time > extracting pressure > extraction temperature > solid-liquid ratio, under best extraction experiments, yield is 0.1%.Gao Xiaoming, Lv Lei, Wang Rui etc. report the processing condition of extraction using alcohol and Purification of Apple Polyphenol by Resin Adsorption in " extraction using alcohol of apple polyphenol and macroporous resin purification technical study ", investigate operational condition to the influence factor of extraction using alcohol rate by single factor test and multifactorial experiment, utilize static test to investigate absorption property and the elution parameters of Purification of Apple Polyphenol by Resin Adsorption.Zhang Zesheng, Xu Ying report in " research of On Adsorption Performance of Macroporous Resins For Apple Polyphenols In Apple Pomace " have studied 8 kinds of macroporous adsorbent resins to apple residue in the adsorption and desorption performance of apple polyphenol, wherein AB-8, NKA, X-5, D4006 resin has larger adsorptive capacity and desorption efficiency, its static adsorbance: AB-8 > X-5 > D4006 > NKA, desorption rate: X-5 > NKA > AB-8 > D4006, adsorption rate: AB-8 > X-5 > NKA > D4006, therefrom select AB-8 resin and purifying is carried out to apple polyphenol, dynamic adsorption experimental study extract concentration, pH, flow velocity is on the impact of AB-8 resin absorption amount.Jiang Hui, nationality is kept tie, Li Bo etc. report apple polyphenol separating-purifying process center pillar length-to-diameter ratio and flow velocity to the impact of yield three indexs of desorption efficiency, l-Epicatechol and chlorogenic acid in " affecting the factor of apple polyphenol separating-purifying ", result shows, when the adsorption rate of gel column be 1.5ml/min, desorption rate is 1.0ml/min, when post length-to-diameter ratio is 20 × 2.5, these three indexs are all best.Wang Yuhong, Zhu Weijun, Pan Zhili etc. report on the Process ba-sis that draws at single factor experiment in " NKA-9 macroporous resin is to the Kinetic adsorption optimization of apple polyphenol ", adopt Response Surface Method to establish the secondary multinomial mathematical model of NKA-9 macroporous resin to apple polyphenol (AP) dynamic adsorption and dynamic desorption, demonstrate the validity of model.Loading speed, sample liquid mass concentration, sample liquid pH value are investigated to AP dynamic adsorbance and elution rate, elution concentration and eluting agent to the impact of AP dynamic desorption.The Kinetic adsorption parameter of optimization NKA-9 macroporous resin.Xu Xianmeng, Dong Wenbin, it is Extraction solvent that Zhang Zengshuai etc. report ethanol in " polyphenols from apple pomace macroporous resin is separated and Study of Antioxidation ", ultrasonic-assisted extraction polyphenol, examine the Adsorption and desorption ability adsorptive capacity of 12 kinds of macroporous resins to gallic acid, select XDA-8 macroporous resin to adsorb polyphenols from apple pomace, desorb, obtain polyphenols from apple pomace powder through concentrated, lyophilize.Chen Baohong reports and utilizes multistage microwave amplifier Polyphenols in Apple Pomace in " in multistage microwave amplifier apple residue polyphenol technology optimization ", with volume fraction of ethanol, solid-to-liquid ratio, microwave power and extraction time for influence factor, by single factor experiment and optimization Test determination Optimization Technology.A kind of method extracting apple polyphenol from apple peel is reported in patent CN201410206893.5, dry apple peel is broken, mix with 20 acetone-water solution, ultrasonic extraction, centrifugal, collect supernatant liquor, obtain apple polyphenol extracting solution to concentrate, obtain apple polyphenol concentrated solution, be separated with macroporous resin loading after dilute with water, wash with deionized water, use ethanol-water solution wash-out again, collect effluent liquid, concentrated, obtain apple polyphenol concentrated solution, at dextrane gel purifying after dilute with water, first wash, use ethanol-water solution wash-out again, finally use acetone-water eluant solution, obtain the elutriant of apple Hydrolysable Tannins and apple condensed tannin respectively, concentrate and lyophilize, obtain apple Hydrolysable Tannins and apple condensed tannin powder respectively, obtain apple polyphenol.The method of extracting apple polyphenol from apple pomace by supercritical CO 2 is reported in patent CN200510048168.0, apple residue is pulverized, adds ethanol and stir into purees, add in supercritical fluid extraction tank, with ethanol for carrying agent extraction, obtain apple polyphenol crude product.The production technique that a kind of apple peel extracts apple polyphenol is reported in patent CN01120589.X, apple peel extraction using alcohol, extracting solution refrigerates after being evaporated to small volume, concentrated solution carries out liquid phase adsorption separation, use organic acid concentrated solution for washing, then use deionized water wash, then carry out wash-out separation with the ethanolic soln gradation of different concns, successively collect different elution fraction concentrating under reduced pressure small volumes, be sprayed to powder or drying under reduced pressure obtains extract to powder.A kind of extracting method of apple polyphenol is reported in patent CN201210413277.8, apple polyphenol is extracted with EtOH Sonicate ripple extraction process, adopt macroporous resin adsorption, ethanol elution, vacuum-drying or spray-dired to apple polyphenol product, alcohol settling, obtains apple pectin.Report a kind of preparation method of apple polyphenol in patent CN201010178402.2, choose that fresh apple is cleaned, shave, blanching is gone out enzyme, cold water cools, and drying and crushing, adds extraction agent, ultrasonic extraction, obtains containing apple polyphenol extraction liquid, centrifugal, concentrated by apple polyphenol extracting solution, obtain apple polyphenol concentrated solution, concentrated solution is by high efficiency chromatography chromatography column, ethanol elution, obtains apple polyphenol elutriant, concentrated, drying, obtains apple polyphenol lyophilized powder.Report a kind of method that microwave extracts apple polyphenol from apple residue in patent CN200610017375.4, extract apple polyphenol with the apple residue of alcohol solution dipping in microwave equipment, microwave power is 100 ~ 1000W.Report kind of an apple polyphenol extracting method in patent CN200910073059.2, choose fresh apple fragmentation, making beating, acetone respectively, with highfield extraction, obtains apple polyphenol extraction liquid, centrifugal, isolate extracting solution and residue, concentrated, obtain the thick polyphenol concentrated solution of apple, chromatographic separation, with ethanol elution, obtain apple polyphenol elutriant, concentrated, dry, obtain apple polyphenol lyophilized powder.Report apple polyphenol preparation method in patent CN200610017479.5, get apple tree root and pulverize, methyl alcohol soaks, and filters to obtain extracting solution, and concentrate to obtain medicinal extract, medicinal extract, through recrystallization, drying, obtains the pharmaceutical intermediate apple polyphenol of purity more than 90%.Report the industrialized preparing process extracting apple polyphenol from apple residue in patent CN201010590775.0, add alcohol in fresh apple residue, heating and refluxing extraction, precipitation, filters, concentrated, carry out column chromatography for separation with resin, methyl alcohol carries out gradient elution, and segmentation detects, abandon impurity section, collect effective section, be concentrated into without alcohol, vacuum drying, pulverize, mixing, packaging.Report the process for separating and purifying of apple polyphenol in patent CN200610044266.1, apple pomace is cleaned, hydrolysis, extraction, extraction liquid adjust ph to 3.0 ~ 3.5, with diatomite filtration, macroporous adsorbent resin is separated, absorption, enrichment apple polyphenol, with ethanol elution, be separated, work in-process are made in collection elutriant is concentrated, drying, obtained work in-process are refined, remove impurity, dry, obtain finished product.

7. phlorizin phlorizin extracts from apple, apple bark and leaf etc. and obtains, and it is the aldehydes matter in apple tree.Phlorizin is the glycosides that glucoside bound becomes by Phloretin and glycoside, and its degraded product phloroglucin, effectively can suppress the effect etc. of microbial activities.Clinical study both domestic and external shows, phlorizin has good curative effect in treatment diabetes.Phlorizin (phlorizin) has another name called phlorrhizen, chemical formula: C ₁₂h ₂₄o ₁₀.2H ₂o, molecular weight: 472.45, CASNo.60-81-1, EINECSNo.200-487-1, chemical name: 1-(2-(beta-D-glucopyra glycosyloxy base)-4,6-dihydroxy phenyls)-3-(4-hydroxy phenyl)-acetone; English name: 1-(2-(beta-D-Glucopyranosyloxy)-4,6-dihydroxyphenyl)-3-(4-hydroxyphenyl)-propan-1-on.Good water solubility when content is low, is insoluble in water during content height, micro-yellow needles body.Structural formula is as follows:

Phlorizin pharmacological action: 1. antibacterial: in apple tree in aldehydes matter total content, phlorizin accounts for 95% is the glycosides that glucoside bound becomes by Phloretin and glycoside, and glycosyl hydrolase forms glucose, and 4-deoxidation phlorizin is also widely studied and applied.Its degradation product phloroglucin, effectively can suppress the effect etc. of microbial activities.2. anti-oxidant: phlorizin has anti-tumor activity, effective in cure to skin carcinoma, can the formation of check melanin, subtract weak tea brown, grey speck and freckle.3. diabetes are treated: phlorizin has good curative effect in treatment diabetes, is having good preventive and therapeutic effect to diabetes and complication thereof.4. excite sexual desires: the functional similarity of phlorizin compound and estradiol, and estradiol is the oestrogenic hormon played an important role in heat process, regularly edible apple can improve femal sexual function.

