CN113355104A - Plastic degradation agent for alkaline soil remediation and preparation method thereof - Google Patents
Plastic degradation agent for alkaline soil remediation and preparation method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 65
- 229920003023 plastic Polymers 0.000 title claims abstract description 55
- 239000004033 plastic Substances 0.000 title claims abstract description 55
- 239000002689 soil Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000005067 remediation Methods 0.000 title claims abstract description 36
- 230000015556 catabolic process Effects 0.000 title claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 92
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- 102000004190 Enzymes Human genes 0.000 claims abstract description 42
- 108090000790 Enzymes Proteins 0.000 claims abstract description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 35
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 34
- 239000011941 photocatalyst Substances 0.000 claims abstract description 34
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 34
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 102000004316 Oxidoreductases Human genes 0.000 claims abstract description 22
- 108090000854 Oxidoreductases Proteins 0.000 claims abstract description 22
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 102000004157 Hydrolases Human genes 0.000 claims abstract description 14
- 108090000604 Hydrolases Proteins 0.000 claims abstract description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000000593 degrading effect Effects 0.000 claims abstract description 14
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 14
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000004246 zinc acetate Substances 0.000 claims abstract description 14
- 102000016680 Dioxygenases Human genes 0.000 claims abstract description 13
- 108010028143 Dioxygenases Proteins 0.000 claims abstract description 13
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 13
- 229960001631 carbomer Drugs 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 102000008109 Mixed Function Oxygenases Human genes 0.000 claims abstract description 11
- 108010074633 Mixed Function Oxygenases Proteins 0.000 claims abstract description 11
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 11
- 229940036811 bone meal Drugs 0.000 claims abstract description 11
- 239000002374 bone meal Substances 0.000 claims abstract description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 229930195729 fatty acid Natural products 0.000 claims abstract description 11
- 239000000194 fatty acid Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 32
- 230000001678 irradiating effect Effects 0.000 claims description 32
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 32
- 229910052753 mercury Inorganic materials 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012634 fragment Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 238000012271 agricultural production Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004162 soil erosion Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a plastic degradation agent for alkaline soil remediation and a preparation method thereof. The plastic degrading agent for alkaline soil remediation is composed of a graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, a pretreating agent, an enzyme preparation, boric acid and citric acid, wherein the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst is prepared by reacting tetrabutyl titanate, zinc acetate, manganese acetate, a graphene ethanol solution, water, polythiourea, acrylic acid and ethanol, the pretreating agent is prepared by reacting 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, butyl acrylate, vinyl acetate, water, ethanol, a 819 photoinitiator and an Sr-10 emulsifier, and the enzyme preparation is prepared by reacting extracellular hydrolase, dioxygenase, monooxygenase, oxidoreductase, bone enzyme, fatty acid oxidase, carbomer resin, bone meal and water. The plastic degradation agent for alkaline soil remediation provided by the invention has excellent plastic degradation performance.
Description
Technical Field
The invention relates to the field of soil remediation, in particular to a plastic degradation agent for alkaline soil remediation and a preparation method thereof.
Background
With the application and popularization of plastic science and technology in the agricultural production process, the problems of recycling of waste plastics generated in the agricultural production process and difficult degradation of waste plastics remained in soil are gradually concerned by agricultural production. The waste plastics remain in the soil, not only can cause soil self can't digest the degradation waste plastics, still lead to in the soil beneficial bacterium and the loose gas permeability of soil to produce fatal influence to destroy soil ecosystem, in the long run, can gradually cause soil hardening, fungus crowd ecological disturbance, fertility loss, soil erosion scheduling problem because of waste plastics remain. In order to further reduce a series of negative effects caused by waste plastic residues in soil, agricultural and chemical researchers have called the relevant field researchers to deeply research and develop theoretical and practical application of plastic degradation agent materials for alkaline soil remediation. Since general agricultural production plastics are difficult-to-degrade materials, the agricultural production plastics need to be improved in degradability.
Disclosure of Invention
The invention aims to provide a plastic degrading agent for alkaline soil remediation, which is prepared from graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, a pretreating agent, an enzyme preparation, boric acid and citric acid and has excellent plastic degrading performance.
The invention also aims to provide a preparation method of the plastic degradation agent for alkaline soil remediation.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a plastic degrading agent for alkaline soil remediation comprises graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, a pretreating agent, an enzyme preparation, boric acid and citric acid, wherein the mass ratio of the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst to the alkaline soil remediation is 32: 21-30: 13-21: 5-11: 3-8; the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst is prepared by reacting tetrabutyl titanate, zinc acetate, manganese acetate, a graphene ethanol solution, water, polythiourea, acrylic acid and ethanol, wherein the tetrabutyl titanate, the zinc acetate, the manganese acetate, the graphene ethanol solution, the water, the polythiourea, the acrylic acid and the ethanol are in a mass ratio of 50: 32-41: 18-25: 10-19: 12-23: 76-93: 2-11: 280-400; the pretreating agent is prepared by reacting 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, butyl acrylate, vinyl acetate, water, ethanol, 819 photoinitiator and Sr-10 emulsifier, wherein the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the 2: 2-7: 1-6: 0.5-4: 39-51: 12-36: 0.03-0.3: 3-9; the enzyme preparation is prepared by reacting extracellular hydrolase, dioxygenase, monooxygenase, oxidoreductase, bone enzyme, fatty acid oxidase, carbomer resin, bone meal and water, wherein the mass ratio of the extracellular hydrolase to the dioxygenase is 6: 2-5: 2-7: 1-8: 1-4: 1-5: 0.05-0.8: 3-6: 51-76.
Preferably, the mass part ratio of the graphene to the zinc sulfide to the manganese sulfide to the titanium dioxide photocatalyst to the pretreatment agent to the enzyme preparation to the boric acid to the citric acid is 32:26:16:7: 5.
The preparation method of the plastic degradation agent for alkaline soil remediation comprises the following steps:
(1) adding extracellular hydrolase, dioxygenase, monooxygenase, oxidoreductase, bone enzyme, fatty acid oxidase, carbomer resin, bone meal and water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation; the carbomer resin is used for ensuring the working humidity of the enzyme preparation;
(2) adding 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, butyl acrylate, vinyl acetate, water, ethanol, 819 photoinitiator and Sr-10 emulsifier into a reaction kettle, stirring at 360r/min, reacting at 33 ℃ for 43min, irradiating the product for 3-10 s by using a 100W high-pressure mercury lamp, irradiating the product for 2-8 s by using a 200W high-pressure mercury lamp, irradiating the product for 2-7 s by using a 400W high-pressure mercury lamp, irradiating the product for 1-5 s by using a 1000W high-pressure mercury lamp, drying the product, and crushing the product at-20 ℃ to obtain a pretreatment agent; the 2-acrylamide-2-methylpropanesulfonic acid, the acrylic acid, the butyl acrylate and the vinyl acetate are used for carrying out surface modification on plastic fragments in soil;
(3) adding zinc acetate, manganese acetate, a graphene ethanol solution, water, polythiourea, acrylic acid and ethanol into a hydrothermal reaction kettle, treating for 25-60 min while maintaining the temperature of the hydrothermal reaction kettle at 80-100 ℃, adding tetrabutyl titanate into the hydrothermal reaction kettle, treating for 3-15 h while maintaining the temperature of the hydrothermal reaction kettle at 130-190 ℃, filtering a product, washing with water, washing with a 5% acetic acid aqueous solution, washing with ethanol, and performing 100 ℃, 200, 300, 400, 500, 550 and 550 ℃ heat treatment for 3h under the protection of nitrogen, and crushing to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst; the purpose of the polythiourea is to improve the dispersibility among materials;
(4) adding the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, the pretreating agent, the enzyme preparation, the boric acid and the citric acid into a mixer, mixing at 33r/min, and reacting for 25min under the condition of maintaining the system temperature at 20 ℃ to obtain the plastic degrading agent for alkaline soil remediation.
The invention has the beneficial effects that:
1. the carbomer resin has excellent water absorption, safety and environmental protection, the degradation efficiency of the enzyme preparation in the optimal humidity environment can be guaranteed, meanwhile, after plastic fragments in soil are subjected to secondary treatment by the pretreatment agent and the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst respectively, the degradation efficiency of the enzyme preparation is obviously improved because the surfaces or the interiors of the plastic fragments are treated, and thus the degradation rate of the plastic degradation agent for repairing alkaline soil can be improved by the enzyme preparation;
2. 2-acrylamide-2-methylpropanesulfonic acid and acrylic acid have a corrosion effect on the surface of plastic, can carry out micro corrosion on plastic fragments, butyl acrylate and vinyl acetate slightly swell the plastic fragments on the basis of the micro corrosion of the acrylamide-2-methylpropanesulfonic acid and the acrylic acid, and the plastic fragments in the soil are pretreated through the micro corrosion-swelling synergistic effect of the 2-acrylamide-2-methylpropanesulfonic acid, the acrylic acid, the butyl acrylate and the vinyl acetate, and meanwhile, because the applied soil is alkaline soil, an acidic substance in the pretreating agent cannot obviously change the pH value of the soil;
3. the polythiourea can generate swelling-hydrolysis phenomena in a high-temperature high-pressure ethanol solution, the phase balance of a reaction system and the dispersion performance among materials are improved, a graphene/zinc sulfide/manganese sulfide/titanium dioxide precursor is gradually formed along with the slow hydrolysis of zinc acetate, manganese acetate, tetrabutyl titanate and polythiourea in the reaction system, the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst is obtained after treatment, the graphene can improve the photoproduction electron-hole conductivity of the photocatalyst, and the zinc sulfide and manganese sulfide can improve the photocatalytic performance of titanium dioxide in visible light, therefore, the prepared graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst has excellent photocatalytic degradation performance, and the prepared graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst can obviously improve the degradation rate of plastic fragments in alkaline soil.
Detailed Description
The following description of specific embodiments of the present invention is provided in connection with examples to facilitate a better understanding of the present invention. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
A plastic degradation agent for alkaline soil remediation, which comprises the following steps:
(1) adding 6 parts of extracellular hydrolase, 2.6 parts of dioxygenase, 3.8 parts of monooxygenase, 4.6 parts of oxidoreductase, 1.8 parts of bone enzyme, 2.3 parts of fatty acid oxidase, 0.08 part of carbomer resin, 4.5 parts of bone meal and 66 parts of water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation;
(2) adding 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 5.5 parts of acrylic acid, 5.3 parts of butyl acrylate, 1.8 parts of vinyl acetate, 43 parts of water, 30 parts of ethanol, 0.18 part of 819 photoinitiator and 7.8 parts of Sr-10 emulsifier into a reaction kettle, stirring at 360r/min and at 33 ℃ for 43min, irradiating the product for 7s by using a 100W high-pressure mercury lamp, irradiating the product for 6s by using a 200W high-pressure mercury lamp, irradiating the product for 5s by using a 400W high-pressure mercury lamp, irradiating the product for 3s by using a 1000W high-pressure mercury lamp, drying the product, and crushing the product at the low temperature of-20 ℃ to obtain a pretreating agent;
(3) adding 36 parts of zinc acetate, 21 parts of manganese acetate, 15 parts of graphene ethanol solution, 18 parts of water, 86 parts of polythiourea, 6.5 parts of acrylic acid and 350 parts of ethanol into a hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 85 ℃ for treatment for 31min, adding 50 parts of tetrabutyl titanate into the hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 150 ℃ for treatment for 9h, filtering, washing with 5% acetic acid aqueous solution, washing with ethanol, performing 100 ℃ heat treatment on the product for 1h, 200 ℃ heat treatment for 1h, 300 ℃ heat treatment for 2h, 400 ℃ heat treatment for 3h, 500 ℃ heat treatment for 3h, 550 ℃ heat treatment for 3h, and crushing to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst;
(4) adding 32 parts of graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, 26 parts of pretreating agent, 16 parts of enzyme preparation, 7 parts of boric acid and 5 parts of citric acid into a mixer, wherein the mixing speed is 33r/min, and the system temperature is maintained at 20 ℃ for reaction for 25min to obtain the plastic degrading agent for alkaline soil remediation.
Example 2
A plastic degradation agent for alkaline soil remediation, which comprises the following steps:
(1) adding 6 parts of extracellular hydrolase, 2 parts of dioxygenase, 2 parts of monooxygenase, 1 part of oxidoreductase, 1 part of bone enzyme, 1 part of fatty acid oxidase, 0.05 part of carbomer resin, 3 parts of bone meal and 51 parts of water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation;
(2) adding 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2 parts of acrylic acid, 1 part of butyl acrylate, 0.5 part of vinyl acetate, 39 parts of water, 12 parts of ethanol, 0.03 part of 819 photoinitiator and 3 parts of Sr-10 emulsifier into a reaction kettle, reacting at the reaction temperature of 33 ℃ for 43min at the stirring speed of 360r/min, irradiating the product for 3s by using a 100W high-pressure mercury lamp, irradiating the product for 2s by using a 200W high-pressure mercury lamp, irradiating the product for 2s by using a 400W high-pressure mercury lamp, irradiating the product for 1s by using a 1000W high-pressure mercury lamp, drying the product, and crushing the product at the low temperature of-20 ℃ to obtain a pretreating agent;
(3) adding 32 parts of zinc acetate, 18 parts of manganese acetate, 10 parts of graphene ethanol solution, 12 parts of water, 76 parts of polythiourea, 2 parts of acrylic acid and 280 parts of ethanol into a hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 80 ℃ for treatment for 60min, adding 50 parts of tetrabutyl titanate into the hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 130 ℃ for treatment for 15h, filtering the product, washing the product with water, washing the product with 5% acetic acid aqueous solution, washing the product with ethanol, performing 100 ℃ heat treatment on the product for 1h, 200 ℃ heat treatment for 1h, 300 ℃ heat treatment for 2h, 400 ℃ heat treatment for 3h, 500 ℃ heat treatment for 3h and 550 ℃ heat treatment for 3h under the protection of nitrogen, and crushing the product to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst;
(4) adding 32 parts of graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, 21 parts of pretreating agent, 13 parts of enzyme preparation, 5 parts of boric acid and 3 parts of citric acid into a mixer, wherein the mixing speed is 33r/min, and the system temperature is maintained at 20 ℃ for reaction for 25min to obtain the plastic degrading agent for alkaline soil remediation.
Example 3
A plastic degradation agent for alkaline soil remediation, which comprises the following steps:
(1) adding 6 parts of extracellular hydrolase, 5 parts of dioxygenase, 7 parts of monooxygenase, 8 parts of oxidoreductase, 4 parts of bone enzyme, 5 parts of fatty acid oxidase, 0.8 part of carbomer resin, 6 parts of bone meal and 76 parts of water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation;
(2) adding 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 7 parts of acrylic acid, 6 parts of butyl acrylate, 4 parts of vinyl acetate, 51 parts of water, 36 parts of ethanol, 0.3 part of 819 photoinitiator and 9 parts of Sr-10 emulsifier into a reaction kettle, reacting at the reaction temperature of 33 ℃ for 43min at the stirring speed of 360r/min, irradiating the product for 10s by using a 100W high-pressure mercury lamp, irradiating the product for 8s by using a 200W high-pressure mercury lamp, irradiating the product for 7s by using a 400W high-pressure mercury lamp, irradiating the product for 5s by using a 1000W high-pressure mercury lamp, drying the product, and crushing the product at the low temperature of-20 ℃ to obtain a pretreating agent;
(3) adding 41 parts of zinc acetate, 25 parts of manganese acetate, 19 parts of graphene ethanol solution, 23 parts of water, 93 parts of polythiourea, 11 parts of acrylic acid and 400 parts of ethanol into a hydrothermal reaction kettle, treating for 25min while maintaining the temperature of the hydrothermal reaction kettle at 100 ℃, adding 50 parts of tetrabutyl titanate into the hydrothermal reaction kettle, treating for 3h while maintaining the temperature of the hydrothermal reaction kettle at 190 ℃, filtering the product, washing with water, washing with 5% acetic acid aqueous solution, washing with ethanol, and then carrying out 100 ℃ heat treatment for 1h, 200 ℃ heat treatment for 1h, 300 ℃ heat treatment for 2h, 400 ℃ heat treatment for 3h, 500 ℃ heat treatment for 3h and 550 ℃ heat treatment for 3h under the protection of nitrogen, and crushing to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst;
(4) adding 32 parts of graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, 30 parts of pretreating agent, 21 parts of enzyme preparation, 11 parts of boric acid and 8 parts of citric acid into a mixer, wherein the mixing speed is 33r/min, and the system temperature is maintained at 20 ℃ for reaction for 25min to obtain the plastic degrading agent for alkaline soil remediation.
Example 4
A plastic degradation agent for alkaline soil remediation, which comprises the following steps:
(1) adding 6 parts of extracellular hydrolase, 2.3 parts of dioxygenase, 3.2 parts of monooxygenase, 3.9 parts of oxidoreductase, 1.9 parts of bone enzyme, 1.8 parts of fatty acid oxidase, 0.2 part of carbomer resin, 3.5 parts of bone meal and 56 parts of water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation;
(2) adding 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 3.6 parts of acrylic acid, 2.6 parts of butyl acrylate, 1.5 parts of vinyl acetate, 43 parts of water, 16 parts of ethanol, 0.09 part of 819 photoinitiator and 4.6 parts of Sr-10 emulsifier into a reaction kettle, stirring at 360r/min and at 33 ℃ for 43min, irradiating the product for 4s by using a 100W high-pressure mercury lamp, irradiating the product for 3s by using a 200W high-pressure mercury lamp, irradiating the product for 5s by using a 400W high-pressure mercury lamp, irradiating the product for 3s by using a 1000W high-pressure mercury lamp, drying the product, and crushing the product at the low temperature of-20 ℃ to obtain a pretreating agent;
(3) adding 35 parts of zinc acetate, 19 parts of manganese acetate, 13 parts of graphene ethanol solution, 15 parts of water, 81 parts of polythiourea, 3.6 parts of acrylic acid and 300 parts of ethanol into a hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 90 ℃ for treatment for 30min, adding 50 parts of tetrabutyl titanate into the hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 140 ℃ for treatment for 5h, filtering the product, washing the product with water, washing the product with 5% of acetic acid aqueous solution, washing the product with ethanol, performing 100 ℃ heat treatment on the product for 1h, 200 ℃ heat treatment for 1h, 300 ℃ heat treatment for 2h, 400 ℃ heat treatment for 3h, 500 ℃ heat treatment for 3h, 550 ℃ heat treatment for 3h, and crushing the product to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst;
(4) adding 32 parts of graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, 25 parts of pretreating agent, 16 parts of enzyme preparation, 7.8 parts of boric acid and 4.3 parts of citric acid into a mixer, wherein the mixing speed is 33r/min, and the system temperature is maintained at 20 ℃ for reaction for 25min, so as to obtain the plastic degrading agent for alkaline soil remediation.
Example 5
A plastic degradation agent for alkaline soil remediation, which comprises the following steps:
(1) adding 6 parts of extracellular hydrolase, 3 parts of dioxygenase, 5 parts of monooxygenase, 3 parts of oxidoreductase, 2 parts of bone enzyme, 3 parts of fatty acid oxidase, 0.3 part of carbomer resin, 4 parts of bone meal and 58 parts of water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation;
(2) adding 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 3 parts of acrylic acid, 3 parts of butyl acrylate, 2 parts of vinyl acetate, 43 parts of water, 18 parts of ethanol, 0.1 part of 819 photoinitiator and 5 parts of Sr-10 emulsifier into a reaction kettle, reacting at the stirring speed of 360r/min and the reaction temperature of 33 ℃ for 43min, irradiating the product for 6s by using a 100W high-pressure mercury lamp, irradiating for 5s by using a 200W high-pressure mercury lamp, irradiating for 4s by using a 400W high-pressure mercury lamp, irradiating for 3s by using a 1000W high-pressure mercury lamp, drying the product, and crushing at the low temperature of-20 ℃ to obtain a pretreating agent;
(3) adding 36 parts of zinc acetate, 21 parts of manganese acetate, 17 parts of graphene ethanol solution, 16 parts of water, 83 parts of polythiourea, 8 parts of acrylic acid and 310 parts of ethanol into a hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 87 ℃ for treatment for 36min, adding 50 parts of tetrabutyl titanate into the hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 150 ℃ for treatment for 7h, filtering, washing with 5% acetic acid solution, washing with ethanol, performing 100 ℃ heat treatment on the product for 1h, 200 ℃ heat treatment for 1h, 300 ℃ heat treatment for 2h, 400 ℃ heat treatment for 3h, 500 ℃ heat treatment for 3h and 550 ℃ heat treatment for 3h under the protection of nitrogen, and crushing to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst;
(4) adding 32 parts of graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, 26 parts of pretreating agent, 17 parts of enzyme preparation, 8 parts of boric acid and 5 parts of citric acid into a mixer, wherein the mixing speed is 33r/min, and the system temperature is maintained at 20 ℃ for reaction for 25min to obtain the plastic degrading agent for alkaline soil remediation.
Example 6
A plastic degradation agent for alkaline soil remediation, which comprises the following steps:
(1) adding 6 parts of extracellular hydrolase, 4.1 parts of dioxygenase, 5.5 parts of monooxygenase, 6.3 parts of oxidoreductase, 3.2 parts of bone enzyme, 3.7 parts of fatty acid oxidase, 0.6 part of carbomer resin, 5.2 parts of bone meal and 65 parts of water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation;
(2) adding 12 parts of 2-acrylamide-2-methylpropanesulfonic acid, 5.3 parts of acrylic acid, 4.6 parts of butyl acrylate, 3.1 parts of vinyl acetate, 44 parts of water, 31 parts of ethanol, 0.21 part of 819 photoinitiator and 7.6 parts of Sr-10 emulsifier into a reaction kettle, stirring at 360r/min and at 33 ℃ for 43min, irradiating the product by a 100W high-pressure mercury lamp for 8s, irradiating by a 200W high-pressure mercury lamp for 6s, irradiating by a 400W high-pressure mercury lamp for 5s, irradiating by a 1000W high-pressure mercury lamp for 4s, drying the product, and crushing at-20 ℃ to obtain a pretreating agent;
(3) adding 38 parts of zinc acetate, 21 parts of manganese acetate, 17 parts of graphene ethanol solution, 21 parts of water, 83 parts of polythiourea, 8.6 parts of acrylic acid and 356 parts of ethanol into a hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 91 ℃ for treatment for 41min, adding 50 parts of tetrabutyl titanate into the hydrothermal reaction kettle, maintaining the temperature of the hydrothermal reaction kettle at 170 ℃ for treatment for 11h, filtering, washing with 5% acetic acid aqueous solution, washing with ethanol, performing 100 ℃ heat treatment on the product for 1h, 200 ℃ heat treatment for 1h, 300 ℃ heat treatment for 2h, 400 ℃ heat treatment for 3h, 500 ℃ heat treatment for 3h and 550 ℃ heat treatment for 3h under the protection of nitrogen, and crushing to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst;
(4) adding 32 parts of graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, 28 parts of pretreating agent, 17.6 parts of enzyme preparation, 9 parts of boric acid and 6.8 parts of citric acid into a mixer, wherein the mixing speed is 33r/min, and the system temperature is maintained at 20 ℃ for reaction for 25min, so as to obtain the plastic degrading agent for alkaline soil remediation.
Comparative example 1
In the comparative example, the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst was not added, and the other components and the preparation method were the same as in example 1.
Comparative example 2
In this comparative example, no pretreatment agent was added, and the other components were prepared in the same manner as in example 1.
Comparative example 3
In this comparative example, the enzyme preparation was not added, and the other components and preparation method were the same as in example 1.
Comparative example 4
In the comparative example, a common titanium dioxide photocatalyst is selected in the formula to replace the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst in the example 1, and other components and the preparation method are the same as those in the example 1.
Comparative example 5
In the comparison example, the common 2-acrylamide-2-methylpropanesulfonic acid is selected in the formula to replace the pretreating agent in the example 1, and other components and the preparation method are the same as those in the example 1.
Comparative example 6
In the comparison example, the general extracellular hydrolase is selected from the formula to replace the enzyme preparation in the example 1, and other components and preparation methods are the same as the example 1.
The decomposition rates of the plastic degradation agents for repairing alkaline soil prepared in examples 1 to 6 and comparative examples 1 to 6 were tested according to GB/T20197, and the test results are shown in tables 1 and 2 below.
TABLE 1 Performance parameters of Plastic degradation Agents for alkaline soil remediation prepared in examples 1 to 6
TABLE 2 Performance parameters of Plastic degradation Agents for alkaline soil remediation prepared in example 1 and comparative examples 1 to 6
As can be seen from tables 1 and 2 above, the alkaline soil remediation plastic degradation agent prepared in each embodiment of the present invention has excellent degradation performance, which indicates that the alkaline soil remediation plastic degradation agent prepared from the raw materials provided by the present invention has good degradation performance; in contrast, the degradation performance of the plastic degradation agent for alkaline soil remediation prepared from the raw materials of each comparative example is poor. In addition, the plastic degradation agent for alkaline soil remediation, which is prepared by the embodiments of the invention, has better degradation performance.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (3)
1. The plastic degrading agent for alkaline soil remediation is characterized by comprising 32: 21-30: 13-21: 5-11: 3-8 parts by mass of graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, a pretreating agent, an enzyme preparation, boric acid and citric acid; the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst is prepared by reacting tetrabutyl titanate, zinc acetate, manganese acetate, a graphene ethanol solution, water, polythiourea, acrylic acid and ethanol, wherein the tetrabutyl titanate, the zinc acetate, the manganese acetate, the graphene ethanol solution, the water, the polythiourea, the acrylic acid and the ethanol are in a mass ratio of 50: 32-41: 18-25: 10-19: 12-23: 76-93: 2-11: 280-400; the pretreating agent is prepared by reacting 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, butyl acrylate, vinyl acetate, water, ethanol, 819 photoinitiator and Sr-10 emulsifier, wherein the mass ratio of the 2-acrylamide-2-methylpropanesulfonic acid to the 2: 2-7: 1-6: 0.5-4: 39-51: 12-36: 0.03-0.3: 3-9; the enzyme preparation is prepared by reacting extracellular hydrolase, dioxygenase, monooxygenase, oxidoreductase, bone enzyme, fatty acid oxidase, carbomer resin, bone meal and water, wherein the mass ratio of the extracellular hydrolase to the dioxygenase is 6: 2-5: 2-7: 1-8: 1-4: 1-5: 0.05-0.8: 3-6: 51-76.
2. The plastic degrading agent for alkaline soil remediation according to claim 1, wherein the mass part ratio of the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, the pretreating agent, the enzyme preparation, the boric acid and the citric acid is 32:26:16:7: 5.
3. The method for preparing the plastic degradation agent for alkaline soil remediation according to any one of claims 1 to 2, comprising the steps of:
(1) adding extracellular hydrolase, dioxygenase, monooxygenase, oxidoreductase, bone enzyme, fatty acid oxidase, carbomer resin, bone meal and water into a reaction kettle, maintaining the mixing temperature of the system at 30 ℃ for reaction for 45min, and spray-drying the product to obtain an enzyme preparation;
(2) adding 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, butyl acrylate, vinyl acetate, water, ethanol, 819 photoinitiator and Sr-10 emulsifier into a reaction kettle, stirring at 360r/min, reacting at 33 ℃ for 43min, irradiating the product for 3-10 s by using a 100W high-pressure mercury lamp, irradiating the product for 2-8 s by using a 200W high-pressure mercury lamp, irradiating the product for 2-7 s by using a 400W high-pressure mercury lamp, irradiating the product for 1-5 s by using a 1000W high-pressure mercury lamp, drying the product, and crushing the product at-20 ℃ to obtain a pretreatment agent;
(3) adding zinc acetate, manganese acetate, a graphene ethanol solution, water, polythiourea, acrylic acid and ethanol into a hydrothermal reaction kettle, treating for 25-60 min while maintaining the temperature of the hydrothermal reaction kettle at 80-100 ℃, adding tetrabutyl titanate into the hydrothermal reaction kettle, treating for 3-15 h while maintaining the temperature of the hydrothermal reaction kettle at 130-190 ℃, filtering a product, washing with water, washing with a 5% acetic acid aqueous solution, washing with ethanol, and performing 100 ℃, 200, 300, 400, 500, 550 and 550 ℃ heat treatment for 3h under the protection of nitrogen, and crushing to obtain the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst;
(4) adding the graphene/zinc sulfide/manganese sulfide/titanium dioxide photocatalyst, the pretreating agent, the enzyme preparation, the boric acid and the citric acid into a mixer, mixing at 33r/min, and reacting for 25min under the condition of maintaining the system temperature at 20 ℃ to obtain the plastic degrading agent for alkaline soil remediation.
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