CN114105331B - Preparation method and application of calcium peroxide composite sustained release agent - Google Patents
Preparation method and application of calcium peroxide composite sustained release agent Download PDFInfo
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- CN114105331B CN114105331B CN202111435634.6A CN202111435634A CN114105331B CN 114105331 B CN114105331 B CN 114105331B CN 202111435634 A CN202111435634 A CN 202111435634A CN 114105331 B CN114105331 B CN 114105331B
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- calcium peroxide
- release agent
- biochar
- peroxide composite
- polyvinyl alcohol
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- 239000004343 Calcium peroxide Substances 0.000 title claims abstract description 99
- 235000019402 calcium peroxide Nutrition 0.000 title claims abstract description 99
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000013268 sustained release Methods 0.000 title claims abstract description 41
- 239000012730 sustained-release form Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 29
- 239000000661 sodium alginate Substances 0.000 claims abstract description 29
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 29
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010257 thawing Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 18
- 230000008014 freezing Effects 0.000 claims abstract description 18
- 238000007710 freezing Methods 0.000 claims abstract description 18
- 239000008103 glucose Substances 0.000 claims abstract description 18
- 239000003673 groundwater Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 238000009776 industrial production Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 244000005700 microbiome Species 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 150000001555 benzenes Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000001963 growth medium Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003895 groundwater pollution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 241000589516 Pseudomonas Species 0.000 description 2
- 241000589776 Pseudomonas putida Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 238000009629 microbiological culture Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229920001817 Agar Polymers 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- -1 calcium peroxide compound Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F7/00—Aeration of stretches of water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/14—Additives which dissolves or releases substances when predefined environmental conditions are reached, e.g. pH or temperature
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a preparation method of a calcium peroxide composite sustained release agent, which comprises the following steps: s1, mixing polyvinyl alcohol, sodium alginate and water to prepare a mixed solution; wherein, the mass ratio of the polyvinyl alcohol, the sodium alginate and the water is 2-5:1:30-50, stirring at the speed of 80-120rpm for 4-5h at the temperature of 60-80 ℃; s2, adding calcium peroxide, glucose, biochar and a pH regulator into the mixed solution, and stirring and uniformly mixing to obtain a mixture, wherein the stirring time is 5-10min, and the temperature is 2-5 ℃; wherein, the mass ratio of the calcium peroxide is as follows: glucose: biochar: the pH regulator is 1:0.5-2.5:0.1-0.2:0.1-0.12; s3, pouring the mixture into a mold, freezing, thawing, and taking out and drying after a plurality of freeze thawing cycles. The composite slow release agent has the advantages of simple preparation process, low cost, good slow release effect, easy realization of large-scale industrial production, high-efficiency restoration of petroleum hydrocarbon polluted groundwater, and high popularization and application value.
Description
Technical Field
The invention belongs to the technical field of polluted groundwater remediation, and particularly relates to a preparation method and application of a calcium peroxide composite slow-release agent.
Background
Groundwater is used as an important strategic resource for supporting sustainable development of economy and society, and plays an irreplaceable role in maintaining healthy development of economy and society and the like. In the process of production and transportation, petroleum hydrocarbon pollutants cannot be prevented from entering a groundwater system due to various reasons such as leakage, production accidents, discharge of sewage and waste, and the like, so that groundwater environment pollution is caused, and production and living of people are seriously threatened.
