CN110387761A - The method for recycling free starch in mthod of white water from paper making - Google Patents
The method for recycling free starch in mthod of white water from paper making Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
- C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0064—Aspects concerning the production and the treatment of green and white liquors, e.g. causticizing green liquor
- D21C11/0078—Treatment of green or white liquors with other means or other compounds than gases, e.g. in order to separate solid compounds such as sodium chloride and carbonate from these liquors; Further treatment of these compounds
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Abstract
The present invention relates to a kind of methods of free starch in recycling mthod of white water from paper making, include the steps that reacting cationic starch complexing agent with the free starch in mthod of white water from paper making so that modification occurs for the free starch;The chemical structure of the cationic starch complexing agent consists of the following parts: i) one or more hydrophobic groupings, wherein at least one hydrophobic grouping can generate clathrate complex with starch reaction, and ii) one or more hydrophilic radical, wherein at least one hydrophilic radical is cationic hydrophilic groups;The hydrophobic grouping is respectively at the both ends of same molecular structure with the hydrophilic radical and is connected with chemical bond, and a kind of asymmetric, polar structure is formed.The free starch content in mthod of white water from paper making can be effectively reduced in this method, to reduce the COD discharge amount of paper waste.
Description
Technical field
The present invention relates to pulp and paper technology technical fields, more particularly to free starch in a kind of recycling mthod of white water from paper making
Method.
Background technique
The entire production process of pulp and paper industry, including from stock at paper, chemical recovery, paper processing etc. all
A large amount of water is needed, for conveying, washing, dispersed material and cooling equipment etc..Although also have in production process recycling, processing,
It uses again, but still there is a large amount of waste water to be discharged into water body, cause water environment and seriously pollute.Worldwide, paper-making industrial waste water
Pollution sources are important, such as paper-making industrial waste water is classified as one of six big public hazards and five big public hazards respectively by Japan, the U.S..
The first place of China's paper-making industrial waste water discharge amount and the China COD discharge amount Jun Ju all types of industries discharge amount at present, it is right
The pollution matter of utmost importance that still China's industrial pollution caused by paper manufacturing does not prevent and treat of water environment, and national industrial wastewater carry out processing up to standard
Matter of utmost importance.According to statistics, China's papermaking and paper products industry wastewater discharge account for the 18.6% of national industrial total release, row
COD in waste water accounts for about national industry COD total release 44.0% is put, wherein accounting for paper-making industrial waste water through handling qualified discharge amount
The 49% of total release.Paper waste COD concentration is high, and BOD content is big, and processing method is different compared with commonly industrial wastewater,
Currently, the processing method of paper waste mainly has physical method, chemical method, bioanalysis and physical-chemical process, wherein bioanalysis is answered
With the most extensively, it has also become one of the main method of paper waste two stage treatment.
Recently as to protecting forest resources and improving ecological attention, waste paper recycling industry is grown rapidly.According to
" the Chinese papermaking annual report in 2016 " published Chinese papermaking association in May, 2017, Chinese paper in 2016 and cardboard total output are
108550000 tons, wherein the four major class industrial paper such as wrapping paper, white board, boxboard and corrugated paper is 66,550,000 tons, accounts for total output
61%, and at present this four major class paper product production raw material composition in, reclaimed waste paper accounts for 80% or more.Due to China this
The Waste Paper raw material paper strength produced that kind is used repeatedly is low, of poor quality.In order to meet user to paper strength and
The demand of other performances, general papermaking enterprise uses starch surface sizing, to improve the various performance indicators of paper and cardboard, including
Paper strength such as bursting strength, ring crush intensity, tensile strength, folding strength etc., air permeability, smoothness, printing, water-resistance and
Resistance to rouge/oil resistance etc..Starch dosage in starch surface sizing is in 30-80 kgs/tonne of paper.
When these paper products are recycled again in use, by works such as shredded paper, purification, screening, concentration, storage slurry, mashing, online
Skill process generates a large amount of waste water.Through analyzing, the major pollutants in waste water mainly include dissolution starch, hemicellulose, lignin
And its pollutants such as derivative, fiber fines, inorganic filler, ink, dyestuff.Wherein, starch, lignin and its derivative biology,
It is the main component to form COD and BOD with hemicellulose.Especially gelatinized starch, in pulping process largely be dissolved or
It is dispersed in water, leads to the high COD concentration of waste water.Estimated according to domestic typical OCC paper plant creation data, the 30- of waste water COD
70% from starch.These dissolutions or colloid starch are degraded by the amylase that microorganism generates in system, cause starch
Chain shortens, or even becomes monosaccharide, is difficult to be fixed on fiber by the sticking agent that wet end of machine adds, so as to cause in plain boiled water
COD pollution concentration increases.Currently, China is more than much 10000ppm, i.e. using the papermaking draining COD of the enterprises of OCC production,
1% concentration.In addition, the starch being degraded also will increase paper machine white water conductivity during white water system, pH is reduced
Value increases plain boiled water microbial activity, generates more VFA, cause paper plant's odor contamination;In addition, the acidification of the degradation because of starch
Cause the multi mineral in the ash content of paper to dissolve, other than reducing the utilization rate of waste paper, also increase the electrolyte concentration of plain boiled water,
Plasm-glue-blending and other chemicals effect are influenced, and the calcareous waste water of high concentration can generate active dirt during Anaerobic Treatment
Mud calcification problem reduces Anaerobic Treatment efficiency.
Therefore, a kind of effective starch retains and the technology of recycling is of great significance to paper production.United States Patent (USP)
US9091024 describes a kind of method that amylase is controlled using sodium hypochlorite and chloramines.United States Patent (USP) US8758562 is introduced
Using the method for weak oxide type fungicide bromo-amine and organic bactericide control microorganism, and add two kinds of different molecular weights and electricity
Starch is fixed on fiber by the sticking agent of lotus density.WO 2012/025228Al Kemira describes a kind of use weak oxide type
The method of fungicide bromo-amine and zinc ion Collaborative Control microorganism and amylase.
But above-mentioned technology comes with some shortcomings: to prevent starch chain from shortening, it is necessary to the sufficiently effectively micro- life of control
Object prevents its secreting amylase, these methods need to add a large amount of fungicide, can cause shadow to subsequent biological wastewater treatment
It rings.Further, since the starch of mthod of white water from paper making is mainly derived from top sizing, starch molecule amount is lower, neutral, is difficult to protect
It is left in paper, is trapped in slurrying and copy paper system so as to cause a large amount of starch, these starch serve not only as microorganism
Nutriment will increase the growth of microorganism, and the accumulative meeting of starch finally causes " starch sicker " deposition problems, leads to paper
Disease and broken end, influence operational efficiency.
Up to the present, there are no a kind of recyclings for really effectively solving the problems, such as to dissolve starch in mthod of white water from paper making.And
Paper industry thirsts for developing a kind of cost-effective technology very to reduce starch dissolution during recycled fiber utilizes, improve
Recovery of starch utilization rate is to reduce the problem that COD discharges last 100 years in these paper productions.
Summary of the invention
Based on this, the present invention provides a kind of method of free starch in recycling mthod of white water from paper making, this method can effectively drop
Free starch content in low mthod of white water from paper making, to reduce the COD discharge amount of paper waste.
Specific technical solution is as follows:
A kind of method of free starch in recycling mthod of white water from paper making, including making in cationic starch complexing agent and mthod of white water from paper making
Free starch is reacted so that modified step occurs for the free starch;The chemical structure of the cationic starch complexing agent
It consists of the following parts:
I) one or more hydrophobic groupings, wherein at least one hydrophobic grouping can generate clathrate complex with starch reaction,
With
Ii) one or more hydrophilic radicals, wherein at least one hydrophilic radical are cationic hydrophilic groups;
The hydrophobic grouping is respectively at the both ends of same molecular structure with the hydrophilic radical and is connected with chemical bond,
Form a kind of asymmetric, polar structure;
The hydrophobic grouping is non-polar group, is selected from straight chain fatty alkyl, branched aliphatic, aryl radical, fat
At least one of alkyl and fluorine-containing alkyl are mixed with fragrance;
The hydrophilic radical is polar group, is selected from carboxyl, sulfonic group, ester group, halogen formoxyl, carbamoyl, cyanogen
At least one of base, aldehyde radical, carbonyl, ether, alcohol radical, phenolic group, sulfydryl, thioether group amido, quaternary ammonium salt, guanidine radicals;
Also, the cationic starch complexing agent generates hydrophobic cations after ionizing in water.
In wherein some embodiments, the hydrophobicity of generation after the cationic starch complexing agent ionizes in water
Cation is selected from amine salt type cation, quaternary ammonium salt cationic, guanidine salt type cation, sulfonium salt type cation, microcosmic salt type are cationic,
At least one of arsenic type cation.
In wherein some embodiments, the cationic starch complexing agent is selected from: aminated compounds or its salt, guanidine chemical combination
The heterocycle virtue of object or its salt, the heterocyclic hydrocarbon of substituted or non-substituted nitrogen atom or its salt, substituted or non-substituted nitrogen atom
At least one of hydrocarbon or its salt, cationic sulfonium salt.
In wherein some embodiments, the aminated compounds or its salt are selected from: primary amine or its salt, secondary amine or its salt, uncle
Amine or its salt, quaternary ammonium salt, polyamines or its salt, multi-quaternary ammonium salt, the fatty amine of polymer matrix substitution or its salt, polymer matrix replace
At least one of quaternary ammonium salt;The polymer matrix is selected from least one of polyethylene oxide base, polypropylene oxide base;
The structural formula of the primary amine is RNH2;
The structural formula of the secondary amine is R1R2NH;
The structure formula of the tertiary amine is R1R2NR3;
The structural formula of the quaternary ammonium salt is R1R2R3R4NX;
The structural formula of the polyamines is R5(CH2CH2CH2NR)n H;
The structural formula of the multi-quaternary ammonium salt is R5(CH2CH2CH2N(CH3)2)n CH3Xn;
The structural formula for the fatty amine that the polymer matrix replaces is
The structural formula for the quaternary ammonium salt that the polymer matrix replaces is
Above-mentioned each R, R1, R2, R3, R4, R5It is separately selected from: substituted or non-substituted straight chained alkyl, substitution or non-
Substituted branched alkyl, substituted or non-substituted alkenyl, substituted or non-substituted naphthenic base, substituted or non-substituted aryl;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted branched alkyl, substituted or non-substituted alkenyl,
Substituent group in substituted or non-substituted naphthenic base and substituted or non-substituted aryl is separately selected from one or more such as
Lower group: ether, ester group, amide groups, aryl, substituted aryl, alkyl, alkenyl, amino, siloxy group, sulfydryl, hydroxyl, halogen,
Thioether group, alkoxy;
R6、R7And R8Separately be selected from: H, C1-C4 alkyl, the degree of polymerization are big greater than 1 polyethylene oxide base, the degree of polymerization
In 1 polypropylene oxide base, and R6、R7In at least one be selected from the degree of polymerization greater than 1 polyethylene oxide base or the degree of polymerization be greater than
1 polypropylene oxide base;
R9、R10It is separately selected from: H, C1-C4 alkyl;
A is selected from the integer between 1-6, and b is selected from the integer between 0-4, c=b+1;
N is selected from the integer not less than 1;
X is the anion being connected by ionic bond with nitrogen-atoms.
In wherein some embodiments, described R, R1, R2, R3, R4, R5It is separately selected from: substituted or non-substituted C1-
C40 straight chained alkyl, substituted or non-substituted C3-C40 branched alkyl, substituted or non-substituted C2-C40 alkenyl, substitution non-take
The C6-C10 aryl in generation;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted branched alkyl, substituted or non-substituted alkenyl,
Substituent group in substituted or non-substituted naphthenic base and substituted or non-substituted aryl is separately selected from one or more such as
Lower group: naphthalene, the C1-C40 alkyl, C2-C16 alkene that ether, C2-C24 ester group, phenyl, naphthalene, C1-C20 alkoxy replace
Base, amino, siloxy group, sulfydryl, hydroxyl, halogen, thioether group, C1-C20 alkoxy.
In wherein some embodiments, R, R5The C6-14 separately replaced selected from C14-32 alkyl, C8-C12 alkenyl
The C6-10 aryl of C6-14 alkyl, the substitution of C14-C20 alkoxy that alkyl, C14-C24 ester group, C14-C20 alkoxy replace;
The alkyl-substituted C6-10 aryl of C10-C20;
R in the secondary amine1、R2At least one of selected from C14-32 alkyl, C8-C12 alkenyl replace C6-14 alkyl,
The C6-10 aryl of C6-14 alkyl, the substitution of C14-C20 alkoxy that C14-C24 ester group, C14-C20 alkoxy replace;
R in the tertiary amine1、R2、R3At least one of selected from C14-32 alkyl, C8-C12 alkenyl replace C6-14 alkane
The C6-10 aryl of C6-14 alkyl, the substitution of C14-C20 alkoxy that base, C14-C24 ester group, C14-C20 alkoxy replace;
R in the quaternary ammonium salt1、R2、R3、R4At least one of selected from C14-32 alkyl, C8-C12 alkenyl replace C6-
The C6-10 aryl of C6-14 alkyl, the substitution of C14-C20 alkoxy that 14 alkyl, C14-C24 ester group, C14-C20 alkoxy replace.
In wherein some embodiments, X is selected from: halide anion, HSO4 -、SO4 2-、CH3SO4 -、SCN-、CH3CO2 -Or
OH-。
In wherein some embodiments, the n in the polyamines salt structural formula is selected from the integer between 2-5;The polycyclic oxygen
The degree of polymerization of ethyl group and polypropylene oxide base is respectively selected from the integer between 1-30.
In wherein some embodiments, the guanidine compound or its salt are selected from: single guanidine or its salt, biguanides or its salt, more
At least one of guanidine or its salt;
The structural formula of the list guanidine are as follows:
The structural formula of the list guanidine salt are as follows:
The structural formula of the biguanides are as follows:
The structural formula of the polyguanidine are as follows:
R, R in formula1、R2、R3、R4、R5、R6Separately be selected from: hydrogen, substituted or non-substituted straight chained alkyl, replace or
Non-substituted branched alkyl, substituted or non-substituted alkenyl, substituted or non-substituted naphthenic base, substituted or non-substituted aryl,
And the carbon atom number of at least one substituent group is greater than 6 in each structural formula of the guanidine compound;
Z is selected from: substituted or non-substituted alkylidene, substituted or non-substituted aryl;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted branched alkyl, substituted or non-substituted alkenyl,
Substituent group difference in substituted or non-substituted naphthenic base, substituted or non-substituted aryl and substituted or non-substituted alkylidene is only
On the spot selected from one or more following groups: ether, ester group, amide groups, aryl, substituted aryl, alkyl, alkenyl, amino, silicon oxygen
Alkyl, sulfydryl, hydroxyl, halogen, thioether group, alkoxy;
X is the anion being connected by ionic bond with nitrogen-atoms.
In wherein some embodiments, at least one substituent group is selected from each structural formula of the guanidine compound:
C7-C30 straight chained alkyl, C7-C30 branched alkyl, C7-C30 alkenyl, C7-C10 aryl;Remaining substituent group is hydrogen;Z is selected from:
C1-C8 alkylidene;X is selected from: halide anion, HSO4 -、SO4 2-、CH3SO4 -、CH3CO2 -Or OH-。
In wherein some embodiments, the structural formula of the cation sulfonium salt is R1R2R3SX, wherein R1, R2, R3It is not independent
Ground is selected from: substituted or non-substituted straight chained alkyl, substituted or non-substituted alkenyl, replaces substituted or non-substituted branched alkyl
Or non-substituted naphthenic base, substituted or non-substituted aryl;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted branched alkyl, substituted or non-substituted alkenyl,
Substituent group in substituted or non-substituted naphthenic base and substituted or non-substituted aryl is separately selected from one or more such as
Lower group: ether, ester group, amide groups, aryl, substituted aryl, alkyl, alkenyl, amino, siloxy group, sulfydryl, hydroxyl, halogen,
Thioether group, alkoxy;
X is the anion being connected by ionic bond with sulphur atom.
In wherein some embodiments, the heterocyclic hydrocarbon is selected from: morpholine, nafoxidine, glyoxalidine, in piperazine at least
It is a kind of;
The heteroaryl hydrocarbon is selected from: pyridine, imidazoles, quinoline, 1,3,5- triazine, up in piperazine, pyrimidine, pyrazine, pyrroles at least
It is a kind of;
The heterocyclic hydrocarbon of the substituted or non-substituted nitrogen atom or the heterocycle of its salt, substituted or non-substituted nitrogen atom
Substituent group in aromatic hydrocarbons or its salt is selected from one or more following groups: alkoxy, ester group, amide groups, phenyl, alkyl, hydroxyl
Substituted alkyl, alkenyl replace alkyl, halogen replace alkyl, alkoxy replace alkyl, alkenyl, amino, siloxy group,
Sulfydryl, hydroxyl, halogen, amido.
In wherein some embodiments, the heterocyclic hydrocarbon is selected from: at least one of nafoxidine, morpholine, glyoxalidine;
The heterocyclic arene is selected from: at least one of pyridine, quinoline, imidazoles and 1,3,5- triazine;
The heterocyclic hydrocarbon of the substituted or non-substituted nitrogen atom or the heterocycle of its salt, substituted or non-substituted nitrogen atom
Substituent group in aromatic hydrocarbons or its salt is selected from one or more following groups: C1-C20 alkyl, C1-C20 alkoxy, C1-C6 alkyl
C1-C20 alkyl, the C1-C20 alkoxy that C1-C20 alkyl, the C2-C20 alkenyl of substituted amido, hydroxyl substitution replace replace
C1-C20 alkyl.
In wherein some embodiments, the heterocyclic hydrocarbon or its salt of the substituted or non-substituted nitrogen atom, substitution or non-
Substituent group in the heterocyclic arene of substituted nitrogen atom or its salt is selected from one or more following groups: C10-C20 alkyl,
C10-C20 alkoxy.
In wherein some embodiments, the cationic starch complexing agent is selected from least one of following compound: institute
It states cationic starch complexing agent and is selected from least one of following compound: hexadecyltrimethylammonium chloride, dodecyl three
Ammonio methacrylate, octadecylamine, oleyl amine, cetylamine, octadecyltrimethylammonium chloride, cetylpyridinium chloride, octadecyl-
N, N- dimethyl benzyl ammonium chloride, oil base-N, N- dimethyl benzyl ammonium chloride, octadecyl methyl ammonium chloride, benzyl hexadecane
Base alkyl dimethyl ammonium chloride, two lauryl amines, tallow base amine, tallow base trimethylene diamines, tallow methyl trimethylene diamines, N- tallow base-
N, N, N ', N ', N ' pentamethyl trimethylene diammonium hydrochloric acid, double propylamine-tallow base tertiary amine, stearic acid ethyl group-N, N, N ', N ', N ' five
Methyl trimethylene di-ammonium salts acid, 1,3 trimethylene diamines of oil base, 1,3 triamine of N- oil base trimethylene, dioctadecyl dimethyl ammonium chloride, chlorine
Change benzyl ethoxy ammonium, tetradecyltrimethylammonium silicon oxychlorination ammonium, dimethyl stearyl [3- (trimethoxy silicon substrate) propyl] chlorination
Ammonium, tridodecylamine, dotriacontyl trimethyl ammonium chloride, dodecyloxy propylamine, dodecyloxy -1,3- trimethylene two
Amine, dodecyl-dipropyl amido secondary amine, dodecyl-N, N ,-bis- (trimerization ethylene oxide) ammonium chlorides, octadecyl-N,
N ,-bis- (trimerization ethylene oxide) ammonium chlorides, N- tallow base-N, N ', N (polyoxyethylene) trimethylene of '-tri- diamines, double propylamine-oxen
Aliphatic radical tertiary amine, sulfydryl-cetylamine hydrochlorate, sulfydryl-undecyl trimethylammonium bromide, ortho position the-the third hydroxyl of oil base-imidazoles, 18
Alkyl imidazole, 1- dodecyl -3- methylimidazole iodide, decyl methylimidazolium chloride, 1,3- didecyl -2- methyl chloride imidazoles
Quinoline, N- tallow oxygroup-N, N ', N (the polyoxyethylene)-methyl-propyl of '-bis- ammonium chloride, bis- (the hexadecane oxygen of 3- amino -1- propyl alcohol
Ether), octadecane epoxide pyridine, octadecane epoxide aniline chloride, N- benzyl-N, N- dimethyl-stearyl oxygroup-Oxidation of Alcohol
Ammonium chloride, 2- octadecane epoxide-N, N, N- trimethyl -2- Oxidation of Alcohol ammonium chloride, N, N '-diethyl -6- octadecane epoxide -
(1,3,5) triazine -2,4- diamines, 3- (2- octadecane epoxide -1- naphthalene) propylamine, 1- (2- dodecyloxy) N-ethyl pyrrole N salt
Acid, 2- (2- dodecyloxy) propoxypropylamine, 4- dodecyloxy aniline, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,
21 fluorine certain herbaceous plants with big flowers amine of 8,9,9,10,10,10-, 11 fluorine certain herbaceous plants with big flowers amine of 5,5,6,6,7,7,8,8,9,9,10,10,10-, double octadecanes
The more ammoniums of base dimethyl hydroxypropyl, octadecyl-N, N, N- methyl bis- (polymerization oxidation propylene) ammonium chlorides, N, N, N, N ', N '-first
Base-three (polyoxyethylene) trimethylene diamines octadecyl quaternary ammonium hydrochloric acid, dodecyl guanidine hydrochloride, dodecyl N, N '-trimethylene two
Require to report his or her problems within a prescribed time and in a prescribed place hydrochloride, tridecyl 2,4- methyl morpholine, dodecyl polyaniline, myristyl quinoline hydrochloric acid, 1- octadecyl of amine-is double
Guanidine mono-hydrochloric salts, Octenidine dihydrochloride, lauryl hydroxyethyl imidazole quinoline.
In wherein some embodiments, the starch in the free solution is selected from: cornstarch, tapioca, sweet potato are formed sediment
At least one of powder, wheaten starch, starch of oxidation modification;The starch of the oxidation modification is that the corn of oxidation modification forms sediment
Powder, the tapioca of oxidation modification, the starch from sweet potato of oxidation modification or the wheaten starch of oxidation modification.
In wherein some embodiments, the preparation method of the starch of the oxidation modification is the following steps are included: take starch to match
Aqueous solution is made, is heated to 80-100 DEG C, starch oxidation agent is added or starch enzyme reaction to viscosity reaches stable, then is cooled to
60-70 DEG C to get.
In wherein some embodiments, the free starch in the cationic starch complexing agent and mthod of white water from paper making carries out anti-
Answer so that the free starch occur it is further comprising the steps of after modified step: addition synergist and gained modified starch into
Row reaction;The synergist is selected from: aluminium polychloride, polyaluminium sulfate, bodied ferric sulfate, diallyl dimethyl chlorination
At least one of ammonium, polyoxyethylene, polyacrylamide and polyacrylamide-polyacrylic acid analog anion copolymer.
In wherein some embodiments, the mass ratio of the synergist and the cationic starch complexing agent is 1:1-35.
In wherein some embodiments, the temperature of the reaction is 10-90 DEG C.
In wherein some embodiments, the time of the reaction is 1min-20h.
In wherein some embodiments, the time of the reaction is 5min-1h.
In wherein some embodiments, the pH of the reaction is 4-11.
In wherein some embodiments, the pH of the reaction is 5-7.
The method of free starch has the following advantages and beneficial effects: in recycling mthod of white water from paper making of the invention
The method of free starch has spy to starch by being added in mthod of white water from paper making in recycling mthod of white water from paper making of the invention
The cation complexing agents of different complexing are reacted with the starch in mthod of white water from paper making, generate " the interior envelope of " starch-compound "
Close object ", to change the physics and chemical property of the starch in mthod of white water from paper making, its solubility in mthod of white water from paper making is reduced, from
And the free starch content in mthod of white water from paper making can be substantially reduced, reduce the COD discharge amount of paper waste.By of the invention
Further add fiber or paper pulp in cation complexing agents treated plain boiled water, can make starch precipitate or be adsorbed on fiber or
In paper pulp, so as to further decrease the free starch content in plain boiled water, and shallow lake is adsorbed with recycling plain boiled water preparation
The fiber or paper pulp of powder can be directly used for papermaking, substantially increase the rate of recovery of starch and the utilization rate in papermaking.
Therefore, the method for free starch can generate various beneficial effects in recycling mthod of white water from paper making of the invention, comprising:
(1) the COD concentration for reducing papermaking draining, reduces organic contamination, improves environmental protection;(2) recovery utilization rate for improving starch, reduces life
Produce cost;(3) consumption of starch for reducing paper industry, increases the food safety of country.It is therefore contemplated that of the invention returns
The method for receiving free starch in mthod of white water from paper making is of great significance to paper production industry.
Detailed description of the invention
Fig. 1 is influence of the reaction time to starch complexing agent C2, C5, C10 and C12 and starch reaction;
Fig. 2 is (to protect to the modified starch of starch complexing agent C2, C5, C10 and C12 in chemical pulp BKP absorption in the reaction time
Stay rate) influence;
Fig. 3 is influence of the reaction time to the modified starch adsorption of starch complexing agent C7;
Fig. 4 is the influence that temperature retains starch binder C7 and starch reaction and starch;
Fig. 5 is the influence that temperature reduces dissolution COD to starch binder C7 and starch reaction;
Fig. 6 is influence of the pH to cationic starch bonding agent C7 and starch reaction;
Fig. 7 is influence of the pH to cationic starch bonding agent C12 and starch reaction;
Fig. 8 is the influence that BKP usage amount retains starch and COD is removed;
Fig. 9 is different slurries (enzyme process cleaning OCC paper pulp (E-OCC), untreated OCC and chemical pulp BKP) to starch adsorption
Influence;
Figure 10 is different amounts ratio pair when two kinds of structures different cationic starch bonding agent C55 and C57 are applied in combination
The influence of starch reserved;
Figure 11 is physical strength (anti-tensile of the cationic starch bonding agent C7 modified starch (cornstarch) to chemical pulp BKP
Index and burst index) influence;
Figure 12 is that cationic starch bonding agent C7 and C14 handles OCC paper pulp to the shadow of starch reservation and plain boiled water COD concentration
It rings;
Figure 13 is that cationic starch bonding agent C7 and C14 handles OCC paper pulp to the physical strength (tensile index of OCC copy paper
And burst index) influence;
Figure 14 is the slurrying flow chart that common craft paper is produced with OCC waste paper.
Specific embodiment
The definition of technical term in the present invention and meaning include as follows.
In the present invention, starch association reaction (Starch Binding), starch complex reaction (Starch
Complexation) and starch modification (Starch Modification) refers to that starch and certain a pair of of starch have the object of affinity
Matter is reacted in water phase, is made Starch formation helical form and is included " comprising complex compound " within spiral by the reactant
(Inclusion Complex).These titles can be used interchangeably in the technology of the present invention.
In above-mentioned reaction, there is the reactant of special affinity to be referred to as starch binder (Starch starch
Binding Agents) or starch complexing agent (Starch ComplexingAgents), the reactant energy and starch reaction
Packet complex compound, chemical structure consist of the following parts in generating:
One or more hydrophobic groupings, wherein at least one have compared with strong affinity starch, can generate and form sediment with starch reaction
Powder-compound " clathrate complex " (Inclusion Complex), and
Ii) one or more hydrophilic radicals, make compound itself reach enough aqueous phase dissolved degree;
The group point that above two class formation is completely contradicted with performance is in the both ends of same molecular structure and with chemical bond phase
Connection forms a kind of asymmetric, polar structure.
Wherein the hydrophobic grouping is non-polar group, is classified according to hydrophobic based structures, can divide straight chain/branch rouge
Fat hydrocarbon, aromatic hydrocarbon, fat and fragrant hydrocarbon mixture, have slightly water-wet base, perfluoroalkyl and fluorine-containing mixing alkyl.
Wherein the hydrophilic radical is polar group, is divided into hydroxyl, aldehyde radical, carboxylate, sulphur according to structure or chemical property
Hydrochlorate, sulfonate, phosphate, amido, quaternary ammonium salt, PEO derivative, lactone, amino acid, amide groups, ehter bond etc..
Above-mentioned starch binder is referred to as starch dressing agent (starch modifier), starch crystals agent (starch
Crystallizing agent), starch precipitating reagent (starch precipitation agent), starch flocculating agent (starch
Aggregating agent), starch crosslinking agent (starch binder), starch adsorption agent (starch absorber), starch
Curing agent (starch solidifier), starch sticking agent (starch fixative), starch fento agent (starch
fibrillation agent)。
Starch binder of the invention has the structure feature of " cationic surfactant ", referred to as cationic starch knot
Mixture (Cationic Starch Binding Agents) or cationic starch complexing agent (Cationic Starch
Complexing Agents).Such starch binder generates hydrophobic cations, the knot of cation after ionizing in water
Structure major part contains by least one nitrogen, sulphur, phosphorus or arsenic atom.Wherein cationic starch bonding agent is usually organic nitridation
Close the derivative of object, cation charge carries by nitrogen-atoms, according to chemical structure, can be divided mainly into amine salt type, quaternary,
Heterocyclic type and hello salt form etc..
Fatty amine.Amine salt type cationic starch bonding agent includes primary amine salt (primary amines, structural formula RNH2)、
Secondary amine salt (secondary amines, formula R1R2) and tertiary ammonium salt (tertiary amines, formula R NH1R2NR3) table
The general name of face activating agent, R, R in formula1, R2And R3For aliphatic group.This kind of bonding agent be mainly fatty amine and inorganic acid (hydrochloric acid,
Bromic acid, acetic acid or sulfuric acid) formed salt, be dissolved only in acid solution, it is positively charged.And under alkaline condition, amine salt is easy and alkali
Effect generates unhindered amina.
Aromatic amine.When aliphatic groups one or more in above-mentioned fatty amine are replaced with aryl, as aromatic amine.Such as
The structural formula of chain alkyl aniline (alkyl aniline) are as follows:
R, R in formula1、R2、R3、R4、R5、R6Represent H, substituted or unsubstituted alkyl.
Quaternary (quaternary ammonium).Quaternary ammonium salt (also known as quarternary ammonium salt) be 4 hydrogen in ammonium ion from
The salt of quaternary ammonium cation that son is formed after all being replaced by alkyl, quaternary ammonium salt have 4 carbon atoms by covalent bond directly and nitrogen-atoms
It is connected, general structure R1R2R3R4NX, R in formula1, R2, R3, R4For identical or different alkyl, replace or it is non-substituted, full
It is sum or unsaturated, there can also be branch or without branch, cyclic structure or linear chain structure, can wrap ether-containing, ester, amide,
It is also possible to aromatic series or aromatic series substituent;X is connected by ionic bond with nitrogen-atoms, mostly halide anion (F?、Cl?、
Br?、I?) or be HSO4 -, CH3CO2 -And OH-.The property of quaternary starch binder is different from amine salt type, and substance of this kind both may be used
It is dissolved in acid solution, and dissolves in alkaline solution, cation is not influenced electrically by pH value of solution.
Polycation type starch binder (Starch Binding Polyamines).Polyamines salt form cationic starch knot
There are two the structures of mixture or more than two nitrogen-atoms composition, and the most common polyamines is by multiple this connection of support propyl, structure
Formula is R (CH2CH2CH2N) n H, R is aliphatic hydrocarbon in formula.N is the integer of 1-10.For example, the third two quaternary ammonium of fat support, structure are as follows:
When the hydrogen atom of end (second) amido is replaced by a long aliphatic hydrocarbon chain, structure is then hydrophobic by two
Chain and two polar head-groups are formed by connecting by linking group, become the dication starch binder of double hydrophobic groups.For example, containing
There are the dication of double dodecyls, structure are as follows:
Polyethylene glycol oxide fatty amine salt.Polyoxyethylated fatty amine cationic starch bonding agent is the knot in fatty amine
Aminic hydrogen atoms in structure are replaced by polyethylene oxide base, obtain nonionic-cation mixed surfactant.Fatty amine
Polyoxyethylene ether has nonionic and cationic characteristic simultaneously, shows as cationic surfactant characteristic in an acidic solution,
And tween is shown as in alkalinity or neutral solution.The chemical structural formula of polyethylene glycol oxide aliphatic monoamine are as follows:
The structure of its salt are as follows:
Methyl addition is carried out on the amido of polyethylene glycol oxide fatty amine, generates quaternary ammonium, and the structural formula of quaternary ammonium salt is
Corresponding polyethylene glycol oxide aliphatic diamine is in the structure basis of aliphatic diamine, to the hydrogen original of the amido in end
Son carries out polyethylene oxide base substitution, exemplary chemical structures formula are as follows:
The structure of its salt are as follows:
The exemplary structural formula of its quaternary ammonium salt are as follows:
Or:
Further two amidos are replaced, generate polyethylene glycol oxide aliphatic diamine, exemplary structure are as follows:
The exemplary structure of its bi-quaternary ammonium salt are as follows:
R in the above polyethylene glycol oxide fatty amine salt is aliphatic hydrocarbon.
Polypropylene oxide fatty amine salt.The fatty amine cationic starch bonding agent of polyoxypropylene refers in fatty amine
In structure basis, replaces hydrogen atom with polypropylene oxide on terminal amido, it is living to obtain nonionic-cation mixed type surface
Property agent.Fatty amine polyethenoxy ether has nonionic and cationic characteristic simultaneously, shows as cationic surface in an acidic solution
Surfactant properties, and tween is shown as in alkalinity or neutral solution.The chemistry knot of polypropylene oxide aliphatic monoamine
Structure formula are as follows:
The structure of its salt are as follows:
The exemplary structural formula of its quaternary ammonium salt are as follows:
Corresponding polypropylene oxide aliphatic diamine is in the structure basis of aliphatic diamine, to the hydrogen original of the amido in end
Son carries out the substitution of polypropylene oxide base, exemplary chemical structures formula are as follows:
The structure of its salt are as follows:
Its quaternary ammonium salt structure formula are as follows:
Or:
Or:
R in the above polypropylene oxide fatty amine salt is aliphatic hydrocarbon.
Long chain guanidine.The general structure of long chain guanidine type starch binder is as follows:
Its corresponding guanidine salt structural formula are as follows:
R is the substituted or unsubstituted alkyl or aryl that carbon atom number is greater than 6, R in formula1、R2、R3、R4、R5Represent H, alkane
Base, aryl, C (=NH) NH2、-CONH2,-C (=S) NH2Deng.
For example, working as R1、R2、R3、R4、R5Dodine, structural formula are obtained when R is dodecyl for H are as follows:
The structural formula of corresponding dodecyl guanidine hydrochloride are as follows:
Work as R1、R2、R3、R4、R5The chemical combination such as flowering structure is obtained when R is laurylamide polyethyene diamine (n=4) for H
Object:
Chain alkyl biguanides (alkyl biguanidine).The structure of chain alkyl biguanides type starch binder are as follows:
R is the substitution room or unsubstituted alkyl or aryl, R that carbon atom number is greater than 6 in formula1、R2、R3、R4、R5、R6It represents
H, alkyl, aryl ,-C (=NH) NH2、-CONH2,-C (=S) NH2Deng.
For example, working as R1、R2、R3、R4、R5When for H, the structural formula of alkyl biguanides is obtained are as follows:
Such as: 1- octadecyl biguanides mono-hydrochloric salts (English name: 1- (diaminomethylidene) -2-
octadecylguanidine hydrochloride;1-Octadecylbiguanide monohydrochloride;CAS
Number: 23604-20-8) structural formula are as follows:
When R is vinylbenzene in above formula, insoral (Phenformin), structural formula are obtained are as follows:
When R is dodecyl, dodecyl biguanides, structural formula are obtained are as follows:
Chain alkyl bisguanides (polyguanidine) type.The structural formula of chain alkyl polyguanidine type starch binder are as follows:
R, R in formula1、R2、R3、R4、R5、R6H, alkyl, aryl are represented, Z represents substituted or unsubstituted alkylidene or aryl
Deng.
For example, Sterwin 904 (English name: 1,1'-Hexamethylene-bis [5- (2-ethylhexyl)
biguanide dihydrochloride;No. CAS: 22573-93-9]) structural formula are as follows:
As R, R1、R2、R4、R5、R6It is propylidene base, R for H, Z3When for cocoyl, cocoyl propane diamine biguanides (English is obtained
Text: Cocoyl-propylenediamine-1,5-bis-guanidinine):
For another example, when Z is dodecyloxy phenyl, synthesis obtains 2- [5- (diaminomethyleneamino) -2- dodecane
Phenyl] guanidine dihydrochloride (English name: 2- [3- (diaminomethylideneamino) -4-dodecoxyphenyl]
guanidine dihydrochloride;N,N"'-(4-dodecyloxy-m-phenylene)-di-guanidine,
dihydrochloride;N,N"'-[4-(dodecyloxy)-1,3-phenylene]bisguanidine
dihydrochloride;No. CAS: 135-42-2) structural formula are as follows:
Alkyl-substituted azacyclo- or its quaternary ammonium salt.This kind of starch binder is non-aromatic containing saturation azacyclo-, unsaturation
The compound or its quaternary ammonium salt of fragrant azacyclo- or aromatic nitrogen heterocycle, including alkyl pyridine, alkyl morpholine, chain alkyl imidazoles
(alkyl imidazoline) etc., the chemical structural formula of alkyl pyridine quaternary amine are as follows:
R represents alkyl or substituted alkyl in formula.
For example, the structure of cetyl pyridinium hydrochloric acid is as follows:
2- (octadecane yloxymethyl) pyridine (English name: 2- ((Octadecyloxy) methyl) pyridine;CAS
Number:
Structural formula 1228182-56-6) are as follows:
4- (the bis- pentadecyl aminostyryls of 4-)-N- methylpyridinium iodide (English name:
4-[2-(1-methylpyridin-1-ium-4-yl)ethenyl]-N,N-di(pentadecyl)aniline,
iodide;
Pyridinium,4-[2-[4-(dipentadecylamino)phenyl]ethenyl]-1-methyl-,
iodide(1:1);
Pyridinium,4-[2-[4-(dipentadecylamino)phenyl]ethenyl]-1-methyl-,
iodide(9CI);No. CAS:
135288-72-1) structural formula are as follows:
Octenidine dihydrochloride (Chinese nickname: octenidine dihydrochloride;English name: Octenidine
Dihydrochloride;N,N'-(decane-1,10-diyldi-1(4H)-pyridyl-4-ylidene)bis
(octylammonium)dichloride;No. CAS: 70775-75-6) structural formula are as follows:
Chain alkyl morpholine (alkyl morpholine), structural formula is
R in formula1、R2、R3、R4It represents H or alkyl (a length of C1-C4 of carbochain), R represents Long carbon chain alkyl (carbochain is greater than 6).
For example, 2,6- dimethyl -4- tridecyl morpholines, structural formula are as follows:
The structural formula of chain alkyl imidazoles (alkyl imidazoline) quaternary amine are as follows:
R in formula1、R2、R3、R4、R5Represent substituted or unsubstituted alkyl.
For example, Bromide (the English name: 1-Tetradecyl-3- of 1- myristyl -3- methylimidazole
Methylimidazolium Bromide;Chinese nickname]: bromination 1- myristyl -3- methylimidazole) structural formula are as follows:
Such as: 2- nonyl benzimidazole (English name: 2-nonyl-1H-benzimidazole;2-nonyl-1H-1,3-
benzodiazole;2-Nonyl benzimidazole;No. CAS: 5851-50-3) structural formula are as follows:
Lauryl hydroxyethyl imidazole quinoline (Chinese nickname: 2- undecyl -2- imidazoles -1- ethyl alcohol;English name: 4,5-
dihydro-2-undecyl-1H-imidazole-1-ethanol;1-(2-Hydroxyethyl)-2-
undecylimidazoline;2-Undecyl-2-imidazoline-1-ethanol;2-Undecyl-4,5-dihydro-
1H-imidazole-1-ethanol;1-(2-Hydroxyethyl)-2-undecylimadazoline;1H-Imidazole-
1-ethanol,4,5-dihydro-2-undecyl;No. CAS: 136-99-2) structural formula are as follows:
Chain alkyl piperazine (alkyl-piperazine), general structure are as follows:
R, R in formula1、R2、R3、R4、R5、R6Represent H, substituted or unsubstituted alkyl.
Chain alkyl quinoline (alkyl quinoline, orbenzo-pyridine) quaternary amine, general structure are as follows:
Chain alkyl pyrroles (alkyl pyrrolidinium), structural formula are as follows:
Other salt form.Other than above nitrogen-atoms cationoid starch binder, there are also other positively charged cations
Bonding agent, the respectively surfactant containing elements such as N, P, As, S, I, Si.The structural formula of cationic phosphonium salt is R1R2R3R4PX,
R in formula1, R2, R3, R4For identical or different alkyl, replace or it is non-substituted, saturated or unsaturated, can also have point
Branch does not have branch, cyclic structure or linear chain structure, can wrap ether-containing, ester, amide, is also possible to aromatic series or aromatic series replaces
Object;X is connected by ionic bond with nitrogen-atoms, mostly halide anion (F-, Cl-, Br-, I-) or be HSO4-, CH3CO2-
And OH-.For example, the structure of three (dodecyl) phosphines (English tridodecyl phosphine) is P (C12H25)3, No. CAS:
6411-24-1。
Non-polar group contains heteroatomic amine salt and quaternary ammonium salt.Here so-called to generally refer to dredge containing heteroatomic quaternary ammonium salt
Containing the heteroatomic quaternary ammonium salt such as O, N, S in aqueous hydrocarbon chain, that is, refer in lipophilic group containing amido bond, ehter bond, ester bond or
The surfactant of thioether bond.Hydrophilic radical quaternary ammonium cation and alkyl hydrophobic group are by groups such as amide, ester, ether or thioethers
It is connected, rather than is directly linked together.Such as: when oxygen atom O replace alkyl among a C when, generate alkoxy.Example
Such as, the knot of 3- (octyl oxygroup) propylamine (English name: 3- (octyloxy) -1-Propanamine, No. CAS: 15930-66-2)
Structure formula are as follows:
When sulphur atom S replaces a carbon atom, alkylthio group is generated.For example, 2- (dodecyl is thio)-acetamide (English
Literary fame claims: 2-dodecylsulfanylacetamide;Acetamide,2-(dodecylthio);2-(Dodecylthio)
acetamide;No. CAS: 10220-53-8) structural formula are as follows:
Gemini cationic starch bonding agent has quaternary, pyridine salt type and guanidine radicals type starch binder.Gemini
(Gemini) such starch binder is a kind of band there are two hydrophobic chains, the chemical combination of two hydrophilic radicals and a bridged group
Object is linked together similar to two cationic starch binding agent molecules by a bridge, and the shape of molecule is such as disjunctor
Twin infants, cation can be quaternary, pyridine salt type and guanidine radicals type.Hydrophobic grouping can be saturated carbon chains type, no
Saturated carbon chain, ether type, ester group type, aroma type and two carbochain Length discrepancies asymmetrical type.Linking group can be thin
Water, be also possible to it is hydrophilic;Can be very short, it can also be very long;It can be rigid, be also possible to flexible.The former includes
Shorter hydrocarbon chain, xylylene, to stilbenes base etc., the latter includes longer hydrocarbon chain, polyoxyethylene chain, miscellaneous original
Son etc..For example, the structural formula of double bis- chlorination ammonium salts of octadecyldimethyl-polyamines-are as follows:
Dendrimer type starch binder.Dendrimer is exactly dendritic macromole, it is from a central core molecule
It sets out, spreads the structure extended step by step by branched monomer, or passed through by centronucleus, several layers of branching unit and peripheral groups
What chemical bond was formed by connecting.There are the types such as polyethers, polyester, polyamide, polyaromatic, poly-organosilicon.Dendritic macromole
Characteristic is that its molecular structure is regular, and molecular volume, shape and functional end-group can be designed and be controlled on a molecular scale, according to need
It asks and its end group is modified, just obtain corresponding dendritic macromole surfactant.
In addition, the hydrophobic group of above all of starch binder can be fluorine-containing hydrophobic group, i.e., hydrophobic group be by carbon and
Two kinds of element compositions of fluorine, or the mixing hydrophobic grouping by fluorine atom substitution part hydrogen atom.Since fluorine atom is instead of hydrophobic
Hydrogen atom on group, is changed into the structure of c h bond the form of C-F key, thus it show it is some specific to fluorine carbon hydrocarbon
Excellent performance, i.e. high surface, high heat resistance stability and high chemical stability, fluorine-containing alkyl not only hydrophobic but also hate oil characteristic.
For example, all hydrogen atoms are all replaced by fluorine in the structure of perfluor certain herbaceous plants with big flowers amine, structural formula are as follows:
Fluorine can partially replace hydrogen atom, such as the hydrogen atom of certain herbaceous plants with big flowers amine wherein five carbon atoms is substituted, obtain (5,5,6,
6,7,7,8,8,9,9,10,10)-ten one fluorine certain herbaceous plants with big flowers amine, structure are as follows:
In compound of the present invention, as any variable (such as R1, R etc.) occurred more than in any component it is primary, then
Its definition occurred every time is independently of other definition occurred every time.Equally, the combination for allowing substituent group and variable, as long as this
Combination stablizes compound.
Starch.Starch is a kind of polysaccharide, molecular formula (C6H10O5) n, starch can be regarded as the high polymer of glucose.It forms sediment
Powder has two class of amylose and amylopectin.Amylose contains several hundred a glucose units, and amylopectin contains thousands of a glucose
Unit;Thus amylose molecule amount is smaller, and 50000 or so, branched amylopectin molecules amount is more much bigger than amylose, In
60000 or so.The composition of plant amylum is generally made of 10%~30% amylose and 70%~90% amylopectin.
Starch, which has, meets the characteristic that iodine becomes blue, this is determined by the design feature of starch itself.The straight chain for being dissolved in water forms sediment
Powder is spiral by the hydrogen bond curling of intramolecular.If iodine solution is added, the iodine molecule in iodine solution is just embedded into helical structure
Gap, and link together by Van der Waals force and amylose, form a kind of complex compound.This complex compound can compare
Other visible lights (wave-length coverage is 400~750nm) other than blue light are relatively evenly absorbed, so that amylose be made to meet iodine
Blue, it is in aubergine that amylopectin, which meets iodine, and dextrin meets iodine in colors such as royal purple, purple, oranges.
Content of starch in all kinds of plants is all higher, starch-containing 62%~86% in rice, starch-containing 57% in wheat~
75%, it is then starch-containing more than 90% in potato starch-containing 65%~72% in maize.
Converted starch (Modified Starch).To improve the performance of starch, expanding its application range, using physics, change
It learns or is enzymatically treated, new functional group is introduced on starch molecule or change starch molecule size and starch granular property, thus
Change the natural characteristic of starch (such as: gelatinization point, thermoviscosity and its stability, freeze-thaw stability, gel force, film forming, transparent
Property etc.), make it more suitable for the requirement centainly applied.This to pass through secondary operation, the starch for changing property is referred to as denaturation and forms sediment
Powder.Currently, the classification of converted starch is usually to be carried out according to processing mode.
Physical modification: pre-gelatinized (α-change) starch, gamma-rays, hyperfrequency radiation treatment starch, mechanical lapping processing starch,
Heat-Moisture Treated Starch etc..
Chemical modification: the converted starch handled with various chemical reagent.Wherein have two major classes: one kind is to make starch point
Son amount decline, such as acidified starch, oxidized starch, bake dextrin;It is another kind of be make starch molecule amount increase, as crosslinked starch,
Esterification starch, etherification starch, graft starch etc..
Enzyme process is denaturalized (bio-modification): various enzyme treated starch.Such as α, β, cyclooctaamylose, maltodextrin, amylose
Deng.
Complex denaturation: the converted starch obtained using two or more processing methods.As oxidative crosslinked starch, cross-linked esterification form sediment
Powder etc..There are two types of the respective advantages of converted starch for the converted starch tool obtained using complex denaturation.
In addition, converted starch can also classify by production process route, have dry method (such as phosphate ester starch, acidified starch,
Cationic starch, carboxymethyl starch etc.), wet process, organic solvent method (as carboxy starch preparation generally use ethanol as solvent), it is crowded
Platen press and cylinder drying (such as native starch or converted starch are that raw material produces pre-gelatinized starch).
Pre-gelatinized starch (Pre-Geletinized Starch).The gelatinization of starch: amylum body is (various at moderate temperatures
The starch required temperature in source is different, and general 60~80 DEG C) swelling, the effect divided, form homogeneous paste solution claim in water
For gelatinization.The essence of gelatinization is between the starch molecule of (crystalloid and noncrystalline) state orderly and unordered in amylum body
Hydrogen bond disconnects, and is dispersed in water as colloidal solution.
The process of gelatinization can be divided into three phases: (1) the reversible water suction stage, and moisture enters the noncrystalline portion of amylum body
Point, volume slightly expands, and cools down drying at this time, and particle can restore, and birefringent phenomenon is constant;(2) the irreversible water suction stage, with
Temperature increase, moisture enters starch crystallite gap, irreversibly a large amount of water suctions, and birefringent phenomenon gradually obscures so that disappear,
" dissolution " also known as is crystallized, amylum body is swollen to 50~100 times of initial volume;(3) amylum body finally disintegrates, starch molecule all into
Enter solution.
The measuring method of gelatinization: there are optical microscopy, electron microscope method, light propagation method, viscosimetric analysis
Method, the measurement of swelling and solubility, the analysis of enzyme, nuclear magnetic resonance, laser light scattering method etc..Industrially common viscosimetry,
The measurement of swelling and solubility.
Denaturated starch by acid (Acidified Starch).Denaturated starch by acid, which draws, to be referred to native starch below gelatinization point
It is handled with inorganic acid, changes one kind converted starch obtained from its property.
The condition for usually preparing denaturated starch by acid is: starch concentration is 36%~40%, and temperature is lower than gelatinization reaction temperature
It spends (35~60 DEG C), the reaction time is 0.5h to a few hours.When the viscosity required for reaching or conversion degree, neutralizes, filters, washes
It washs, be drying to obtain product.
Influence of the reaction condition to denaturated starch by acid performance:
1. thermotonus temperature is to influence the principal element of denaturated starch by acid performance, when temperature is at 40~55 DEG C, viscosity
Variation tends to temperature, and temperature has been gelatinized when rising to 70 DEG C.Therefore reaction temperature is generally selected within the scope of 40~55 DEG C.
2. the type and dosage acid of acid are not involved in reaction as catalyst.Different acid catalysis is different, and hydrochloric acid is most
By force, sulfuric acid and nitric acid it is similar, when temperature is higher, when sour dosage is larger, nitric acid converted starch makes the product be in because side reaction occurs
It is light yellow, so being rarely employed in actual production.The catalytic action of acid is related with the dosage of acid, and sour dosage is big, then reaction is violent.
3. starch concentration starch concentration should be controlled 40% or so.
Esterification starch (Acetylated Starch).Esterification starch refers in the following starch milk of gelatinization point and organic acid
Acid anhydride (acetic anhydride, succinic anhydride etc.) carries out one kind converted starch obtained from esterification under certain condition.
Acid esterification series converted starch accesses acetyl group in the C6 of glucose unit, and acetyl group belongs to hydrophilic group
Group, substantially increases the binding ability of starch and water, thus improves the water swelling degree of starch granules, reduces gelatinization temperature
Degree, improves peak viscosity, acid esterification series converted starch protein, and fatty content is very low, so color is pure white, tool
Have natural fluoresence, can effectively improve the color of face body, at the same its gelatinization point compared in flour ative starch it is low, in flour cake pansman
In sequence prior to ative starch be gelatinized, shorten digestion time, due to acetyl group presence and converted starch noodles surface film forming
Property, it can effectively barrier oil and flour cake adhere to, reduce oil absorbency, the peak value viscosity of converted starch shows that its starch granules is inhaled
Water degrees of expansion is big, this is very helpful to the rehydration of instant noodles.
Oxidized starch (Oxidized Starch).Many chemical oxidizing agents can oxidized starch, but in industrial production most often
It is alkaline hypochlorite.
Crosslinked starch (Cross-linked Starch).The concept of crosslinked starch is, the alcoholic extract hydroxyl group of starch and crosslinking agent
Polynary functional group forms diether bond or diester linkage, makes between two or more starch molecules " bridge formation " together, in more
Tie up the reaction of network structure, referred to as cross-linking reaction.
Crosslinked action, which refers to build bridge between molecule, forms chemical bond, strengthens the effect of hydrogen bond between molecule.Work as crosslinking
When starch heats in water, hydrogen bond can be made to die down even and destroyed, however due to the presence that chemistry is built bridge, the particle of starch will not
With degree remain unchanged.
Domestic most common crosslinking agent has: sodium trimetaphosphate, sodium tripolyphosphate, formaldehyde, phosphorus oxychloride, epoxychloropropane.
Resistant starch (Resistant Starch), also known as enzyme resistant starch and indigestibility starch, cannot be by small intestine
Enzymatic hydrolysis, but in the intestines and stomach colon of people fermentation reaction can be played with volatile fatty acid.Resistant starch is present in certain natural
In food, such as potato, banana, rice all contain the cornstarch of resistant starch, especially high amylose starches containing resistance shallow lake
Powder is up to 60%.This starch is difficult to degrade compared with other starch, and digestion slowly, absorbs and enters blood all relatively slowly in vivo.Its
Property has certain slimming effect similar to disappearing fibre.
Starch-iodine inclusion compound (Starch-Iodine Inclusion Complex).Amylose is by phlorose point
Son condensation still has hydroxyl to be exposed to outside spiral into spiral helicine long conveyor screw, each glucose unit.Iodine molecule with
The effect of these hydroxyls makes the axis part of iodine molecule insertion starch conveyor screw.Iodine is called clathration with this effect of starch,
Product is called inclusion compound.
In the inclusion compound that starch is generated with iodine, each iodine molecule cooperates with 6 glucose units, and starch chain is with diameter
0.13pm coiled, iodine molecule are in the axis part of spiral.
The color for the inclusion compound that starch is generated with iodine, it is related with the degree of polymerization or relative molecular mass of starch.Certain
Within the scope of the degree of polymerization or relative molecular mass, with the increase of the degree of polymerization or relative molecular mass, the variation of the color of inclusion compound by
Colourless, orange, light red, purple to blue.For example, the degree of polymerization of amylose be 200~980 or relative molecular mass range be
When 32000~160000, the color of inclusion compound is blue.The many amylopectin of branch, the straight chain average polymerization on branch
Degree 20~28, the inclusion compound formed in this way is purple.The degree of polymerization of dextrin is lower, shows brownish red, red, pale red etc..
Amylase (Amylase).Amylase be act on soluble starch, amylose, glycogen etc. the Portugal α -1,4- it is poly-
Enzyme that is sugared and making α -1,4- hydrolysis of glycoside bond.According to the difference of enzymic hydrolysates heterogeneous types, alpha-amylase can be divided into
(EC3.2.1.1) with beta amylase (EC3.2.1.2).
Alpha-amylase (α-Amylase), systematic name are Isosorbide-5-Nitrae-α-D- glucan glucan hydrolase, (Isosorbide-5-Nitrae-α-D-
Glucan-glucanohydrolase).Alpha-amylase can hydrolyze α-Isosorbide-5-Nitrae-glycosidic bond inside starch, and hydrolysate is paste
Essence, oligosaccharide and monosaccharide can be such that the viscosity of gelatinized starch reduces rapidly after enzyme effect, become liquefying starch, therefore also known as liquefy
Amylase, α-amylase, α -1,4- dextromase.
When alpha-amylase is using chain starch as substrate, reaction is generally carried out by two stages.Firstly, chain starch is rapidly degraded,
Oligosaccharide is generated, the viscosity of this stage chain starch and the ability that color reaction occurs with iodine decline rapidly.The reaction of second stage
Than first stage it is slower very much, including oligosaccharide slowly hydrolyzes and generates final product glucose and maltose.Alpha-amylase acts on
Glucose, maltose and a series of limitation dextrin (constituting oligosaccharide by 4 or more glucosyl groups) are generated when branch starch, after
Person contains α -1,6- glycosidic bond.
Considerably strong calcium ion is combined to obtain containing one in alpha-amylase molecule, this calcium ion does not participate in enzyme-directly
The formation of substrate complex, function are to maintain the structure of enzyme, and enzyme is made to have maximum stability and highest activity.
Thermostable α-Amylase and medium temperature-amylase can be divided into according to the thermal stability of alpha-amylase.In high temperature resistant α-shallow lake
In powder enzyme, food processing has been widely used in by the enzyme preparation that bacillus amyloliquefaciens and bacillus licheniformis generate
In.Temperature is different to the effect of vigor of both enzymes, and bacillus licheniformis-amylase optimum temperature is 92 DEG C, and starch liquefacation
Bacillus-amylase optimum temperature is only 70%, and except thermal stability is there are in addition to difference, both enzyme effects are in the end of starch
Product is not also identical.
Beta amylase (β-amylase), also known as starch β-Isosorbide-5-Nitrae-maltoside enzyme (α-Isosorbide-5-Nitrae-glucan
Maltohydrolase), it is one of amylases, amylose can be resolved into the amylase of maltose.Beta amylase
Exclusive product be maltose, be not glucose.Beta amylase is a kind of exoamylase, is gone back when it acts on starch from non-
α-Isosorbide-5-Nitrae the key being separated by successively is cut in originality end, and hydrolysate is all maltose.Due to the amylase in hydrolytic process by water
The configuration of C1 is changed into β type by α type in solution product maltose molecule, so referred to as beta amylase.
Beta amylase is primarily present in higher plant, especially in cereal, such as barley, wheat, in sweet potato, soybean
Also there is presence, be not present in animal body.Sulfydryl (- SH) is contained in beta amylase activated centre, therefore, some oxidants, a huge sum of money
Its inactivation can be made by belonging to ion and mercapto reagent, and the glutathione of reproducibility, cysteine have protective effect to it.
Beta amylase is unable to α -1 of hydrolyzing amylopectin, and 6 keys can not continue to hydrolyze across branch point, therefore hydrolyzes branch
Starch is incomplete, β-limit dextrin of macromolecular under remaining.When beta amylase hydrolyzes amylose, if starch molecule is by idol
Several glucose unit compositions, then final hydrolysate is entirely maltose;If starch molecule is by odd number glucose unit group
At then final hydrolysate is in addition to maltose, and there are also a small amount of glucose.When beta amylase hydrolyzes starch, due to from molecular end
Start, always with the presence of macromolecular, therefore viscosity decline is very slow, it cannot function as α-amylase use, and beta amylase hydrolyzes starch water
When solving product such as maltodextrin, malto-oligosaccharide, hydrolysis rate quickly, is pretended as carbohydrase use.
Gamma amylase (γ-amylase).Number E.C.3.2.1.3.Gamma amylase is excision enzyme, non-from starch molecule
Reducing end successively cuts α (1 → 4) chain glycosidic bond and α (1 → 6) chain glycosidic bond, cuts glucose residue one by one, hydrolyzes generation
Indexing effect occurs for free hemiacetal hydroxyl, discharges β-glucose.So amylose or amylopectin no matter are acted on,
Final product is glucose.Therefore, also known as glucoamylase, carbohydrase.
Isoamylase (isoamylase).Number E.C.3.2.1.33.The α-of Isoamylase hydrolyses amylopectin or glycogen
1,6- glycosidic bond only hydrolyzes-the 1 of glycogen or amylopectin branching-point, and 6 glycosidic linkages cut entire side shoot, are formed different in size
Amylose.Therefore, isoamylase is also referred to as amylo-1:4,1:6-transglucosidase, 6- glucuroide.Animal, plant, microorganism all generate different starch
Enzyme.Source is different, and title is also different, such as: debranching enzyme, Q enzyme, R enzyme, general Shandong indigo plant enzyme, K. aerogenes Pullulanase.
Cyclodextrin glycosyltransferase (Cyclodextrin Glucosyltransferase, CGT).Cyclodextrin
(Cyclodextrins, often referred to simply as CD) is a kind of raw under cyclodextrin glycosyltransferase effect by starch or polysaccharide
At by D- glucopyranose units by α-Isosorbide-5-Nitrae-glycosidic bond end to end cyclic compound general name, usually by 6-12
D- glucopyranose units composition, therefore, according to the quantity of glucose unit in ring, common are 6,7 and 8 glucose units
Molecule, be referred to as α-, β-and gamma-cyclodextrin.The most important feature of cyclodextrin glycosyltransferase is exactly to have catalysis
The oligomeric sugar chain of linear type starch generates the ability of cyclodextrin.CGT cyclization is a kind of special shape for turning glucosides reaction, it is
Using the non-reducing end of donor chain as receptor, to form cyclisation product.
COD (Chemical Oxygen Demand, COD).COD definition: water sample under certain condition, with oxygen
The amount for changing oxidant consumed by reducing substances in 1 liter of water sample is index, is converted to after every liter of water sample is all oxidized, needs
Oxygen milligram number, indicated with mg/L (ppm).It reflects the degree polluted in water by reducing substances, as organic matter phase
It is an organic pollution parameter that is important and can comparatively fast measuring to one of the overall target of content.Therefore, chemical oxygen demand
Measure (COD) and indexs often how many as measurement Organic substance in water matter content.COD is bigger, illustrates water body by organic
The pollution of object is more serious.
The measurement of COD (COD) is surveyed with the difference of reducing substances and measuring method in measurement water sample
Definite value is also different.It is acid potassium permanganate oxidizing process and potassium dichromate oxidation that application is most common at present.Potassium permanganate
(KMnO4) method, oxygenation efficiency is lower, but easier, when the relative value of content of organics is bigger in measuring water sample, can adopt
With potassium bichromate (K2Cr2O7) method, oxygenation efficiency is high, and reproducibility is good, the total amount suitable for measuring organic matter water sample.
Experimental material used, laboratory apparatus and General Experimental Procedures are as follows in following embodiment.
Experimental material:
Starch binder: table 1 lists the details for the starch binder material that the present invention is tested, including Chinese and English
Title, chemical structural formula and material number.All starch binders are commercial products, the purity range effectively formed
It is pure to pharmaceutical purity for reagent.In all embodiments, all starch binders are sold (as-is) according to it and are directly used, and do not have
Further purification.
Table 1
Starch: cornstarch is " emerging trade " edible corn starch, is purchased from Xingmao Corn Development Co., Ltd., Zhucheng;Cassava
Starch, wheaten starch, starch from sweet potato are purchased from 001 Bioisystech Co., Ltd of Shenzhen, and the corn in 11 table 13 of embodiment becomes
Property starch, cassava oxidized starch-business, cassava modified starch-business, potato acetate starch-commercially from Wuhan far at
Create Science and Technology Ltd.'s buying, code name YC-20170701.
Bleach chemical pulp: bleach chemical pulp is derived from Dongguan white swan Paper Co., Ltd (BKP).
Group unbleached chemical pulp: group unbleached chemical pulp is derived from Zhejiang Rongcheng Paper Industry Co., Ltd., is the primary needle chemistry in import North America
It starches (UKP).
OCC waste paper: body paper is derived from Dongguan Jun Ye Paper Co., Ltd, is the useless corrugation produced of OCC state using 100%
Paper, starch surface sizing amount is about in 40-60kg/T paper.
Test apparatus:
CBJ-A fiber type standard dissociation device: Changchun month bright small-scale test machine Co., Ltd.
CPO1A-3A sheet forming apparatus: Dongguan City Ying Tenaisen precision instrument Co., Ltd.
BS-30KA electronic balance: Shanghai Yousheng Balance Co., Ltd..
COD clears up instrument: the III COD TP TN digestion instrument of XJ- of Shaoguan enviromental protection instrument tomorrow Co., Ltd production.
Ultraviolet-visible spectrophotometer: the UVmini-1240 UV, visible light of Japanese Shimadzu instrument company manufacture is divided light
Degree meter.
DHG-9070A electric heating constant-temperature blowing drying box: Shanghai Qi Xin scientific instrument Co., Ltd
TDL-80-2B: Anting Scientific Instrument Factory, Shanghai.
Test method
Standard iodine solution is prepared: 11g iodine and 22g potassium iodide are weighed, iodine is completely dissolved with a small amount of distilled water, is finally settled to
500ml is stored in brown bottle.
Dilute iodine solution is prepared: 10g potassium iodide is weighed, is dissolved with a small amount of water, the dense iodine solution of 2ml is drawn, is settled to distilled water
100ml volumetric flask, is stored in brown bottle.