Liu Jingxin, He Yunhua reports in apple branch and leaf in " different model macroporous resin is to the characterization of adsorption of apple polyphenol material " has phlorizin to exist, in leaf phlorizin 9, October content the highest, average content is 16.31mg/g, in branch, phlorizin content is the highest when June, average content is 11.93mg/g, only contain Phloretin in Folium Mali pumilae, May, content was up to 2.541mg/g, do not detect in branch, apple branch and leaf can be used as the resource extracting phlorizin and Phloretin and are used.Xu Kai, Lv Haitao report and adopt orthogonal table determination optimum extraction process in " in orthogonal experiment preferably apple skin phlorizin extraction process ", and result circumfluence method extraction effect is better.Liu Di, Shang Hua, Song Xiaoyu reports and extracts phlorizin with ethanolic soln in " apple residue phlorizin optimal extraction technology and Antioxidation Behavior thereof ", with high effective liquid chromatography for measuring phlorizin content, utilize BoxBehnken center combination design principle, application response surface optimum experimental method determines optimum extraction conditions, the extracted amount of phlorizin can reach 2.79mg/kg, and each factor on adsorption rate impact order is: Extracting temperature > solid-liquid ratio > extraction time > alcohol concn.Liu Di, Shang Hua, Song Xiaoyu etc. report with apple residue crude extract as raw material in " response phase method optimizes the technique that macroporous adsorbent resin is separated apple residue phlorizin ", phlorizin is separated with macroporous adsorbent resin, with high effective liquid chromatography for measuring phlorizin content, utilize Box-Behnken center combination design principle, the optimum separation condition of application response surface experiments optimization method determination macroporous adsorbent resin, the impact order of each factor on adsorption rate is adsorption flow rate > adsorption liquid pH > adsorption liquid concentration, the impact order of each factor on eluting rate is elutriant pH > ethanol eluate concentration > eluting temperature.Zhao Feiwen reports with the branch of apple, leaf as raw material in the extraction of phlorizin " in the apple branches and leaves ", 70% methyl alcohol is extraction agent, and temperature controls 50-60 DEG C of refluxing extraction three times, 60 DEG C of reclaim under reduced pressure methyl alcohol, through flocculation, suction filtration, merging filtrate, then extract by ethyl acetate, 60 DEG C are concentrated near dry, recrystallization, obtain phlorizin crude product, measure its productive rate by method of UV spectral analysis, result shows that in apple cauline leaf, phlorizin content is higher.The separation purification method of phlorizin in a kind of apple residue is reported in patent CN201310109318.9, apple residue and ethanol mixing, lixiviate, filtration, merging filtrate, centrifugation, obtains supernatant liquor, adjust ph is after 3.5-4.0, adopt D-101 absorption with macroporous adsorbent resin, adopt that pH value is 7.0, the ethanol eluate of volumetric concentration 75%-90% carries out wash-out, concentrated, dry, obtain purifying phlorizin powder.Report a kind of method of extraction purification phlorizin from apple fruit root bark in patent CN201310108251.7, apple fruit root bark is pulverized, uses low ethanol-extracted, collect extracting solution concentrates, through macroporous resin adsorption, collect 50% alcohol eluen, concentrating under reduced pressure, cooling, crystallization at 0 DEG C-40 DEG C, crystallization centrifuge dehydration, the crystallization of distilled water heating for dissolving, adds gac dehydration, after centrifugal, filtrate reduced in volume, recrystallize, crystallization centrifuge dehydration, dry, the phlorizin product of more than 98% can be obtained.Report a kind of extraction process of high-purity phlorizin in patent CN200710132394.6, raw material is added pure water and soak, be heated to boil, protect to obtain extracting solution, united extraction liquid, cooling, filters, and collects filtered liquid, through macroporous resin adsorption, with ethanol gradient elution, by effluent liquid Fractional Collections, vacuum concentration, leave standstill, cooling, 0-4 DEG C of crystallization, high speed centrifugation dewaters, dissolve, vacuum concentration, recrystallize, high speed centrifugation dewaters, dry, obtains finished product.

8. Phloretin (Phloretin) molecular formula: C ₁₅h ₁₄o ₅, molecular weight: 274.27, CASNo.60-82-2, chemical name: three hydroxyl phenol-acetone 2,4,6-trihydroxy--3-(4-hydroxy phenyl) Propiophenones, 3-(4-hydroxy phenyl)-1-(2,4,6-trihydroxy-phenyl)-1-acetone.English name: 2 ', 4 ', 6 '-Trihydroxy-3-(4-Hydroxyphenyl) Propiophenone; 3-(4-Hydroxyphenyl)-1-(2,4,6-trihydroxyphenyl)-1-propanone; 3-(4-hydroxyphenyl)-1-(2,4,6-trihydroxyphenyl) propan-1-one; 1-(2,6-dihydroxy-4-methoxyphenyl) ethanone.Light yellow to fine white powder shape, be dissolved in methyl alcohol, ethanol and acetone, water-soluble hardly.Structural formula is as follows:

Phloretin is a kind of new type natural skin-whitening agents, is mainly distributed in apple pericarp and root skin.Phloretin can suppress the excessive secretion of sebiferous gland, is used for the treatment of the vigorous type acne of secretion, and energy check melanin cytoactive, has desalination effect to various skin splash; Phloretin moisture-keeping function is very strong, the weight 4-5 of energy absorption water doubly own; Anti-oxidant function is very strong, can remove the free radical in skin, carbohydrate content can be stoped to enter epidermic cell, and Phloretin can be applicable in facial mask, cold cream frost, emulsion and essence.The semi-synthesizing technology of Phloretin is reported in patent CN201310238175.1, phlorizin crude product is placed in stainless steel cauldron, the simple refining filtering of strong alkali solution being dissolved in 5% obtains phlorizin salts solution, proceed to jacketed enamel reaction still, and add Lewis acid and metal catalyst at low temperatures, about 35 DEG C of reaction 10-15h, be cooled to 0 DEG C of crystallization again, filter, deionized water wash obtains Phloretin coarse-grain, this coarse-grain again with 95% dissolve with ethanol solution, essence filter, concentrate and crystallization of lowering the temperature, filter, content is obtained and purity is all greater than 99.0% Phloretin fine work after drying.Report a kind of method of method for producing phloretin by enzymatic hydrolysis in patent CN200910228671.2, be dissolved in by phlorizin in deionized water, add the sino-β lytic enzyme of activation, under agitation enzyme digestion reaction, deactivation, solid-liquid separation, solid drying, obtains Phloretin.A kind of purifying technique of Phloretin is reported in patent CN201010510889.X, raw material pulverizing adds alcohol reflux, reclaim ethanol, obtain concentrated solution, concentrated solution adds water-saturated n-butanol solution extraction, and collect organic phase and concentrate, concentrated solution adds macroporous resin column in water-dispersion, washing is without fried sugar, ethanol elution validity composition, elutriant reclaims ethanol, filtered while hot, obtain filtrate, filtrate adds biological enzyme insulation enzymolysis, and concentrated enzymolysis solution places precipitation, leaches solids, dissolving crystallized with alcohol reflux, crystallisate is drying to obtain product.A kind of preparation method of Phloretin is reported in patent CN201310152063.4, with naringin dihydrochalcone heating hydrolysis under diluted acid effect, purifying obtains Phloretin, naringin dihydrochalcone adopts naringin under the existence of alkali lye and rare metal catalyzer, under middle pressure and normal temperature or heating, carry out catalytic hydrogenation with hydrogen, then from reaction system, collect naringin dihydrochalcone.

The present invention is from China's Apple Industry and agriculture production reality, according to social demand and self study condition, for apple residue current resources situation, active response national policy calls the Circular Economy promoting resource-product-waste-renewable resources, brute force makes chain circulation economic structure, implement apple function composition--extract the integrated extraction purification of biological wax, pectin, food fibre, apple polysaccharide, oxysuccinic acid, apple polyphenol, phlorizin and Phloretin in apple residue, overcome the drawback that background technology " is got it general, abandoned its elite ".The present invention not only concerning exploitation future and the vital interests of hundreds of millions orchard workers of agriculture, woods, fruit, more replenishes integrated extracting and purifying method that is domestic and Asia apple residue effective constituent.

Summary of the invention

For overcoming the deficiency in background technology, the present invention aims to provide the integrated extracting method of apple residue effective constituent.

Technical solution of the present invention is:

The integrated extracting method of apple residue effective constituent, comprises the steps:

(1) water extraction, concentrated, obtain water-soluble general extractive.

(2) preparation of apple polyphenol in water extract.

(3) separation of phlorizin in apple polyphenol.

(4) phlorizin prepares Phloretin.

(5) preparation of apple pectin in water extract.

(6) preparation of apple polysaccharide in water extract.

(7) preparation of oxysuccinic acid in water extract.

(8) the slag potass extraction after water extraction.

(9) preparation of apple wax.

(10) preparation of apple Microcrystalline Cellulose.

Embodiment

Dropped into by apple residue in multi-function extractor, adverse current pump circulation, in the middle of tank body, set out mouth, bottom pump suction cover, mineralization pressure formula upwardly, and raw material decocts in tank, and centre is stirred.Decoct end need to carry out vacuum fluid, equipment in working order time, the valve of fastening system gas circuit of rising to the bait is also in running order, relief cylinder must be used during work, so as not to pressure release break off relations and have an accident.Add 8 times (V/W) and measure deionized water, 2h is extracted in 70-80 DEG C of heating, collect the feed liquid extracted, filter residue adds 6 times (V/W) again and measures deionized water, 1.5h is extracted in 70-80 DEG C of heating, and collect the feed liquid extracted, filter residue adds 5 times (V/W) again and measures deionized water, 1.0h is extracted in 70-80 DEG C of heating, collects the feed liquid extracted.The feed liquid of front extracted twice merged, third time extracts the extracting solution of feed liquid as next batch of material, and material slag is waited until for subsequent use, so circulates.The feed liquid merging of front extracted twice is concentrated into ρ=1.05 ~ 1.10.Add 2-3 times (V/W) and measure deionized water, fully stir, press filtration, collect filtrate, obtain apple residue Aqueous extracts.

Macroporous adsorbent resin is added ethanol, methyl alcohol or acetone to stir, at soaking at room temperature 1-2.Discard solution, with purified water by macroporous adsorbent resin repetitive scrubbing several times, avoid undue agitation, avoid use magnetic stirring apparatus.Before dress post, used water flotation process removes the impurity in macroporous adsorbent resin, the bubble of discharging in macroporous adsorbent resin and vacuum available pump is bled.Whole packed column must be made very even, otherwise must refill.Post is vertically fixed, adds a small amount of purified water to get rid of the bubble of bottom in post, add purified water in post about 1/4 height.Then under agitation, slowly, equably, continuously add macroporous adsorbent resin, open the outlet of chromatographic column simultaneously, maintain suitable flow velocity, macroporous adsorbent resin particle will successively horizontal rise, and deposit equably, until desired height position in post.Cover resin surface with absorbent cotton, then use large-scale purification water washing for some time.Before loading, with elutriant balance chromatography column at least two column volumes until baseline becomes steadily, before sample is separated, must whether check uniformly chromatographic column.Put one as the parallel fluorescent lamp of post post is other, in the post that detects by an unaided eye, whether have " lines " or bubble.If it is narrow, even, smooth to observe bands of a spectrum in post, namely illustrate that column performance is good.Otherwise, must loaded resin post again.Add apple residue Aqueous extracts sample, and start to collect effluent liquid, first use purified water wash-out, collect water lotion, wait until for subsequent use.Then be the ethanol elution of 50-80% by volume fraction, collect ethanol eluate, concentrating under reduced pressure, spraying dry, obtains apple polyphenol.Apple polyphenol is dissolved with purified water, respectively with extraction one of in normal hexane, sherwood oil, No. 6 solvent oils or ether 3 times, first time 5 times amount (V/W) extracts degreasing, second time 4 times amount (V/W) extracts degreasing, third time 3 times amount (V/W) extracts degreasing, collect the liquid after degreasing, degreasing solvent reclaims.After degreasing, the apple polyphenol aqueous solution is with ethyl acetate or n-butanol extraction, first time 5 times amount (V/W) extraction, second time 4 times amount (V/W) extraction, third time 3 times amount (V/W) extraction, collect extraction liquid, concentrating under reduced pressure solvent recuperation, is concentrated into proportion 1.05-1.08, add 3-5% gac reflux decolour 30min, suction filtration while hot, filtrate reduced in volume proportion 1.10-1.15, adds a small amount of ether, abundant stirring, place, crystallization, suction filtration, vacuum-drying at 50-60 DEG C, obtains phlorizin.

By the 1500kg purified water suction reactor of accurate measurement, under stirring, water liquid pH1-2 is regulated with the vitriol oil, add phlorizin 300.0kg, sealed reactor mouth, heating, heat-carrying steam valve is closed when question response still upward pressure table indicator pressure reaches 0.10MPa, treat that pressure rises to 0.15MPa and starts timing, keep still internal pressure at 0.12-0.15Mpa, reaction 1-4h.Clarify bright solution in reaction process and become muddy gradually, detect after sampling process, start step-down after reacting completely, obtain Phloretin reactant.Cooling, leave standstill, use plate-and-frame filter press press filtration, filter cake purified water is washed, until filtrate pH value is in neutral.Transfer in drying machine by Phloretin wet product good for press filtration, dry 6-8h under-(0.01-0.03) Mpa, obtains Phloretin crude product.By the 450k ethanol of accurate-metering negative pressure sucting reaction still, under stirring, Phloretin crude product 50kg is added reactor, add gac 2.5kg, reflux, closing volume after temperature 65 ± 5 DEG C of stirring and refluxing dissolve 30min, starts boosting, starts to filter when pressure rises to 0.10-0.12MPa.The feed liquid of filtering squeezes into crystallizer be concentrated into 1/3 of original volume under-(0.03-0.05) Mpa after, opens and stirs, open water coolant, stirred crystallization.Pour advantages of good crystallization material into centrifuge, when whizzer liquid outlet mother liquor becomes to drip, the Phloretin wet product after centrifugal is transferred in drying machine, dry under-(0.02-0.04) MPa, obtain Phloretin fine work.

Water elution liquid in macroporous resin column, is evaporated to proportion 1.10-1.15, is acidified to pH1-3, adds the saturated A1 of 3-5% (v/v) ₂(SO ₄) ₃solution, fully stirs, and saltouts, press filtration, and filtrate is waited until for subsequent use.The filter cake 20-30% ethanol of 4-6 times amount mixes, and heating for dissolving, adds 3-5% (v/v) hydrogen peroxide, continuous stirring, 60-70 DEG C of insulation 1-2h, press filtration, the filter cake ethanol purge of pH2-4 volume fraction 70-80%, 50-60 DEG C of vacuum-drying, obtains high ester pectin finished product.High ester pectin is dissolved with the sodium hydroxide of the pH value 9-11 of 3-5 times amount (v/w), at 30-40 DEG C of heating 30-60min, be evaporated to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling, press filtration, the sodium hydroxide remained is removed in filter cake washing, suction filtration, 50-60 DEG C of vacuum-drying, obtains low-ester pectin finished product.

By above-mentioned pressing filtering liquid of saltouing, be evaporated to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling, press filtration, filtrate collection, waits until for subsequent use.Filter cake, with water dissolution, adds the sodium hydroxide solution of 5-10%, until generate without precipitation, suction filtration, discards aluminum hydroxide precipitation, and filtrate adds 3-5% (v/w) gac, 70-80 DEG C of insulation 30min, while hot suction filtration, filtrate reduced in volume is to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling, press filtration, discards filtrate, filter cake washing with alcohol, 50-60 vacuum-drying, obtains apple polysaccharide.

By the pressing filtering liquid after above-mentioned alcohol precipitation, then add hydrated barta powder, heated and boiled, oxysuccinic acid and barium salt are dissolved, and barium malate is insoluble.Press filtration, filtrate removes.The precipitation hot water wash decon of 80-90 DEG C.The method checked is added drop-wise to the potassium permanganate solution 1 of 1-2% to add in 1mL washing water, and nondiscoloration in 3min, illustrates that sugar is cleaned.Barium malate precipitation after washing is put into dilution drum, adds water and break into pulpous state, with pump, slurries are squeezed into acidolysis bucket, under agitation slowly add the vitriol oil and decompose.The control method of acidolysis terminal is: get first, second two test tubes, put into 1mL15-20% sulfuric acid, put into 1mL15-20% barium chloride solution in second pipe in first pipe.Add the acid hydrolysis solution after 1mL filtration in each test tube respectively, water-bath is heated to boil, after cooling, all muddiness does not occur, then add the ethanol of 95% respectively.After adding ethanol, first pipe slightly in muddy, represent and has reached acidolysis terminal.If before adding ethanol, first pipe is just muddy, represents that in acid hydrolysis solution, sulfuric acid amount is not enough; After adding ethanol, second pipe is muddy, represents excess sulfuric acid in acid hydrolysis solution.After adding sulfuric acid, acid hydrolysis solution is heated to 90-95 DEG C, insulation 30min, promotes the generation of barium sulfate precipitate, and oxysuccinic acid dissociates.Acid hydrolysis solution is cooled to 60-70 DEG C of press filtration, discards after the hot wash of filter cake barium sulfate, and filtrate and washings merge, and are rare malic acid solution.After rare malic acid solution flows through decolorizing resin or activated carbon decolorizing, then flow through the exchange column that storng-acid cation exchange resin (as 732 type ion exchange resin) are housed, to remove the cation impurity such as calcium, iron.From rare Ping Guo Suan Rong liquid that ion exchange column flows out, at 50-60 DEG C, reduction vaporization concentrates, and is concentrated into proportion 1.10-1.15, in malic acid solution suction crystallizing pan after concentrated, slowly stir, open chuck water coolant and solution is chilled to 30-35 DEG C, be sprinkled into a small amount of crystal seed, crystallization 24-48h.Centrifugal under whizzer, filtrate can concentrate further, crystallization.Filter cake is with after the cold water washing of 20 DEG C, and 30-40 DEG C of vacuum-drying, get product oxysuccinic acid.

Slag after apple residue water extraction is swelling with the sodium hydroxide solution of 8 times amount (v/v) pH9-11, obtain solute, isothermal holding 60-90min at 80-90 DEG C of temperature, press filtration, obtain filtrate and filter residue, filtrate reduced in volume to proportion 1.10-1.15, in suction extractor.For making two-phase can layering faster in extractor, require that extraction agent and separated mixture have larger density difference, larger density difference can accelerate layering, improves the throughput of equipment.When the interfacial tension of extraction system is larger, dispersed phase drop is easily coalescent, is conducive to layering, but interfacial tension is excessive, and liquid not easily disperses, and is difficult to two-phase is fully mixed, and makes effect of extracting reduce on the contrary.Interfacial tension is too small, although liquid easily disperses, easily produces emulsion, makes two to compare difficult separation.Utilize different solubility in two liquid phases of each component in concentrated solution and concentrate mixture is separated.A certain amount of extraction agent normal hexane is added in concentrated solution, then stirred and concentrated solution is fully mixed with extraction agent, solute is spread by stock liquid by phase interface in extraction agent, stir after stopping, two liquid phases layering because density is different: one deck is based on extraction agent normal hexane, and be dissolved with the biological wax of more apple, another layer is based on former concentrated solution, containing the biological wax of the apple be not extracted, repetitive operation 3-5 time, 3-5% (W/V) gac and 3-5% (W/V) atlapulgite is added in extraction liquid, at 50-60 DEG C of heating 30-60min, suction filtration, filtrate reduced in volume, obtain the biological wax of apple.

Alkali aqueous solution after above-mentioned extraction, be evaporated to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling precipitation, press filtration, pulverize after filter cake 50-60 DEG C vacuum-drying, obtain water-insoluble apple residue Mierocrystalline cellulose, add 5-8 times amount (v/w) distilled water swelling, obtain solute, add the hydrochloric acid soln of pH1-2, make its pH value reach 4-5, add cellulase, at 40-50 DEG C of insulation enzymolysis 6-8h, press filtration, 50-60 DEG C of vacuum-drying, pulverizes, obtains apple Microcrystalline Cellulose.

Claims (11)

1. the integrated extracting and purifying method of apple residue effective constituent, be raw material with apple residue, the method includes the steps of:

(1) water extraction, concentrated, obtain water-soluble general extractive;

(2) preparation of apple polyphenol in water extract;

(3) separation of phlorizin in apple polyphenol;

(4) phlorizin prepares Phloretin;

(5) preparation of apple pectin in water extract;

(6) preparation of apple polysaccharide in water extract;

(7) preparation of oxysuccinic acid in water extract;

(8) the slag potass extraction after water extraction;

(9) preparation of apple wax;

(10) preparation of apple Microcrystalline Cellulose.

2. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, add 8 times (WW) in apple residue in step (1) and measure deionized water, 2h is extracted in 70-80 DEG C of heating, collect the feed liquid extracted, filter residue adds 6 times (V/W) again and measures deionized water, 1.5h is extracted in 70-80 DEG C of heating, collect the feed liquid extracted, filter residue adds 5 times (V/W) again and measures deionized water, 1.0h is extracted in 70-80 DEG C of heating, collects the feed liquid extracted.The feed liquid of front extracted twice merged, third time extracts the extracting solution of feed liquid as next batch of material, and material slag is waited until for subsequent use, so circulates.The feed liquid merging of front extracted twice is concentrated into ρ=1.05 ~ 1.10.Add 2-3 times (V/W) and measure deionized water, fully stir, press filtration, collect filtrate, obtain apple residue Aqueous extracts.

3. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, in step (2), apple residue Aqueous extracts is with macroporous resin adsorption, resin used is one of in D-101, AB-8, ADS-17ADS-7, NKA-9, X-5, ADS-F8, HPD826, HPD-200A, HPD-400, HPD-750, HPD-826, HPD-200L or HPD-300L, first use purified water wash-out, collect water lotion, wait until for subsequent use.Then be the ethanol elution of 50-80% by volume fraction, collect ethanol eluate, concentrating under reduced pressure, spraying dry, obtains apple polyphenol.

4. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, apple polyphenol is dissolved with purified water in (3) by step, respectively with extraction one of in normal hexane, sherwood oil, No. 6 solvent oils or ether 3 times, first time 5 times amount (V/W) extracts degreasing, and second time 4 times amount (V/W) extracts degreasing, and third time 3 times amount (V/W) extracts degreasing, collect the liquid after degreasing, degreasing solvent reclaims.After degreasing, the apple polyphenol aqueous solution is with ethyl acetate or n-butanol extraction, first time 5 times amount (V/W) extraction, second time 4 times amount (V/W) extraction, third time 3 times amount (V/W) extraction, collect extraction liquid, concentrating under reduced pressure solvent recuperation, is concentrated into proportion 1.05-1.08, add 3-5% gac reflux decolour 30min, suction filtration while hot, filtrate reduced in volume proportion 1.10-1.15, adds a small amount of ether, abundant stirring, place, crystallization, suction filtration, vacuum-drying at 50-60 DEG C, obtains phlorizin.

5. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, in step (4), phlorizin is with the deionized water dissolving of 5-8 times amount (V/W), add the vitriol oil and regulate water liquid pH1-2, keep still internal pressure at 0.12-0.15Mpa, reaction 1-4h.Cooling, press filtration, water washing is to filtrate pH value in neutral, and drying, obtains Phloretin crude product.By Phloretin crude product with ethanol or methyl alcohol heating for dissolving, add 3-5% (W/W) gac reflux decolour 30min, filter, after filtrate is concentrated into 1/3 of original volume, stirred crystallization, centrifugal, dry under-(0.02-0.04) MPa, obtain Phloretin fine work.

6. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, in step (5), the water elution liquid in (2) is evaporated to proportion 1.10-1.15, is acidified to pH1-3, adds the saturated Al of 3-5% (v/v) ₂(SO ₄) ₃solution, fully stirs, and saltouts, press filtration, and filtrate is waited until for subsequent use.The filter cake 20-30% ethanol heating for dissolving of 4-6 times amount, adds 3-5% (v/v) hydrogen peroxide, and 60-70 DEG C of insulation 1-2h, press filtration, filter cake pH2-4 volume fraction is the washing with alcohol of 70-80%, and 50-60 DEG C of vacuum-drying, obtains high ester pectin finished product.High ester pectin is dissolved with the sodium hydroxide of the pH value 9-11 of 3-5 times amount (v/w), at 30-40 DEG C of heating 30-60min, be evaporated to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling, press filtration, filter cake is washed, suction filtration, 50-60 DEG C of vacuum-drying, obtains low-ester pectin finished product.

7. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, in step (6) by middle to (5) filtrate reduced in volume to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling, press filtration, filter cake is with water dissolution, add the sodium hydroxide solution of 5-10%, until generate without precipitation, suction filtration, filtrate adds 3-5% (v/w) gac, 70-80 DEG C of insulation 30min, suction filtration while hot, filtrate reduced in volume is to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling, press filtration, filter cake washing with alcohol, 50-60 vacuum-drying, obtain apple polysaccharide.

8. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, by the pressing filtering liquid after alcohol precipitation in (6) in step (7), then add hydrated barta powder, heated and boiled, the precipitation hot water wash decon of 80-90 DEG C.The method checked is added drop-wise to the potassium permanganate solution 1 of 1-2% to add in 1mL washing water, and nondiscoloration in 3min, illustrates that sugar is cleaned.Barium malate precipitation after washing is added water and breaks into pulpous state, add the vitriol oil and decompose.The control method of acidolysis terminal is: get first, second two test tubes, put into 1mL15-20% sulfuric acid, put into 1mL15-20% barium chloride solution in second pipe in first pipe.Add the acid hydrolysis solution after 1mL filtration in each test tube respectively, water-bath is heated to boil, after cooling, all muddiness does not occur, then add the ethanol of 95% respectively.After adding ethanol, first pipe slightly in muddy, represent and has reached acidolysis terminal.If before adding ethanol, first pipe is just muddy, represents that in acid hydrolysis solution, sulfuric acid amount is not enough; After adding ethanol, second pipe is muddy, represents excess sulfuric acid in acid hydrolysis solution.After adding sulfuric acid, acid hydrolysis solution is heated to 90-95 DEG C, insulation 30min, promotes the generation of barium sulfate precipitate, and oxysuccinic acid dissociates.Acid hydrolysis solution is cooled to 60-70 DEG C of press filtration, discards after the hot wash of filter cake barium sulfate, and filtrate and washings merge, and are rare malic acid solution.After rare malic acid solution flows through decolorizing resin or activated carbon decolorizing, flow through the exchange column that storng-acid cation exchange resin (as 732 type ion exchange resin) are housed again, from rare Ping Guo Suan Rong liquid that ion exchange column flows out, at 50-60 DEG C, reduction vaporization concentrates, be concentrated into proportion 1.10-1.15, malic acid solution cooling after concentrated, be sprinkled into a small amount of crystal seed, crystallization 24-48h, centrifugal, filtrate can concentrate further, crystallization, and filter cake is with after the cold water washing of 20 DEG C, 30-40 DEG C of vacuum-drying, get product oxysuccinic acid.

9. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, by swelling with the sodium hydroxide solution of 8 times amount (v/v) pH9-11 for the apple residue after water extraction in (1) in step (8), obtain solute, isothermal holding 60-90min at 80-90 DEG C of temperature, press filtration, obtains filtrate and filter residue, and filtrate reduced in volume is to proportion 1.10-1.15.

10. the integrated extracting and purifying method of apple residue effective constituent as claimed in claim 1, it is characterized in that, in step (9) by middle to (8) concentrated solution with normal hexane, sherwood oil, extraction 3 times one of in No. 6 solvent oils or ether, first time 5 times amount (V/W) extraction, second time 4 times amount (V/W) extraction, third time 3 times amount (V/W) extraction, collect extraction liquid, 3-5% (W/V) gac and 3-5% (W/V) atlapulgite is added in extraction liquid, at 50-60 DEG C of heating 30-60min, suction filtration, filtrate reduced in volume, obtain the biological wax of apple.

The integrated extracting and purifying method of 11. apple residue effective constituents as claimed in claim 1, it is characterized in that, in step (10), the alkaline solution after the extraction in (9) is evaporated to proportion 1.10-1.15, add 5-8 times amount (v/w) 95% alcohol settling precipitation, press filtration, pulverize after filter cake 50-60 DEG C vacuum-drying, obtain water-insoluble apple residue Mierocrystalline cellulose, add 5-8 times amount (v/w) distilled water swelling, obtain solute, add the hydrochloric acid soln of pH1-2, its pH value is made to reach 4-5, add cellulase, at 40-50 DEG C of insulation enzymolysis 6-8h, press filtration, 50-60 DEG C of vacuum-drying, pulverize, obtain apple Microcrystalline Cellulose.