At present, the method for removing petroleum hydrocarbon pollutants in groundwater mainly comprises technologies such as extraction treatment, air disturbance, in-situ chemical oxidation, permeable reaction walls and the like, but the technologies often need to inject a large amount of chemical reagents, have high construction and long-term operation and maintenance costs, and have unsatisfactory effects on tailing or rebound phenomena occurring in the later stage of pollution repair. In recent years, in-situ bioremediation has received great attention because of its advantages of small disturbance to sites, low cost of remediation, environmental friendliness, and the like. Researches show that the aerobic degradation rate of organic pollutants such as petroleum hydrocarbon is obviously higher than the anaerobic degradation rate, and key factors of aerobic biodegradation are oxygen, moisture, temperature, nutritional ingredients and the like respectively, however, the natural underground water has no light, low temperature and low oxygen and similar extreme environment so that the problems of less total microorganisms, low degradation efficiency and the like exist in the indigenous microorganism restoration. How to keep the aquifer in an aerobic environment and enough nutrients to activate indigenous microorganisms is critical to the success of the repair of the technology. By utilizing the characteristic that the slow release agent slowly releases oxygen and nutrient substances in the hydrolysis process, the aquifer can be maintained in an aerobic state for a long period, the degradation and metabolism of indigenous aerobic microorganisms are stably promoted, and the effect of repairing underground water is achieved.
CN201811509728.1 discloses a granular calcium peroxide slow release agent, the preparation method specifically comprises the following steps: (1) Completely dissolving anhydrous calcium chloride in absolute ethyl alcohol to obtain a clear solution; (2) Adding nylon 66 into the clear solution, stirring to obtain white non-clear mixed solution, oscillating to obtain colloidal uniform transparent slurry, and adding calcium peroxide powder to stir to obtain white slurry; (3) And (3) dripping the white slurry into a spherical particle forming die, drying to form spherical particles, and collecting to finish the preparation of the granular calcium peroxide slow release agent. The granular calcium peroxide slow release agent can slow down the release speed of oxygen and the release process of calcium peroxide, but has poor slow release effect and is not beneficial to popularization and use.
In conclusion, the research on the preparation process of the calcium peroxide slow release agent with simple process, low cost and good slow release effect has wide application prospect.
Disclosure of Invention
The invention provides a preparation method of a calcium peroxide compound sustained release agent, which aims to solve the problem of long-acting sustained release of oxygen and nutrient substances. The invention also aims to provide the application of the compound sustained release agent in petroleum hydrocarbon polluted groundwater remediation.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a preparation method of a calcium peroxide composite sustained release agent comprises the following steps:
s1, mixing polyvinyl alcohol, sodium alginate and water to prepare a mixed solution;
Wherein, the mass ratio of the polyvinyl alcohol, the sodium alginate and the water is 2-5:1:30-50, stirring at the speed of 80-120rpm for 4-5h at the temperature of 60-80 ℃;
s2, adding calcium peroxide, glucose, biochar and a pH regulator into the mixed solution, and stirring and uniformly mixing to obtain a mixture, wherein the stirring time is 5-10min, and the temperature is 2-5 ℃;
wherein, calcium peroxide: glucose: biochar: the mass ratio of the pH regulator is 1:0.5-2.5:0.1-0.2:0.1-0.12;
S3, pouring the mixture into a mold, freezing, thawing, and taking out and drying after a plurality of freeze thawing cycles.
The composite slow release agent provided by the invention takes calcium peroxide, glucose and biochar as oxygen sources and carbon sources of microorganisms, takes polyvinyl alcohol and sodium alginate as embedding agents, optimizes the preparation process of the embedding agents, comprises the proportion of the polyvinyl alcohol and the sodium alginate and the preparation conditions, ensures proper embedding property, has good embedding effect and shows excellent slow release performance. The calcium peroxide composite slow release agent is used for repairing groundwater pollution, especially repairing petroleum hydrocarbon polluted groundwater, can activate indigenous degrading bacteria in situ, has the advantages of high pollutant removal efficiency, low cost and the like, and can be widely applied to repairing petroleum hydrocarbon polluted groundwater of oil fields, refining enterprises and the like.
In the invention, preferably, the mass ratio of the polyvinyl alcohol, the sodium alginate and the water in the mixed solution is 3:1:40, the preparation condition is that stirring is carried out at the speed of 100rpm for 4-5h at the temperature of 70 ℃. According to the invention, through theoretical and experimental adjustment, polyvinyl alcohol and sodium alginate are selected as embedding agents, and the proportion of the polyvinyl alcohol and the sodium alginate and the preparation conditions of the embedding agents are optimized, so that the embedding effect on components such as calcium peroxide, glucose, biochar and the like is good.
In the present invention, preferably, calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: the mass ratio of the sodium alginate is 1:0.5-2.5:0.1-0.2:0.1-0.12:7.5-8.5:2.5-2.8.
Further preferably, the calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: the mass ratio of the sodium alginate is 1:2.5:0.10:0.11:7.5:2.5.
The mass ratio of the components is obtained after the inventor adjusts a large amount of experiments, and the concentration of the slow-release components in the slow-release agent and the specific weight of the embedding agent caused by the proportion of the components lead to uniform embedding and good slow-release effect.
In the invention, preferably, the biomass raw material of the biochar is one or more of rice straw, peanut shell and wood dust; the thermal anaerobic cracking temperature in the preparation process of the biochar is 400-450 ℃, and the particle size of the biochar is 100-200 meshes. The specification of the biochar is selected, so that small organic molecules in the biochar can be absorbed by microorganisms more easily, and the particle size enables the biochar to have good slow release effect, large surface energy and stronger adsorptivity.
In the present invention, preferably, the pH adjuster includes citric acid and/or potassium dihydrogen phosphate.
In the present invention, preferably, the freezing time is 48-72 hours each time, the freezing temperature is-20 ℃ and the thawing time is 1-2 hours each time during the freeze-thaw cycle. The mixture itself is viscous, and water is required to be discharged in order to prepare solid particles. Freezing can freeze and separate out water molecules from the solution, and then the frozen water molecules are melted and lost. The inventors found that after repeated freeze thawing of the above mixture, the material can be cured completely without affecting the properties of the material itself. The setting of the freezing temperature and the freezing time is the comprehensive optimization effect of the inventor, and the freezing time temperature can be increased from the viewpoint of energy conservation, but if the temperature is lower than 48 hours or higher, the material is incompletely frozen and still is a viscous colloid.
In the present invention, preferably, the number of freeze-thaw cycles is 2 to 3. The inventor researches and discovers that the shortest frequency required by the complete solidification of the material is 2-3 times, the material is frozen and thawed once, the material is unshaped and still a viscous colloid, the freezing and thawing period is too long, calcium peroxide therein is easy to react with water and can be gradually deactivated, and the effect of providing slow release oxygen for microorganisms can not be achieved.
According to the invention, the calcium peroxide powder, glucose and biochar are coated by using the bonding effect of the polyvinyl alcohol and the sodium alginate, and the composite slow-release agent particles are formed through freeze thawing, so that the composite slow-release agent has the effects of stabilizing the pH value and slowing down the release rate of oxygen, can continuously provide oxygen and nutrient substances for the metabolism of microorganisms, and can obviously improve the degradation rate of organic pollutants by aerobic microorganisms.
The invention also protects the calcium peroxide composite sustained release agent prepared by the preparation method of the calcium peroxide composite sustained release agent, the particle size of the calcium peroxide composite sustained release agent is 1cm 3, and the particle size of the embedded calcium peroxide particles is 0.2-1mm. The compound sustained-release agent is granular, and the preparation method is simple and the transportation is safe and convenient.
The invention also protects the application of the calcium peroxide composite sustained-release agent prepared by the preparation method of the calcium peroxide composite sustained-release agent in groundwater pollution restoration.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention utilizes the chemical property of generating oxygen by the reaction of calcium peroxide and water to prepare the calcium peroxide composite slow-release agent, plays a role in improving the content of dissolved oxygen in underground water, and solves the problem of inhibiting the activity of microbial degradation due to the rise of the pH value of a system after the reaction of calcium peroxide and water by adding the pH regulator.
2. The invention uses biochar as an auxiliary additive of the composite slow release agent. The biochar contains unstable low molecular organic matters, can be used as a carbon source of microorganisms, has a porous structure and rich surface functional groups, has strong adsorption capacity on hydrophobic organic matters, and has the dual functions of improving the biomass and activity of microorganisms and accelerating the removal of organic pollutants.
3. The calcium peroxide composite slow release agent is used for repairing groundwater pollution, especially repairing petroleum hydrocarbon polluted groundwater, can activate indigenous degrading bacteria in situ, has the advantages of high pollutant removal efficiency, low cost and the like, and can be widely applied to repairing petroleum hydrocarbon polluted groundwater of oil fields, refining enterprises and the like.
Drawings
FIG. 1 is a photograph of a composite slow-release agent of calcium peroxide prepared by the invention.
FIG. 2 shows the oxygen release curves of calcium peroxide powder, commercial calcium peroxide oxygen release tablets and the calcium peroxide composite sustained release agent prepared by the invention.
FIG. 3 shows the oxygen release profile of the calcium peroxide composite sustained release agent prepared in example 1 and comparative examples 1 to 5.
FIG. 4 shows the degradation effect of the calcium peroxide composite slow release agent prepared by the invention on 2mg/L benzene series by indigenous microorganisms in the polluted groundwater.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples and the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, but the scope of the present invention is not limited to the examples.
In the following specific examples, all the raw materials used are commercially available unless otherwise specified.
Example 1
A preparation method of a calcium peroxide composite sustained release agent comprises the following steps:
Step a, weighing 7.5g of polyvinyl alcohol and 2.5g of sodium alginate, dissolving in 100ml of water, stirring at 70 ℃ for 4 hours at a rotating speed of 100rpm, and placing the solution in a refrigerator at 4 ℃ for standby after the polyvinyl alcohol and the sodium alginate are completely dissolved.
And b, weighing 1g of calcium peroxide, 0.11g of citric acid, 2.5g of glucose and 0.1g of biochar, adding the mixture into the mixed solution of polyvinyl alcohol and sodium alginate, and stirring the mixture at the temperature of 4 ℃ for 5min to mix uniformly.
And c, pouring the mixture into a mould with the temperature of 1cm multiplied by 1cm, freezing for 48 hours at the temperature of minus 20 ℃, thawing for 1 hour at room temperature, freezing for 48 hours, and finally drying for 4 hours in a blast drying box at the temperature of 50 ℃ to obtain the calcium peroxide composite slow release agent.
The preparation method provided by the embodiment can obtain the calcium peroxide composite sustained release agent with good morphology, the particle size is 1cm 3, wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1mm. See fig. 1 for a specific shape.
Example 2
A preparation method of a calcium peroxide composite sustained release agent comprises the following steps:
step a, weighing 8.5g of polyvinyl alcohol and 2.8g of sodium alginate, dissolving in 100ml of water, stirring at a temperature of 60 ℃ for 5 hours at a rotating speed of 120rpm, and placing the solution in a refrigerator at a temperature of 2 ℃ for standby after the polyvinyl alcohol and the sodium alginate are completely dissolved.
And step b, 1.0g of calcium peroxide, 0.1g of monopotassium phosphate, 0.5g of glucose and 0.2g of biochar are weighed and added into the mixed solution of polyvinyl alcohol and sodium alginate, and the mixture is stirred for 10min at the temperature of 3 ℃ and uniformly mixed.
And c, pouring the mixture into a mould with the temperature of 1cm multiplied by 1cm, freezing for 72 hours at the temperature of minus 20 ℃, thawing for 2 hours at the room temperature, freezing for 48 hours, and finally drying for 5 hours in a blast drying box at the temperature of 50 ℃ to obtain the calcium peroxide composite slow release agent.
The preparation method provided by the embodiment can obtain the calcium peroxide composite sustained release agent with good morphology, the particle size is 1cm 3, wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1mm.
Example 3
A preparation method of a calcium peroxide composite sustained release agent comprises the following steps:
Step a, weighing 8.0g of polyvinyl alcohol and 2.6g of sodium alginate, dissolving in 100ml of water, stirring at 80 ℃ for 5 hours at a rotating speed of 80rpm, and placing the solution in a refrigerator at 3 ℃ for standby after the polyvinyl alcohol and the sodium alginate are completely dissolved.
And step b, weighing 1.0g of calcium peroxide, 0.12g of citric acid, 2.0g of glucose and 0.15g of biochar, adding the mixture into the mixed solution of polyvinyl alcohol and sodium alginate, and stirring the mixture at the temperature of 4 ℃ for 10min to mix uniformly.
And c, pouring the mixture into a mould with the temperature of 1cm multiplied by 1cm, freezing for 60 hours at the temperature of minus 20 ℃, thawing for 1.5 hours at room temperature, thawing for 48 hours at room temperature, thawing for 1.5 hours at room temperature, thawing for 48 hours, and drying for 4 hours in a blast drying box at the temperature of 50 ℃ to obtain the calcium peroxide composite slow release agent.
The preparation method provided by the embodiment can obtain the calcium peroxide composite sustained release agent with good morphology, the particle size is 1cm 3, wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1mm.
Example 4
A preparation method of a calcium peroxide composite sustained release agent comprises the following steps:
Step a, weighing 7.9g of polyvinyl alcohol and 2.5g of sodium alginate, dissolving in 100ml of water, stirring at a temperature of 75 ℃ for 4 hours at a rotating speed of 110rpm, and placing the solution in a refrigerator at a temperature of 4 ℃ for standby after the polyvinyl alcohol and the sodium alginate are completely dissolved.
And step b, weighing 1.0g of calcium peroxide, 0.11g of monopotassium phosphate, 1.5g of glucose and 0.12g of biochar, adding the mixture into the mixed solution of polyvinyl alcohol and sodium alginate, and stirring the mixture at the temperature of 5 ℃ for 10min to mix uniformly.
And c, pouring the mixture into a mould with the temperature of 1cm multiplied by 1cm, freezing for 48 hours at the temperature of minus 20 ℃, thawing for 2 hours at room temperature, thawing for 60 hours at room temperature for 1.5 hours, thawing for 48 hours, and finally drying for 4 hours in a blast drying box at the temperature of 55 ℃ to obtain the calcium peroxide composite slow release agent.
The preparation method provided by the embodiment can obtain the calcium peroxide composite sustained release agent with good morphology, the particle size is 1cm 3, wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1mm.
Comparative example 1
The comparative example provides a method for preparing a calcium peroxide composite sustained release agent, which is exactly the same as in example 1, except that 0.5g of calcium peroxide and 0.055g of citric acid are added in step b.
Comparative example 2
The comparative example provides a preparation method of a calcium peroxide composite sustained-release agent, which is exactly the same as that of example 1, except that citric acid is not added in step b.
Comparative example 3
The comparative example provides a preparation method of a calcium peroxide composite sustained-release agent, which is exactly the same as that of example 1, except that glucose is not added in step b.
Comparative example 4
The comparative example provides a preparation method of a calcium peroxide composite sustained-release agent, which is exactly the same as that of example 1, except that biochar is not added in step b.
Comparative example 5
The comparative example provides a preparation method of a calcium peroxide composite sustained-release agent, which is exactly the same as that of example 1, except that glucose and biochar are not added in step b.
Performance testing
(1) The calcium peroxide composite sustained release agent, the commercial calcium peroxide oxygen release tablet and the calcium peroxide powder prepared in example 1 and comparative examples 1 to 5 were subjected to oxygen release performance test.
The testing method comprises the following steps: the materials are respectively added into an conical flask filled with 100ml of pure water, so that the concentration of calcium peroxide in the solution is 0.8g/L, the pure water is aerated for 1h under the nitrogen atmosphere, the dissolved oxygen content of the pure water is lower than 0.2mg/L, the bottle mouth of the conical flask is sealed by a rubber plug, a dissolved oxygen analysis probe is inserted into the conical flask, and the concentration of the dissolved oxygen in the solution is recorded according to a certain time interval. The reaction was carried out using a pH analysis probe to determine the pH of the solution. The results of the dissolved oxygen test are shown in fig. 2 and 3, and the pH values of the sustained release agent solutions prepared in example 1 and comparative examples 1 to 5 after the reaction were 7.81, 7.19, 11.46, 7.83, 7.97, 8.24, respectively.
(2) The calcium peroxide composite sustained release agent prepared in example 1 and comparative examples 1 to 5 was subjected to a long-term oxygen release performance test. The testing method comprises the following steps: 0.3g of sodium sulfite is weighed and dissolved in 1L of pure water, the content of dissolved oxygen in the solution is measured to be 0.0mg/L, the sodium sulfite solution is injected into a glass column filled with the calcium peroxide composite slow release agent through a peristaltic pump at a flow rate of 1.5PV/d, and the concentration of the dissolved oxygen in the effluent is measured according to a certain time interval. The test results are shown in Table 1.
TABLE 1
(3) The calcium peroxide composite sustained release agent prepared in the example 1 is subjected to a degradation experiment of the benzene series by reinforced pseudomonas putida.
Preparing an inorganic salt culture medium: 1500mg/L disodium hydrogen phosphate, 1g/L potassium dihydrogen phosphate, 100mg/L magnesium sulfate, 2000mg/L potassium chloride, 800mg/L ammonium sulfate, 1200mg/L potassium nitrate, 38mg/L calcium chloride, 9mg/L ethylenediamine tetraacetic acid, 5mg/L ferrous sulfate, 1mg/L manganese sulfate, 0.2mg/L zinc sulfate, 0.3mg/L boric acid, 0.2mg/L cobalt chloride, 0.3mg/L sodium molybdate, 0.3mg/L cupric chloride, 0.03mg/L nickel chloride.
The experimental method comprises the following steps: pseudomonas putida with the strain number 1.8829 is purchased from China general microbiological culture collection center, a seawater 2216 agar culture medium is selected for strain reviving according to a method suggested by the management center, then 1ml of microbial bacteria liquid is inoculated into a glass bottle filled with an inorganic salt culture medium, wherein the benzene content is 0.5mg/L each of benzene, toluene, ethylbenzene and xylene, a certain mass of the calcium peroxide composite slow release agent prepared in the example 1 is added into the glass bottle, the initial concentration of the calcium peroxide is 0.8g/L, and a gas phase mass spectrometer and an ultra-differential photometer are used for monitoring the concentration of the benzene in the solution and the growth of microorganisms after 3 days. The results show that the addition of the calcium peroxide composite slow release agent improves the removal rate of benzene, toluene, ethylbenzene and xylene by 28.1%, 31.3%, 29.1% and 28.5% respectively, and the microorganism OD600 value is increased from 0.01 to 0.23.
(4) The calcium peroxide composite slow release agent prepared in the example 1 is subjected to a degradation experiment of the reinforced fluorescent pseudomonas on benzene series.
The experimental method comprises the following steps: fluorescent pseudomonas with a strain number of 1.15059 is purchased from China general microbiological culture collection center, LB culture medium is selected for strain reviving according to the method suggested by the management center, then 1ml of microbial liquid is inoculated into a glass bottle filled with inorganic salt culture medium, wherein the benzene content is 0.5mg/L each of benzene, toluene, ethylbenzene and xylene, a certain mass of the calcium peroxide composite slow release agent prepared in example 1 is added into the glass bottle, the initial concentration of the calcium peroxide is 0.8g/L, and a gas phase mass spectrometer and an ultra-differential spectrophotometer are used for monitoring the concentration of the benzene content and the growth condition of microorganisms in the solution after 3 days. The results show that the addition of the calcium peroxide composite slow release agent prepared in the example 1 improves the removal rate of benzene, toluene, ethylbenzene and xylene by 21.1%, 27.5%, 31.8% and 26.6% respectively, and the microorganism OD600 value is increased from 0.01 to 0.22.
(5) The calcium peroxide composite sustained release agent prepared in the example 1 and the comparative examples 3 and 4 are subjected to a degradation experiment of benzene series by indigenous microorganisms of the polluted groundwater.
The experimental method comprises the following steps: collecting groundwater of a gas station, wherein benzene, toluene, ethylbenzene and xylene are all out of standard, amplifying indigenous microorganisms in the groundwater by using an LB culture medium, carrying out induced domestication on the indigenous microorganisms by using benzene series as the only carbon source under aerobic conditions, inoculating 1ml of domesticated microorganism bacterial liquid into a glass bottle containing an inorganic salt culture medium, wherein the benzene series content is 0.5mg/L of benzene, toluene, ethylbenzene and xylene, respectively adding the calcium peroxide composite slow release agents prepared in the examples 1 and the comparative examples 3-5 with a certain mass into the glass bottle, so that the initial concentration of the calcium peroxide is 0.8g/L, and monitoring the concentration of the benzene series and the growth condition of microorganisms in the solution by using a gas phase mass spectrometer and an ultra-differential spectrophotometer after 3 days.
The results are shown in FIG. 4. The calcium peroxide composite slow release agent remarkably improves the benzene series removal efficiency, and the repairing effect of the embodiment 1 is better than that of the comparative examples 3, 4 and 5.
The addition of the calcium peroxide composite slow release agent prepared in the embodiment 1 improves the removal rate of benzene, toluene, ethylbenzene and xylene by 22.3%, 21.5%, 26.9% and 16.0% respectively, and the microorganism OD600 value is increased from 0.01 to 0.74.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (8)
1. The application of the calcium peroxide composite slow release agent is characterized in that the calcium peroxide composite slow release agent is applied to the restoration of petroleum hydrocarbon polluted groundwater, and the preparation of the calcium peroxide composite slow release agent comprises the following steps:
s1, mixing polyvinyl alcohol, sodium alginate and water to prepare a mixed solution;
Wherein, the mass ratio of the polyvinyl alcohol, the sodium alginate and the water is 2-5:1:30-50, stirring at 80-120rpm for 4-5h at 60-80deg.C, and storing the obtained mixed solution in refrigerator at 4deg.C;
s2, adding calcium peroxide, glucose, biochar and a pH regulator into the mixed solution, and stirring and uniformly mixing to obtain a mixture, wherein the stirring time is 5-10min, and the temperature is 2-5 ℃;
Wherein, calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: the mass ratio of the sodium alginate is 1:0.5-2.5:0.1-0.2:0.1-0.12:7.5-8.5:2.5-2.8;
S3, pouring the mixture into a mold, freezing, thawing, and taking out and drying after a plurality of freeze thawing cycles.
2. The application of the calcium peroxide composite sustained-release agent according to claim 1, wherein the mass ratio of polyvinyl alcohol, sodium alginate and water in the mixed solution is 3:1:40, the preparation condition is that stirring is carried out at the speed of 100rpm for 4-5h at the temperature of 70 ℃.
3. The use of a calcium peroxide composite sustained release agent according to claim 1, wherein the calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: the mass ratio of the sodium alginate is 1:2.5:0.10:0.11:7.5:2.5.
4. The application of the calcium peroxide composite sustained-release agent according to claim 1, wherein the biomass raw material of the biochar is one or more of rice straw, peanut shell and wood dust; the thermal anaerobic cracking temperature in the preparation process of the biochar is 400-450 ℃, and the particle size of the biochar is 100-200 meshes.
5. The use of a calcium peroxide composite sustained release agent according to claim 1, wherein the pH adjuster comprises citric acid and/or potassium dihydrogen phosphate.
6. The use of the calcium peroxide composite sustained release agent according to claim 1, wherein in the freeze-thawing cycle, the freezing time is 48-72 hours each time, the freezing temperature is-20 ℃, and the thawing time is 1-2 hours each time.
7. The use of a calcium peroxide composite sustained release agent according to claim 1, wherein the number of freeze-thawing cycles is 2-3.
8. The use of a calcium peroxide composite sustained release agent according to any one of claims 1 to 7, wherein the particle size of the calcium peroxide composite sustained release agent is 1cm 3, and wherein the particle size of the embedded calcium peroxide particles is 0.2 to 1mm.
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