Ative starch solutionIt prepares: (1) take starch sample first to prepare 7% starch solution;(2) by starch liquor heating to 95 degree
(DEG C) is reacted to viscosity and reaches stable;(3) 65 DEG C are cooled to, starch solution is kept in water bath with thermostatic control, it is spare.Implement below
In example unless otherwise specified, taken starch sample is ative starch, and 7% " the standard starch solution " is all according to said method to carry out
It is prepared.
Oxidized starch solution is prepared: in the magnetic force water-bath for taking 465g deionized water to place it in 97 DEG C, it is slowly added to 35g
Starch adds 0.14g ammonium persulfate (that is, 0.4%), cooks 40 minutes, is then cooled to 65 DEG C, keeps starch molten
Liquid is made 7% " standard " starch solution (its viscosity is in 30mPa.s or so), saves backup at 60 DEG C.
Chemical pulp slurry is produced: a certain amount of bleaching or group unbleached chemical pulp plate are taken, fritter is torn into, weighs 300g fritter
Slurry adds 45 DEG C of warm water to 2307g, and starching dense is 13%, after impregnating several minutes, pours into PL12-00 type high density hydraulic pulper, broken
Slurry 15 minutes, squeezing saves backup later.
OCC old paper stock and plain boiled water are produced: waste paper 300g is taken, fritter is torn into, then plus tap water is diluted to 13%
Concentration impregnates 5-10min, pours into PL12-00 type high density hydraulic pulper, pulping 15 minutes, takes out broken good slurry, then plus originally
Water is diluted to 3% concentration;Then plain boiled water and slurry are separated with filter bag, OCC is madeOld paper stockPlain boiled water and OCCWaste paperPaper pulp, point
It does not save backup.
Starch complex reaction step:(1) starch solution or amyloid OCC old paper stock plain boiled water of above-mentioned preparation are taken
500mL is placed into water bath with thermostatic control (reaction temperature is set as needed), at the uniform velocity stirs, and reaches balance, and it is molten optionally to adjust its
Liquid pH;(2) starch complexing agent is added according to designed dosage, is reacted, reaches 5,10,15,30,60 in the reaction time,
Solution is taken at 90 or 120 minutes, is placed in 30mL test tube, separation (x4000g.5 minutes) is then centrifuged for, finally takes supernatant point
Analyse its starch or COD concentration.
Absorption/retention test of the starch in paper pulp fiber: (1) take the starch solution of above-mentioned preparation or amyloid OCC useless
Paper white water 800mL, is placed into water bath with thermostatic control (reaction temperature is set as needed), at the uniform velocity stirs, and reaches balance, and regarding need to
Adjust its pH value of solution;(2) starch complexing agent is added according to designed dosage, is reacted, is reached 30,60 or 120 minutes
When take solution and place it in 30mL test tube;(3) chemical pulp is added according to required pulp density or OCC is starched, stirring
Carry out adsorption reaction;(4) when reaction reaches 10,30,60 or 120 minutes, slurries is taken and are placed it in 30mL test tube;(5) right
All taken solution are centrifuged (x4000g.5 minutes) and are analyzed, and supernatant is taken to analyze its starch or COD concentration.
The test procedure of chemical pulp copy paper: (1) bleaching or group unbleached chemical pulp 300g are taken, fritter is torn into, then plus certainly
Water is diluted to 13% concentration, impregnates 5-10min, pours into PL12-00 type high density hydraulic pulper, pulping 15 minutes, takes out broken
Good slurry, saves backup;(2) the above-mentioned starch solution made or OCC secondary stock plain boiled water 800g are taken, test reagent (starch is added
Complexing agent) reaction 30min;(3) after reacting 30min, synergist is added and is stirred to react 2-3min, chemical pulp is added, is stirred to react
Total time 10min;(4) slurry is taken to be placed in 30mL test tube, and after centrifugal treating, the starch concentration and COD for testing supernatant contain
Amount;(5) remaining slurry pours into standard fibre dissociation device immediately and discongests 1500r, after having discongested, is diluted with water to 0.5% concentration, claims
The slurry 640g of 0.5% concentration is taken to carry out copy paper (Substance 100g or so) with sheet forming apparatus;(6) after having copied paper, by paper
Sample is placed on the thermostatic constant wet chamber balance 16h of 25 DEG C, moisture 50%, then tests paper physical property and at paper content of starch.
The separation of OCC waste paper plain boiled water handles the test procedure of then copy paper respectively: (1) OCC waste paper 300g is taken, is torn into small
Block, then plus tap water is diluted to 13% concentration, impregnates 5-10min, pours into PL12-00 type high density hydraulic pulper, pulping 15
Minute, take out broken good slurry, then plus tap water be diluted to 3% concentration, then plain boiled water and slurry are separated with filter bag, saved respectively standby
With;(2) the above-mentioned plain boiled water 800g made is taken, test reagent (starch complexing agent) is added and reacts 30min;(3) after reacting 30min,
Synergist is added and is stirred to react 2-3min, the OCC slurry prepared above is added, is stirred to react total time 10min;(4) slurry is taken to set
In 30mL test tube, the starch concentration and COD content of supernatant are tested after centrifugal treating;(5) remaining slurry pours into fiber immediately
Standard dissociation device discongests 1500r, after having discongested, is diluted with water to 0.5% concentration, weighs the slurry 730g paper of 0.5% concentration
Page former carries out copy paper (Substance 100g or so);(6) after having copied paper, pattern is placed on to the perseverance of 25 DEG C, moisture 50%
Constant temperature and humidity room balances 16h, then tests paper physical property and at paper content of starch.
The magma copy paper experimental procedure of OCC waste paper:(1) waste paper 300g is taken, fritter is torn into, then plus tap water dilutes
To 13% concentration, 5-10min is impregnated, PL12-00 type high density hydraulic pulper is poured into, pulping 15 minutes, takes out broken good slurry, then
Add tap water to be diluted to 3% concentration, saves backup;(2) above-mentioned 3%OCC magma 800g is taken, test reagent (starch complexing is added
Agent) reaction 30min;(3) after reacting 30min, synergist is added and is stirred to react 10min;(4) slurry is taken to be placed in 30mL test tube
In, the starch concentration and COD content of supernatant are tested after centrifugal treating;(5) remaining slurry pours into standard fibre dissociation device immediately
Discongest 1500r, after having discongested, be diluted with water to 0.5% concentration, weigh the slurry 730g sheet forming apparatus of 0.5% concentration into
Row copy paper (Substance 100g or so);(6) after having copied paper, by pattern is placed on 25 DEG C, the thermostatic constant wet chamber of moisture 50% puts down
Weigh 16h, then tests paper physical property and at paper content of starch.
Iodine colour developing starch test method: sample after taking 0.5ml to be centrifuged is added the dilute iodine solution of 4ml, measures extinction at 600nm
Degree, determines starch concentration according to absorbance concentration graticule.
Resolution method tests COD content: 3.00mL sample to be tested is accurately pipetted in digestion tube, accurate addition 1.00mL screening agent
(not the water sample of chloride ion-containing change plus 10% sulfuric acid 1.00mL), add 3.00mL digestive juice, 5.00mL catalyst screws close
Digestion tube is successively put into temperature by capping (the not water sample of chloride ion-containing and low-boiling-point organic compound can be tested with open pipe, and method is identical)
It spends in the digestion instrument of 160.C, clears up 25 minutes.Digestion process finishes, and after cooling, digestion tube is taken out in order, with than
Color method measures COD value.
At paper content of starch test method:(1) paper pattern is taken into, baking oven is placed and dries 15min, use plant micro after drying
Pulverizer crushes pattern, then smashed pattern is placed baking oven and dries 15min;(2) the crushing pattern for taking 1g to dry is placed
In 100ml beaker, after 70-80ml boiled water is added, it is placed in 100 DEG C of thermostat water bath 40min;(3) it is taken out after 40min, adds water
To 100g, the content of starch of test supernatant after slurry and centrifugal treating is taken.
Starch slippage (also known as the starch amount of settling out or starch reserved)Refer to that starch solution reacts it with starch complexing agent
Afterwards, in solution starch concentration (St) and initial starch concentration (So) difference, i.e. starch reserved=So-St (mg/L).
Starch retention rate (also known as starch settle out rate)Refer to that starch reserved accounts for the percentage of initial starch total amount, i.e.,
Starch retention rate (%)=(So-St)/So × 100
COD degradation amount (the also known as COD amount of settling out)After referring to that starch solution is reacted with starch complexing agent, COD is dense in solution
The difference of (COD1) and initial COD concentration (CODo) are spent, i.e.,
COD degradation amount=CODo-COD1 (mg/L)
COD rate of descent (also known as COD settle out rate)Refer to that starch reserved accounts for the percentage of initial starch total amount, i.e.,
COD rate of descent (%)=(CODo-COD1)/CODo × 100.
To starch after 1 cationic starch bonding agent cetyl pyridinium hydrochloric acid (number C7) of embodiment and starch association reaction
The influence of dissolution and fiber surface absorption
Experimental procedure: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) take appropriate standard starch molten
Liquid adds deionized water to be diluted to the concentration of required starch solution;(3) the starch solution 500mL of institute's compound concentration is taken, places and burns
It in cup, and is put into 45 DEG C of waters bath with thermostatic control, equilibrates to assigned temperature;(4) C7 is added according to required concentration, reacts 60 points
Clock obtains modified starch solution;(5) sampling centrifugation (4000x g) 5 minutes take supernatant to test starch concentration;(6) change toward residue
Property starch solution according to 1% solid concentration be added bleach chemical pulp (BKP), be kept stirring the time 10 minutes;(7) it has reacted
Finish, take slurries centrifugation (4000x g) 5 minutes, takes starch concentration in supernatant test plain boiled water.
As a result as shown in the following table 2 and table 3.As it can be seen that C7 complexing agent is very strong to the respond of starch.It is dense when initial starch
When degree is 850mg/L, the C7 of 30mg/L is added, the starch for having more than 700mg/L is reacted and be adsorbed to fiber surface, i.e. phase
When the total starch in 77% is adsorbed away from solution.When the concentration of initial starch increases to 1450mg/L, C7 network is added
Object 30mg/L is closed, starch concentration reduces 1116mg/L in solution, is equivalent to and removes 75%.And when starch initial concentration is
When 3000mg/L, the starch concentration of solution has dropped 1785mg/L, that is, the starch removed is 60 times of complexing agent C7 itself.
Influence of the 2 starch binder C7 concentration of table in different initial starch concentration to starch reaction
The relationship of table 3 starch binder C7 dosage and starch retention rate
Influence of 2 reaction time of embodiment to starch association reaction
The experimental procedure of starch reaction: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) it takes appropriate
Standard starch solution adds deionized water to be diluted to starch concentration about 1800mg/L (or other required concentration);(3) it takes and is prepared
Starch solution 500mL or the OCC plain boiled water of concentration is placed in beaker, and is put into 45 DEG C of waters bath with thermostatic control, and specified temperature is equilibrated to
Degree;(4) according to required addition 30mg/L starch binder, reach 1,3,5,10,30,60,90,120,300,600 Hes in reaction
At 1200 minutes, sampling centrifugation (4000x g) 5 minutes takes supernatant test content of starch and COD concentration;
The test procedure in starch adsorption reaction time: step (1)-(4) ibid, (5) when starch reaction reaches 60 minutes,
3% chemical pulp (BKP) is added according to required pulp density, stir and starts to carry out adsorption reaction;(6) adsorption reaction reaches
10,30,60 or 120 minutes when, take slurries and place it in 30mL test tube;(7) all taken solution are centrifuged
It analyzes within (x4000g.5 minutes), supernatant is taken to analyze its starch or COD concentration.
Five kinds of cationic starch complexing agents are tested, test result is summarized shown in as shown in Figure 1, Figure 2, Fig. 3 and table 4.From
Fig. 1 is as it can be seen that the reaction speed of such starch complexing agent and starch is very fast, i.e., within ten minutes, reaction basically reaches balance
90% or more of state;After 30 minutes, reaction tends to balance.Equally, Fig. 2 shows changing after reacting with starch complexing agent
Property starch and paper pulp adsorption reaction speed it is also very fast, reaching balance or maximum value ten minutes later, after 10 minutes,
Starch adsorption reaches saturation, and the extension reaction time may result in the starch desorption adsorbed part.Fig. 3 starch as the result is shown
Complexing agent C7 and reacting for starch are extremely rapid, just had 3% starch to be reacted at first minute, and within ten minutes 50%
Starch is reacted, and with the continuity in reaction time, starch retention rate is continued growing, after more than 30 minutes, retention rate
Increase speed and slow down, at 20 hours, retention rate reached 70%.
The reaction time retains starch the influence of (i.e. variable quantity) after the display addition of table 4 starch binder C14.As it can be seen that
For pure starch solution, starch binder C14 is very quick in the reaction of starch, substantially within ten minutes complete 70% with
On, later with the continuity of time, reaction has further progress, but speed is many slowly.For shallow lake obtained from OCC paper pulp
Powder, the starch retention rate after the modified plain boiled water starch of starch binder C14 are relatively low, it appears that C14 and OCC starch reaction be not so good as with
Pure starch is so strong;In fact this is because containing interfering substance in OCC plain boiled water, part C14 is consumed.Resist when addition is certain
After interfering chemical pulp (i.e. synergist) shielding interfering substance, the effect of starch binder can be greatly improved.
The relationship of table 4 starch binder C14 and starch association reaction and reaction time
Influence of 3 reaction temperature of embodiment to starch association reaction and to modified starch adsorption effect
Experimental procedure: (1) extracting corn starch sample preparation 7% " standard starch solution ";(2) appropriate standard starch solution is taken
Deionized water is added to be diluted to starch concentration about 600mg/L;(3) the starch solution 500mL of institute's compound concentration is taken, beaker is placed
In, and be put into the water bath with thermostatic control for presetting required test temperature, equilibrate to assigned temperature;(4) according to needed for test, add
Enter 30mg/L cationic starch bonding agent C7, reacts 60 minutes, obtain modified starch solution;(5) 5 points of sampling centrifugation (4000x g)
Clock takes supernatant test content of starch and COD concentration;(6) dense according to 2.5% pulp solids into remaining modified starch solution
Chemical pulp (BKP) (note: starch binder dosage is equivalent to 1000g/T oven dry stock) is added in degree, is kept stirring;(7) 10 points are reacted
Clock takes slurries centrifugation (4000x g) 5 minutes, takes starch concentration and COD concentration in supernatant test plain boiled water.
Fig. 4 shows at different temperatures, cationic starch bonding agent C7 and with starch reaction to starch chemical pulp guarantor
The influence stayed.As it can be seen that absorption of the starch on paper pulp surface declines as the temperature rises under the conditions of blank;With cation
After starch binder reaction, Modified Starch is adsorbed within tested temperature range fiber surface, is held essentially constant.
Fig. 5 shows under different temperatures, influence of the starch binder to dissolution COD.As it can be seen that the cationic starch tested
After bonding agent and starch reaction, dissolution COD decline is significant.But temperature is increased, the rate of descent of COD is slightly negatively affected.
Embodiment 4 react pH to starch binder and starch react and the influence of the adsorption effect to modified starch
Experimental procedure: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) take appropriate standard starch molten
Liquid adds deionized water to be diluted to starch concentration about 600mg/L;(3) the starch solution 500mL of institute's compound concentration is taken, beaker is placed
In, and be put into the water bath with thermostatic control for presetting 45 DEG C, the pH of starch solution is adjusted by the way that hydrochloric acid or sodium hydroxide is added;
(4) 30mg/L cationic starch bonding agent C7 or C12 is added, reacts 60 minutes, obtains modified starch solution;(5) sampling centrifugation
(4000x g) 5 minutes takes supernatant test content of starch and COD concentration;(6) into remaining modified starch solution according to 2.5%
Pulp solids concentration be added chemical pulp (BKP), be kept stirring;(7) it reacts 10 minutes, takes 5 points of slurries centrifugation (4000x g)
Clock takes starch concentration and COD concentration in supernatant test plain boiled water.
Fig. 6 and Fig. 7 shows under different pH that cationic starch bonding agent C7 and C12 is with starch reaction and in chemical pulp
The result that the starch of fiber retains.As it can be seen that bonding agent C7 is not influenced with reacting for starch by pH substantially;Bonding agent C12 and starch
Reaction it is unaffected in acid condition, but when being more than 7 with pH, as pH rises starch retention rate decline, illustrate to increase
PH has negative effect to starch retention rate.
Effect of the 5 paper pulp dosage (surface area) of embodiment to starch dissolution and absorption
Experimental procedure: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) take appropriate standard starch molten
Liquid adds deionized water to be diluted to starch concentration about 1500mg/L;(3) the starch solution 500mL of institute's compound concentration is taken, places and burns
It in cup, and is put into 45 DEG C of waters bath with thermostatic control, equilibrates to assigned temperature;(4) C7 is added according to required concentration, reacts 60 points
Clock obtains modified starch solution;(5) sampling centrifugation (4000x g) 5 minutes take supernatant test content of starch and COD concentration;(6)
Chemical pulp is added according to required pulp solids concentration into remaining modified starch solution, is kept stirring the time 10 minutes;(7) anti-
It should finish, take slurries centrifugation (4000x g) 5 minutes, take content of starch and COD concentration in supernatant test plain boiled water.
The results are shown in Table 5.As it can be seen that starch itself is very small in the absorption of bleach chemical pulp (BKP) fiber surface.Through
It crosses after being reacted with C7, starch is greatly increased in the absorption of fiber surface;And as the surface area of fiber increases, starch
Adsorbance dramatically increases.For example, BKP dosage increases to 5% from 1%, dissolves the concentration of starch when the dosage of C7 is 30mg/L
Drop to 178mg/L from 420mg/L, reduces 58%;Corresponding COD concentration drops to 638mg/L from 1042mg/L, has dropped
39%.According to the concentration variation of absorption front and back, when BKP dosage is 5%, dissolution starch concentration has dropped 412mg/L, and COD is dense
Degree then has dropped 404mg/L, shows that the absorption of starch and COD decline have direct linear relationship.Fig. 8 compared in two kinds of differences
C7 dosage under, relationship of the BKP usage amount to starch reserved and COD removal amount.
The influence that different chemical pulp (BKP) concentration of table 5 react starch with C7
Comparison of the different paper pulp types of embodiment 6 to the starch adsorption effect after starch binder modification
Experimental procedure: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) take appropriate standard starch molten
Liquid adds deionized water to be diluted to required starch concentration (1500mg/L);(3) the starch solution 500mL of institute's compound concentration is taken, is placed
It in beaker, and is put into 45 DEG C of waters bath with thermostatic control, equilibrates to assigned temperature;(4) according to required addition 30mg/L starch binder
C14 or a certain amount of C7 reacts 60 minutes, obtains modified starch solution;(5) sampling centrifugation (4000x g) 5 minutes, take supernatant
Test content of starch and COD concentration;(6) paper pulp is added according to 2.5% pulp solids concentration into remaining modified starch solution,
It is kept stirring;(7) react 10 minutes, take slurries centrifugation (4000x g) 5 minutes, take in supernatant test plain boiled water starch concentration and
COD concentration.
Test result is summarized in table 6.As it can be seen that different types of paper pulp is for starch binder-starch reaction product
Absorption has biggish difference.The adsorption capacity of bleach chemical pulp (BKP) is most strong, and group unbleached chemical pulp (UBKP) is more slightly worse than BKP, and
Reclaimed waste paper OCC slurry is worst.Recycle OCC paper pulp for the starch binder of all tests and the reaction product of starch absorption all
Be it is minimum, conjecture main cause is likely to the paper pulp itself and contains a large amount of starch, and few fibers surface is by starch
Covering, thus it is little to the adsorption capacity of the reaction product of starch binder;In addition, the starch of institute's band itself may be dissolved and is desorbed
Into solution, starch total concentration (i.e. higher than initial starch concentration) in increase system, thus disturbed test " real "
Starch reaction product adsorbance.
The influence that the different paper pulp types of table 6 retain starch
To confirm that OCC slurry brings the influence that starch adsorbs starch combination product into, determine first to carry out following pre- place to OCC slurry
Reason.The OCC paper pulp of 1% concentration is first heated to 70-75 DEG C, amylase, reaction is added according to the dosage of 1000g/T (oven dry stock)
60 minutes;Paper pulp is fitted into filter bag, the solid concentration of centrifuge dripping to 30%;Then the slurry of addition pure water to 1% is dense
Degree, heating paper pulp boil 60 minutes, again with filter bag dress and centrifuge dripping;OCC paper pulp (the enzyme with enzyme cleaning is made
Treated OCC), number E-OCC.
Table 7 compared former OCC slurry, and enzyme cleaning OCC starches (E-OCC) and bleach chemical pulp (BKP) and handles starch to bonding agent
The influence of reaction.As it can be seen that E-OCC to after C7- starch reaction starch and COD concentration it is all more much lower than OCC.Fig. 9 shows, E-
The starch adsorption rate of OCC reaches 50%, significantly improves than adsorption rate (29%) of OCC.
The influence that the different paper pulp types of table 7 adsorb C7- starch complex compound
Influence of the 7 starch binder hydrophobic grouping structure of embodiment to bonding agent and starch reaction
Experimental procedure: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) take appropriate standard starch molten
Liquid adds deionized water to be diluted to starch concentration about 1600mg/L;(3) the starch solution 500mL of institute's compound concentration is taken, places and burns
In cup, and it is put into the water bath with thermostatic control for presetting 45 DEG C;(4) 30mg/L starch binder is added, reacts 30 minutes, must change
Property starch solution;(5) sampling centrifugation (4000x g) 5 minutes take supernatant test content of starch and COD concentration;(6) toward remaining
Chemical pulp (BKP) is added according to 2.5% pulp solids concentration in modified starch solution, is kept stirring;(7) it reacts 10 minutes,
Slurries centrifugation (4000x g) 5 minutes is taken, starch concentration and COD concentration in supernatant test plain boiled water are taken.
The influence that the hydrophobic grouping structure of 8 cationic starch bonding agent of table retains starch
Bonding agent number | The hydrophobic carbon-chain structure of bonding agent | Starch reserved (mg/L) | Opposite retention rate (%) |
C2 | 12 carbon of saturated straight chain | 736 | 46 |
C5 | 16 carbon of saturated straight chain | 944 | 59 |
C3 | 18 carbon of saturated straight chain | 1072 | 67 |
C4 | 18 carbon of unsaturation straight chain | 1120 | 70 |
C12 | 22 carbon of saturated straight chain | 1472 | 92 |
C25 | 32 carbon of saturated straight chain | 960 | 60 |
C21 | Double 18 carbon of saturated straight chain | 1200 | 75 |
8 data of table are shown, are parameter, the response intensity and hydrophobic group unity of starch binder and starch according to starch retention rate
Structure has direct relation.For cationic starch bonding agent, the response intensity of bonding agent and starch increases as carbochain increases,
Up to carbochain to 22 carbon;When carbon chain length is more than 22, the response intensity of bonding agent and starch has decline.
Influence of 8 synergist of embodiment to starch adsorption effect
OCC old paper stock and plain boiled water are produced: being taken waste paper 300g, be torn into fritter, then plus tap water is diluted to 13%
Concentration impregnates 5-10min, pours into PL12-00 type high density hydraulic pulper, pulping 15 minutes, takes out broken good slurry, then plus originally
Water is diluted to 3% concentration;Then plain boiled water and slurry are separated with filter bag, OCC plain boiled water and OCC paper pulp is made, saves backup respectively.
The experimental procedure of starch reaction is dissolved in starch binder and plain boiled water: (1) being taken from above the prepared OCC plain boiled water
500mL is placed in beaker, and is put into 45 DEG C of waters bath with thermostatic control, equilibrates to assigned temperature;(2) it is added according to required concentration
C7 or C19 reacts 60 minutes;(3) sampling centrifugation (4000x g) 5 minutes take supernatant test content of starch and COD concentration;
(4) into surplus solution, the synergist Y1 (polyacrylamide-diallyl dimethyl ammoniumchloride high score of concentration needed for being added
Sub- copolymer, High molecular weight comopolymer ofcationic acrylamide-DADMAC
(diallyldimethylammonium chloride), is purchased from: SNF Floeger company, the U.S.), it mixes;Then according to
Prepared OCC slurry or BKP slurry is added in 2.5% pulp solids concentration, stirs and evenly mixs;(5) react 10 minutes, take slurries from
The heart (4000x g) 5 minutes, take starch concentration and COD concentration in supernatant test plain boiled water.
Test result is as shown in table 9.As it can be seen that the suction that synergist Y1 starches unmodified plain boiled water dissolution starch in OCC
It is attached to have no significant effect;Since OCC slurry also has much starch, it is added among plain boiled water, surface starch carries out secondary dissolution
And desorption, cause dissolution starch concentration and COD concentration in solution all higher before than adding paper pulp.But it is combined in starch
For agent C19 with after starch reaction, the concentration for dissolving starch drops to 280mg/L from 758mg/L or so, shows to react by C19
Modified Starch afterwards significantly changes the solubility of starch;After adding OCC paper pulp, when being not added with C19, starch concentration is from 682mg/
L is promoted to 715-776mg/L (depending on the dosage of Y1);After C19 Modified Starch, modified starch is largely adsorbed to OCC slurry table
Face and make to dissolve starch concentration sharp fall, have decreased to 360mg/L-202mg/L, dissolution COD also decreased significantly, and
As the dosage of synergist increases and successively decrease, it is apparent to illustrate that the addition of synergist is adsorbed with C19- Modified Starch in OCC slurry
Reinforcing effect.When synergist dosage reaches 12mg/L, the terminal starch concentration of plain boiled water has decreased to 202mg/L, while under COD
Fall below 472mg/L;Correspondingly, 73% He is reduced respectively than the initial starch concentration of unprocessed plain boiled water and COD concentration
58%.These results illustrate that Y1 remains with apparent facilitation in OCC fiber for C19- Modified Starch.
Table 10 compared the absorption that synergist Y1 starches C7- Modified Starch in OCC slurry and BKP.As it can be seen that starch binder C7
There is " combination among the strong ones effect " (synergism) of highly significant with synergist Y1, Y1 can greatly improve C7- Modified Starch in paper
The reservation of slurry, and then dissolution COD content is greatly lowered.
The influence that 9 synergist Y1 of table adsorbs Modified Starch in OCC slurry
10 synergist Y1 of table is to Modified Starch in the influence that OCC is starched and BKP slurry adsorbs
Note: initial starch concentration=563mg/L;Initial COD concentration=710mg/L.
The effect that 9 mixing starch complexing agent of embodiment processing starch solution retains starch
Experimental procedure: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) take appropriate standard starch molten
Liquid adds deionized water to be diluted to starch concentration about 1600mg/L;(3) the starch solution 500mL of institute's compound concentration is taken, places and burns
In cup, and it is put into the water bath with thermostatic control for presetting 45 DEG C;(4) starch binder 1 is added, react 15 minutes and then adds
Enter starch binder 2, then react 15 minutes, obtains modified starch solution;(5) sampling centrifugation (4000x g) 5 minutes, take supernatant
Test content of starch and COD concentration;(6) chemistry is added according to 2.5% pulp solids concentration into remaining modified starch solution
It starches (BKP), is kept stirring;(7) it reacts 10 minutes, takes slurries centrifugation (4000x g) 5 minutes, go in supernatant test plain boiled water to form sediment
Powder concentration and COD concentration.
Table 11 summarizes order of addition of ingredients and the influence retained starch is applied in combination in different bonding agents.As it can be seen that two kinds
Being applied in combination for cationic starch bonding agent is more preferable than a kind of effect of exclusive use, and starch retention rate is all than each bonding agent list
It to significantly improve when solely using, especially when the carbochain of the hydrophobic grouping of two starch binders is different long, be applied in combination
Apparent synergistic effect (Synergy).Figure 10 shows that C55 and C57 two basic change agent different ratio is applied in combination and retains starch
The influence of amount.As it can be seen that although the effect ratio C55 of C57 is far better, and C55 is combined with C57 with certain proportion when being used alone
It is more preferable using the effect being used alone than C57.
The influence of 11 bi-component cationic starch bonding agent of table and its order of addition to the reserved of dissolution starch
The influence that the 10 starch degree of polymerization (viscosity) of embodiment reacts Modified Starch
Starch solution is prepared: (1) in the magnetic force water-bath for taking 465g deionized water to place it in 97 DEG C, it is slowly added to 35g
Cornstarch;(2) according to the viscosity (degree of degradation) of required configuration starch, quantitative ammonium persulfate is added, ammonium persulfate is suitable
In the weight percent of starch be respectively 0-0.5%;(3) it boils 40 minutes, is then cooled to 65 DEG C, starch solution is kept to exist
60 DEG C, 7% " standard " starch solution is made, saves backup.
The reaction of starch modification and testing procedure: (1) 7% starch solution of above-mentioned preparation is taken, deionized water is added to dilute
To starch concentration about 1600mg/L;(2) the starch solution 500mL of institute's compound concentration is taken, is placed in beaker, and is put into advance
In the water bath with thermostatic control of 45 DEG C of setting;(3) starch binder C14 is added, reacts 30 minutes, obtains modified starch solution;(4) sample from
The heart (4000x g) 5 minutes, take supernatant test content of starch and COD concentration;(5) into remaining modified starch solution according to
Chemical pulp (BKP) is added in 2.5% pulp solids concentration, is kept stirring;(6) it reacts 10 minutes, slurries is taken to be centrifuged (4000x g)
5 minutes, take starch concentration and COD concentration in supernatant test plain boiled water.
Table 12 compared the starch solution with the prepared different molecular chain length of oxidant of different amounts in BKP fiber
Retain result.As it can be seen that starch all including raw starch, before being reacted with starch binder C14, in BKP fiber
The reservation on surface is extremely limited (< 25%), and dissolution COD is basically unchanged.But after C14 reaction modification, all shallow lakes
Powder is increased to 80% or more in BKP retention rate;Since starch is retained from solution by absorption, remaining starch is big in plain boiled water
Big to reduce, so that COD concentration declines, rate of descent is up to 40-86%.These data illustrate that starch binder of the invention is being gone
Except different size of starch molecule is all very efficient, and the molecular chain length of starch is bigger (degree of polymerization is higher), and starch combines
The reservation efficiency of agent is also higher.
The relationship between efficiency that the 12 starch degree of polymerization (molecular size) of table is reacted with starch binder
11 cationic starch bonding agent of embodiment and influence of separate sources/type starch reaction to starch retention rate
Ative starch solution making step: (1) starch sample is taken first to prepare 7% starch solution;(2) extremely by starch liquor heating
It 95 degree (DEG C), is reacted to viscosity and reaches stable;(3) 65 DEG C are cooled to, starch solution is kept in water bath with thermostatic control.
The preparation of commercialization oxidation starch solution is same as above.
Oxidized starch solution is prepared: (1) in the magnetic force water-bath for taking 465g deionized water to place it in 97 DEG C, being slowly added to
35g ative starch;(2) quantitative ammonium persulfate is added, the weight percent that ammonium persulfate is equivalent to starch is respectively 0.5%;
(3) it boils 40 minutes, is then cooled to 65 DEG C, keep starch solution at 60 DEG C, 7% " oxidized starch solution " is made, save
It is spare.
Test reaction step: (1) solution or oxidized starch solution prepared according to standard starch adds deionized water to be diluted to
Starch concentration about 1200mg/L;(2) the starch solution 500mL of prepared starch concentration is taken, is placed in beaker, and be put into 45
In DEG C water bath with thermostatic control, assigned temperature is equilibrated to;(3) C7 is added according to required concentration, reacts 30 minutes, it is molten obtains modified starch
Liquid;(4) sampling centrifugation (4000x g) 5 minutes take supernatant test content of starch and COD concentration;(5) toward remaining modified starch
Chemical pulp is added according to 3% pulp solids concentration in solution, is kept stirring the time 10 minutes;(6) end of reaction takes slurries to be centrifuged
(4000x g) 5 minutes takes content of starch and COD concentration in supernatant test plain boiled water.
As a result such as table 13: as it can be seen that starch of separate sources itself bleach chemical pulp (BKP) fiber surface reservation very
It is small;The retention rate of oxidized starch and business modified starch in BKP is similarly very low.After reacting with C7, all starch exist
The absorption of fiber surface greatly increases, but the improvement degree difference of each starch is larger.For example, the dosage as C7 is
When 30mg/L, cornstarch increases to 82% in the retention rate of BKP, and the retention rate of tapioca only has 43%.This difference
May be related to the structure of tapioca with cornstarch, the ratio of the former amylose is higher (> 25%), and the latter is generally straight
Chain content of starch highest only accounts for 17%.After oxidation processes, amylopectin is broken into amylose, oxidized starch itself
Improve in the retention rate of BKP little;But after reacting with C7, the retention rate of all oxidized starch is increased substantially, especially
The retention rate of tapioca increases to 72%, and correspondingly, the retention rate of cornstarch reaches 96%.The retention rate of Commercial starch exists
After being reacted with C7, also greatly improved in the retention rate of BKP.
13 different type ative starch of table and modified starch react the influence retained starch with cationic starch bonding agent
Influence of the 12 cationic starch bonding agent Modified Starch of embodiment to bleach chemical pulp (BKP) paper strength
The test procedure of chemical pulp copy paper: (1) bleach chemical pulp 300g is taken, fritter is torn into, then plus tap water is dilute
It releases to 13% concentration, impregnates 5-10min, pour into PL12-00 type high density hydraulic pulper, pulping 15 minutes, take out broken good slurry,
It saves backup;(2) extracting corn starch configures 7% " standard starch solution " 800mL according to the starch solution preparation method of standard;
(3) starch binder is added as needed, reacts 30min, obtains modified starch solution;(4) BKP is added in modified starch solution,
It is stirred to react 10min;(5) it takes slurry to be placed in 30mL test tube, and after centrifugal treating, tests the starch concentration and COD of supernatant
Content;(6) remaining slurry pours into standard fibre dissociation device immediately and discongests 1500r, after having discongested, is diluted with water to 0.5% concentration,
The slurry 640g for weighing 0.5% concentration carries out copy paper (Substance 100g or so) with sheet forming apparatus;It (7), will after having copied paper
Pattern is placed on the thermostatic constant wet chamber balance 16h of 25 DEG C, moisture 50%, then tests paper physical property and contains at paper starch
Amount.
Table 14 compared under a variety of reaction conditions, and starch binder C14 retains starch, reduction COD and paper physical refer to
Target influences result.By taking 1% slurry is dense as an example, (starch is not added, only add the C14 of 15mg/L) under the conditions of blank, paper
Tensile index and burst index be respectively 19.7m.N/g and 1.7kPa.m2/g;When paper pulp and starch solution, (note: concentration is
890mg/L, if 100% retain, the content of starch of paper be equivalent to 8.9%) carry out mixing 10 minutes after, plain boiled water
Content of starch drops to 722mg/L (being equivalent to 18.9% retention rate) from 890mg/L, and COD drops to 605mg/L from 722mg/L
(being equivalent to decline 16%);The tensile index of paper is increased to 28.6mN/g, and burst index is increased to 2.5kPa.m2/ g, respectively
Improve 45% and 47%;Starch is analysis shows that the content of starch of paper reaches 1.8%.Formerly addition 15mg/L (note: is equivalent to
1.5kg/ tons of paper) starch binder C14, adds BKP after reaction, the starch concentration and COD concentration of plain boiled water are respectively 170 Hes again
487mg/L, i.e. starch retention rate are 80.9%, COD rate of descent 32.5%.Correspondingly, the anti-tensile of paper and burst index difference
36.8mN/g and 3.7kPa.m are reached2/ g is the 187% and 218% of blank index, than comparison condition (there was only starch) point
29% and 48% are not higher by it.Trend of the result of other reaction additions with more than is consistent, and it is different to have change amplitude only.
Figure 11 is shown using starch binder C7 (dosage=1.5kg/T paper) to adding BKP after starch conversion again to copying
The influence of piece physical strength.As it can be seen that improvement and C14 very phase to tensile index and burst index is used in combination in C7 and starch
Seemingly.
After these by starch binder reaction the results show that modify, reservation of the starch in BKP is substantially improved, thus
Greatly improve the physical strength of paper.
The influence of 14 starch binder dosage of table and pulp density to the paper strength of BKP
Note: initial starch concentration=889mg/L;Initial COD concentration=722mg/L.Preparation cornstarch viscosity=
30mPa.S。
13 cationic starch bonding agent of embodiment and combinations thereof is to reservation starch, reduction COD and paper in OCC removal process
The influence of Zhang Qiangdu
The pulping and copy paper experimental procedure of OCC waste paper:(1) waste paper 300g is taken, fritter is torn into, then plus tap water is dilute
It releases to 13% concentration, impregnates 5-10min, pour into PL12-00 type high density hydraulic pulper, pulping 15 minutes;(2) it is broken good to take out
Slurry, adds tap water to be diluted to 3% concentration, saves backup;(3) above-mentioned 3%OCC magma 800g is taken, test reagent (starch knot is added
Mixture) reaction 30min;(4) it is needed according to test, addition synergist Y2 (diallyl dimethyl ammoniumchloride,
PolyDADMAC), it is uniformly mixed 10min;(5) it takes slurry to be placed in 30mL test tube, supernatant is tested after centrifugal treating
Starch concentration and COD content;(6) remaining slurry pours into standard fibre dissociation device immediately and discongests 1500r, after having discongested, adds water
It is diluted to 0.5% concentration, the slurry 730g for weighing 0.5% concentration carries out the copy paper (left side Substance 100g with sheet forming apparatus
It is right);(7) after having copied paper, pattern is placed on to the thermostatic constant wet chamber balance 16h of 25 DEG C, moisture 50%, then tests paper physical
Performance and at paper content of starch.
Figure 12 shows the shadow that starch binder C7 and C14 (dosage=1.5kg/ tons of oven dry stock) keeps OCC plain boiled water starch
It rings, it is seen then that in addition C7 and C14 to OCC pulping process, starch is increased substantially in the retention rate of paper, and the starch of plain boiled water is dense
Degree is remarkably decreased, corresponding to dissolve the decline of COD concentration.
Figure 13 shows after adding C7 and C14 that the tensile index and burst index of paper are significantly improved.
These are the results show that the starch in OCC waste paper can largely very after the reaction modification of starch binder
To all remaining, the comprehensive utilization of waste paper resources can not only be improved, improves the physical strength of paper, and can substantially improve
The environmental benefit of wastepaper pulping and papermaking.
The influence modified starch with reservation starch is added in the segmentation of 14 cationic starch bonding agent of embodiment
The pulping and copy paper experimental procedure of OCC waste paper: (1) taking waste paper 300g, be torn into fritter, and then plus tap water is dilute
It releases to required 13% concentration of pulp density, impregnates 5-10min, pour into PL12-00 type high density hydraulic pulper, needed according to test
It is added starch binder, pulping 15 minutes;(2) broken good slurry is taken out, adds tap water to be diluted to 3% concentration, saves backup;
(3) above-mentioned 3%OCC magma 800g is taken, starch binder needed for being added adds synergist Y2 (diallyl dimethyl chlorine
Change ammonium, PolyDADMAC), it is uniformly mixed 10min;(4) slurry is taken to be placed in 30mL test tube, after centrifugal treating in test
The starch concentration and COD content of clear liquid;(5) remaining slurry pours into standard fibre dissociation device immediately and discongests 1500r, after having discongested,
It is diluted with water to 0.5% concentration, the slurry 730g for weighing 0.5% concentration carries out copy paper (Substance 100g with sheet forming apparatus
Left and right);(6) after having copied paper, pattern is placed on to the thermostatic constant wet chamber balance 16h of 25 DEG C, moisture 50%, then tests paper object
Rationality energy and at paper content of starch.
As a result as shown in Table 15 and Table 16.As it can be seen that initial starch concentration can significantly reduce after starch binder is added, from
From the point of view of various indexs, segmentation is added more significant than the effect that single hop is added.
The influence retained starch is added in the segmentation of 15 cationic starch bonding agent of table
The influence to paper physical index is added in the segmentation of 16 cationic starch bonding agent of table
15 cationic starch bonding agent of embodiment is to reservation starch, paper strength and paper water-resistance in OCC removal process
Influence
The pulping and copy paper experimental procedure of OCC waste paper: (1) taking waste paper 300g, be torn into fritter, and then plus tap water is dilute
It releases to 13% concentration, impregnates 5-10min, pour into PL12-00 type high density hydraulic pulper, pulping 15 minutes;(2) it is broken good to take out
Slurry, adds tap water to be diluted to 3% concentration, saves backup;(3) above-mentioned 3%OCC magma 800g is taken, test reagent (starch knot is added
Mixture C56, C24, C40, C63) reaction 30min;(4) add 500g/T synergist Y2 (diallyl dimethyl ammoniumchloride,
PolyDADMAC), it is uniformly mixed 10min;(5) it takes slurry to be placed in 30mL test tube, supernatant is tested after centrifugal treating
Starch concentration and COD content;(6) remaining slurry pours into standard fibre dissociation device immediately and discongests 1500r, after having discongested, adds water
It is diluted to 0.5% concentration, the slurry 730g for weighing 0.5% concentration carries out the copy paper (left side Substance 100g with sheet forming apparatus
It is right);(7) after having copied paper, pattern is placed on to the thermostatic constant wet chamber balance 16h of 25 DEG C, moisture 50%, then tests paper physical
Performance and at paper content of starch.
Table 17 shows starch binder (dosage=1.5kg/ tons of oven dry stock) to OCC plain boiled water starch concentration, COD concentration, paper
Open the influence of tensile index and water resistant value (Cobb value).The results show that OCC is useless after the reaction modification of starch binder
Starch in paper can be effectively retained, and reduce plain boiled water COD content, not only improve the physical strength of paper, but also can be significantly
The Cobb value of paper is reduced, that is, improves the water repelling property of paper.This is that traditional starch conversion technology can not be attainable.
17 cationic starch bonding agent of table is to the result for improving paper physical intensity index and water-resistance
The result of embodiment 16 different cationic starch bonding agents and starch association reaction
Experimental procedure: (1) extracting corn starch sample first prepares 7% " standard starch solution ";(2) take appropriate standard starch molten
Liquid adds deionized water to be diluted to starch concentration about 1600mg/L;(3) the starch solution 500mL of institute's compound concentration is taken, places and burns
In cup, and it is put into the water bath with thermostatic control for presetting 45 DEG C;(4) starch binder of 30mg/L is added, reacts 30 minutes, obtains
Modified starch solution;(5) sampling centrifugation (4000x g) 5 minutes take supernatant test content of starch and COD concentration;(6) toward surplus
Chemical pulp (BKP) is added according to 2.5% pulp solids concentration in remaining modified starch solution, is kept stirring;(7) 10 points are reacted
Clock takes slurries centrifugation (4000x g) 5 minutes, takes starch concentration and COD concentration in supernatant test plain boiled water.According to starch concentration
Difference calculates starch in the retention rate of paper pulp.
As a result as shown in table 18.
The result of table 18 cationic starch bonding agent and starch association reaction
The commerical test of the extensive paper machine of embodiment 17 production
Pulp production process and paper machine production overview: the factory is located at East part of Zhejiang Province, raw using 100% recycling OCC waste paper
Quantification range is produced in the common craft paper of 140gsm -250gsm, the daily output is at 1300-1500 ton/days.Its slurrying process is as schemed
Shown in 14.Paper machine copy paper breadth 6600mm, wet end use three folded net formers, and the pressure of splenium one is squeezed using hard roll-in, and two pressures are adopted
It is squeezed with boots, paper machine top sizing is glued using film transfer formula.
Test arrangement: this test is organized as follows:
(1) test products: it is the C19 (technical grade) in table 1 that this, which tests used cationic starch complexing agent,.
(2) chemical feeding points: being directly added to pulper using chemical agent metering pump, by the stirring action of pulper, with
Slurry is sufficiently mixed, and is allowed to sufficiently be reacted with the starch in plain boiled water and paper pulp.
(3) dosage: C19 dosage is in 1000-2000g/ tons of paper ranges.In order to which entire test can steadily be carried out, produce
Product are added since low dosage (1000g/T), are stepped up dosage, up to 2000g/T during testing and carrying out.
Test process: the two weeks before test (i.e. before adding cationic starch complexing agent), start the production to the factory
The test and tracking of the progress system such as process, physico chemical factor and paper index.Test duration has carried out eight days in total, entire to test
Period paper machine produces same veriety, and the grammes per square metre of only paper is different.
Test data analyzer: in order to before and after comparative test as a result, having selected the preceding raw material proportioning with during test of test
It is for statistical analysis to data under conditions of essentially identical.
Test result: a variety of creation datas according to provided by manufacturer test the plain boiled water chemical parameters of tracking in conjunction with this,
The statistical analysis of system has been carried out to the various change of test front and back.Main result is as shown in table 19 and table 20.
After adding C19, the starch concentration of the starch concentration and paper machine drainge at each position is all with C19's in white-water system
Dosage is incremented by and declines, while the pH of entire white-water system rises gradually, such as the slurry pH of pulper outlet average from test
Preceding 6.3 have risen to 6.7, and paper machine drainge pH is promoted by 6.4 to 7.0.This display C19 not only increases starch in fiber/paper
The reservation (18.6%, table 19) opened, while also controlling the degradation of starch in plain boiled water and being acidified by its bring, illustrate that C19 has
There is the function of the growth of consumption of starch bacterium in control plain boiled water, detailed Biochemical Mechanism needs further to be studied.By C19 to shallow lake
Powder be effectively retained and Inhibition of degradation, dissolution COD concentration is remarkably decreased in water, and paper machine system significantly becomes completely, paper machine water
It can more be recycled, so that the draining of paper machine declines (table 19), and paper machine drainge COD concentration has dropped 8.8%, comprehensive
Closing effect makes ton paper COD discharge drop to 24.7kg/T from the 37.2kg/T before test, decreases by 33%.Due to starch and ash
That divides is effectively retained, and raw material is more fully utilized, and the unit consumption of ton paper raw materials for production drops to 1.09T/T from 1.16T/T,
It is equivalent to yield and improves 5.8%.Further, since starch is obtained retaining and is utilized in waste paper, the spray starch that adds in production and
Gelatinized starch is significantly reduced.
The resultant effect of the above large-scale industry test fully confirms the efficient of cationic starch complexing agent of the invention
Property and economic feasibility.
Table 19 compares before testing with the index of paper product and paper machine drainge during test
The comparison of paper machine production target before table 20 is tested and during test
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (24)
1. a kind of method of free starch in recycling mthod of white water from paper making, which is characterized in that including making cationic starch complexing agent and making
Free starch in paper plain boiled water is reacted so that modified step occurs for the free starch;The cationic starch complexing agent
Chemical structure consist of the following parts:
I) one or more hydrophobic groupings, wherein at least one hydrophobic grouping can generate clathrate complex with starch reaction, and
Ii) one or more hydrophilic radicals, wherein at least one hydrophilic radical are cationic hydrophilic groups;
The hydrophobic grouping is respectively at the both ends of same molecular structure with the hydrophilic radical and is connected with chemical bond, is formed
A kind of asymmetric, polar structure;
The hydrophobic grouping is non-polar group, is selected from straight chain fatty alkyl, branched aliphatic, aryl radical, fat and virtue
Perfume mixing at least one of alkyl and fluorine-containing alkyl;
The hydrophilic radical is polar group, is selected from carboxyl, sulfonic group, ester group, halogen formoxyl, carbamoyl, cyano, aldehyde
At least one of base, carbonyl, ether, alcohol radical, phenolic group, sulfydryl, thioether group amido, quaternary ammonium salt, guanidine radicals;
Also, the cationic starch complexing agent generates hydrophobic cations after ionizing in water.
2. the method for free starch in recycling mthod of white water from paper making according to claim 1, which is characterized in that the cation forms sediment
Powder complexing agent ionize in water after generate the hydrophobic cations be selected from amine salt type cation, quaternary ammonium salt cationic,
At least one of guanidine salt type cation, sulfonium salt type cation, microcosmic salt type cation, arsenic type cation.
3. the method for free starch in recycling mthod of white water from paper making according to claim 1, which is characterized in that the cation forms sediment
Powder complexing agent is selected from: the heterocyclic hydrocarbon of aminated compounds or its salt, guanidine compound or its salt, substituted or non-substituted nitrogen atom
Or the heterocyclic arene or at least one of its salt, cationic sulfonium salt of its salt, substituted or non-substituted nitrogen atom.
4. the method for free starch in recycling mthod of white water from paper making according to claim 3, which is characterized in that the amine chemical combination
Object or its salt are selected from: primary amine or its salt, secondary amine or its salt, tertiary amine or its salt, quaternary ammonium salt, polyamines or its salt, multi-quaternary ammonium salt, polymerization
At least one of the quaternary ammonium salt that the fatty amine or its salt of the substitution of object base, polymer matrix replace;The polymer matrix is selected from polycyclic
At least one of oxirane group, polypropylene oxide base;
The structural formula of the primary amine is RNH2;
The structural formula of the secondary amine is R1R2NH;
The structure formula of the tertiary amine is R1R2NR3;
The structural formula of the quaternary ammonium salt is R1R2R3R4NX;
The structural formula of the polyamines is R5(CH2CH2CH2NR)n H;
The structural formula of the multi-quaternary ammonium salt is R5(CH2CH2CH2N(CH3)2)n CH3Xn;
The structural formula for the fatty amine that the polymer matrix replaces is
The structural formula for the quaternary ammonium salt that the polymer matrix replaces is
Above-mentioned each R, R1, R2, R3, R4, R5It is separately selected from: substituted or non-substituted straight chained alkyl, substituted or non-substituted
Branched alkyl, substituted or non-substituted alkenyl, substituted or non-substituted naphthenic base, substituted or non-substituted aryl;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted alkenyl, replaces substituted or non-substituted branched alkyl
Or the substituent group in non-substituted naphthenic base and substituted or non-substituted aryl is separately selected from one or more following bases
Group: ether, ester group, amide groups, aryl, substituted aryl, alkyl, alkenyl, amino, siloxy group, sulfydryl, hydroxyl, halogen, thioether
Base, alkoxy;
R6、R7And R8Separately be selected from: the polyethylene oxide base of H, C1-C4 alkyl, the degree of polymerization greater than 1, the degree of polymerization are greater than 1
Polypropylene oxide base, and R6、R7In at least one be selected from polyethylene oxide base of the degree of polymerization greater than 1 or the degree of polymerization greater than 1
Polypropylene oxide base;
R9、R10It is separately selected from: H, C1-C4 alkyl;
A is selected from the integer between 1-6, and b is selected from the integer between 0-4, c=b+1;
N is selected from the integer not less than 1;
X is the anion being connected by ionic bond with nitrogen-atoms.
5. the method for free starch in recycling mthod of white water from paper making according to claim 4, which is characterized in that described R, R1, R2,
R3, R4, R5It is separately selected from: substituted or non-substituted C1-C40 straight chained alkyl, substituted or non-substituted C3-C40 branched alkane
Base, substituted or non-substituted C2-C40 alkenyl, substituted or non-substituted C6-C10 aryl;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted alkenyl, replaces substituted or non-substituted branched alkyl
Or the substituent group in non-substituted naphthenic base and substituted or non-substituted aryl is separately selected from one or more following bases
Group: naphthalene, the C1-C40 alkyl, C2-C16 alkenyl, ammonia that ether, C2-C24 ester group, phenyl, naphthalene, C1-C20 alkoxy replace
Base, siloxy group, sulfydryl, hydroxyl, halogen, thioether group, C1-C20 alkoxy.
6. the method for free starch in recycling mthod of white water from paper making according to claim 5, which is characterized in that R, R5Independently
Ground is selected from the C6- that C14-32 alkyl, the C6-14 alkyl that C8-C12 alkenyl replaces, C14-C24 ester group, C14-C20 alkoxy replace
The C6-10 aryl that 14 alkyl, C14-C20 alkoxy replace;The alkyl-substituted C6-10 aryl of C10-C20;
R in the secondary amine1、R2At least one of selected from C14-32 alkyl, C8-C12 alkenyl replace C6-14 alkyl, C14-
The C6-10 aryl of C6-14 alkyl, the substitution of C14-C20 alkoxy that C24 ester group, C14-C20 alkoxy replace;
R in the tertiary amine1、R2、R3At least one of selected from C14-32 alkyl, C8-C12 alkenyl replace C6-14 alkyl,
The C6-10 aryl of C6-14 alkyl, the substitution of C14-C20 alkoxy that C14-C24 ester group, C14-C20 alkoxy replace;
R in the quaternary ammonium salt1、R2、R3、R4At least one of selected from C14-32 alkyl, C8-C12 alkenyl replace C6-14 alkane
The C6-10 aryl of C6-14 alkyl, the substitution of C14-C20 alkoxy that base, C14-C24 ester group, C14-C20 alkoxy replace.
7. the method for free starch in recycling mthod of white water from paper making according to claim 4, which is characterized in that X is selected from: halogen yin
Ion, HSO4 -、SO4 2-、CH3SO4 -、SCN-、CH3CO2 -Or OH-。
8. the method for free starch in recycling mthod of white water from paper making according to claim 4, which is characterized in that the polyamines salt knot
N in structure formula is selected from the integer between 2-5;The degree of polymerization of the polyethylene oxide base and polypropylene oxide base is respectively selected from 1-30
Between integer.
9. the method for free starch in recycling mthod of white water from paper making according to claim 3, which is characterized in that the guanidine chemical combination
Object or its salt are selected from: at least one of single guanidine or its salt, biguanides or its salt, polyguanidine or its salt;
The structural formula of the list guanidine are as follows:
The structural formula of the list guanidine salt are as follows:
The structural formula of the biguanides are as follows:
The structural formula of the polyguanidine are as follows:
R, R in formula1、R2、R3、R4、R5、R6Separately be selected from: hydrogen, substituted or non-substituted straight chained alkyl, substitution non-take
The branched alkyl in generation, substituted or non-substituted alkenyl, substituted or non-substituted naphthenic base, substituted or non-substituted aryl, and
The carbon atom number of at least one substituent group is greater than 6 in each structural formula of the guanidine compound;
Z is selected from: substituted or non-substituted alkylidene, substituted or non-substituted aryl;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted alkenyl, replaces substituted or non-substituted branched alkyl
Or the substituent group in non-substituted naphthenic base, substituted or non-substituted aryl and substituted or non-substituted alkylidene is separately
Selected from one or more following groups: ether, ester group, amide groups, aryl, substituted aryl, alkyl, alkenyl, amino, siloxanes
Base, sulfydryl, hydroxyl, halogen, thioether group, alkoxy;
X is the anion being connected by ionic bond with nitrogen-atoms.
10. the method for free starch in recycling mthod of white water from paper making according to claim 9, which is characterized in that the guanidine
It closes at least one substituent group in each structural formula of object to be selected from: C7-C30 straight chained alkyl, C7-C30 branched alkyl, C7-C30 alkene
Base, C7-C10 aryl;Remaining substituent group is hydrogen;Z is selected from: C1-C8 alkylidene;X is selected from: halide anion, HSO4 -、SO4 2-、
CH3SO4 -、CH3CO2 -Or OH-。
11. the method for free starch in recycling mthod of white water from paper making according to claim 3, which is characterized in that the cation
The structural formula of sulfonium salt is R1R2R3SX, wherein R1, R2, R3Not independently selected from: substituted or non-substituted straight chained alkyl, substitution or non-
Substituted branched alkyl, substituted or non-substituted alkenyl, substituted or non-substituted naphthenic base, substituted or non-substituted aryl;
The substituted or non-substituted straight chained alkyl, substituted or non-substituted alkenyl, replaces substituted or non-substituted branched alkyl
Or the substituent group in non-substituted naphthenic base and substituted or non-substituted aryl is separately selected from one or more following bases
Group: ether, ester group, amide groups, aryl, substituted aryl, alkyl, alkenyl, amino, siloxy group, sulfydryl, hydroxyl, halogen, thioether
Base, alkoxy;
X is the anion being connected by ionic bond with sulphur atom.
12. the method for free starch in recycling mthod of white water from paper making according to claim 3, which is characterized in that the heterocyclic hydrocarbon
It is selected from: at least one of morpholine, nafoxidine, glyoxalidine, piperazine;
The heteroaryl hydrocarbon is selected from: pyridine, quinoline, 1,3,5- triazine, reaches at least one of piperazine, pyrimidine, pyrazine, pyrroles at imidazoles;
The heterocyclic hydrocarbon of the substituted or non-substituted nitrogen atom or the heterocyclic arene of its salt, substituted or non-substituted nitrogen atom
Or the substituent group in its salt is selected from one or more following groups: alkoxy, ester group, amide groups, phenyl, alkyl, hydroxyl replace
Alkyl, alkenyl replace alkyl, halogen replace alkyl, alkoxy replace alkyl, alkenyl, amino, siloxy group, mercapto
Base, hydroxyl, halogen, amido.
13. the method for free starch in recycling mthod of white water from paper making according to claim 12, which is characterized in that the heterocyclic hydrocarbon
It is selected from: at least one of nafoxidine, morpholine, glyoxalidine;The heterocyclic arene is selected from: pyridine, quinoline, imidazoles and 1,3,
At least one of 5- triazine;
The heterocyclic hydrocarbon of the substituted or non-substituted nitrogen atom or the heterocyclic arene of its salt, substituted or non-substituted nitrogen atom
Or the substituent group in its salt is selected from one or more following groups: C1-C20 alkyl, C1-C20 alkoxy, C1-C6 alkyl replace
Amido, hydroxyl replace C1-C20 alkyl, C2-C20 alkenyl replace C1-C20 alkyl, C1-C20 alkoxy replace C1-
C20 alkyl.
14. it is according to claim 13 recycling mthod of white water from paper making in free starch method, which is characterized in that it is described substitution or
The heterocyclic hydrocarbon of non-substituted nitrogen atom or its salt, the heterocyclic arene of substituted or non-substituted nitrogen atom or the substitution in its salt
Base is selected from one or more following groups: C10-C20 alkyl, C10-C20 alkoxy.
15. the method for free starch in recycling mthod of white water from paper making according to claim 1, which is characterized in that the cation
Starch complexing agent is selected from least one of following compound: the cationic starch complexing agent in following compound extremely
Few one kind: hexadecyltrimethylammonium chloride, dodecyl trimethyl ammonium chloride, octadecylamine, oleyl amine, cetylamine, octadecyl
Trimethyl ammonium chloride, cetylpyridinium chloride, octadecyl-N, N- dimethyl benzyl ammonium chloride, oil base-N, N- dimethylbenzyl
Ammonium chloride, octadecyl methyl ammonium chloride, benzyl hexadecyldimethyl benzyl ammonium ammonium chloride, two lauryl amines, tallow base amine, tallow base
Trimethylene diamines, tallow methyl trimethylene diamines, N- tallow base-N, N, N ', N ', N ' pentamethyl trimethylene diammonium hydrochloric acid, double propylamine-oxen
Aliphatic radical tertiary amine, stearic acid ethyl group-N, N, N ', N ', N ' pentamethyl trimethylene diammonium hydrochloric acid, 1,3 trimethylene diamines of oil base, N- oil base third
Support 1,3 triamines, dioctadecyl dimethyl ammonium chloride, benzethonium chloride, tetradecyltrimethylammonium silicon oxychlorination ammonium, dimethyl
Octadecyl [3- (trimethoxy silicon substrate) propyl] ammonium chloride, tridodecylamine, dotriacontyl trimethyl ammonium chloride, 12
Alkoxy propyl amine, dodecyloxy -1,3- trimethylene diamines, dodecyl-dipropyl amido secondary amine, dodecyl-N, N,-bis- (three
Polymerization oxidation ethylene) ammonium chloride, octadecyl-N, N ,-bis- (trimerization ethylene oxide) ammonium chlorides, N- tallow base-N, N ', N '-
Three (polyoxyethylene) trimethylene diamines, double propylamine-tallow base tertiary amine, sulfydryl-cetylamine hydrochlorate, sulfydryl-undecyl front three bromide
Change ammonium, ortho position the-the third hydroxyl of oil base-imidazoles, octadecyl imidazoles, 1- dodecyl -3- methylimidazole iodide, decyl methyl chloride
Change imidazoles, 1,3- didecyl -2- methyl climiqualine, N- tallow oxygroup-N, N ', N (the polyoxyethylene)-methyl-propyl chlorine of '-bis-
Change ammonium, 3- amino -1- propyl alcohol bis- (hexadecane oxygen ethers), octadecane epoxide pyridine, octadecane epoxide aniline chloride, N- benzyl -
N, N- dimethyl-stearyl oxygroup-Oxidation of Alcohol ammonium chloride, 2- octadecane epoxide-N, N, N- trimethyl -2- Oxidation of Alcohol chlorination
Ammonium, N, N '-diethyl -6- octadecane epoxide-(1,3,5) triazine -2,4- diamines, 3- (2- octadecane epoxide -1- naphthalene) propylamine,
1- (2- dodecyloxy) N-ethyl pyrrole N hydrochloric acid, 2- (2- dodecyloxy) propoxypropylamine, 4- dodecyloxy aniline, 1,1,
21 fluorine certain herbaceous plants with big flowers amine of 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-, 5,5,6,6,7,7,8,8,9,9,10,
11 fluorine certain herbaceous plants with big flowers amine of 10,10-, the more ammoniums of double octadecyldimethyl hydroxypropyls, the bis- (polymerization oxidations third of octadecyl-N, N, N- methyl
Alkene) ammonium chloride, N, N, N, N ', N '-methyl-three (polyoxyethylene) trimethylene diamines octadecyl quaternary ammonium hydrochloric acid, dodecyl guanidine salt
Hydrochlorate, dodecyl N, N '-trimethylene diamines-hydrochloride of requiring to report his or her problems within a prescribed time and in a prescribed place, tridecyl 2,4- methyl morpholine, dodecyl polyaniline, 14
Alkyl quinoline hydrochloric acid, 1- octadecyl biguanides mono-hydrochloric salts, Octenidine dihydrochloride, lauryl hydroxyethyl imidazole quinoline.
16. -15 described in any item methods for recycling free starch in mthod of white water from paper making according to claim 1, which is characterized in that institute
Free starch is stated to be selected from: cornstarch, tapioca, starch from sweet potato, wheaten starch, oxidation modification starch at least one
Kind;The starch of the oxidation modification be the cornstarch of oxidation modification, the tapioca of oxidation modification, oxidation modification sweet potato form sediment
Powder or the wheaten starch of oxidation modification.
17. the method for free starch in recycling mthod of white water from paper making according to claim 16, which is characterized in that the oxidation changes
Property starch preparation method the following steps are included: starch is taken to be configured to aqueous solution, be heated to 80-100 DEG C, starch oxidation be added
Agent or starch enzyme reaction to viscosity reach stable, then be cooled to 60-70 DEG C to get.
18. -15 described in any item methods for recycling free starch in mthod of white water from paper making according to claim 1, which is characterized in that In
The cationic starch complexing agent is reacted with the free starch in mthod of white water from paper making so that modification occurs for the free starch
Further comprising the steps of after step: addition synergist is reacted with gained modified starch;The synergist is selected from: polymerization chlorine
Change aluminium, polyaluminium sulfate, bodied ferric sulfate, diallyl dimethyl ammoniumchloride, polyoxyethylene, polyacrylamide and polypropylene
At least one of amide-polyacrylic acid analog anion copolymer.
19. the method for free starch in recycling mthod of white water from paper making according to claim 18, which is characterized in that the synergist
Mass ratio with the cationic starch complexing agent is 1:1-35.
20. -15 described in any item methods for recycling free starch in mthod of white water from paper making according to claim 1, which is characterized in that institute
The temperature for stating reaction is 10-90 DEG C.
21. -15 described in any item methods for recycling free starch in mthod of white water from paper making according to claim 1, which is characterized in that institute
The time for stating reaction is 1min-20h.
22. the method for free starch in recycling mthod of white water from paper making according to claim 21, which is characterized in that the reaction
Time is 5min-1h.
23. -15 described in any item methods for recycling free starch in mthod of white water from paper making according to claim 1, which is characterized in that institute
The pH for stating reaction is 4-11.
24. the method for free starch in recycling mthod of white water from paper making according to claim 23, which is characterized in that the reaction
PH is 5-7.
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WO2021161564A1 (en) * | 2020-02-14 | 2021-08-19 | 栗田工業株式会社 | Method and device for measuring starch concentration in water |
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