CN100497397C - Method for preparing fibre-containing pectin and products and uses hereof - Google Patents
Method for preparing fibre-containing pectin and products and uses hereof Download PDFInfo
- Publication number
- CN100497397C CN100497397C CNB2004800193992A CN200480019399A CN100497397C CN 100497397 C CN100497397 C CN 100497397C CN B2004800193992 A CNB2004800193992 A CN B2004800193992A CN 200480019399 A CN200480019399 A CN 200480019399A CN 100497397 C CN100497397 C CN 100497397C
- Authority
- CN
- China
- Prior art keywords
- pectin
- product
- fibre
- weight
- bearing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
A method is provided for treating pectin-containing plant materials in a manner to obtain fibre-containing pectin products, and subsequently pectin products, having an high molecular weight of the pectin polymer and a homogeneous distribution of the deesterified sites in the pectin polymer and thereby providing products having improved gelforming and/or viscous giving properties.
Description
Technical field
The present invention relates to prepare the field of pectin product by pectous vegetable material.Especially, provide a kind of novel method of novel fibre-bearing pectin product and novel pectin product that obtains by described fibre-bearing pectin product of preparing.
Background technology
Preparing by potato in the industrial production of yam starch, comprising the fibrous matter of so-called potato syrup and potato in the resulting byproduct.Knownly also obtain similar byproduct or waste product, for example prepare sugar beet slices in the sugared process, produce orange peel and tangerine slurry in fruit juice and the essential oil process and the pomace residue in the hard cider production process by citrus fruit by beet by other agricultural-food.
These plant by-products often are considered to waste product and handle in the most suitable and the most cheap mode.Yet, can understand, these plant by-products further are developed as the product that has more commercial value, have very significantly advantage.
The common trait of these byproducts is that their main (about 80～100%) are made up of solvable and insoluble vegetable fibre, wherein about 60～80% is edible fibers, comprise three kinds of biopolymers: Mierocrystalline cellulose, hemicellulose and pectin in all vegetable cell wall constructions, it is considered to the network structure of Mierocrystalline cellulose-hemicellulose-pectin, pectin also constitutes " joint compound " that vegetable cell provides hardness except as a kind of structural element therein.Pectin is attached to complex structure on other cell walls by covalent linkage, hydrogen bond and/or ionic interaction, and so-called is protopectin-(protopectin).Pectin itself can extract by acid that protopectin-is controlled or basic hydrolysis and obtain.
Pectin is linear polymkeric substance, and it contains α-D-galacturonic acid unit, and it is by α-1, and the 4-glycosidic link is in conjunction with the polygalacturonic acid that forms long-chain.The galacturonic acid unit with different degree by methanol esterification.Like this, being higher than 50% high ester pectin and degree of esterification in degree of esterification (DE) is lower than 50% low-ester pectin and has just caused difference.Degree of esterification is defined as methyl-unitary number of esterification galacturonic acid, and it is expressed as the per-cent of total galacturonic acid unit in pectin molecule, therefore can be the numerical value between 0%～100%.
In pectin from some kind of vegetable material of for example potato and beet; the unitary different piece of galacturonic acid can be acetylation in addition; be expressed as degree of acetylation (DAc); it is similar definition to degree of esterification, i.e. the unitary per-cent of acetylize galacturonic acid in whole galacturonic acid units.
Neutral sugar (neutral sugar), for example semi-lactosi, glucose, rhamnosyl, pectinose and wood sugar also can be the parts of pectin polymkeric substance, as the side chain or the composition of polygalacturonic acid chain.
Hemicellulose is the allos monoid (heterogeneous group) of polysaccharide, and it contains multiple hexose and pentose, and contains uronic acid residue in some cases.Kind according to main saccharide residue is classified polymkeric substance, is called xylan, arabogalactan and glucomannan etc.
Formerly in the technology known acid or the alkali of how using to pectin with contain pectin material and carry out de-esterifying and handle.
US-5,567,462 disclose a kind of from containing the method that the pectin material of vegetable origin for example prepares pectin-cellulose composition and pectin tangerine peel, beet pulp, Sunflower Receptacle residue and the pomace.This method is made up of following steps, uses the acid of phosphoric acid for example or nitric acid or the alkali of sodium hydroxide or yellow soda ash for example, handles the starting material of claying into power, with provide by the solid phase that contains fibre fractionation with contain the mixture that pectolytic liquid phase is formed.Mixture is ground, neutralizes and final drying, to form pectin-Mierocrystalline cellulose dry-matter.Also the mixture of smashing to pieces can be divided into solid phase and liquid phase, it is neutralized respectively and is dry to obtain pectin product and pectin-cellulose prods.
The also known ammoniacal liquor that how uses in the organic solvent of for example Virahol is to pectin or contain pectin material and carry out de-esterifying and handle in the prior art, and wherein pectin is insoluble.US-2,480,710 disclose the example of this technology.
DE-4,013,765 and DE-4,042,405 disclose the use ammonia to the exsiccant plant residue for example beet pulp carry out in the treating processes, and the sodium hydroxide of water or high dilution is carried out in the process of follow-up extraction, prepare amino pectin, food fiber and filler (filler).By in spissated extract, adding acid, obtain amino pectin, and insoluble residue becomes food fiber and filler after extraction.
Have been found that, dissolving pectin and not with an organic solvent not, also can in processing contains complete aqueous systems in the pectin vegetable material process, carry out the de-esterifying of pectin, before de-esterifying is handled, contain in the aqueous solution that the pectin vegetable material contained neutral salt and expand.
Therefore, the purpose of this invention is to provide and a kind ofly under the de-esterifying condition, handle the novel and simple method contain the pectin plant, and then the fibrous pectin product and the isolating pectin product that obtain having high commercial value and high practical value.
Invention is concise and to the point to be described
Therefore, one aspect of the present invention provides a kind of method that is prepared fibre-bearing pectin by vegetable material.Described method comprises following step:
(i) provide a kind of reaction in system by turgid plant material in the aqueous solution, the wherein said aqueous solution contains at least a salt;
(ii) the pectin the turgid plant material that obtains from step (i) being carried out de-esterifying handles; With
The fibre-bearing pectin product that (iii) divides the ester of leaving away.
In another aspect of the present invention, a kind of method for preparing pectin product is provided, described method comprises following step:
(i) provide aforesaid fibre-bearing pectin product;
(ii) in the fibre-bearing pectin product, add and extract medium to obtain extracting suspension;
(iii) will extract in the scope of pH regulator to 1～12 of suspension;
(iv) will extract in the temperature range of temperature regulation to 20～100 ℃ of suspension; With
(v) separate pectin product from the aqueous phase that extracts medium.
Of the present invention further aspect in, a kind of fibre-bearing product and/or pectin product that obtains by preceding method is provided.
Another aspect of the present invention provides a kind of pectous product, and it satisfies at least a following the requirement:
(i) concentration of pectin mostly is 1% (w/w) most and mixes in solution, and when detecting with method A, product has the viscosity of 5cp at least, perhaps
(ii) mix when mostly being most 1% (w/w), and when detecting with method A, the viscosity of product is higher than at least 2 times of traditional pectin products of processing with concentration of pectin in the solution.
Detailed description of the Invention
Main purpose of the present invention provides a kind of method, it is handled in one way and contains the pectin vegetable material to obtain fibre-bearing pectin product and follow-up pectin product, its have the high molecular of pectin polymkeric substance and in the pectin polymkeric substance the more uniform distribution in de-esterifying site, therefore the product that has improved formation gel and/or adhering performance is provided is provided.
In the present invention, term " high molecular of pectin polymkeric substance " relates to the size of pectin polymkeric substance, be used for illustrating pectin polymkeric substance-unitary number of D-galacturonic acid, it is greater than the size that obtains the pectin polymkeric substance by the use traditional method, because in the method that tradition is used, is littler chain with the bronsted lowry acids and bases bronsted lowry solution-treated with the dissolved pectin polymer unwinds, but processing provided by the present invention keeps the pectin polymkeric substance substantial complete.
In the present invention, term " uniform distribution in de-esterifying site " relates to being evenly distributed of in pectin polymkeric substance ester group, thus this pectin polymkeric substance by de-esterifying can be by metal ion in stable and average mode in conjunction with other pectin polymkeric substance.On the contrary, the frequent cluster of the distribution in de-esterifying site occurs in traditional pectin polymkeric substance, and this can cause that very active and reaction pectin of the reaction of pectin polymkeric substance and metal ion becomes and be difficult to control.
The more uniform distribution in the high molecular of this pectin polymkeric substance and de-esterifying site can obtain by the method according to this invention, a kind of method that obtains the fibre-bearing pectin product from vegetable material for example is provided, described method comprises step: a kind of reaction in system by turgid plant material in the aqueous solution (i) is provided, and the wherein said aqueous solution contains at least a salt; (ii) the pectin that exists the turgid plant material that obtains from step (i) being carried out de-esterifying handles; The fibre-bearing pectin product that (iii) divides the ester of leaving away.
Vegetable material
In the present invention, term " vegetable material ", " pectous vegetable material " and " pectous material of vegetable origin " can exchange use, and relate to the vegetable material of any kind of, its contain can/can be used in the pectin of preparation fibre-bearing pectin product or pectin product.
The material that is fit to be the vegetable material of or drying regime fresh from this locality obtain contain pectin material, the degree of esterification that contains pectin is preferably more than 40% greater than 30%, is preferably more than 50%, is typically 60%～70%.
In the preferred embodiment of the present invention, suitable local pectous vegetable material comprises for example skin or the slurry of the tangerine class fruit of lemon, orange, oranges and tangerines, bitter orange and natsudaidai.Other local pectous vegetable material comprises the pomace of sugar beet slices, potato syrup and apple.
Contain in the pectin vegetable material at these, the content of pectin has difference because of bion material difference, based on dry substance, for example, contains the pectin of 30～40% weight in the orange skin, contains the pectin of 15～30% weight in potato syrup.
Expand
Pectin can be insoluble in fact or indissoluble just in the aqueous solution, as method of the present invention, can be preferably based on the alkali de-esterifying of pectin, and its natural place that occurs in pectin in the vegetable material is original position just.
In the preferred embodiment of the present invention, vegetable material is expanded in the aqueous solution, it provides the reaction in system.Herein, term " reaction in system " relates to a kind of state, wherein by the turgid plant material as reaction chamber and become and can permeate, and then for example allow alkali reagent to enter that vegetable material and dissolved material leave vegetable material and dissolving pectin polymkeric substance not.And " reaction in system " makes and can carry out de-esterifying processing and/or amidation processing in the vegetable material inside configuration to pectin polymkeric substance in the vegetable material.
In using the process that for example alkali reagent is handled, formation water soluble pectin keep insoluble state and with insoluble plant cell constituents for example under Mierocrystalline cellulose and the hemicellulose accumulative condition, protopectin-in the vegetable material is changed into water soluble pectin, and at least a portion is non-under this condition contains pectin substance for example protein, sugar and tinting material are removed.
Institute's dissolved pectin will tend to break away from reaction mixture in the process of handling with the aqueous solution and/or alkali reagent, and then cause the loss of pectin.Another shortcoming of dissolved pectin is increasing of reaction mixture viscosity, the transport disengaging height difficulty of the feasible vegetable material of handling.
The aqueous solution can make vegetable material keep a kind of state, i.e. its structural integrity in fact.This is because a fact, and promptly for example the reaction of alkali de-esterifying is to depend on to expand and permeable vegetable material, and then allows that for example alkali reagent enters vegetable material and dissolved material leaves vegetable material.Because Mierocrystalline cellulose-hemicellulose-pectin network can be used as " container " that reaction takes place, therefore the structure of this network is kept perfectly and must be able to not be decomposed, because this can cause forming reluctant jelly.
In a preferred embodiment of the present invention, the aqueous solution does not contain organic solvent.Preferably, the aqueous solution is inorganic aqueous solution.
Above-mentioned condition can be according to the present invention suspends in salt brine solution and expands and obtain by containing the pectin material of vegetable origin.In the context of the invention, term " salts solution " relates to the solution that contains at least a salt.
Contain the water-soluble neutral salt that the aqueous solution that the pectin material of vegetable origin is inflated therein can contain at least a adding, be selected from sodium salt, sylvite, calcium salt and composition thereof.Especially preferably muriate, for example sodium-chlor, Repone K, calcium chloride and composition thereof.Yet, also can use nitrate, for example SODIUMNITRATE, saltpetre and nitrocalcite.Can find other operable in the present invention salt at EP 0 664 300, quote as a reference here.
Join the amount of salt in the solution, containing the pectin material of vegetable origin in this solution is suspended and is expanded, can be chosen as and to be fit to every gram to contain pectin vegetable material dry-matter salt concn be 1mmol～30mmol, be preferably every gram dry-matter and contain pectin vegetable material 5mmol～15mmol.
In a preferred embodiment of the invention, the expansion of vegetable material provides a kind of suspension, wherein the content of vegetable material dry-matter is 1% weight～50% weight, 1% weight～30% weight for example, for example 1% weight～25% weight, for example 1% weight～15% weight, for example 1% weight～10% weight, be typically 4% weight～8% weight, for example 6% weight.
Contain when the pectin material of vegetable origin stirs in salt brine solution and suspend, temperature is about 0 ℃～about 120 ℃ scope, is preferably 0 ℃～50 ℃ scope, for example 0～20 ℃, and for example 0～10 ℃, for example 0～5 ℃, for example about 3.5 ℃.Usually the temperature in preferred 0～20 ℃ of scope, because otherwise have the vegetable material rapid expansion and begin the dissolved risk, and temperature can be hanged down in-10 ℃～20 ℃ the scope in some cases.
Select reasonable time so that vegetable material fully expands, so that the structure of fully being permeated and allowing liquid and dissolved substance to pass through.In preferred implementation according to the present invention, vegetable material is carried out the expansible time depend on type and the state that contains the pectin vegetable material in the aqueous solution, from 1 to 120 minute to obtain containing the abundant expansion and the salt loading of pectin vegetable material.In another embodiment, the selected time is 1～100 minute, for example 1～80 minute, and for example 1～70 minute, for example 10～70 minutes, for example 10～60 minutes, for example 15～40 minutes, for example 20～30 minutes.
Fully expanded and the salt loading required time relies on, and other factors, depend on the physical size that contains the pectin material of vegetable origin, it can be to have average footpath from 1mm or be smaller to part and be about 5mm particulate form to the maximum.
De-esterifying
In first treatment step, make and contain pectin material of vegetable origin entering part aquation and swelling state, it is the pre-treatment of carrying out suitable subsequent processing steps, this subsequent disposal comprises that with acid or alkali reagent the suspension expansible being contained the pectin material of vegetable origin handles according to the present invention, so that the pectin polymkeric substance is carried out de-esterifying or part de-esterifying.Preferably, use alkali reagent to handle containing the pectin vegetable material, its pH is 7～14 scopes, for example 8～14, for example 8～13, for example 9～13, for example 10～13, for example 10～12, for example 11.5～12.5.In yet another embodiment of the present invention, provide and be higher than 7 pH, for example be higher than 8 by adding alkali condition that alkali reagent provided, for example 9, for example be higher than 10, for example be higher than 11, for example be higher than 12, for example be higher than 13, for example 14.
Term among the present invention " de-esterifying " relates to the process of removing at least one ester group from the pectin polymkeric substance.
In an embodiment of the invention, it is to carry out in about 0 ℃～120 ℃ temperature range that de-esterifying is handled, preferably at 0 ℃～50 ℃, and for example 0 ℃～20 ℃, for example 0 ℃～10 ℃, for example 0 ℃～5 ℃, for example 3.5 ℃.Under some situation, temperature for example can be hanged down in-10 ℃～20 ℃ the scope.
In an embodiment of the invention, de-esterifying is handled and was carried out 1～120 minute, and for example 1～100 minute, for example 1～80 minute, for example 1～70 minute, for example 10～70 minutes, for example 10～60 minutes, for example 15～40 minutes, for example 20～120 minutes, for example 20～30 minutes.
In an embodiment of the invention, the dry matter content that de-esterifying is handled with vegetable material is that 1～50% weight is carried out, 1% weight～30% weight for example, 1% weight～25% weight for example, 1% weight～15% weight for example, for example 1% weight～10% weight is typically 4% weight～8% weight, for example 6% weight.
In an embodiment of the invention, the de-esterifying processing is alkaline purification.
In another embodiment of the inventive method, provide alkaline purification by alkali reagent, use this alkali reagent that suspension expansible material of vegetable origin is handled.
In the further embodiment of the present invention, the alkali reagent that is used for handling suspension expansible material of vegetable origin is selected from ammonia or other low molecular amine, diamines or amino acid, the oxyhydroxide of sodium, potassium and calcium, for example sodium hydroxide, potassium hydroxide, calcium hydroxide, the oxyhydroxide of organic bases, tetramethyl ammonium hydroxide for example, and composition thereof.The consumption of alkali reagent is that every gram contains pectin plant dry matter 0.5mmol～5mmol alkali.
In embodiments of the present invention, amino acid is selected from Methionin, Histidine, arginine, glutamine, l-asparagine and tryptophane.
Alkali reagent can use with solid form or as the aqueous solution, and can add guaranteeing by vigorous stirring and be distributed to fast in the suspension of expansible material of vegetable origin.
Preferred alkali reagent is ammonia, calcium hydroxide and sodium hydroxide.Ammonia is most preferred, but calcium hydroxide also is preferred, because its solubleness limited in water guarantees to discharge slowly hydroxide ion.
Optimally be, alkali reagent can join in the expansible material of vegetable origin in one way gradually, and wherein the pH value in the entire reaction course can maintain the almost stable pH in 11.5～12.5 scopes, and for example 12.0 ± 0.1.Adding the amount of alkali reagent in this processing, can be in the alkali scope of per kilogram reaction mixture 20mmol～80mmol, for example 25mmol～50mmol.
In according to a preferred embodiment of the present invention, use ammoniacal liquor as alkali reagent, its amount contains pectin plant dry matter 20mmol～80mmol ammonia for every gram, and for example every gram contains pectin plant dry matter 40mmol～80mmol ammonia.
Preferably, the form that ammonia can concentrated liquor is used, 25% solution for example, but also can use more low intensive ammoniacal liquor.
Optimally be that ammoniacal liquor can once join in the suspension of expansible material of vegetable origin and stirred suspension simultaneously.In processing the amount of employed adding ammonia can scope for per kilogram reaction mixture 1mol～3.5mol ammonia in, 1.4～2.7mol ammonia for example guarantees to keep the pH of almost stable in entire reaction course.
In an embodiment of the invention, can be in 0 ℃～120 ℃ temperature range, to carry out with the processing of ammonia, be preferably 0 ℃～50 ℃, for example 0～20 ℃, for example 0～10 ℃, for example 0～5 ℃, for example about 3.5 ℃.
In yet another embodiment of the present invention, processing with ammonia can be carried out 1～120 minute, for example 1～100 minute, for example 1～80 minute, for example 1～70 minute, for example 10～70 minutes, for example 10～60 minutes, for example 15～40 minutes, for example 20～30 minutes, preferably carried out about 40 minutes～about 60 minutes.
In an embodiment of the invention, contain the pectin vegetable material with ammonia treatment, it provides the pH of 7～14 scopes, and for example 8～14, for example 8～13, for example 9～13, for example 10～13, for example 10～12, for example 11.5～12.5.
Carrying out in the process of de-esterifying processing the balanced type below having occurred at aqueous reaction mixture with ammonia:
NH
3+H
2O＝NH
4 ++OH
-
At two kinds of nucleophilic reagent (NH
3And OH
-) between have competition, this is to use OH
-Carry out the reason of de-esterifying reaction, just the OCH of methyl-esterified carboxyl in the pectin
3Replaced formation COOH by OH, it can be accompanied by amidation, wherein OCH
3By NH
2Replace and to have formed methane amide, wherein under the de-esterifying condition, the methyl-esterified carboxyl that is converted into carbonylamino group in the pectin can reach at least 20% and no more than 70%, is typically 25%～50%.
In above-mentioned embodiment of the present invention, can obtain the fibre-bearing pectin product and have degree of esterification and be not higher than 40% at least 3%, for example be not higher than 35%, and at least 5% degree of amidation, for example at least 10% and be not higher than 30%.
Be similar to degree of esterification, degree of amidation is defined as the unitary number of formamide galacturonic acid, is expressed as the unitary per-cent of all galacturonic acids in pectin molecule.
In embodiments of the present invention, the processing that oxyhydroxide that uses sodium, potassium or calcium and composition thereof is carried out is to carry out about 0 ℃～about 20 ℃ of temperature ranges, 0 ℃～about 5 ℃ of preferably approximatelies, for example 2 ℃～3 ℃, continue 20 minutes～75 minutes, be typically 20 minutes～45 minutes.It is 2%～40% fibre-bearing pectin product that present embodiment obtains having degree of esterification.
The present invention another preferred embodiment in, relate to a kind of processing and contain the pectin plant to obtain to have the method that forms gel and/or the fibre-bearing pectin product of adhering performance is provided, it comprises the following steps:
(a) under about 0 ℃～20 ℃ range temperature, in the salt brine solution, suspension contains the pectin material of vegetable origin, expanded 10～70 minutes, this salt brine solution contains the water-soluble neutral salt of at least a interpolation, it is selected from sodium salt, sylvite, calcium salt and composition thereof, and consumption is that corresponding salt concn is that every gram contains pectin plant dry matter 1mmol～30mmol, forms to contain the suspension that pectin plant dry matter content is 1% weight～10% weight;
(b) use alkali reagent in pH is 11.5～12.5 scopes and temperature be in about 0 ℃～20 ℃ scopes the suspension expansible to be contained the pectin material of vegetable origin to handle 5 minutes～120 minutes; With
(c) vegetable material of separating treatment from reaction mixture, described material is carried out cleaning step at least one time, then described material is pressurizeed to obtain fibre-bearing pectin product, it has dry matter content and is at least 16% weight, degree of esterification is 2%～40%, and degree of amidation is not higher than 30%, and it is dried to dry matter content and is at least 80% weight, if wish, can selectivity grind.
Amidation
In embodiments of the present invention, by adding amidation reagent, vegetable material further can be carried out amidation and handle to the expansible vegetable material.
In this article, term " amidation " relates to the process that at least a ammoniation is contacted with the pectin polymkeric substance.
In embodiments of the present invention, amidation reagent is selected from ammonia or other low molecular amine, diamines or amino acid for example Methionin, Histidine, arginine, glutamine, l-asparagine and tryptophane.
Preferably, the expansible vegetable material can be handled 1～120 minute by amidation reagent, and for example 1～100 minute, for example 1～80 minute, for example 1～70 minute, for example 10～70 minutes, for example 10～60 minutes, for example 15～40 minutes, for example 20～30 minutes, be preferably 40 minutes～60 minutes.
In embodiments of the present invention, the expansible vegetable material can be handled under the temperature of-10 ℃～120 ℃ of scopes by amidation reagent, for example-5 ℃～120 ℃ scope, for example 0 ℃～120 ℃ scope, be preferably 0 ℃～50 ℃ scope, for example 0 ℃～20 ℃, for example 0 ℃～10 ℃, for example 0 ℃～5 ℃.
In the preferred embodiment of the present invention, the de-esterifying of pectin polymkeric substance and amidation step are simultaneously or carry out continuously.Carry out de-esterifying simultaneously and an amidated suitable embodiment can use ammoniacal liquor to carry out two reactions.
Separate, clean and pressurization
The vegetable material (after carrying out de-esterifying and selectivity amidation) of separating treatment from alkali reaction mixture for example, and it is carried out at least one cleaning step and/or at least once pressurization, obtain the fibre-bearing pectin product.In embodiments of the present invention, such fibre-bearing pectin product contains the dry-matter of at least 5% weight, for example at least 10% weight, for example at least 16% weight, for example at least 20% weight, for example at least 25% weight, for example at least 50% weight.
In the further embodiment of the present invention, it is 0～80% that isolating, cleaning and/or exsiccant fibre-bearing pectin product contains degree of esterification, for example 0～50%, for example 2～50%, for example 2～45%, for example 2～40%, for example 5～50%, for example 10～50%, for example 10～40%, for example 15～35%, and/or degree of amidation is for being no more than 95%, for example be no more than 75%, for example be no more than 60%, for example be no more than 50%, for example be no more than 40%, for example be no more than 30%, for example be no more than 25%, for example be no more than 20%.
In embodiments of the present invention, the fibre-bearing pectin product that obtains can be dried to dry matter content and be at least 40% weight, at least 50% weight for example, at least 60% weight for example, at least 70% weight for example, at least 80% weight for example, at least 90% weight for example, and can optionally grind.
The vegetable material of separating treatment can be undertaken by any appropriate means from reaction mixture, for example draining, filtration or centrifugal.
The isolating vegetable material that uses alkali reagent to handle can clean at least once, during stirring material is suspended in inorganic acid aqueous solution for example in sulfuric acid, hydrochloric acid or the nitric acid, make that the pH of suspension is 1～6, particularly 1～4, more particularly 1～2, most particularly be lower than 1.5, for example 1.3～1.5.Then, separate the vegetable material that is cleaned, and can follow water and clean at least once, it is resuspended in the water that for example desalts.Clean to product can be carried out under about 15 ℃ temperature, and can in aqueous acid and water, repeat respectively, has stable p H up to cleaning suspension, for example in 2～2.5 scope, then can be from cleaning solution the separate solid material, and on filter pressurization to reduce in the material content liquid to minimum.
Use dilute acid to carry out this cleaning, stop the de-esterifying reaction of pectin, and wash salt and water-soluble impurity off so that the pectin in the fibre-bearing product changes into sour form by neutralization bases reagent.
Contain the reaction mixture of the vegetable material of handling can be at first mix with the mineral acid of dilution so that pH 1～6, particularly 1～4, more particularly 1～2, most particularly be lower than 1.5, for example 1.3～1.5, rather than come the vegetable material of separating treatment mutually by the alkali lye of draining immediately.Like this, realize the neutralization immediately of alkali reagent, then the vegetable material of handling by the liquid phase separation of draining.Then be suspended in dilute acid and for example salt-free water of water cleans respectively by aforesaid respectively, have scope in 2～2.5 stable p H values up to cleaning suspension.
In dampness, the fibre-bearing pectin product that separates and clean can selectivity for example Sodium Hydrogen Carbonate or potassium bicarbonate are mediated with hydrocarbonate, the free carboxyl group of pectin become salt form substantially and with gas form evaporation carbonic acid gas, then with product drying with grind.
Drying to the fibre-bearing pectin product that cleans can be undertaken by the method for traditional drying equipment, for example drying oven, conveyor dryer, heated drum or fluidized bed dryer carry out the fully long time, and the content that obtains dry-matter in the material is at least 80% weight.Drying can be no less than 36 hours under 25 ℃～100 ℃ temperature.Advantageously, drying can be carried out being lower than under the pressure by air pressure, therefore can use low relatively drying temperature or short relatively time of drying, this means the more careful processing of product.
Drying products ground also can use legacy equipment to carry out, therefore available grated product has the particle diameter less than 1mm, for example less than 0.5mm, for example less than 0.2mm.
Separate pectin product
According to the present invention, can provide pectin product according to following method:
(i) provide according to fibre-bearing pectin product of the present invention;
(ii) in the fibre-bearing pectin product, add and extract medium to obtain extracting suspension;
(iii) will extract in the scope of pH regulator to 1～12 of suspension;
(iv) will extract in the temperature range of temperature regulation to 20～100 ℃ of suspension; With
(v) separate pectin product from the aqueous phase that extracts medium.
By carrying out the available fibre-bearing pectin product of top disclosed processing to containing the pectin material of vegetable origin, also be the starting material that the pectin product of purifying is produced in highly suitable being used to, the pectin product of this purifying has surprising high glue intensity and the adhering performance above these pectin.Traditionally, use nitric acid being higher than under 50 ℃ the temperature, obtain by the high ester pectin with de-esterifying acid extraction and purifying, wherein purified high ester pectin has about 65%～about 50% or littler degree of esterification.
In the traditional method of this preparation low-ester pectin, the further processing of amidation product is normally carried out according to following: will go the ester product to precipitate in ethanol, and therefore at first carry out the reaction of aforesaid strong acid reaction and last and ammonia.Like this, the pectin polymkeric substance carried out acid-respons more than twice hours being higher than under 50 ℃ the temperature, and it reduces the molecular weight of polymkeric substance significantly, and as causing opposite influence with the reaction of ammonia, it is in conjunction with having lowered the performance that forms gel and viscosity is provided significantly.
If the fibre-bearing pectin product that the inventive method is obtained then comprises the processing of purifying, can obtain having the pectin product that forms gel and adhering performance is provided, it surpasses corresponding product of processing by the aforementioned conventional mode usually.
Therefore, the invention further relates to a kind of method for preparing the pectin product of purifying, comprise by aforementioned containing the pectin vegetable material by processing and obtaining the step that the fibre-bearing pectin product is formed.In embodiments of the present invention, extract the fibre-bearing pectin product, dry matter content is 2%～40% at least 16% weight, degree of esterification, and degree of amidation is no more than 30%.
Preferably, extract medium and have the interior pH of 1～12 scope, for example 1～11 scope, for example 1～10 scope, 1～9 scope for example, for example 1～7 scope, for example 1～6 scope, for example 2～6 scope, 2～5 scope for example, 3～5 scope for example, for example in 4～5 the scope, for example 4.5.
In embodiments of the present invention, extract medium in 20～120 ℃ scope, for example in 40～100 ℃ the scope, for example in 60～80 ℃ the scope, from isolating aqueous extract, can reclaim the pectin product of purifying.
The fibre-bearing pectin product can be extracted 30 minutes～time of 30 hours, for example 1～20 hour, be preferably 1～10 hour, for example 1～5 hour.
The acidity of suspension can be adjusted to the pH of expectation, by adding for example such as vitriolic strong acid, and the perhaps alkali of sodium hydroxide or ammoniacal liquor for example.
After mixture heating up is arrived the extraction temperature of expectation, can extract by regulating the pH that extracts mixture.
In along with the leaching process that suspension carried out that stirs the fibre-bearing pectin product, the amount of fibre-bearing pectin product and extraction medium, can be chosen as and make suspension contain dry matter content in the scope of 1% weight～5% weight, be preferably in the scope of 2% weight～4% weight.Use the amount of the extraction medium of being mentioned that the suspension that is easy to stir is provided, and be not sticking especially extract.
After carrying out suitable extraction time, the extraction mixture that comprises the fibre-bearing pectin product and extract medium can be cooled, and extract can separate from insoluble extraction resistates, for example by filtering or draining.Alternatively, extraction resistates that still contains a large amount of extracts that water cleans on strainer or extraction resistates can be suspended in the water and be filtered again to remove extract as much as possible.Behind separation cleaning fluid body from extract resistates, cleaning liquid can with the extract combination.
The pectin product of purifying can reclaim from extract by known method.For example, product can be precipitated out from extract, and it can be optionally centrifugal, for example evaporate by under the low pressure, by extract is added to be easy to water blended organic solvent in.Organic solvent can be that any being easy to mixed and the undissolved substantially therein organic solvent of pectin product with water.This organic solvent can be for example monovalent alcohol, for example methyl alcohol, ethanol or Virahol.Also can use two kinds or more kinds of mixtures in these solvents.
It is at least a that other appropriate methodology that separates pectin product is selected from any bonded of precipitation, extraction, centrifugal, filtration, chromatography, drying or above-mentioned technology.
When precipitation during product, can in spissated extract, add for example combining of calcium of strong acid or strong acid and metal ion.Operable acid is mineral acid, for example hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, and composition thereof.
By for example filtering and the pectin product of pressurization or any above-mentioned isolation technique precipitation separation from liquid, and clean on strainer to remove soluble salt and impurity, then, the pectin product and the selectivity of dry purifying grind.
Under dampness, sedimentary pectin product can be optionally with weakly alkaline salt for example hydrocarbonate knead together, for example Sodium Hydrogen Carbonate or potassium bicarbonate become salifiable form with the free carboxyl group of pectin and substantially with gas form evaporation carbonic acid gas, and be then dry and grind pectin product.
Product
The fibre-bearing pectin product that can obtain by the inventive method except pectin, mainly contains solvable and insoluble fiber comprises Mierocrystalline cellulose, hemicellulose and xylogen.Described edible fibers, for example Mierocrystalline cellulose, hemicellulose, pectin and xylogen, its amount reaches about 60～80% weight.
According to the present invention, in to the processing that contains the pectin material of vegetable origin, the pectin polymkeric substance is unclamped from Mierocrystalline cellulose-hemicellulose network but not dissolving, and at least by the part de-esterifying, and this makes and can obtain the fibre-bearing pectin product on the function.
The pectin material of vegetable origin is different with containing, and the fibre-bearing pectin product of acquisition has the performance that forms gel and viscosity is provided dissimilar metal ions being arranged for example during calcium ion.When in the aqueous solution calcium ion being arranged, the fibre-bearing pectin product that the method according to this invention obtains can form stable glue with quite high glue intensity or the viscous soln with high viscosity.
The formation gel of fibre-bearing pectin product makes that with the performance that viscosity is provided the product that obtains by the inventive method is very useful in processing fibre-bearing and lower fat food, pectin product is as the use of general fiber product under for example various situations, as in industrial processes food, feed and pet food as the composition that forms gel and combination water, and as the diarrhoea inhibitor or the healthy toughener of animal and human's class.
Like this, the present invention relates to dissimilar products, that is: the fibre-bearing pectin product that obtains by above-mentioned open method by the pectin product of above-mentioned separation method acquisition, and comprises all having for example product of the pectin of viscosity, de-esterifying degree and degree of amidation of identical feature.
In embodiments of the present invention, the fibre-bearing pectin product is provided, described product has 2%～40% degree of esterification, is not higher than 30% degree of amidation, the dry matter content of at least 16% weight, and can form the aqueous solution of stable gel and viscosity, wherein calcium ion content is 25～65% weight in the aqueous solution, for example 25～50% weight of sucrose, for example 30% weight of sucrose, the pH of solution for example is about 3 in 1～7 scope.
In the preferred embodiment of the present invention, fibre-bearing pectin product, isolating pectin product and/or pectous product, wherein the degree of esterification of pectin polymkeric substance is 0～80, for example 0～50, for example 2～50, for example 2～45, for example 2～40, for example 5～50, for example 10～50, for example 10～40, for example 15～35.
In another preferred implementation of the present invention, fibre-bearing pectin product, isolating pectin product and/or contain the product of pectin, wherein the degree of amidation of pectin polymkeric substance is not for being higher than 95%, for example be not higher than 75%, for example be not higher than 60%, be not higher than 50%, for example be not higher than 40%, for example be not higher than 30%, for example be not higher than 25%, for example be not higher than 20%.
In further preferred embodiment of the present invention, fibre-bearing pectin product, isolating pectin product and/or contain the product of pectin, wherein dry matter content is the dry-matter of at least 1% weight, at least 5% weight dry-matter for example, the dry-matter of at least 10% weight for example, the dry-matter of at least 15% weight for example, the dry-matter of at least 25% weight for example, the dry-matter of at least 50% weight for example, the dry-matter of at least 75% weight for example, the for example dry-matter of at least 85% weight, for example dry-matter of at least 95% weight.
In this article, term " fibre-bearing pectin product " relates to the product that contains pectin and fiber.In the preferred embodiment of the present invention, fibre content is 1% weight of dry-matter at least in the fibre-bearing pectin product, 5% weight of dry-matter at least for example, 10% weight of dry-matter at least for example, 15% weight of dry-matter at least for example, for example 25% weight of dry-matter at least, 50% weight of dry-matter at least for example, 75% weight of dry-matter at least for example, 85% weight of dry-matter at least for example, for example 95% weight of dry-matter at least.
In this article, term " pectin product " relates to the product that obtains by separation method described here.In embodiments of the present invention, pectin product does not contain or does not contain in fact fiber.
In this article, term " pectous product " relates to the mixture of composition, solution or other type, and wherein the pectin polymkeric substance accounts for 1～100% weight of product, for example 1～50%, for example 1～25%, for example 1～10%, for example 10～100%, for example 25～75%, for example 50～75%.
In embodiments of the present invention, included pectin has 0～80 degree of esterification in fibre-bearing pectin product, isolating pectin product and/or pectous product, and for example 0～50, for example 2～50, for example 2～45, for example 2～40, for example 5～50, for example 10～50, and/or degree of amidation is not for being higher than 95%, for example be not higher than 75%, for example be not higher than 60%, for example be not higher than 50%, for example be not higher than 40%, for example be not higher than 30%, for example be not higher than 25%, for example be not higher than 20%.
Product characteristic is according to the present invention, with the pectin polymer phase ratio that tradition provides, the raising of pectin polymer molecule size.This difference between two types of polymkeric substance can be expressed as the difference that product provides adhering performance.
In order to estimate pectin product, provide following method A with regard to its viscosity aspect.
Method A:
The 200ml beaker that will have magnetic stirring apparatus is coated tar.
1.000 gram pectin materials are changed in the beaker, under magnetic agitation, add 3ml Virahol (IPA).When suspension is even, under condition of stirring, add 100ml ebullient citrate buffer (as follows).After polymkeric substance dissolves fully, add the 250mg Sodium hexametaphosphate 99.With solution stirring two hours, and quality reached 100.0 grams.If temperature is 20.0 ℃, under Haake Rheostress 1 (as follows), it is 15～1501/ seconds that flow curve is defined as shearing rate.
The citric acid/citrate damping fluid:
A: whenever lift away from 21.02g monohydrate potassium in the sub-exchanged water.
B: whenever lift away from 29.41g two hydration trisodium citrates in the sub-exchanged water.
17 parts of A and 33 parts of B mixing are obtained final solution.
Haake Rheostress 1：
Sensing system rotor Z34 DIN 53019 Seriel.
Use temperature is set at 20.0 ℃ water-bath test cup is heated.
Like this, in the preferred embodiment of the present invention, provide according to the available product of method described here or contain the product of pectin, wherein said product satisfies at least and requires with the next item down:
(i) detect in the solution that is blended in maximum 1% (w/w) pectin and by method A, product has 5cp viscosity at least; Perhaps
(ii) ought be blended in the solution of maximum 1% (w/w) pectin and by method A and detect, product has and is higher than tradition and uses the pectin product viscosity of twice at least.
In embodiments of the present invention, when mixing in the solution that mostly is most 1% weight in concentration of pectin, product has the viscosity of 5cp (centipoise) at least, 10cp at least for example, 15cp at least for example, for example 20cp at least, 25cp at least for example, 35cp at least for example, for example 40cp at least, 45cp at least for example, 50cp at least for example, 75cp at least for example, for example 100cp at least, 150cp at least for example, for example 200cp at least.In the further embodiment of the present invention, product has the viscosity that is higher than at least 2.5 times of tradition use pectin products, for example is higher than at least 3 times, for example is higher than at least 3.5 times, for example is higher than at least 4 times, for example is higher than at least 5 times.
Technology is used
Has the technical feature in the various fields of direct application by available fibre-bearing pectin product of treatment process disclosed herein and pectin product.The unsurpassed glue intensity of product, viscosity and emulsifying property make it be suitable for as for example encapsulating for example volatile liquid and/or water-soluble fragrant agent and tinting material.Its performance can be used for the production of food and feed, and in medicine and the cosmetic industry, for example encapsulates trace nutrient, seasonings and VITAMIN etc.Pectin product of the present invention can be produced the medicinal compositions of solid and liquid, comprises for example tablet, suspension, emulsion etc., and as the component in the cosmetics production, for example perfume, face cream and washing lotion etc.
In some cases, product of the present invention produces protective membrane around the reagent that needs protection, prevent for example influence such as oxygen, light and heat.Can be alternatively, the reagent that needs protection can be embedded in according in the packaging plastic of the present invention.
And this product can be used as structurizing reagent, its by direct adding and/or re-construct food and feed in component.In feed, for example become piece with sticky agent as gravy by re-constructing remaining food, form the reagent of gel with meat and bone meal, and extrude down structured components as dry feed in low pressure.And the meeting of adding this product improves the high-voltage stability of feeds product, and strong emulsifying effectiveness can prevent the fat that runs off in autoclaving.
In food, pectin product of the present invention can be advantageously used for the alternative compositions of neutral grease in what is called " gently " product.The particularly advantageous aspect of this application is that the significant emulsifying effectiveness of pectin product can omit traditional emulsifying agent.
The special application that shows the technical feature of pectin product characteristic of the present invention is the application in tobacco product, for example as the part substitute of tobacco or as the auxiliary when processing tobacco leaf.And adding pectin product of the present invention can directly constitute and/or will be used for the reconstruct tobacco product in tobacco product.Pectin product of the present invention is easy to high-concentration suspension in water, and the high-viscous solution that the activation degree that can depend on product is used as the high per-cent of dry-matter is operated.Based on same reason, before drying, can stick together with tobacco material reconstruct and by injecting such suspension.Pectin product is present in and has water bonded effect in the final tobacco product, therefore prevents to be dried to unacceptable level.Can dissolve other tobacco component, perhaps in polymeric blends, form salt, and mix with the pectin product of " activation ".It should be noted that fragrance protective value recited above, it is the feature of pectin product of the present invention, and it also can be applied to protect fragrance and aromatised fraction in the tobacco.
And the present invention contains the component to skin-friendly that pectin product can be used as diaper, thin paper, toilet paper etc.
In another embodiment of the present invention, relate to the handled pectin material of vegetable origin that contains in the preparation of pectin, the preparation of animal-feed and the effect in the food applications.
In the further embodiment of the present invention, also relate to the application of described pectin.Application comprises food, makeup, medicinal product and household product.
According to pectin of the present invention, it is for making jam and jelly, comprising jam and no matter whether bakery, acidifying protein beverage, wound care prepared product and the neostomy product etc. of laminated dough/pasta are useful especially.
In embodiments of the present invention, fibre-bearing pectin product, pectin product and/or the product that contains pectin can be used for the encapsulation of volatile liquid for example and/or water-soluble fragrant agent and tinting material, perhaps be used to encapsulate trace nutrient, seasonings and VITAMIN etc., perhaps be used to produce the medicinal compositions thing of solid and liquid, comprise for example tablet, suspension, emulsion etc., and as the component of cosmetic product, for example perfume, face cream and washing lotion etc., perhaps, perhaps be used for fat substitute as sticky agent and/or the emulsifying agent of tobacco.
In the further embodiment of the present invention, the pectin polymkeric substance that is provided also can provide suitable delivery systme carrying out drug release, because at the ester group of pectin molecule with will discharge coupling between medicine or the compound.
Present invention will be further described for following non-limitative drawings.
Description of drawings
Fig. 1: be illustrated in the viscosity differences (cp: centipoise) between citrus pectin product of the present invention (triangle) and the traditional citrus pectin product (square).
Embodiment
Material and method
Determine degree of esterification (DE), degree of amidation (DA), degree of acetylation (DAc) and dehydration
Galacturonic acid (AGA)
According to the 4th edition National Academic Press of Food Chemical Codex, Washington1996, the 283rd page of described method determined %DE, %DA, %DAc and fully dehydrating galacturonic acid (%AGA).
Determine glue intensity
In the time of about 20 ℃, moisture calcium sucrose glue based on the solid sucrose content that has 30% weight, by " Texture Analyser " (Stable Micro Systems, model TA-XT2i) improve calcium ion content (pH=about 3 ± 0.1), parameter obtains glue intensity (with the gram expression) below using:
Pressure cylinder piston (SMS P/O5R): diameter 5mm
Length: 4mm
Speed: 0.5mm/ second.
Make glue in the following manner:
Will corresponding to the fibre-bearing pectin product of 1.2g pectin amount (3～4g), the perhaps pectin product of 1.2g purifying, the no salt solution that contains the 0.100g Sodium hexametaphosphate 99 at 110.5g forms slurries.Along with Ultra Turrax (UT) stirrer vigorous stirring,, pH is transferred to 4.5 by dropwise adding spissated ammoniacal liquor (25%).In microwave oven,, and handle once, then add 60g sucrose, under UT stirs, make in its mixture that is dissolved in temperature with UT with mixture heating up to 70～80 ℃.
At the ship of weighing (weighing boat) to secondary calcium phosphate (CaHPO
42H
2O) weigh, and under the UT-condition of stirring, do not have salt solution it is changed in the thermopolymer mixture quantitatively with 2 * 5ml.With 2.2g glucono delta lactone (C
6H
10O
6) be dissolved in the cold no salt solution of 12.5ml, and similarly do not have salt solution with 2.5ml and quantitatively change in the thermopolymer mixture, contain ground slightly soluble secondary calcium phosphate in the mixture.After using UT to stir to hot mixt, the mixture of 200g is placed in the dish (diameter 60mm, height 15mm) that the plane twines with band.Under room temperature (about 20 ℃), be cooled to second day, formed glue like this.Remove band and excise unnecessary glue with cutting caseic blade.
Embodiment 1
Orange peel (%AGA:40.6 with the dry chopping of 50g; %DE:71.8) be suspended in and contain 11.25g sodium-chlor and 4.125g calcium chloride (CaCl
22H
2O) in the 550g aqueous solution, corresponding every gram plant dry matter 4.375mmol sodium-chlor of difference and 0.6488mmol calcium chloride, wherein the orange peel dry matter content is 88% weight, maximum diameter is 5mm.
Under 17 ℃ suspension was stirred 70 minutes, then cool the temperature to 6.5 ℃, add the spissated ammoniacal liquor of 150g (25%) along with stirring, it is corresponding to every gram plant dry matter 2.22mol or 50.45mmol.To add the ammonia amount be per kilogram reaction mixture 2.96mol, pH is 11.8 in the reaction mixture.
Along with stirring slowly, suspension is maintained 6.5 ℃.Suspension is easy to stir, and leather material is assigned to the inviscid liquid phase of deep yellow.
Stir after 40 minutes, liquid phase flows out by filter cloth.Solid material is pressed/squeeze to remove liquid as much as possible.By in the sulfuric acid (600ml) that material is suspended in dilution solid material being cleaned repeatedly 2.2～2.5 stable p H in obtaining suspension.Behind each cleaning step, all liquid is flowed out.After last cleaning step, liquid is flowed out by filter cloth, solid material is pressed/squeeze to remove liquid as much as possible.
Material (dry matter content is about 25% weight) 40 ℃ of following dried overnight in loft drier with humidity.Drying products is worn at least fine powder less than the 0.2mm particle diameter.The output of fibre-bearing pectin product is 42g, and dry matter content is 89.8% weight.The analytical characteristic of having represented product in the table 1.Product forms the stable glue that contains calcium ion.Table 2 expression has 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Table 1
*The weight percent of dry-matter
Table 2
| The concentration of calcium (ppm) in the glue | The intensity of glue (g) |
| 117 | Do not determine |
| 233 | 629 |
| 466 | 711 |
| 699 | 898 |
Contain in the Virahol (100%) that ammonia solution is injected into two volumes effusive.Do not find the precipitation of polymer materials, this explanation is having dissolving and the extraction that does not cause pectin under the situation of salt with the ammonia treatment orange peel.
For relatively,, just do not add sodium-chlor and calcium chloride by handling the 50g orange peel with top described identical mode.With in the process of ammonia treatment, reaction mixture becomes more and more sticking and finally becomes the mixture of high sticking and polylith, is difficult to operate.Isolating solid material from liquid portion is time consuming operation (about 30 minutes).
To isolating material with the dilution sulfuric acid cleaned, drying and grind after, obtain the material that the 37g dry matter content is 90.1% weight.
Ammoniated solution is injected in the Virahol (100%), causes the precipitation of number of polymers material.By separation and drying, obtain the material that the 12g dry matter content is 95.7% weight to deposited material.
Embodiment 2～7
In embodiment 2～7, with the orange peel (%AGA:40.6 of the dry chopping of 50g (maximum diameter 5mm); %DE:71.8) according to embodiment 1 described the processing, wherein the orange peel dry matter content is 88% weight, compares with embodiment 1, except expansion time, expansion temperature, de-esterifying temperature, de-esterifying time or salt concn change.In all embodiment, the content of plant dry matter is 7.33% weight in the solution, and the processing of using ammoniacal liquor is by using the ammoniacal liquor that every gram plant dry substance contains 50.5mmol ammonia amount to carry out.Add ammoniacal liquor amount be per kilogram reaction mixture 2.96mol ammonia.
According to embodiment 1 described separation fibre-bearing pectin product, and analyze degree of esterification and degree of amidation.Reaction parameter and %DE and %DA have been represented in the table 3.
Table 3
Embodiment 8
Will with have≤0.5mm particle diameter particulate form and dry matter content are the 937.5g potato syrup (%AGA:17.0 in the dry pulp of 18% weight; %DE:56.9; %DAc:17.4) be suspended in the about 3075g aqueous solution that contains 66.9g (1.1447mol) sodium-chlor and 24.54g (0.1669mol) calcium chloride, respectively corresponding every gram dry-matter 7.6313mmol sodium-chlor and 1.1126mmol calcium chloride.The weight of suspension is 4013.6g.
Under the vigorous stirring, suspension is transferred to pH=7, and under about 20 ℃ of temperature, continue to stir 70 minutes, then add the spissated ammoniacal liquor of 445.9g (25%), corresponding to every gram plant dry matter 6.609mol or 44.06mmol with ammoniacal liquor.The ammonia amount that is added is per kilogram reaction mixture 1.482mol.In entire reaction course, pH is about 12.
Along with continuing to stir, suspension is maintained about 20 ℃.Suspension is easy to stir, and liquid phase is easy to flow and low viscosity.Stir after 30 minutes, liquid phase flows out by filter cloth.Solid material is pressed/squeeze to remove liquid as much as possible, then to be suspended in 5 liters of no salt solution that contain the 200ml20% sulphuric acid soln.By flowing liquid solid material is separated once more.After using 5 liters of other twice processing of no salt solution, the pH of suspension is 2.2.After last cleaning step, liquid flows out by filter cloth, the solids slurry material is pressed/squeeze to remove liquid as much as possible.
With moist product (dry matter content is about 25% weight) 40 ℃ of following dried overnight in loft drier.Drying products is worn into (Fritsch mill) at least less than the fine powder of 0.2mm particle diameter.The output of fibre-bearing pectin product is 120g, and dry matter content is 93.0% weight.The analytical characteristic of having represented product in the table 4.Product forms the stable glue that contains calcium ion.Table 5 has represented to have respectively 233,466 and the glue intensity of the glue of 699ppm calcium.
Table 4
*The weight percent of dry-matter
Table 5
| The concentration of calcium (ppm) in the glue | The intensity of glue (g) |
| 117 | There is not plastic structure |
| 233 | 73 |
| 466 | 124 |
| 699 | 145 |
Contain in the Virahol (100%) that ammonia solution is injected into two volumes effusive.Do not find the precipitation of polymer materials, this explanation is having dissolving and the extraction that does not cause pectin under the situation of salt with the ammonia treatment potato syrup.
As embodiment 1, handle the potato syrup of same amount with top described identical mode, just do not add sodium-chlor and calcium chloride.In using the process of ammonia treatment, suspension glues and is difficult to and stirs very much.From liquid contain ammonia mutually about 30 minutes of cutting out partial solids slurry material require.
1234g is contained ammoniacal liquor be injected into mutually in the Virahol, cause the precipitation of number of polymers material.By separation and drying, obtain the material that the 16.3g dry matter content is 90.4% weight to deposited material.
Use the sulphuric acid soln of dilution to clean to 800g part solids slurry material, dry and grind, obtain the material that the 56.7g dry matter content is 90.7% weight.
Embodiment 9～14
In embodiment 9～14, be the potato syrup (%AGA:17.0 in the dry pulp of 18% weight with 130.81 dry matter contents; %DE:56.9; %DAc:17.4), compare, except de-esterifying temperature, de-esterifying time, salt concn or ammonia concn change with embodiment 2 according to embodiment 2 described processing.
In all embodiment, the content of plant dry matter is 4.11% weight in the solution, with before the ammonia treatment, pulp material is expanded 10 minutes down at 3.5 ℃.
According to embodiment 2 described separation fibre-bearing pectin products, and analyze %DE and %DA.Expression reaction parameter and %DE and %DA in the table 6.
Table 6
*Reaction mixture
Embodiment 15
Morocco orange peel (%AGA:41.5 with the dry chopping of 200g; %DE:70.7), wherein the orange peel dry matter content is 85% weight, is suspended in to contain 45.0g (0.7700mol) sodium-chlor and 16.5g (0.1122mol) calcium chloride (CaCl
22H
2O) in about 2379g aqueous solution.
Under about 15 ℃, suspension (2640g) was stirred 30 minutes, then cool the temperature to 3～4 ℃, add the spissated ammoniacal liquor of 360g (25%) along with stirring, corresponding to 5.336mmol.The ammonia amount is per kilogram reaction mixture 2.02mol.
Stir down, suspension is maintained 3～4 ℃ continue 30 minutes.Suspension is easy to stir, and leather material is disperseed to enter inviscid liquid phase.
Stir after 30 minutes, liquid phase flows out by filter cloth.Solid material is pressed/squeeze to remove liquid as much as possible, then clean according to embodiment 1 described sulfuric acid with dilution.The analytical characteristic of having represented product in the table 7.Product forms the stable glue that contains calcium ion.It is 117,233,466 and the glue intensity of the glue of 699ppm calcium that table 8 expression has respectively.
Table 7
*The weight percent of dry-matter
Table 8
| The concentration of calcium (ppm) in the glue | The intensity of glue (g) |
| 117 | 87 |
| 233 | 295 |
| 466 | 365 |
| 699 | 457 |
With the 900g dry matter content is that the moist fibre-bearing pectin product of 16.1% weight is suspended in 9000ml and does not have in the salt brine solution, and with the spissated ammoniacal liquor of 12.1g (25%) pH is transferred to 4.5.In whipping process, with suspension heating and remain on 75 ℃ of stable down stirrings 60 minutes, the then filtering separation extract by filtering layer from insoluble extraction resistates.
Filtrate is injected in the Virahol (100%) of two volumes, pectin product precipitates.At the pectin product of precipitation separation and purifying and after the drying under cleaning with 40 ℃, obtain the material that the 37.3g dry matter content is 92.9% weight.Product is worn into the fine powder that has at least less than the 2mm particle diameter.The analytical characteristic of expression purifying pectin product in the table 9.Product forms the stable glue that contains calcium ion.Table 10 expression has 117,233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Table 9
*The weight percent of dry-matter
Table 10
| The concentration of calcium (ppm) in the glue | The intensity of glue (gram) |
| 117 | 104 |
| 233 | 489 |
| 466 | 661 |
| 699 | 675 |
Embodiment 16
With the 2812.5g dry matter content is that the moist potato syrup of 14% weight is suspended in and contains 200g (3.4223mol) sodium-chlor and 73.6g (0.5006mol) calcium chloride (CaCl
22H
2O) in about 9200g aqueous solution, correspond respectively to every gram plant dry matter 8.69mmol sodium-chlor and 1.27mmol calcium chloride.The quality of suspended substance is 12041g.
Under 19 ℃ the suspension stirring after 10 minutes, is being added the spissated ammoniacal liquor of 1337.8g (25%), corresponding to every gram plant dry matter 19.829mol or 50.36mmol.The ammonia amount that is added is per kilogram reaction mixture 1.482mol.
Mixture is maintained 19 ℃ stirred 30 minutes, then liquid phase flows out by filter cloth.Solid material is pressed/squeeze to remove liquid as much as possible, solid material is suspended in 15 liters of no salt solution, along with stirring, (1200ml) is transferred to about 1.3 with pH with 20% sulphuric acid soln.By scavenging solution is flowed out through filter cloth, solid material is separated once more and under agitation be suspended in 15 liters of no salt solution.Repeat such wash procedure 2 times.After last the cleaning, the pH of washing lotion is 2.5.
After last washing lotion was pushed by the filter cloth outflow and to isolating solid fibre-bearing pectin product, its amount was 1785g.Dry matter content is 18.6% weight.
Under 60 ℃ with fibre-bearing pectin product dried overnight and wear into (Fritsch mill) at least less than the fine powder of 0.2mm particle diameter.The analytical characteristic of expression exsiccant fibre-bearing pectin product in the table 11.Product forms the stable glue that contains calcium ion.Table 12 has represented to have respectively 117,233,466 and the glue intensity of the glue of 699ppm calcium.
Table 11
*The weight percent of dry-matter
Table 12
| The concentration of calcium (ppm) in the glue | The intensity of glue (gram) |
| 117 | 58 |
| 233 | 175 |
| 466 | 231 |
| 699 | 168 |
Embodiment 17
893g is suspended in 8640g from the moist fibre-bearing pectin product (dry matter content is 18.6% weight) of embodiment 16 by vigorous stirring not to be had in the salt solution, and adds spissated ammoniacal liquor (25%) pH is transferred to 4.5.
In whipping process, stablize stirring 30 minutes with the suspension heating and under remaining on 75 ℃, then the filtration through filter cloth separates liquid phase (extract) from insoluble extraction resistates.Insoluble extraction resistates is pushed to discharge extract as much as possible.By cooled extract (6800ml) being injected in the Virahol of the isopyknic 1233g of containing sulphuric acid soln (15.6%) pectin product that precipitation is extracted.On filter cloth, separate pectin product, push with strength and clean twice by utilizing vigorous stirring that it is suspended in the 800ml Virahol.On filter cloth, filter and pressurization after, under 40 ℃ with the pectin product dried overnight of purifying.The output of purifying pectin product is 31g, and dry matter content is 93% weight.The analytical characteristic of expression purifying pectin product in the table 13.Product forms the stable glue that contains calcium ion.Table 14 expression has 117,233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Table 13
*The weight percent of dry-matter
Table 14
| The concentration of calcium (ppm) in the glue | The intensity of glue (gram) |
| 117 | 103 |
| 233 | 257 |
| 466 | 304 |
| 699 | 308 |
Embodiment 18
The sugar beet slices that is chilled in-20 ℃ is thawed and in the high speed chopper, be cut into particle diameter≤5mm.By stirring, be 11% weight (AGA:23.9 in the dry pulp with the 366.7g dry matter content; %DE:42.7; %DAc:15.2) be suspended in and contain 26.17g sodium-chlor and 9.60g calcium chloride (CaCl
22H
2O) in the 1200g aqueous solution (about 2 ℃), correspond respectively to 11.101mmol sodium-chlor and 1.619mmol calcium chloride in every gram plant dry matter.The weight of suspension is 1571g.
Under about 2 ℃, suspension was stirred 20 minutes, then add the spissated ammoniacal liquor of 174.4g (25%), corresponding to every gram plant dry matter 2.585mol or 64.08mmol.The ammonia amount that is added is per kilogram reaction mixture 1.482mol.
After stirring the mixture 60 minutes under about 2 ℃ and about 12 conditions of pH, liquid phase flows out by filter cloth, and solid material is pressed/squeeze to remove liquid as much as possible, then solid material is suspended in the no salt solution, and with the sulphuric acid soln that dilutes pH is transferred to 1.3.Utilize liquid phase to flow out also by filter cloth and under agitation solid material is suspended in the no salt solution, solid material separates once more.Use the sulfuric acid of dilution that pH is set in 1.3.
After the separate solid material,, it cleans by being suspended in the no salt solution.Scavenging solution flows out the material that is cleaned to separate by filter cloth, push with the liquid that removes as much as possible, and in loft drier 40 ℃ of following dried overnight.Drying material is worn into particle diameter at least less than the fine powder of 0.2mm.The output of fibre-bearing pectin product is 29.81g, and dry matter content is 92.9% weight.The analytical characteristic of table 17 expression product.
Product forms the stable glue that contains calcium ion.Table 15 expression has 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Table 15
| The concentration of calcium (ppm) in the glue | The intensity of glue (gram) |
| 233 | 17.5 |
| 466 | 51.0 |
| 699 | 67.2 |
Embodiment 19
Sugar beet slices (identical with employed rank among the embodiment 18) to the 366.7g chopping carries out processing as described in example 18 above, except the time of using ammonia treatment is 30 minutes.
The output of fibre-bearing pectin product is 30.0g, and dry matter content is 92.3% weight.The analytical characteristic of table 17 expression product.
Fibre-bearing pectin product and calcium ion form viscous soln in 3.5 the solution containing 30% weight sucrose and pH.Described in definite glue intensity, prepare solution.Use Haake mobilometer (DIN 53019 for Rheostress, Sensor System Z34, series 1), detect and contain 233,466 and the viscosity of the solution of 699ppm calcium respectively.Its result of table 16 expression.
Table 16
Table 17
| Analytical characteristic from the pectin product of sugar beet slices | Embodiment 18 | Embodiment 19 |
| Anhydrogalactose aldehydic acid (%AGA) * | 26.1 | 24.8 |
| Degree of esterification (%DE) | 12.2 | 15.7 |
| Degree of amidation (%DA) | 16.2 | 13.7 |
| Degree of acetylation (%DAc) | 6.3 | 10.7 |
*The weight percent of dry-matter
Limepeel (%AGA:40.6 with the dry chopping of 100g; %DE:71.8), wherein maximum particle diameter is 5mm, and dry matter content is 88% weight, is suspended in to contain 22.5g sodium-chlor and 8.25g calcium chloride (CaCl
22H
2O) in about 1280g aqueous solution (3 ℃), correspond respectively to every gram plant dry matter 4.375mmol sodium-chlor and 0.6378mmol calcium chloride.The weight of suspension is 1378.5g.
Under 3 ℃, suspension was stirred 30 minutes, then along with vigorous stirring adds the calcium hydroxide [Ca (OH) that 4.75g is crushed into powder gradually
2], corresponding to every gram plant dry matter 64.11mmol or 0.728mmol calcium, pH maintains pH=12.0 ± 0.1.The amount of the calcium hydroxide that is added is per kilogram reaction mixture 46.35mmol.Under 3 ℃ mixture was stirred 35 minutes, then add the sulfuric acid of dilution so that pH=1.3.
Liquid phase flows out by filter cloth, and solid material is pressed/squeeze as much as possible liquid is removed, then solid material is suspended in the no salt solution, and with the sulfuric acid that dilutes with pH regulator to 1.3.
Liquid phase is carried out last cleaning by solid material is suspended in the no salt solution to it after pressing/squeeze by the filter cloth outflow and with solid material.
After liquid phase flowed out by filter cloth, solid material is dried overnight in 40 ℃ of nowels.Drying material is worn into particle diameter at least less than the fine powder of 0.2mm.The output of fibre-bearing pectin product is 87.3g, and dry matter content is 92.8% weight.The analytical characteristic of table 18 expression product.
Product forms the stable glue that contains calcium ion.The glue intensity that table 19 expression is detected.
Embodiment 21
Limepeel (identical with employed rank among the embodiment 20) to the dry chopping of 100g carries out processing as described in example 20 above, except the sodium hydroxide (107.9mmol) rather than 4.75g calcium hydroxide of use corresponding to the 215.8g0.5N of every gram plant dry matter 1.226mmol sodium.Add sodium hydroxide amount be per kilogram reaction mixture 76.69mmol.
The output of fibre-bearing pectin product is 85.5g, and dry matter content is 98.3% weight.The analytical characteristic of table 18 expression product, table 19 expression contain 233,466 and the glue intensity of 699ppm calcium respectively.
Table 18
| Analytical characteristic from the pectin product of | Embodiment | 20 | Embodiment 21 |
| Anhydrogalactose aldehydic acid (%AGA) * | 44.8 | 40.6 | |
| Degree of esterification (%DE) | 38.4 | 38.7 | |
| Degree of acetylation (%DAc) | - | - |
*The weight percent of dry-matter
Table 19
Embodiment 22
Lemon peel (%AGA:41.7 with the dry chopping of 100g; %DE:74.3), wherein maximum particle diameter is 5mm, and dry matter content is 91% weight, under agitation is suspended in to contain 22.5g sodium-chlor and 8.25g calcium chloride (CaCl
22H
2O) in about 1280g aqueous solution (2.5 ℃), correspond respectively to every gram plant dry matter 4.231mmol sodium-chlor and 0.6167mmol calcium chloride.The weight of suspension is 1378.5g.
Under 2.5 ℃, suspension was stirred 30 minutes, then along with vigorous stirring adds the calcium hydroxide [Ca (OH) that 4.69g is crushed into powder gradually
2], corresponding to every gram plant dry matter 63.30mmol or 0.695mmol calcium, pH maintains pH=12 ± 0.1.The amount of the calcium hydroxide that is added is per kilogram reaction mixture 45.77mmol.2.5 under ℃ reaction mixture was stirred 35 minutes, then adds the sulfuric acid of dilution so that pH=1.3.
Described according to embodiment 20, the fibre-bearing pectin product is processed and separated.Output is 80.0g, and dry matter content is 92.3% weight.The analytical characteristic of table 20 expression product.
Product forms the stable glue that contains calcium ion.Table 21 expression contains 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Embodiment 23
Lemon peel (identical with employed rank among the embodiment 22) to the dry chopping of 100g carries out processing as described in example 22 above, and difference is that the expansion of sheating material carries out under 20 ℃, and using the processing of calcium hydroxide is to carry out under 20 ℃ 26 minutes.
The output of fibre-bearing pectin product is 78.0g, and dry matter content is 92.6% weight.The analytical characteristic of table 20 expression product.
Product forms the stable glue that contains calcium ion.Table 21 expression contains 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Table 20
| Analytical characteristic from the pectin product of limepeel | Embodiment 22 | Embodiment 23 |
| Anhydrogalactose aldehydic acid (%AGA) * | 41.6 | 41.2 |
| Degree of esterification (%DE) | 33.1 | 29.4 |
| Degree of acetylation (%DAc) | - | - |
*The weight percent of dry-matter
Table 21
Embodiment 24
With 281.3 moist potato syrup (%AGA:16.4; %DE:46.1; %DAc:11), wherein particle diameter is less than 0.5mm, and dry matter content is 14% weight, under agitation is suspended in to contain 20.0g sodium-chlor and 7.36g calcium chloride (CaCl
22H
2O) in about 1020g aqueous solution (2.5 ℃), correspond respectively to 8.69mmol sodium-chlor and 1.271mmol calcium chloride in every gram plant dry matter.The weight of suspension is 1304.5g.
Under 2.5～3 ℃, suspension was stirred 20 minutes, then along with vigorous stirring adds the calcium hydroxide [Ca (OH) that 2.56g is crushed into powder gradually
2], corresponding to every gram plant dry matter 34.55mmol or 0.887mmol calcium, keep pH=12.0 ± 0.1.The amount of the calcium hydroxide that is added is per kilogram reaction mixture 26.43mmol.2.5 under～3 ℃ reaction mixture was stirred 45 minutes, then adds the sulfuric acid of dilution so that pH=1.3.
Described according to embodiment 20, the fibre-bearing pectin product is processed and separated.Output is 37.0g, and dry matter content is 91.8% weight.The analytical characteristic of table 22 expression product.
Product forms the stable glue that contains calcium ion.Table 23 expression contains 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Embodiment 25
Potato syrup (identical with employed rank among the embodiment 24) to the 281.3g humidity carries out according to the processing described in the embodiment 24, and difference is to use sodium hydroxide (56.55mmol) rather than the 2.56g calcium hydroxide corresponding to the 113.1g 0.5N of every gram plant dry matter 1.436mmol sodium hydroxide.The amount of the sodium hydroxide that is added is per kilogram 39.91mmol.
The output of fibre-bearing pectin product is 37.0g, and dry matter content is 91.6% weight.The analytical characteristic of table 22 expression product.The product that contains calcium ion has formed stable glue.Table 23 expression contains 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Table 22
| Analytical characteristic from the pectin product of potato syrup | Embodiment 24 | Embodiment 25 |
| Anhydrogalactose aldehydic acid (%AGA) * | 17.2 | 15.9 |
| Degree of esterification (%DE) | 14.7 | 5.5 |
| Degree of acetylation (%DAc) | 7.8 | 7.7 |
*The weight percent of dry-matter
Table 23
Embodiment 26
The sugar beet slices (the same with employed grade among the embodiment 18) of 281.3g chopping under agitation is suspended in about 1020g contains 20.0g sodium-chlor and 7.36g calcium chloride (CaCl
22H
2O) in the aqueous solution (2.5 ℃), correspond respectively to 11.061mmol sodium-chlor and 1.618mmol calcium chloride in every gram plant dry matter.The weight of suspension is 1304.5g.
Under 2～3 ℃, suspension was stirred 20 minutes, then along with vigorous stirring adds the calcium hydroxide [Ca (OH) that 3.048g is crushed into powder gradually
2], corresponding to every gram plant dry matter 41.14mmol or 1.329mmol calcium, keep pH about 12.The amount of the calcium hydroxide that is added is per kilogram reaction mixture 31.47mmol.Under 2～3 ℃ mixture was stirred 45 minutes, then add the sulfuric acid of dilution so that pH=1.3.
Described according to embodiment 20, the fibre-bearing pectin product is processed and separated.Output is 23.4g, and dry matter content is 93.8% weight.The analytical characteristic of table 24 expression product.Product forms the stable glue that contains calcium ion.Table 25 expression contains 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Embodiment 27
The sugar beet slices (the same with employed grade among the embodiment 18) of 562.5g chopping under agitation is suspended in about 1020g contains 20.0g sodium-chlor and 7.36g calcium chloride (CaCl
22H
2O) in the aqueous solution (2 ℃), correspond respectively to 5.531mmol sodium-chlor and 0.809mmol calcium chloride in every gram plant dry matter.The weight of suspension is 1585.6g.
Under 2 ℃, suspension was stirred 20 minutes, then along with vigorous stirring adds the calcium hydroxide [Ca (OH) that 6.66g is crushed into powder gradually
2], keep pH=12.0 ± 0.1.The amount of the calcium hydroxide that is added is per kilogram reaction mixture 56.46mmol.Under 2～3 ℃ mixture was stirred 75 minutes, then add the sulfuric acid of dilution so that pH=1.3.
Described according to embodiment 20, the fibre-bearing pectin product is processed and separated.Output is 47.0g, and dry matter content is 92.7% weight.The analytical characteristic of table 24 expression product.Product forms the stable glue that contains calcium ion.Table 25 expression contains 233,466 and the glue intensity of the glue of 699ppm calcium respectively.
Embodiment 28
With the sugar beet slices (the same) of 562.5g chopping with employed grade among the embodiment 18 according to handling described in the embodiment 27, except using the sodium hydroxide (107.9mmol) of 263.3g 0.5N, corresponding to every gram plant dry matter 2.127mmol sodium hydroxide or per kilogram reaction mixture 71.24mmol, rather than 6.66g calcium hydroxide, and the treatment time be 35 minutes.
The output of fibre-bearing pectin product is 47.1g, and dry matter content is 93.2% weight.Table 24 has been represented the analytical characteristic of product.Product forms the stable glue that contains calcium ion.Table 25 expression contains 466 and the glue intensity of the glue of 699ppm calcium respectively.Under lower Ca content, the calcium of 233ppm for example, product form very sticking solution.
Table 24
| Analytical characteristic from the fibre-bearing pectin product of sugar beet slices | Embodiment 26 | Embodiment 27 | Embodiment 28 |
| Anhydrogalactose aldehydic acid (%AGA) * | 29.3 | 25.2 | 30.2 |
| Degree of esterification (%DE) | 25.2 | 2.2 | 36.7 |
| Degree of acetylation (%DAc) | 6.3 | 5.2 | 7.8 |
*The weight percent of dry-matter
Table 25
Embodiment 29
The 200ml beaker that will have magnetic stirring apparatus is coated tar.
The citrus pectin product that 0.600% weight, 0.8000% weight and 1.000% weight the present invention are obtained, and traditional citrus pectin product of 1.000% weight, 1.200% weight and 1.400% weight changes in the beaker respectively, and adds 3ml Virahol (IPA) under magnetic agitation.Under the uniform situation of suspension, under agitation add 100ml ebullient citrate buffer solution (as follows).After polymer dissolution, add the 250mg Sodium hexametaphosphate 99.With solution stirring two hours, and weight reached 100.0 grams.When temperature was 20.0 ℃, under Haake Rheostress 1 (as follows), it was 15～1501/ seconds that flow curve is defined as shearing rate.Viscosity in the time of 901/ second is the independent variable(s) mapping with concentration (%).Carry out comparison with standard or other sample by determining to provide the necessary sample size of 40 centipoises.
The citric acid/citrate damping fluid:
A: whenever lift away from 21.02g monohydrate potassium in the sub-exchanged water.
B: whenever lift away from 29.41g two hydration trisodium citrates in the sub-exchanged water.
17 parts of A and 33 parts of B mixing are obtained final solution.
Haake Rheostress 1：
Sensing system rotor Z34 DIN 53019 Seriel.
Temperature is set at 20.0 ℃ water-bath test cup is heated.
The result
Fig. 1 represents that the resulting pectin product of the present invention has higher viscosity in the solution of certain concentration of pectin.This means the gap that exists between two kinds of pectin products on the function, the identical adhering performance (40 centipoise) that provides provided by the present invention is provided the amount that the traditional pectin product that need to use twice is described.
Reference
US 5,567,462
US 2,480,710
DE 4 013 765
DE 4 042 405
Food Chemical Codex, the 4th edition, National Academic Press, 1996, the 283 pages of Washington
Claims (34)
1. one kind obtains the method for fibre-bearing pectin product from vegetable material, and it comprises the following steps: described method
(i) by in the aqueous solution in 0-120 ℃ temperature range the turgid plant material a kind of reaction in system is provided, the wherein said aqueous solution contains at least a water-soluble neutral salt, wherein said water-soluble neutral salt is selected from sodium salt, sylvite, calcium salt, chloride salt, nitrate and their mixture, and the consumption of wherein said at least a water-soluble neutral salt is every gram vegetable material dry-matter 1mmol～30mmol;
(ii) in 0-120 ℃ temperature range the pectin that exists in the turgid plant material that is obtained by step (i) being carried out de-esterifying handles; And
The fibre-bearing pectin product that (iii) divides the ester of leaving away;
Wherein to handle be the alkaline purification of pH value at 7.0-14.0 to the de-esterifying of step in (ii).
2. method according to claim 1 does not wherein contain organic solvent in the aqueous solution.
3. according to claim 1 or 2 any one described method, wherein vegetable material expanded in the aqueous solution 1～120 minute.
4. according to any one described method of claim 1-2, wherein the dry matter content of the resulting vegetable material of step (i) is in 1～50 weight % scope.
5. according to any one described method of claim 1-2, the consumption of wherein said at least a salt is every gram vegetable material dry-matter 5mmol～15mmol.
6. according to any one described method of claim 1-2, wherein the aqueous solution is inorganic aqueous solution.
7. according to any one described method of claim 1-2, wherein de-esterifying is handled and is continued 1～120 minute.
8. according to any one described method of claim 1-2, wherein de-esterifying handle be to the vegetable material dry matter content in 1～50 weight % scope and carry out.
9. method according to claim 1, wherein the alkali condition that provided in (ii) of step is by adding alkali reagent so that pH reaches 8-14.
10. method according to claim 9, wherein alkali reagent is selected from ammoniacal liquor, diamines, Methionin, Histidine, arginine, glutamine, l-asparagine or tryptophane, the oxyhydroxide of sodium, potassium and calcium, perhaps at least a in the oxyhydroxide of organic bases.
11. method according to claim 10, wherein the amount of alkali reagent is that the every gram of 20mmol～80mmol contains the pectin plant dry matter.
12., wherein further vegetable material is carried out amidation and handles according to claim 1-2 or any one described method of 9-11.
13. method according to claim 12, wherein amidation is to be selected from ammonia, diamines or amino acid whose amidation reagent by interpolation to realize.
14. method according to claim 12 wherein uses amidation reagent that the turgid plant material that obtains in step (i) was handled 1～120 minute.
15. method according to claim 12 wherein uses amidation reagent that the turgid plant material that obtains in step (i) is handled in-15～75 ℃ of temperature ranges.
16. according to claim 1-2,9-11 or any one described method of 13-15, wherein to carrying out at least one cleaning step and/or at least one pressurization steps, thereby obtain the fibre-bearing pectin product at the (iii) resulting isolating de-esterifying fibre-bearing product of step.
17. method according to claim 16, wherein clean and/or exsiccant fibre-bearing pectin product be dried to dry matter content and be at least 90% weight.
18. method according to claim 16, wherein to clean and/or exsiccant fibre-bearing pectin product grind.
19. according to claim 1 or 18 any one described method, wherein to have degree of esterification be 0～80% to the fibre-bearing pectin product.
20. according to any one described method of claim 1-2,9-11,13-15 or 17-19, wherein the fibre-bearing pectin product has and is no more than 95% degree of amidation.
21. according to any one described method of claim 1-2,9-11,13-15 or 17-19, the dry matter content of the fibre-bearing pectin product that obtains in (iii) in step wherein with 1-95% weight.
22. according to any one described method of claim 1-2,9-11,13-15 or 17-19, wherein vegetable material is that the vegetable material of or drying regime fresh from this locality obtains.
23. according to any one described method of claim 1-2,9-11,13-15 or 17-19, wherein vegetable material is selected from the skin or the slurry of potato syrup, beet pulp, apple residue or tangerine class fruit.
24. the fibre-bearing pectin product that obtains according to any one described method of claim 1-23.
25. product according to claim 24, wherein the content of fiber is the 1-95% weight of dry-matter in the product.
26. a method for preparing pectin product, described method comprises step:
(i) provide according to claim 24 or 25 any one described fibre-bearing pectin product;
Add in the fibre-bearing pectin product (ii) that to have pH be that the extraction medium of 1～6 scope is to obtain extracting suspension;
(iii) will extract in the scope of pH regulator to 1～12 of suspension;
(iv) will get in the temperature range of temperature regulation to 20～100 ℃ of suspension; With
(v) separate pectin product from the aqueous phase that extracts medium.
27. method according to claim 26, wherein pectin product is to separate by precipitation, extraction, centrifugal, filtration, chromatography, drying.
28. the pectin product that method according to claim 26 obtains.
29. product according to claim 28, wherein said product satisfy following the requirement:
(i) be blended in the solution that concentration is maximum 1% weight pectin when product, and as described in the method A, when using citric acid/citrate damping fluid and Haake Rheostress 1 viscometer to detect, product has the viscosity of 40-200cp;
Wherein said method A is as follows:
The 200ml beaker that will have magnetic stirring apparatus is coated tar;
1.000 gram pectin materials are changed in the beaker, under magnetic agitation, add the 3ml Virahol; When suspension is even, under condition of stirring, add 100ml ebullient citrate buffer as described below; After polymkeric substance dissolves fully, add the 250mg Sodium hexametaphosphate 99; With solution stirring two hours, and quality reached 100.0 grams; If temperature is 20.0 ℃, Haake Rheostress as described below 1 time, it is 15～150 1/ seconds that flow curve is defined as shearing rate;
The citric acid/citrate damping fluid:
A: whenever lift away from 21.02g monohydrate potassium in the sub-exchanged water;
B: whenever lift away from 29.41g two hydration trisodium citrates in the sub-exchanged water;
17 parts of A and 33 parts of B mixing are obtained final solution;
Haake Rheostress 1：
Sensing system rotor Z34 DIN 53019 Seriel;
Use temperature is set at 20.0 ℃ water-bath test cup is heated.
30. product according to claim 28, wherein to have degree of esterification be 0～80% to pectin.
31. at encapsulation volatile liquid and/or water-soluble fragrant agent and tinting material, perhaps encapsulate the application in trace nutrient, seasonings or the VITAMIN according to claim 24～25,28～30 any one described product.
32. according to the application in producing solid pharmaceutical composition and liquid pharmaceutical composition and in cosmetics production of claim 24～25,28～30 any one described product as component.
33. according to the application of claim 24～25,28～30 any one described product as sticky agent and/or emulsifying agent.
34. according to the application of claim 24～25,28～30 any one described product as fat-replacer or tobacco substitute.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA200301037 | 2003-07-07 | ||
| DKPA200301037 | 2003-07-07 | ||
| DKPA200400112 | 2004-01-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1820029A CN1820029A (en) | 2006-08-16 |
| CN100497397C true CN100497397C (en) | 2009-06-10 |
Family
ID=36919460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800193992A Active CN100497397C (en) | 2003-07-07 | 2004-07-07 | Method for preparing fibre-containing pectin and products and uses hereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100497397C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11891588B2 (en) | 2019-07-31 | 2024-02-06 | Ecolab Usa Inc. | Personal protective equipment free delimer compositions o |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TR201909135T4 (en) * | 2007-08-29 | 2019-07-22 | Kmc Kartoffelmelcentralen Amba | Fiber-containing pectin product preparation method and related pectin products. |
| WO2014010577A1 (en) * | 2012-07-09 | 2014-01-16 | キユーピー株式会社 | Aqueous pectin solution |
| CN103044573A (en) * | 2012-11-16 | 2013-04-17 | 烟台安德利果胶股份有限公司 | Production method of amidated pectin for improving stability of baking jam |
| CN103319624A (en) * | 2013-07-05 | 2013-09-25 | 天茁（上海）生物科技有限公司 | Method for preparing amidated pectin with pericarp serving as raw material |
| KR101517511B1 (en) * | 2013-11-27 | 2015-05-04 | 주식회사 파리크라상 | Glazing agent for pastry of manufacturing methods |
| CN108219026A (en) * | 2016-12-14 | 2018-06-29 | 杭州垚信生物科技有限公司 | A kind of preparation method of high gelling beet pectin |
| CA3053043C (en) * | 2017-02-15 | 2021-12-21 | Cp Kelco Aps | Activated pectin-containing biomass compositions, products, and methods of producing |
| KR20200081428A (en) * | 2017-12-05 | 2020-07-07 | 니뽄 다바코 산교 가부시키가이샤 | Filling for smoking articles |
| CN116462858B (en) * | 2023-03-06 | 2024-03-01 | 中国农业科学院农产品加工研究所 | Preparation method and application of amidated pectin gel |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261626B1 (en) * | 1997-06-23 | 2001-07-17 | Danisco A/S | Methods of obtaining selected pectin fractions, such fractions and their use |
-
2004
- 2004-07-07 CN CNB2004800193992A patent/CN100497397C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6261626B1 (en) * | 1997-06-23 | 2001-07-17 | Danisco A/S | Methods of obtaining selected pectin fractions, such fractions and their use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11891588B2 (en) | 2019-07-31 | 2024-02-06 | Ecolab Usa Inc. | Personal protective equipment free delimer compositions o |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1820029A (en) | 2006-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101802018B (en) | Method of preparing fibre-containing pectin product and pectin products hereof | |
| US7833558B2 (en) | Method for preparing fibre-containing pectin and products and uses thereof | |
| CA1069751A (en) | Gelling and thickening agents | |
| KR102560013B1 (en) | Methods for Producing One or More Products of Interest from Insects by Chitin, Hydrolysates, and Enzymatic Hydrolysis | |
| Torres et al. | Biorefinery concept for discarded potatoes: Recovery of starch and bioactive compounds | |
| Twinomuhwezi et al. | Extraction and characterization of pectin from orange (Citrus sinensis), lemon (Citrus limon) and tangerine (Citrus tangerina) | |
| CN100497397C (en) | Method for preparing fibre-containing pectin and products and uses hereof | |
| JPS6154383B2 (en) | ||
| MX2008013706A (en) | Inulin of very high chain length. | |
| Alamineh | Extraction of pectin from orange peels and characterizing its physical and chemical properties | |
| Kalse et al. | Recent application of jackfruit waste in food and material engineering: A review | |
| Buathongjan et al. | Studies on chemical composition, rheological and antioxidant properties of pectin isolated from Riang (Parkia timoriana (DC.) Merr.) pod | |
| CN104431773A (en) | Horseradish tree health noodles with good mouth feel and nutrition and preparation method of horseradish tree health noodles | |
| CN112293502A (en) | Carbon quantum dot antioxidant, preparation method thereof and application thereof in frying oil | |
| CN103319624A (en) | Method for preparing amidated pectin with pericarp serving as raw material | |
| CN101664213B (en) | Preparation method of enzymolysis vegetable juice beverage | |
| CN102919890A (en) | Composite, preparation method thereof and food comprising composite | |
| JP2018012652A (en) | Method for decolorizing eucommia ulmoides oliver leaf extract, decolorized eucommia ulmoides oliver leaf extract and use of the same | |
| IL47115A (en) | Food compositions and their manufacture | |
| WO2018178119A1 (en) | Method for the procedurally economical removal/fractionation of constituents of vegetal starting material, and the production and use of same | |
| EP4223128A1 (en) | Use of an activatable, deesterified, pectin-converted fruit fiber for making sausages without added phosphates or meat substitutes | |
| CN105146503A (en) | Enzymolysis lentinus edodes stem ultrafine powder and preparation method | |
| CN104693312A (en) | Method for simultaneously extracting various effective constituents from callicarpa cathayana and application thereof | |
| CN100429235C (en) | Process for preparing water soluble soybean polysaccharide with bean pulp and bean dreg as raw materials | |
| CN108795063B (en) | High-oxidation-resistance edible film based on shrimp shell protein and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |