CN115260397A - Hydrogen peroxide bleaching silicon-free stabilizer - Google Patents
Hydrogen peroxide bleaching silicon-free stabilizer Download PDFInfo
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- CN115260397A CN115260397A CN202210985346.6A CN202210985346A CN115260397A CN 115260397 A CN115260397 A CN 115260397A CN 202210985346 A CN202210985346 A CN 202210985346A CN 115260397 A CN115260397 A CN 115260397A
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 45
- 238000009897 hydrogen peroxide bleaching Methods 0.000 title claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 229920002472 Starch Polymers 0.000 claims abstract description 53
- 239000008107 starch Substances 0.000 claims abstract description 53
- 235000019698 starch Nutrition 0.000 claims abstract description 53
- 102000013142 Amylases Human genes 0.000 claims abstract description 36
- 108010065511 Amylases Proteins 0.000 claims abstract description 36
- 235000019418 amylase Nutrition 0.000 claims abstract description 36
- 239000004382 Amylase Substances 0.000 claims abstract description 35
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000002255 enzymatic effect Effects 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 64
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 8
- 102000004190 Enzymes Human genes 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 8
- 229930003268 Vitamin C Natural products 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 235000019154 vitamin C Nutrition 0.000 claims description 8
- 239000011718 vitamin C Substances 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002261 Corn starch Polymers 0.000 claims description 6
- 240000003183 Manihot esculenta Species 0.000 claims description 6
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000008120 corn starch Substances 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Chemical group 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims 1
- 230000000415 inactivating effect Effects 0.000 claims 1
- 238000004061 bleaching Methods 0.000 abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 239000007788 liquid Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000007142 ring opening reaction Methods 0.000 description 11
- 229920002521 macromolecule Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- -1 silicate ions Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/12—Preparation of cellulose esters of organic acids of polybasic organic acids
-
- 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
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to a hydrogen peroxide bleaching silicon-free stabilizer and a preparation method thereof, belonging to the technical field of fine chemical engineering. The stabilizer comprises the following components in parts by weight: 10-20 parts of starch, 0.1-0.4 part of amylase, 0.2-1 part of oxidant, 2-10 parts of maleic anhydride, 2-10 parts of monomer A, 2-5 parts of monomer B, 1-5 parts of monomer C, 0.2-0.4 part of initiator and 40-70 parts of deionized water; the enzymatic starch is used as a carrier, the grafting activity and the stability are high, and carboxyl is introduced through maleic anhydride to adsorb and chelateComposite Fe 3+ Other metal ions such as the inner metal ions firmly grasp free catalytic particles in the solution, and then the monomer A and the monomer B containing double bonds are subjected to graft copolymerization with tertiary ethylene carbonate on starch short chains, so that the concentrated alkali resistance and the oxidation resistance of a surface layer polymer are improved, the aim of stabilizing catalysis is fulfilled, and the raw materials do not contain silicon substances, so that the scale formation of a bleaching system caused by adding a stabilizer is avoided.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a hydrogen peroxide bleaching silicon-free stabilizer and a preparation method thereof.
Background
At present, wood fiber resources are in short supply, and the pulping concept of efficiently utilizing fiber raw materials becomes an important guarantee for sustainable development of wood paper and realization of circular economy; high yield pulp H 2 O 2 The bleaching process has the unique advantages of: the bleaching whiteness has large ascending value amplitude, good whiteness stability, lower bleaching cost, no sulfur and chlorine, convenient closed circulation of production water, cleanness and environmental protection.
The paper making industry requires a high-yield pulping production system to realize high sealing performance, reduce discharged wastewater and heat to the maximum extent and save the use of clear water. However, due to the severe scaling phenomenon of the pulping system, the system has to be opened periodically in order to maintain the normal operation of the production, which not only wastes a large amount of heat energy and water resources, but also causes severe environmental pollution. Meanwhile, the generated dirt is dispersed in various parts of a system (for bleaching pulp and using bleaching washing water), the surface of the dirt is compact, the cleaning of high-pressure water and a surfactant is resisted, the cleaning of common acid and alkali is resisted strongly, the influence on key parts (a disc grinder, a pulp screening machine, a wet part and a dry part) of a production system is very large, valuable devices such as blades of the disc grinder, a sieve plate of the pulp screening machine, a press felt and the like are damaged, and the normal operation of the production system is seriously disturbed.
The formation of scale is a complex physical and chemical process, and is a result of the combined action of metal ions, anion garbage and silicate ions, and the main reason is that sodium silicate is adopted as a stabilizer for hydrogen peroxide bleaching, so that the finding of a non-silicon stabilizer capable of replacing the sodium silicate stabilizer in the hydrogen peroxide bleaching process of paper pulp becomes a research hotspot.
The application aims to prepare the silicon-free stabilizer by taking cheap starch as a carrier through functional modification.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention aims to provide a hydrogen peroxide bleaching silicon-free stabilizer and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of hydrogen peroxide bleaching silicon-free stabilizer specifically comprises the following steps:
step S1: stirring and mixing starch and deionized water to obtain starch slurry, adding amylase to mix, setting the stirring speed to be 180-360rpm, heating to 80-90 ℃, keeping the temperature, stirring and performing enzymolysis for 5-7 hours, introducing saturated steam to quickly inactivate enzyme for 5min after the enzymolysis is finished, and cutting long chains of macromolecules into short chains containing a large number of hydroxyl groups by using the amylase to prepare an enzymolysis solution;
furthermore, the starch is selected from corn starch or cassava starch, and has the advantages of high amylose content, high solubility, easy enzymolysis and low price.
Further, the amylase is selected from the group consisting of alpha mesophilic amylases.
Step S2: maintaining the temperature of the enzymolysis liquid at 75-80 ℃, setting the stirring speed at 180-240rpm, slowly adding maleic anhydride, carrying out heat preservation stirring reaction for 30-40min, carrying out ring opening on the maleic anhydride, esterifying the maleic anhydride with hydroxyl on the starch short chain, grafting carboxyl on the starch short chain, and enabling the starch short chain to contain a large amount of hydroxyl and carboxyl, thereby effectively adsorbing and chelating Fe 3+ Other metal ions such as the inner ions absorb the metal ions through the adsorption chelation, free catalytic particles in the solution are firmly held, the aim of stably catalyzing hydrogen peroxide is achieved, a part of maleic anhydride is condensed after ring opening to form a cyclic complex, the decomposition stability of the hydrogen peroxide is improved, and the grafting solution is prepared;
and step S3: taking the grafting solution and an oxidant, stirring and mixing, then sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 70-80 ℃, setting the stirring speed at 80-120rpm, slowly dripping the initiator, keeping the temperature, stirring and reacting for 60-90min, and cooling to 40 ℃ to prepare the stabilizer.
Further, the oxidant is ammonium persulfate, and the initiator is formed by mixing hydrogen peroxide and vitamin C.
Further, the monomer a is acrylic acid or methacrylic acid.
Further, the monomer B is hydroxyethyl acrylate or hydroxyethyl methacrylate.
The monomer A and the monomer B are esterified with a macromolecular graft containing hydroxyl and carboxyl in the grafting solution, and a branched chain containing double bonds is grafted on the macromolecular graft.
Further, the monomer C is vinyl versatate, the vinyl versatate is copolymerized with the monomer A and the monomer B under the catalysis of an oxidant and an initiator, the vinyl versatate is introduced for copolymerization, the concentrated alkali resistance and the oxidation resistance of the surface polymer are improved, and the purpose of stable catalysis is achieved.
The hydrogen peroxide bleaching silicon-free stabilizer is prepared by the method, wherein the hydrogen peroxide bleaching silicon-free stabilizer comprises the following raw materials in parts by weight: 10-20 parts of starch, 0.1-0.4 part of amylase, 0.2-1 part of oxidant, 2-10 parts of maleic anhydride, 2-10 parts of monomer A, 2-5 parts of monomer B, 1-5 parts of monomer C, 0.2-0.4 part of initiator and 40-70 parts of deionized water.
The invention has the beneficial effects that:
1. the invention takes corn starch or cassava starch with high amylose content as a raw material, carries out enzymolysis through alpha moderate temperature amylase, cuts a long chain of a macromolecule into a short chain through the amylase, and the short chain contains a large amount of hydroxyl groups, shows high grafting activity and has the stability of a macromolecule polymer.
2. The invention grafts carboxyl on the short chain of the starch through the ring-opening reaction of maleic anhydride, so that the short chain of the starch contains a large amount of hydroxyl and carboxyl, thereby effectively adsorbing and chelating Fe 3+ Other metal ions such as the inner ions absorb the metal ions through the adsorption chelation, free catalytic particles in the solution are firmly held, the aim of stably catalyzing hydrogen peroxide is achieved, a part of maleic anhydride is condensed after ring opening to form a cyclic complex, and the decomposition stability of the hydrogen peroxide is improved.
3. According to the invention, the double-bond monomer A and the double-bond monomer B are subjected to graft copolymerization with the vinyl versatate on the short chain of the starch, so that the concentrated alkali resistance and the oxidation resistance of the surface layer polymer are improved, and the purpose of stable catalysis is achieved.
4. According to the invention, silicon-containing substances are not introduced in the process of preparing the stabilizer, and the added stabilizer does not cause the scaling of a bleaching system in the bleaching process.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment of the preparation of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
preparing materials: the raw materials are as follows according to the parts by weight:
18 parts of starch selected from corn starch;
0.1 part of amylase, selected from alpha moderate temperature amylase;
0.2 part of oxidant selected from ammonium persulfate;
5 parts of maleic anhydride;
4 parts of a monomer A selected from acrylic acid;
5 parts of a monomer B; selected from hydroxyethyl methacrylate;
2 parts of monomer C, selected from vinyl versatate provided by a chemical company Limited in Guangzhou;
0.2 part of initiator, which is prepared by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1;
67.5 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring into uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, heating to 90 ℃ at a stirring speed of 360rpm, keeping the temperature, stirring, and performing enzymolysis for 5 hours, wherein the amylase cuts long chains of macromolecules into short chains of which the micromolecules contain a large number of hydroxyl groups, and introducing saturated steam to rapidly inactivate enzyme for 5 minutes after the enzymolysis is finished, so as to prepare an enzymolysis solution;
ring-opening grafting: maintaining the enzymolysis liquid at 80 ℃, setting the stirring speed to 240rpm, slowly adding maleic anhydride into the enzymolysis liquid within 3min, keeping the temperature, stirring and reacting for 30min, and reacting the open ring of the maleic anhydride with the short chain of the starch to prepare a grafting liquid;
copolymerization grafting: stirring and mixing the grafting solution and an oxidant, uniformly dispersing the oxidant in the grafting solution, sequentially adding a monomer A, a monomer B and a monomer C, maintaining the temperature at 80 ℃, setting the stirring speed at 120rpm, slowly adding an initiator, keeping the temperature, stirring and reacting for 60min, and cooling to 40 ℃ to obtain the stabilizer.
Example 2
The embodiment of the preparation of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
preparing materials: the raw materials are taken according to the parts by weight:
20 parts of starch selected from cassava starch;
0.2 part of amylase selected from alpha moderate temperature amylase;
0.3 part of oxidant selected from ammonium persulfate;
6 parts of maleic anhydride;
5 parts of a monomer A selected from methacrylic acid;
4 parts of a monomer B; selected from hydroxyethyl acrylate;
3 parts of monomer C, selected from vinyl versatate provided by a chemical company Limited in Guangzhou;
0.3 part of initiator, which is prepared by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1;
61.2 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring into uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, heating to 90 ℃ at a stirring speed of 240rpm, keeping the temperature, stirring, and performing enzymolysis for 6 hours, wherein the amylase cuts long chains of macromolecules into short chains of which the micromolecules contain a large number of hydroxyl groups, and introducing saturated steam to rapidly inactivate enzyme for 5min after the enzymolysis is finished, so as to prepare an enzymolysis solution;
ring-opening grafting: maintaining the enzymolysis liquid at 80 deg.C, setting stirring speed at 240rpm, slowly adding maleic anhydride into the enzymolysis liquid within 3min, stirring and reacting for 35min under heat preservation, and allowing the ring of maleic anhydride to react with short chain of starch to obtain grafting liquid;
copolymerization grafting: stirring and mixing the grafting solution and an oxidant, uniformly dispersing the oxidant in the grafting solution, sequentially adding a monomer A, a monomer B and a monomer C, maintaining the temperature at 80 ℃, setting the stirring speed at 120rpm, slowly adding an initiator, keeping the temperature, stirring and reacting for 60min, and cooling to 40 ℃ to obtain the stabilizer.
Example 3
The embodiment of the preparation of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
preparing materials: the raw materials are taken according to the parts by weight:
20 parts of starch selected from cassava starch;
0.22 part of amylase selected from alpha moderate temperature amylase;
0.35 part of oxidant selected from ammonium persulfate;
7 parts of maleic anhydride;
6 parts of a monomer A selected from methacrylic acid;
4.5 parts of a monomer B; selected from hydroxyethyl acrylate;
3.5 parts of monomer C, selected from vinyl versatate and provided by a chemical industry Co., ltd of Guangzhou;
0.35 part of initiator, which is prepared by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1;
58.08 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring into uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting the stirring speed at 180rpm, heating to 80 ℃, keeping the temperature, stirring, and performing enzymolysis for 7 hours, wherein the amylase cuts long chains of macromolecules into short chains of which the micromolecules contain a large number of hydroxyl groups, and introducing saturated steam to rapidly inactivate enzyme for 5min after the enzymolysis is finished, so as to prepare an enzymolysis solution;
ring-opening grafting: maintaining the enzymolysis liquid at 75 ℃, setting the stirring speed to be 180rpm, slowly adding maleic anhydride into the enzymolysis liquid within 3min, keeping the temperature, stirring and reacting for 40min, and reacting the ring-opened maleic anhydride with the short chain of the starch to prepare a grafting liquid;
copolymerization grafting: stirring and mixing the grafting solution and an oxidant, uniformly dispersing the oxidant in the grafting solution, sequentially adding a monomer A, a monomer B and a monomer C, maintaining the temperature at 70 ℃, setting the stirring speed at 80rpm, slowly adding an initiator, keeping the temperature, stirring and reacting for 90min, and cooling to 40 ℃ to obtain the stabilizer.
Example 4
The embodiment of the preparation of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
preparing materials: the raw materials are as follows according to the parts by weight:
10 parts of starch selected from corn starch;
0.1 part of amylase selected from alpha moderate temperature amylase;
1 part of an oxidant selected from ammonium persulfate;
5.5 parts of maleic anhydride;
10 parts of a monomer A selected from acrylic acid;
2 parts of a monomer B; selected from hydroxyethyl acrylate;
1 part of monomer C, selected from vinyl versatate provided by a chemical company Limited in Guangzhou;
0.4 part of initiator, which is prepared by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1;
70 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring into uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting the stirring speed at 240rpm, heating to 85 ℃, keeping the temperature, stirring, and performing enzymolysis for 6 hours, wherein the amylase cuts long chains of macromolecules into short chains of which the micromolecules contain a large number of hydroxyl groups, and introducing saturated steam to rapidly inactivate enzyme for 5min after the enzymolysis is finished, so as to prepare an enzymolysis solution;
ring-opening grafting: maintaining the enzymolysis liquid at 75 ℃, setting the stirring speed to 240rpm, slowly adding maleic anhydride into the enzymolysis liquid within 3min, keeping the temperature, stirring and reacting for 35min, and reacting the open ring of the maleic anhydride with the short chain of the starch to prepare a grafting liquid;
and (3) copolymerization grafting: stirring and mixing the grafting solution and an oxidant, uniformly dispersing the oxidant in the grafting solution, sequentially adding a monomer A, a monomer B and a monomer C, maintaining the temperature at 80 ℃, setting the stirring speed at 80rpm, slowly adding an initiator, keeping the temperature, stirring and reacting for 70min, and cooling to 40 ℃ to obtain the stabilizer.
Example 5
The embodiment of the preparation of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
preparing materials: the raw materials are as follows according to the parts by weight:
20 parts of starch selected from corn starch;
0.4 part of amylase selected from alpha moderate temperature amylase;
1 part of an oxidant selected from ammonium persulfate;
10 parts of maleic anhydride;
10 parts of a monomer A selected from methacrylic acid;
5 parts of a monomer B; selected from hydroxyethyl methacrylate;
5 parts of monomer C, selected from vinyl versatate and provided by a chemical industry Co., ltd of Guangzhou;
0.4 part of initiator, which is prepared by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1;
40 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring into uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting the stirring speed at 240rpm, heating to 85 ℃, keeping the temperature, stirring, and performing enzymolysis for 6.5 hours, wherein the amylase cuts long chains of macromolecules into short chains of which the micromolecules contain a large number of hydroxyl groups, and saturated steam is introduced to rapidly inactivate enzyme for 5min after the enzymolysis is finished, so as to prepare an enzymolysis solution;
ring-opening grafting: maintaining the enzymolysis liquid at 78 deg.C, setting stirring speed at 240rpm, slowly adding maleic anhydride into the enzymolysis liquid within 3min, stirring under heat preservation for 35min, and allowing the maleic anhydride to open loop and react with short chain of starch to obtain grafting liquid;
and (3) copolymerization grafting: stirring and mixing the grafting solution and an oxidant, uniformly dispersing the oxidant in the grafting solution, sequentially adding a monomer A, a monomer B and a monomer C, maintaining the temperature at 85 ℃, setting the stirring speed at 100rpm, slowly adding an initiator, keeping the temperature, stirring and reacting for 75min, and cooling to 40 ℃ to obtain the stabilizer.
Example 6
The embodiment of the preparation of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
preparing materials: the raw materials are as follows according to the parts by weight:
18 parts of starch selected from cassava starch;
0.25 part of amylase selected from alpha moderate temperature amylase;
0.55 part of oxidant selected from ammonium persulfate;
2 parts of maleic anhydride;
2 parts of monomer A, selected from methacrylic acid;
4.2 parts of a monomer B; selected from hydroxyethyl acrylate;
4.5 parts of monomer C, selected from vinyl versatate provided by a chemical company Limited in Guangzhou;
0.4 part of initiator, which is prepared by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1;
68.1 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring into uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting the stirring speed at 240rpm, heating to 88 ℃, keeping the temperature, stirring, and performing enzymolysis for 5.8 hours, wherein the amylase cuts long chains of macromolecules into short chains of which the micromolecules contain a large number of hydroxyl groups, and saturated steam is introduced to rapidly inactivate enzyme for 5min after the enzymolysis is finished, so as to prepare an enzymolysis solution;
ring-opening grafting: maintaining the enzymolysis liquid at 75 ℃, setting the stirring speed at 240rpm, slowly adding maleic anhydride into the enzymolysis liquid within 3min, keeping the temperature, stirring and reacting for 40min, and reacting the ring-opened maleic anhydride with the short chain of the starch to prepare a grafting liquid;
and (3) copolymerization grafting: stirring and mixing the grafting solution and an oxidant, uniformly dispersing the oxidant in the grafting solution, sequentially adding a monomer A, a monomer B and a monomer C, maintaining the temperature at 75 ℃, setting the stirring speed at 120rpm, slowly adding an initiator, keeping the temperature, stirring and reacting for 75min, and cooling to 40 ℃ to obtain the stabilizer.
Comparative example 1
This comparative example is identical to example 1, except that no maleic anhydride was added for ring-opening grafting, and the remaining steps were identical.
Comparative example 2
The comparative example is a stabilizer prepared by the method provided in Chinese patent application No. 201710431120.0.
The stable hydrogen peroxide decomposition rate test and the pulp bleaching test prepared in the examples 1 to 6 and the comparative examples 1 to 2 are carried out, and the following tests are carried out:
the decomposition rate test method comprises the following steps:
accurately transferring 20mL of hydrogen peroxide and 60mL of deionized water into a flask, adding 2g of stabilizer, heating to boiling at 98 ℃, transferring 10mL of mixed solution into a conical flask every 15min after boiling, adding 2.5mL of 6mol/L sulfuric acid solution, and adding 0.2mol/L KMnO 4 And (5) calibrating the standard solution. When the solution is colorless to just appear red and the red does not fade within 30s, the titration end point is determined, and the consumed KMnO is recorded 4 The volume of (a). The hydrogen peroxide decomposition rate was calculated, and the specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the stabilizer prepared by the invention has a good stabilizing effect on the decomposition of hydrogen peroxide, and the stabilizing effect is better than that of the existing stabilizer at the early stage of bleaching.
Bleaching test:
drying 20g of unbleached poplar chemi-mechanical pulp in an oven to prepare 20% of the pulp, putting the pulp into a zipper bag, and sequentially adding 10kg/t of NaOH, 1.5kg/t of DTPA and H 2 O 2 30kg/t and 2kg/t stabilizer, extruding and kneading to ensure that chemicals and water are uniformly mixed with the pulp, transferring the mixture into a water bath kettle after 10min, starting a timer, setting the bleaching temperature to be 95 ℃, bleaching for 60min, taking out the bag from the water bath, washing with pure water, and squeezing to dry;
weighing 8g of squeezed wet pulpAdding 800mL of water, adding 4mL of 5-percent EDTA solution, uniformly stirring, soaking for 30 minutes, adjusting the pH value to 4.0-5.5 by using hydrochloric acid, uniformly stirring, dividing into 4 parts, adding 500mL of water into each part, and making a fixed quantity of about 100g/m by using a Buchner funnel 2 The pulp sheet is placed in an oven and dried at the temperature of not more than 60 ℃, and the dried pulp sheet adopts Swedish L&The whiteness is respectively detected by a model Elrepho 070 spectro-whiteness meter manufactured by W company, and the specific test data is shown in Table 2:
TABLE 2
| Front whiteness (ISO) | Back side whiteness (ISO) | Average whiteness (ISO) | |
| Example 1 | 75.82 | 75.80 | 75.81 |
| Example 2 | 76.22 | 76.12 | 76.17 |
| Example 3 | 76.32 | 76.30 | 76.31 |
| Example 4 | 73.38 | 73.42 | 73.40 |
| Example 5 | 74.26 | 74.30 | 74.28 |
| Example 6 | 75.62 | 75.56 | 75.59 |
| Comparative example 1 | 73.44 | 73.12 | 73.28 |
| Comparative example 2 | 74.38 | 74.30 | 74.34 |
As can be seen from the data in Table 2, the stabilizer prepared by the invention is applied to hydrogen peroxide bleaching, and hydrogen peroxide can play a good bleaching role.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (9)
1. A hydrogen peroxide bleaching silicon-free stabilizer is characterized by comprising the following raw materials in parts by weight:
10-20 parts of starch, 0.1-0.4 part of amylase, 0.2-1 part of oxidant, 2-10 parts of maleic anhydride, 2-10 parts of monomer A, 2-5 parts of monomer B, 1-5 parts of monomer C, 0.2-0.4 part of initiator and 40-70 parts of deionized water.
2. The preparation method of the hydrogen peroxide bleaching silicon-free stabilizer according to claim 1, which is characterized by comprising the following steps:
step S1: mixing starch and deionized water, adding amylase, mixing, heating to 80-90 deg.C, maintaining the temperature, stirring, and performing enzymolysis for 5-7 hr, and inactivating enzyme to obtain enzymatic hydrolysate;
step S2: maintaining the temperature of the enzymolysis solution at 75-80 deg.C, stirring at 180-240rpm, adding maleic anhydride, stirring at constant temperature for 30-40min to obtain grafting solution;
and step S3: stirring and mixing the grafting solution and an oxidant, sequentially adding a monomer A, a monomer B and a monomer C, maintaining the temperature at 70-80 ℃, stirring at the speed of 80-120rpm, dropwise adding an initiator, carrying out heat preservation and stirring reaction for 60-90min, and cooling to 40 ℃ to prepare the stabilizer.
3. The method for preparing the hydrogen peroxide bleached silicon-free stabilizer according to claim 2, wherein the starch is corn starch or tapioca starch.
4. The method for preparing hydrogen peroxide bleaching silicon-free stabilizer according to claim 3, wherein the amylase is alpha medium temperature amylase.
5. The method for preparing hydrogen peroxide bleaching silicon-free stabilizer according to claim 2, wherein the monomer A is acrylic acid or methacrylic acid.
6. The method for preparing a hydrogen peroxide bleaching silicon-free stabilizer according to claim 5, wherein the monomer B is hydroxyethyl acrylate or hydroxyethyl methacrylate.
7. The method for preparing a hydrogen peroxide bleaching silicon-free stabilizer according to claim 6, wherein the monomer C is vinyl versatate.
8. The method for preparing hydrogen peroxide bleaching silicon-free stabilizer according to claim 7, wherein the oxidant is ammonium persulfate.
9. The method for preparing a hydrogen peroxide bleaching silicon-free stabilizer according to claim 7, wherein the initiator is formed by mixing hydrogen peroxide and vitamin C.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278597A (en) * | 1994-04-14 | 1995-10-24 | Kao Corp | Bleaching powder composition |
| WO1995033813A1 (en) * | 1994-06-02 | 1995-12-14 | Unilever N.V. | Improved detergent composition |
| DE19521695A1 (en) * | 1995-06-14 | 1996-12-19 | Sandoz Ag | Polymers, their production and use |
| JPH11241294A (en) * | 1998-02-20 | 1999-09-07 | Seiko Kagaku Kogyo Co Ltd | Paper-strengthening agent for paper making and production of strengthened paper |
| US20170211019A1 (en) * | 2016-01-26 | 2017-07-27 | The Procter & Gamble Company | Treatment compositions |
| CN109280130A (en) * | 2018-10-09 | 2019-01-29 | 江南大学 | A kind of starch graft copolymers of fully biodegradable and preparation method thereof |
| CN115181214A (en) * | 2022-07-28 | 2022-10-14 | 深圳百市达生物技术有限公司 | Hydrogen peroxide bleaching scale-free stabilizer and preparation method thereof |
-
2022
- 2022-08-17 CN CN202210985346.6A patent/CN115260397B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07278597A (en) * | 1994-04-14 | 1995-10-24 | Kao Corp | Bleaching powder composition |
| WO1995033813A1 (en) * | 1994-06-02 | 1995-12-14 | Unilever N.V. | Improved detergent composition |
| DE19521695A1 (en) * | 1995-06-14 | 1996-12-19 | Sandoz Ag | Polymers, their production and use |
| JPH11241294A (en) * | 1998-02-20 | 1999-09-07 | Seiko Kagaku Kogyo Co Ltd | Paper-strengthening agent for paper making and production of strengthened paper |
| US20170211019A1 (en) * | 2016-01-26 | 2017-07-27 | The Procter & Gamble Company | Treatment compositions |
| CN109280130A (en) * | 2018-10-09 | 2019-01-29 | 江南大学 | A kind of starch graft copolymers of fully biodegradable and preparation method thereof |
| CN115181214A (en) * | 2022-07-28 | 2022-10-14 | 深圳百市达生物技术有限公司 | Hydrogen peroxide bleaching scale-free stabilizer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ANIS, P: "Enzymatic Pre-Treatment of Cotton. Part 2: Peroxide Generation in Desizing Liquor and Bleaching", FIBRES & TEXTILES IN EASTERN EUROPE, vol. 17, no. 2, pages 87 - 90 * |
| 陈春霞，等: "有机助剂对纸浆H2O2漂白的影响", 《中国造纸学会第十四届学术年会论文集》, pages 194 - 199 * |
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