CN115260397B - Hydrogen peroxide bleaching silicon-free stabilizer - Google Patents
Hydrogen peroxide bleaching silicon-free stabilizer Download PDFInfo
- Publication number
- CN115260397B CN115260397B CN202210985346.6A CN202210985346A CN115260397B CN 115260397 B CN115260397 B CN 115260397B CN 202210985346 A CN202210985346 A CN 202210985346A CN 115260397 B CN115260397 B CN 115260397B
- Authority
- CN
- China
- Prior art keywords
- parts
- monomer
- hydrogen peroxide
- starch
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003381 stabilizer Substances 0.000 title claims abstract description 42
- 238000009897 hydrogen peroxide bleaching Methods 0.000 title claims abstract description 22
- 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 34
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 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 25
- 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 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 63
- 239000007788 liquid Substances 0.000 claims description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 26
- 238000006243 chemical reaction 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
- 238000004321 preservation Methods 0.000 claims description 15
- 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
- 230000000415 inactivating effect Effects 0.000 claims description 5
- 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
- 238000004061 bleaching Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 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
- 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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract 1
- 239000013522 chelant Substances 0.000 abstract 1
- 230000002255 enzymatic effect Effects 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 19
- 238000007142 ring opening reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 229920002521 macromolecule Polymers 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 229940088598 enzyme Drugs 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002023 wood Substances 0.000 description 4
- 241000219000 Populus Species 0.000 description 3
- 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
- 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
- 229940025131 amylases Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 230000000087 stabilizing effect Effects 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
- 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development 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
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 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)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
Abstract
The application 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 taken as a carrier, so that the grafting activity is high and the stability is high, and the carboxyl is introduced through maleic anhydride to adsorb and chelate Fe 3+ And the free catalytic particles in the solution are firmly grasped by other metal ions such as inner metal ions, and then the monomer A and the monomer B containing double bonds are grafted and copolymerized with tertiary ethylene carbonate on a starch short chain, so that the strong alkali resistance and the oxidation resistance of the surface polymer are improved, the purpose of stable catalysis is achieved, and silicon-containing substances in the raw materials are avoided, and the scaling of a bleaching system caused by adding a stabilizer is avoided.
Description
Technical Field
The application 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 shortage, 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; h of high yield pulp 2 O 2 The bleaching process has the unique advantage: the bleaching whiteness has large value-increasing amplitude, good whiteness stability, lower bleaching cost, no sulfur or chlorine, convenient production water closed circulation, cleanness and environmental protection.
The papermaking industry requires a high-yield pulping production system to realize high sealing performance, so that discharged wastewater and heat are reduced to the greatest extent, and clean water is saved. However, due to the severe scale formation of the pulping system, in order to maintain the normal operation of production, the system has to be opened periodically, not only wasting a lot of heat energy and water resources, but also causing serious environmental pollution. Meanwhile, the generated scale is scattered in various parts of the system (bleached pulp and bleached washing water), the surface of the scale is compact, the scale is refused to be cleaned by high-pressure water and surfactant, the scale has strong resistance to common acid and alkali cleaning, the key parts of the production system (disc mill, pulp screen, wet part and dry part) are greatly influenced, and valuable devices such as disc mill blades, pulp screen plates and press blankets are damaged, and the normal operation of the production system is seriously disturbed.
The formation of scale is a complex physicochemical process, and is the result of the combined action of metal ions, anionic trash and silicate ions, and the main reason is that sodium silicate is adopted as a stabilizer for hydrogen peroxide bleaching, so that in the pulp hydrogen peroxide bleaching process, a non-silicon stabilizer which can replace the sodium silicate stabilizer is found to be a research hot spot.
The application aims to prepare a stabilizer without silicon by taking cheap starch as a carrier and performing functional modification.
Disclosure of Invention
In order to solve the technical problems in the background art, the application aims to provide a hydrogen peroxide bleaching silicon-free stabilizer and a preparation method thereof.
The aim of the application can be achieved by the following technical scheme:
the preparation method of the hydrogen peroxide bleaching silicon-free stabilizer specifically comprises the following steps:
step S1: mixing starch and deionized water under stirring to obtain starch slurry, adding amylase, mixing, setting stirring speed at 180-360rpm, heating to 80-90deg.C, maintaining temperature, stirring for enzymolysis for 5-7 hr, introducing saturated steam after enzymolysis is completed, rapidly inactivating enzyme for 5min, and cutting long chain of macromolecules into short chain containing a large amount of hydroxyl groups by amylase to obtain enzymolysis solution;
further, the starch is selected from corn starch or tapioca starch, has 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 75-80deg.C, setting stirring speed at 180-240rpm, slowly adding maleic anhydride, maintaining the temperature, stirring for 30-40min, opening loop of maleic anhydride, esterifying with hydroxy groups on starch short chain, and grafting carboxyl groups on starch short chain to make the starch short chain contain a large amount of hydroxy groups and carboxyl groups, thereby effectively adsorbing and chelating Fe 3+ The inner metal ions are absorbed by adsorption and chelation, so that free catalytic particles in the solution are firmly grasped, the aim of stably catalyzing hydrogen peroxide is fulfilled, partial maleic anhydride is condensed to form a ring-shaped complex after ring opening, the decomposition stability of the hydrogen peroxide is improved, and the grafting liquid is prepared;
step S3: mixing the grafting liquid and the oxidant, 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, carrying out heat preservation, stirring, 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, 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 macromolecular grafts containing hydroxyl groups and carboxyl groups in the grafting liquid, and branched chains containing double bonds are grafted on the macromolecular grafts.
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, and the vinyl versatate is introduced for copolymerization, so that the strong 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 raw materials comprise 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 application has the beneficial effects that:
1. according to the application, corn starch or tapioca starch with high amylose content is used as a raw material, long chains of macromolecules are cut into short chains by amylase through enzymolysis of alpha-medium temperature amylase, and the short chains contain a large number of hydroxyl groups, so that the high grafting activity is shown, and meanwhile, the stability of macromolecular polymers is realized.
2. The application grafts carboxyl on the starch short chain through maleic anhydride ring opening reaction, so that the starch short chain contains a large amount of hydroxyl and carboxyl, and Fe is effectively adsorbed and chelated 3+ The inner metal ions absorb the metal ions through adsorption and chelation, so that free catalytic particles in the solution are firmly grasped, the aim of stably catalyzing hydrogen peroxide is fulfilled, partial maleic anhydride is condensed to form a cyclic complex after ring opening, and the decomposition stability of the hydrogen peroxide is improved.
3. According to the application, through graft copolymerization of the monomer A and the monomer B containing double bonds and vinyl versatate on starch short chains, the strong alkali resistance and the oxidation resistance of the surface polymer are improved, and the purpose of stable catalysis is achieved.
4. The application does not introduce siliceous substances in the process of preparing the stabilizer, and does not cause scaling of a bleaching system due to the added stabilizer in the bleaching process.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The preparation method of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
and (3) batching: the following raw materials are taken according to parts by weight:
18 parts of starch selected from corn starch;
0.1 part of amylase selected from alpha-medium temperature amylase;
0.2 parts of an oxidant selected from ammonium persulfate;
5 parts of maleic anhydride;
4 parts of a monomer A selected from acrylic acid;
5 parts of monomer B; selected from hydroxyethyl methacrylate;
2 parts of monomer C, selected from vinyl versatate, supplied by Guangzhou chemical industry Co., ltd;
0.2 part of initiator, which is formed by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1:1;
67.5 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring to form uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting stirring speed to be 360rpm, heating to 90 ℃, preserving heat, stirring and carrying out enzymolysis for 5 hours, cutting long chains of macromolecules into short chains of macromolecules containing a large number of hydroxyl groups by using amylase, and introducing saturated steam to quickly inactivate enzymes for 5 minutes after enzymolysis is finished, thus preparing enzymolysis liquid;
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, and carrying out heat preservation stirring reaction for 30min to carry out ring opening reaction on the maleic anhydride and starch short chain reaction to prepare a grafting liquid;
and (3) copolymerization grafting: and (3) stirring and mixing the grafting liquid and the oxidant, uniformly dispersing the oxidant in the grafting liquid, sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 80 ℃, setting the stirring speed at 120rpm, slowly adding the initiator, carrying out heat preservation and stirring reaction for 60min, and cooling to 40 ℃ to obtain the stabilizer.
Example 2
The preparation method of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
and (3) batching: the following raw materials are taken according to parts by weight:
20 parts of starch selected from tapioca starch;
0.2 parts of amylase selected from alpha-medium temperature amylase;
0.3 parts of an oxidant selected from ammonium persulfate;
6 parts of maleic anhydride;
5 parts of a monomer selected from methacrylic acid;
4 parts of monomer B; selected from hydroxyethyl acrylate;
3 parts of monomer C, selected from vinyl versatate, supplied by Guangzhou chemical industry Co., ltd;
0.3 part of initiator, which is formed by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1:1;
61.2 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring to form uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting stirring speed to be 240rpm, heating to 90 ℃, preserving heat, stirring and carrying out enzymolysis for 6 hours, cutting long chains of macromolecules into short chains with a large number of hydroxyl groups by using amylase, and rapidly inactivating enzyme by introducing saturated steam for 5 minutes after enzymolysis is finished to prepare enzymolysis liquid;
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, and carrying out heat preservation stirring reaction for 35min to carry out ring opening reaction on maleic anhydride and starch short chain reaction to prepare a grafting liquid;
and (3) copolymerization grafting: and (3) stirring and mixing the grafting liquid and the oxidant, uniformly dispersing the oxidant in the grafting liquid, sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 80 ℃, setting the stirring speed at 120rpm, slowly adding the initiator, carrying out heat preservation and stirring reaction for 60min, and cooling to 40 ℃ to obtain the stabilizer.
Example 3
The preparation method of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
and (3) batching: the following raw materials are taken according to parts by weight:
20 parts of starch selected from tapioca starch;
0.22 parts of amylase selected from alpha-medium temperature amylase;
0.35 parts of an oxidant selected from ammonium persulfate;
7 parts of maleic anhydride;
6 parts of a monomer selected from methacrylic acid;
4.5 parts of monomer B; selected from hydroxyethyl acrylate;
3.5 parts of monomer C, selected from vinyl versatate, supplied by Guangzhou chemical Co., ltd;
0.35 part of initiator, which is formed by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1:1;
58.08 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring to form uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting stirring speed to be 180rpm, heating to 80 ℃, preserving heat, stirring and carrying out enzymolysis for 7h, cutting long chains of macromolecules into short chains with a large number of hydroxyl groups by using amylase, and rapidly inactivating enzyme by introducing saturated steam for 5min after enzymolysis is finished to prepare enzymolysis liquid;
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, and carrying out heat preservation stirring reaction for 40min to carry out ring opening reaction on the maleic anhydride and starch short chain reaction to prepare a grafting liquid;
and (3) copolymerization grafting: and (3) stirring and mixing the grafting liquid and the oxidant, uniformly dispersing the oxidant in the grafting liquid, sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 70 ℃, setting the stirring speed at 80rpm, slowly adding the initiator, carrying out heat preservation and stirring reaction for 90min, and cooling to 40 ℃ to obtain the stabilizer.
Example 4
The preparation method of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
and (3) batching: the following raw materials are taken according to parts by weight:
10 parts of starch selected from corn starch;
0.1 part of amylase selected from alpha-medium temperature amylase;
1 part of 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, supplied by Guangzhou chemical industry Co., ltd;
0.4 part of initiator, which is formed by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1:1;
70 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring to form uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting stirring speed to be 240rpm, heating to 85 ℃, preserving heat, stirring and carrying out enzymolysis for 6 hours, cutting long chains of macromolecules into short chains with a large number of hydroxyl groups by using amylase, and rapidly inactivating enzyme by introducing saturated steam for 5 minutes after enzymolysis is finished to prepare enzymolysis liquid;
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, and carrying out heat preservation stirring reaction for 35min to carry out ring opening reaction on maleic anhydride and starch short chain reaction to prepare a grafting liquid;
and (3) copolymerization grafting: and (3) stirring and mixing the grafting liquid and the oxidant, uniformly dispersing the oxidant in the grafting liquid, sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 80 ℃, setting the stirring speed at 80rpm, slowly adding the initiator, carrying out heat preservation and stirring reaction for 70min, and cooling to 40 ℃ to obtain the stabilizer.
Example 5
The preparation method of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
and (3) batching: the following raw materials are taken according to parts by weight:
20 parts of starch selected from corn starch;
0.4 parts of amylase selected from alpha-medium temperature amylase;
1 part of oxidant selected from ammonium persulfate;
10 parts of maleic anhydride;
10 parts of a monomer A selected from methacrylic acid;
5 parts of monomer B; selected from hydroxyethyl methacrylate;
5 parts of monomer C, selected from vinyl versatate, supplied by Guangzhou chemical industry Co., ltd;
0.4 part of initiator, which is formed by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1:1;
40 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring to form uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting stirring speed to be 240rpm, heating to 85 ℃, preserving heat, stirring and carrying out enzymolysis for 6.5h, cutting long chains of macromolecules into short chains with a large number of hydroxyl groups by using amylase, and introducing saturated steam to quickly inactivate enzymes for 5min after enzymolysis is finished to prepare enzymolysis liquid;
ring-opening grafting: maintaining the enzymolysis liquid at 78 ℃, setting the stirring speed to 240rpm, slowly adding maleic anhydride into the enzymolysis liquid within 3min, and carrying out heat preservation stirring reaction for 35min to carry out ring opening reaction on maleic anhydride and starch short chain reaction to prepare a grafting liquid;
and (3) copolymerization grafting: and (3) stirring and mixing the grafting liquid and the oxidant, uniformly dispersing the oxidant in the grafting liquid, sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 85 ℃, setting the stirring speed at 100rpm, slowly adding the initiator, carrying out heat preservation and stirring reaction for 75min, and cooling to 40 ℃ to obtain the stabilizer.
Example 6
The preparation method of the hydrogen peroxide bleaching silicon-free stabilizer comprises the following specific implementation processes:
and (3) batching: the following raw materials are taken according to parts by weight:
18 parts of starch selected from tapioca starch;
0.25 parts of amylase selected from alpha-medium temperature amylases;
0.55 parts of an oxidant selected from ammonium persulfate;
2 parts of maleic anhydride;
2 parts of a monomer selected from methacrylic acid;
4.2 parts of monomer B; selected from hydroxyethyl acrylate;
4.5 parts of monomer C, selected from vinyl versatate, supplied by Guangzhou chemical industry Co., ltd;
0.4 part of initiator, which is formed by mixing hydrogen peroxide and vitamin C according to the mass ratio of 1:1;
68.1 parts of deionized water;
enzymolysis: adding starch and deionized water into a stirrer, stirring to form uniform slurry, preparing starch slurry, adding amylase into the starch slurry, mixing, setting stirring speed to be 240rpm, heating to 88 ℃, preserving heat, stirring and carrying out enzymolysis for 5.8 hours, cutting long chains of macromolecules into short chains with a large number of hydroxyl groups by using amylase, and introducing saturated steam to quickly inactivate enzymes for 5 minutes after enzymolysis is finished, so as to prepare enzymolysis liquid;
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, and carrying out heat preservation stirring reaction for 40min to carry out ring opening reaction on the maleic anhydride and starch short chain reaction to prepare a grafting liquid;
and (3) copolymerization grafting: and (3) stirring and mixing the grafting liquid and the oxidant, uniformly dispersing the oxidant in the grafting liquid, sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 75 ℃, setting the stirring speed at 120rpm, slowly adding the initiator, carrying out heat preservation and stirring reaction for 75min, and cooling to 40 ℃ to obtain the stabilizer.
Comparative example 1
This comparative example was identical to the preparation of example 1, except that maleic anhydride was not added for ring-opening grafting, and the remaining steps were exactly the same.
Comparative example 2
The comparative example is a stabilizer prepared by the method provided in Chinese patent application No. 201710431120.0.
The stability prepared in examples 1 to 6 and comparative examples 1 to 2 was subjected to a hydrogen peroxide decomposition rate test and a pulp bleaching test, and the following were specific:
the decomposition rate testing 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 boil at 98 ℃, transferring 10mL of mixed solution into a conical flask every 15min after boiling, adding 2.5mL of sulfuric acid solution with the concentration of 6mol/L, and using KMnO with the concentration of 0.2mol/L 4 And (5) calibrating a standard solution. When the solution had no color until just red appears and the red does not fade within 30 seconds, the titration endpoint was determined and the spent KMnO was recorded 4 Is a volume of (c). The hydrogen peroxide decomposition rate was calculated, and 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 application has a better stabilizing effect on the decomposition of hydrogen peroxide, and the stabilizing effect is better than that of the existing stabilizer in the earlier stage of bleaching.
Bleaching test:
taking unbleached poplar wood machine pulp to be absolute-dried 20g, preparing the unbleached poplar wood machine pulp into 20 percent of concentration, putting the unbleached poplar wood machine pulp into a zipper bag, and sequentially adding 10kg/t NaOH, 1.5kg/t DTPA and H 2 O 2 30kg/t of stabilizer, 2kg/t of stabilizer, extruding and kneading to ensure that chemicals and water are uniformly mixed with pulp, transferring into a water bath kettle after 10min, starting a timer, setting the bleaching temperature at 95 ℃ for 60min, taking out the bag from the water bath, washing with pure water, and extruding to dry;
weighing 8g of squeezed wet pulp, adding 800mL of water, adding 4mL of 5% EDTA solution, stirring, soaking for 30min, regulating pH to 4.0-5.5 with hydrochloric acid, stirring, dividing into 4 parts, adding 500mL of water each part, and making into paper with a Buchner funnel with quantitative ratio of about 100g/m 2 Is placed in a baking oven and dried at a temperature not exceeding 60 ℃, and the dried pulp adopts Swedish L&The whiteness is detected by a model Elrepho 070 spectrowhiteness meter manufactured by W company, and specific test data are shown in table 2:
TABLE 2
As can be seen from the data in table 2, the stabilizer prepared by the application is applied to hydrogen peroxide bleaching, and hydrogen peroxide can play a good bleaching role.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 merely illustrative and explanatory of the application, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the application or exceeding the scope of the application as defined in the claims.
Claims (5)
1. The 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;
wherein the monomer A is acrylic acid or methacrylic acid, the monomer B is hydroxyethyl acrylate or hydroxyethyl methacrylate, and the monomer C is vinyl versatate;
the preparation method of the hydrogen peroxide bleaching silicon-free stabilizer specifically comprises the following steps:
step S1: mixing starch and deionized water, adding amylase, mixing, heating to 80-90 ℃, preserving heat, stirring, performing enzymolysis for 5-7h, and inactivating enzyme after the enzymolysis is finished to prepare enzymolysis liquid;
step S2: maintaining the temperature of the enzymolysis liquid at 75-80 ℃, stirring at 180-240rpm, adding maleic anhydride, and reacting for 30-40min under heat preservation and stirring to prepare a grafting liquid;
step S3: and (3) stirring and mixing the grafting liquid and the oxidant, sequentially adding the monomer A, the monomer B and the monomer C, maintaining the temperature at 70-80 ℃, dropwise adding an initiator at the stirring speed of 80-120rpm, carrying out heat preservation and stirring reaction for 60-90min, and cooling to 40 ℃ to prepare the stabilizer.
2. The hydrogen peroxide bleaching silica-free stabilizer according to claim 1, wherein the starch is corn starch or tapioca starch.
3. The hydrogen peroxide bleaching silica-free stabilizer according to claim 2, wherein the amylase is an alpha-medium temperature amylase.
4. The hydrogen peroxide bleaching silica-free stabilizer according to claim 1, wherein the oxidizing agent is ammonium persulfate.
5. The hydrogen peroxide bleaching silica-free stabilizer according to claim 1, wherein the initiator is formed by mixing hydrogen peroxide and vitamin C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210985346.6A CN115260397B (en) | 2022-08-17 | 2022-08-17 | Hydrogen peroxide bleaching silicon-free stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210985346.6A CN115260397B (en) | 2022-08-17 | 2022-08-17 | Hydrogen peroxide bleaching silicon-free stabilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115260397A CN115260397A (en) | 2022-11-01 |
| CN115260397B true CN115260397B (en) | 2023-11-21 |
Family
ID=83753823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210985346.6A Active CN115260397B (en) | 2022-08-17 | 2022-08-17 | Hydrogen peroxide bleaching silicon-free stabilizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115260397B (en) |
Citations (6)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170211019A1 (en) * | 2016-01-26 | 2017-07-27 | The Procter & Gamble Company | Treatment compositions |
-
2022
- 2022-08-17 CN CN202210985346.6A patent/CN115260397B/en active Active
Patent Citations (6)
| 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 |
| 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 |
|---|
| Enzymatic Pre-Treatment of Cotton. Part 2: Peroxide Generation in Desizing Liquor and Bleaching;Anis, P;FIBRES & TEXTILES IN EASTERN EUROPE;第17卷(第2期);87-90 * |
| 有机助剂对纸浆H2O2漂白的影响;陈春霞，等;《中国造纸学会第十四届学术年会论文集》;194-199 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115260397A (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102080331B (en) | Process for pre-treating fabrics by bio-enzymatic method | |
| CN102121201B (en) | Preparation method of bamboo dissolving pulp | |
| CN102978960A (en) | Low-alkali pretreatment method for in-situ catalytic degradation of impurities in cotton and cotton fabrics | |
| CN106492763A (en) | The preparation method and applications of esterification modification bagasse | |
| CN103669064B (en) | A kind of preparation technology of vinegar-grade bamboo pulp | |
| CN101215794A (en) | Zero residual base normal-pressure or low-pressure boiling high-concentration pulp preparing method by using base process | |
| CN115260397B (en) | Hydrogen peroxide bleaching silicon-free stabilizer | |
| CN105839449B (en) | A kind of clean method for preparing of viscose grade bamboo pulp | |
| CN106939525A (en) | A kind of method that reduction APMP starches YI yellow index | |
| CN102154869B (en) | Cooking aid for preparing chemical fiber pulp | |
| CN104109978A (en) | Method for preparing cotton linter dissolving pulp | |
| CN115181214B (en) | Hydrogen peroxide bleaching scale-free stabilizer and preparation method thereof | |
| CN102174755A (en) | Boiling assistant for preparing high polymerised pulp | |
| CN109736119B (en) | Paper pulp bleaching method | |
| CN110541302B (en) | Method for modifying surface of paper-based material | |
| CN108130708A (en) | A kind of desizing ferment that single bath process is washed suitable for cowboy's desizing ferment washes auxiliary agent and preparation method thereof | |
| CN102174756B (en) | Method for preparing chemical fiber pulp | |
| CN111424419B (en) | Hydrogen peroxide catalytic system containing benzophenone structure derivative and application of hydrogen peroxide catalytic system in low-temperature pretreatment of textiles | |
| CN109736071A (en) | A kind of cloth cover low temperature cold-pad batch pretreatment | |
| CN115637603B (en) | Method for preparing pulp from waste pure cotton fabric, product obtained by method and application of pulp | |
| CN114908598B (en) | Oxygen bleaching method for paper pulp | |
| CN111321620B (en) | Waste paper pulp deinking stabilizer and preparation method thereof | |
| CN111424433B (en) | Biological enzyme pretreatment method for cotton woven fabric | |
| CN117867886A (en) | Production process of cotton pulp for lithium battery-grade cellulose ether | |
| CN115012226A (en) | Refining method of cotton fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |