CN114105331A - 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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- CN114105331A CN114105331A CN202111435634.6A CN202111435634A CN114105331A CN 114105331 A CN114105331 A CN 114105331A CN 202111435634 A CN202111435634 A CN 202111435634A CN 114105331 A CN114105331 A CN 114105331A
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- calcium peroxide
- release agent
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- sustained
- biochar
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- 239000004343 Calcium peroxide Substances 0.000 title claims abstract description 102
- 235000019402 calcium peroxide Nutrition 0.000 title claims abstract description 102
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 78
- 238000013268 sustained release Methods 0.000 title claims abstract description 68
- 239000012730 sustained-release form Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 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 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 30
- 239000000661 sodium alginate Substances 0.000 claims abstract description 30
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 30
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 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 19
- 230000008014 freezing Effects 0.000 claims abstract description 19
- 238000007710 freezing Methods 0.000 claims abstract description 19
- 239000008103 glucose Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010257 thawing Methods 0.000 claims abstract description 8
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 24
- 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
- 238000000034 method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 6
- 238000005067 remediation Methods 0.000 claims description 6
- 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
- 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
- 238000003895 groundwater pollution Methods 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 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 15
- 239000003209 petroleum derivative Substances 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 33
- 239000001301 oxygen Substances 0.000 description 33
- 229910052760 oxygen Inorganic materials 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 22
- 244000005700 microbiome Species 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 12
- 150000001555 benzenes Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000001963 growth medium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 235000015097 nutrients Nutrition 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- -1 calcium peroxide compound Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 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
- 241000589540 Pseudomonas fluorescens 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
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000002068 microbial inoculum Substances 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 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
- 238000010998 test method Methods 0.000 description 2
- 238000003911 water pollution Methods 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
- 230000009471 action Effects 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
- 230000004888 barrier function Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 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
- 238000012824 chemical production Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- 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
- 230000005484 gravity Effects 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
- 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
- 230000007269 microbial metabolism Effects 0.000 description 1
- 238000012544 monitoring process Methods 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
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 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
- 238000005086 pumping Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000008439 repair process Effects 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
- 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
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- 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
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- 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
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- 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
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- 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)
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- 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
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- 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
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- 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
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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 to the sodium alginate to the water is 2-5: 1: 30-50, the preparation condition is that the mixture is stirred for 4-5 hours at the temperature of 60-80 ℃ and the speed of 80-120 rpm; s2, adding calcium peroxide, glucose, biochar and a pH regulator into the mixed solution, and uniformly stirring to obtain a mixture, wherein the stirring time is 5-10min and the temperature is 2-5 ℃; wherein, the mass ratio of calcium peroxide: glucose: biochar: the pH regulator is 1: 0.5-2.5: 0.1-0.2: 0.1-0.12; and S3, pouring the mixture into a mold, freezing, thawing, performing freeze-thaw cycles for a plurality of times, taking out, and drying to obtain the product. The composite sustained-release agent has the advantages of simple preparation process, low cost, good sustained-release effect, easy realization of large-scale industrial production, capability of efficiently repairing petroleum hydrocarbon polluted underground water and higher popularization and application values.
Description
Technical Field
The invention belongs to the technical field of polluted underground water remediation, and particularly relates to a preparation method and application of a calcium peroxide composite slow-release agent.
Background
The underground water is used as an important strategic resource for supporting the sustainable development of the economic society, and plays an irreplaceable role in the aspects of maintaining the healthy development of the economic society and the like. However, as the economic society develops and the industrialization progresses, the problem of underground water petroleum hydrocarbon pollution is increasingly highlighted. Petroleum, as industrial "blood", is an important fundamental energy source for national economic development and is widely used in chemical production. In the process of production and transportation, petroleum hydrocarbon pollutants can not avoid entering a groundwater system due to a plurality of reasons such as 'leakage and leakage', production accidents, sewage and waste discharge and the like, so that the groundwater environment is polluted, and the production and life of people are seriously threatened. Therefore, the treatment of polluted groundwater has become an environmental, economic and social problem which China must face.
At present, the methods for removing petroleum hydrocarbon pollutants in underground water mainly comprise technologies such as pumping treatment, air disturbance, in-situ chemical oxidation, permeable reactive barrier and the like, but the technologies usually need to inject a large amount of chemical reagents, have high construction and long-term operation and maintenance cost, and have an unsatisfactory effect on trailing or rebound phenomena in the later stage of pollution remediation. In recent years, in-situ bioremediation is widely concerned due to the advantages of small disturbance to the field, low restoration cost, 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, the key factors of aerobic biodegradation are oxygen, moisture, temperature, nutrient components and the like, however, the approximate extreme environment of natural underground water without light, low temperature and low oxygen causes the problems of little total microbial quantity, low degradation efficiency and the like in indigenous microbial remediation. How to keep the aquifer in an aerobic environment and enough nutrients to activate indigenous microorganisms is the key to the success 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 time, the degrading and metabolizing capacity of indigenous aerobic microorganisms is stably promoted, and the effect of repairing underground water is achieved.
CN201811509728.1 discloses a granular calcium peroxide sustained-release agent, and 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 a white non-clear mixed solution, then oscillating to obtain a colloidal uniform transparent slurry, adding calcium peroxide powder, and stirring to obtain a 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 sustained 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 sustained-release agent with simple process, low cost and good sustained-release effect has wide application prospect.
Disclosure of Invention
In order to solve the problem of long-acting slow release of oxygen and nutrient substances, the invention provides a preparation method of a calcium peroxide composite slow release agent. The invention also aims to provide the application of the composite slow-release agent in the remediation of petroleum hydrocarbon polluted underground water.
In order to achieve the 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 to the sodium alginate to the water is 2-5: 1: 30-50, the preparation condition is that the mixture is stirred for 4-5 hours at the temperature of 60-80 ℃ and the speed of 80-120 rpm;
s2, adding calcium peroxide, glucose, biochar and a pH regulator into the mixed solution, and uniformly stirring to obtain a mixture, wherein the stirring time is 5-10min and the temperature is 2-5 ℃; wherein, the mass ratio of calcium peroxide: glucose: biochar: the pH regulator is 1: 0.5-2.5: 0.1-0.2: 0.1-0.12;
and S3, pouring the mixture into a mold, freezing, thawing, performing freeze-thaw cycles for a plurality of times, taking out, and drying to obtain the product.
The composite sustained 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 preparation conditions, ensures that the embedding properties are appropriate, the embedding effect is good, and shows excellent sustained release performance. The calcium peroxide composite slow-release agent is used for repairing underground water pollution, particularly petroleum hydrocarbon polluted underground water, 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 underground water in oil fields, refining and chemical enterprises and the like.
In the present invention, preferably, the mass ratio of the polyvinyl alcohol, the sodium alginate and the water in the mixed solution is 3: 1: 40, stirring at the speed of 100rpm for 4-5h at the temperature of 70 ℃. Through theoretical and experimental adjustment, the invention selects the polyvinyl alcohol and the sodium alginate as the embedding agents, optimizes the proportion of the polyvinyl alcohol and the sodium alginate and the preparation conditions of the embedding agents, and ensures that the embedding effect of the embedding agents on calcium peroxide, glucose, biochar and other components is good.
In the present invention, preferably, the weight ratio of calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: 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 weight ratio of calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: sodium alginate is 1: 2.5: 0.10: 0.11: 7.5: 2.5. the mass ratio of the components is obtained by the inventor after a large number of experiments and adjustments, and the concentration of the slow-release components in the slow-release agent and the specific gravity of the embedding agent are caused by the mixture ratio, so that the embedding is uniform and the slow-release effect is good.
In the invention, preferably, the biomass raw material of the biochar is one or a mixture of rice straw, peanut shell and wood chip; 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 organic micromolecules in the biochar can be absorbed by microorganisms more easily, and the biochar has good slow release effect, large surface energy and stronger adsorbability due to the particle size.
In the present invention, preferably, the pH adjusting agent includes citric acid and/or potassium dihydrogen phosphate.
In the invention, preferably, in the freeze-thaw cycle process, each freezing time is 48-72h, the freezing temperature is-20 ℃, and each thawing time is 1-2 h. The mixture is sticky, and the moisture in the mixture needs to be discharged when the mixture is prepared into solid particles. Freezing can freeze and separate out water molecules from the solution, and the frozen water molecules are then lost by thawing. The inventor finds that after the mixture is repeatedly frozen and thawed, the material can be completely solidified, and the performance of the material is not influenced. The setting of the freezing temperature and the freezing time is the comprehensive optimization effect of the inventor, and from the viewpoint of energy saving, the freezing time and the temperature can be increased, but if the temperature is lower than 48 hours or the temperature is higher, the material is not completely frozen and still is sticky colloid.
In the present invention, it is preferable that the number of freeze-thaw cycles is 2 to 3. The inventor researches and discovers that the minimum frequency required by the material to be completely solidified is 2-3 times, the material is frozen and thawed once, the material is not shaped, is still viscous colloid, the freezing and thawing period is too long, calcium peroxide in the material is easy to react with water, is gradually inactivated and cannot play a role in providing slow oxygen release for microorganisms.
According to the invention, the composite sustained-release agent particles are formed by coating calcium peroxide powder, glucose and biochar in the polyvinyl alcohol and sodium alginate under the bonding action of the polyvinyl alcohol and the sodium alginate, and freeze thawing, so that the composite sustained-release agent particles have the effects of stabilizing pH and slowing down the release rate of oxygen, can continuously provide oxygen and nutrient substances for microbial metabolism, and can remarkably improve the rate of degrading organic pollutants by aerobic microorganisms.
The invention also provides the calcium peroxide composite sustained-release agent prepared by the preparation method of the calcium peroxide composite sustained-release agent, wherein the particle size of the calcium peroxide composite sustained-release agent is 1cm3Wherein the particle diameter of the embedded calcium peroxide particles is 0.2-1 mm. The compound sustained-release agent is granular, and has simple preparation method and safe and convenient transportation.
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 remediation.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes the chemical property that calcium peroxide reacts with water to generate oxygen to prepare the calcium peroxide compound sustained-release agent, plays a role in improving the content of dissolved oxygen in underground water, and simultaneously solves the problem that the pH value of a system rises after the calcium peroxide reacts with the water so as to inhibit the degradation activity of microorganisms by adding the pH regulator.
2. The invention utilizes the biochar as an auxiliary additive of the composite sustained-release agent. The biochar contains unstable low-molecular organic matters and can be used as a carbon source of microorganisms, the biochar has a porous structure and rich surface functional groups, and has strong adsorption capacity on hydrophobic organic matters, and the prepared composite sustained-release agent simultaneously has double functions of improving the biomass and activity of the microorganisms and accelerating the removal of organic pollutants.
3. The calcium peroxide composite slow-release agent is used for repairing underground water pollution, particularly petroleum hydrocarbon polluted underground water, 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 underground water in oil fields, refining and chemical enterprises and the like.
Drawings
FIG. 1 is a photograph of the calcium peroxide composite sustained-release formulation prepared by the present invention.
FIG. 2 is the oxygen release curve of calcium peroxide powder, commercial calcium peroxide oxygen release tablet and the calcium peroxide composite sustained release agent prepared by the invention.
FIG. 3 is an oxygen release curve of the calcium peroxide composite sustained-release formulation prepared in example 1 and comparative examples 1 to 5.
FIG. 4 shows the degradation effect of the indigenous microorganisms of the polluted groundwater reinforced by the calcium peroxide composite sustained-release agent on 2mg/L benzene series.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to specific embodiments and the accompanying drawings, but the scope of the present invention is not limited to the embodiments.
In the following embodiments, the raw materials 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 the temperature of 70 ℃ and the rotating speed of 100rpm for 4h, and after the polyvinyl alcohol and the sodium alginate are completely dissolved, placing the solution in a refrigerator at the temperature of 4 ℃ for later use.
And b, weighing 1g of calcium peroxide, 0.11g of citric acid, 2.5g of glucose and 0.1g of biochar, adding the materials into the mixed solution of the polyvinyl alcohol and the sodium alginate, and stirring for 5min at the temperature of 4 ℃ to uniformly mix.
And c, pouring the mixture into a mold with the thickness of 1cm multiplied by 1cm, freezing for 48 hours at the temperature of-20 ℃, then unfreezing for 1 hour at the room temperature, then freezing for 48 hours, and finally drying for 4 hours in a forced air drying oven with the temperature of 50 ℃ to obtain the calcium peroxide compound sustained-release agent.
The preparation method provided by the embodiment can be used for obtaining the calcium peroxide composite sustained-release agent with good form, and the particle size is 1cm3Wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1 mm. The specific shape is shown in figure 1.
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 the temperature of 60 ℃ for 5h at the rotating speed of 120rpm, and after the polyvinyl alcohol and the sodium alginate are completely dissolved, placing the solution in a refrigerator at the temperature of 2 ℃ for later use.
And b, weighing 1.0g of calcium peroxide, 0.1g of monopotassium phosphate, 0.5g of glucose and 0.2g of biochar, adding the materials into the mixed solution of the polyvinyl alcohol and the sodium alginate, and stirring for 10min at the temperature of 3 ℃ to uniformly mix.
And c, pouring the mixture into a mold with the thickness of 1cm multiplied by 1cm, freezing for 72 hours at the temperature of-20 ℃, then unfreezing for 2 hours at the room temperature, then freezing for 48 hours, and finally drying for 5 hours in a forced air drying oven with the temperature of 50 ℃ to obtain the calcium peroxide compound sustained-release agent.
The preparation method provided by the embodiment can be used for obtaining the calcium peroxide composite sustained-release agent with good form, and the particle size is 1cm3Wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1 mm.
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 ℃ and 80rpm for 5h, and after the polyvinyl alcohol and the sodium alginate are completely dissolved, placing the solution in a refrigerator at 3 ℃ for later use.
And b, weighing 1.0g of calcium peroxide, 0.12g of citric acid, 2.0g of glucose and 0.15g of biochar, adding the materials into the mixed solution of the polyvinyl alcohol and the sodium alginate, and stirring for 10min at the temperature of 4 ℃ to uniformly mix.
And c, pouring the mixture into a mold with the temperature of 1cm multiplied by 1cm, freezing for 60 hours at the temperature of-20 ℃, then unfreezing for 1.5 hours at the room temperature, then unfreezing for 48 hours at the room temperature, unfreezing for 1.5 hours at the room temperature, then unfreezing for 48 hours, and finally drying for 4 hours in a forced air drying oven with the temperature of 50 ℃ to obtain the calcium peroxide composite sustained-release agent.
The preparation method provided by the embodiment can be used for obtaining the calcium peroxide composite sustained-release agent with good form, and the particle size is 1cm3Wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1 mm.
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 the temperature of 75 ℃ for 4h at the rotating speed of 110rpm, and after the polyvinyl alcohol and the sodium alginate are completely dissolved, placing the solution in a refrigerator at the temperature of 4 ℃ for later use.
And b, weighing 1.0g of calcium peroxide, 0.11g of monopotassium phosphate, 1.5g of glucose and 0.12g of biochar, adding the materials into the mixed solution of the polyvinyl alcohol and the sodium alginate, and stirring for 10min at the temperature of 5 ℃ to uniformly mix.
And c, pouring the mixture into a mold with the thickness of 1cm multiplied by 1cm, freezing for 48 hours at the temperature of-20 ℃, then unfreezing for 2 hours at room temperature, then unfreezing for 60 hours at room temperature, unfreezing for 1.5 hours at room temperature, then freezing for 48 hours, and finally drying for 4 hours in a blast drying oven with the temperature of 55 ℃ to obtain the calcium peroxide composite sustained-release agent.
The preparation method provided by the embodiment can be used for obtaining the calcium peroxide composite sustained-release agent with good form, and the particle size is 1cm3Wherein the particle size of the embedded calcium peroxide particles is mainly 0.2-1 mm.
Comparative example 1
The comparative example provides a preparation method of a calcium peroxide composite sustained-release agent, which is completely the same as the example 1 except that 0.5g of calcium peroxide and 0.055g of citric acid are added in the step b.
Comparative example 2
The present comparative example provides a method for preparing a calcium peroxide composite sustained-release formulation, which is completely the same as in example 1 except that citric acid was not added in step b.
Comparative example 3
The present comparative example provides a method for preparing a calcium peroxide composite sustained-release formulation, which is completely the same as in 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 completely the same as that in example 1, except that no biochar is added in the step b.
Comparative example 5
The comparative example provides a preparation method of a calcium peroxide composite sustained-release agent, which is completely 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 an oxygen release performance test.
The test method comprises the following steps: the materials were added to conical flasks containing 100ml of pure water, respectively, to give a calcium peroxide concentration of 0.8g/L in the solution, the pure water had been aerated for 1h under nitrogen atmosphere and had a dissolved oxygen content of less than 0.2mg/L, the mouth of the conical flask was sealed with a rubber stopper, into which a dissolved oxygen analysis probe was inserted, and the dissolved oxygen concentration in the solution was recorded at regular intervals. The pH value of the solution is measured by a pH analysis probe. The results of the dissolved oxygen test are shown in FIGS. 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 and 8.24, respectively.
(2) The calcium peroxide composite sustained-release agents prepared in example 1 and comparative examples 1 to 5 were subjected to a long-term oxygen release performance test. The test 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 sustained-release agent through a peristaltic pump at the flow rate of 1.5PV/d, and the concentration of the dissolved oxygen in the effluent liquid is measured according to certain time intervals. The test results are shown in Table 1.
TABLE 1
| Time | Index (I) | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Day 0 | Dissolved oxygen (mg/L) | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| 1 day | Dissolved oxygen (mg/L) | 7.60 | 7.63 | 7.32 | 7.87 | 7.31 | 7.84 |
| 2 days | Dissolved oxygen (mg/L) | 7.92 | 7.57 | 7.77 | 8.21 | 7.89 | 8.18 |
| 4 days | Dissolved oxygen (mg/L) | 8.56 | 7.33 | 8.10 | 7.82 | 8.39 | 7.87 |
| 6 days | Dissolved oxygen (mg/L) | 7.90 | 7.28 | 8.05 | 8.29 | 7.84 | 8.19 |
| 8 days | Dissolved oxygen (mg/L) | 8.24 | 6.94 | 8.27 | 8.34 | 8.11 | 8.14 |
| 12 days | Dissolved oxygen (mg/L) | 8.11 | 5.76 | 8.55 | 8.10 | 8.33 | 8.01 |
| 18 days | Dissolved oxygen (mg/L) | 7.06 | 5.51 | 7.23 | 6.86 | 7.92 | 7.39 |
| 24 days | Dissolved oxygen (mg/L) | 6.46 | 3.34 | 7.05 | 5.61 | 6.44 | 5.96 |
| 30 days | Dissolved oxygen (mg/L) | 4.34 | 1.51 | 6.32 | 3.85 | 5.60 | 4.60 |
(3) The calcium peroxide composite sustained-release agent prepared in example 1 was subjected to an experiment for enhancing the degradation of pseudomonas putida to a benzene series.
Preparing an inorganic salt culture medium: 1500mg/L disodium hydrogen phosphate, 1g/L monopotassium phosphate, 100mg/L magnesium sulfate, 2000mg/L potassium chloride, 800mg/L ammonium sulfate, 1200mg/L potassium nitrate, 38mg/L calcium chloride, 9mg/L ethylenediaminetetraacetic 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 copper chloride and 0.03mg/L nickel chloride.
The experimental method comprises the following steps: pseudomonas putida with a strain number of 1.8829 is purchased from China general microbiological culture Collection center, a seawater 2216 agar culture medium is selected according to a method suggested by the management center for strain reactivation, then 1ml of microbial inoculum is inoculated into a glass bottle filled with an inorganic salt culture medium, wherein the content of benzene series is 0.5mg/L of benzene, toluene, ethylbenzene and xylene respectively, a certain mass of the calcium peroxide composite sustained-release agent prepared in the example 1 is added into the glass bottle, the initial concentration of calcium peroxide is 0.8g/L, and the concentration of the benzene series in the solution and the growth condition of the microorganisms are monitored by a gas phase mass spectrometer and an ultramicro spectrophotometer after 3 days. The results show that the removal rates of benzene, toluene, ethylbenzene and xylene are respectively improved by 28.1%, 31.3%, 29.1% and 28.5% by adding the calcium peroxide composite sustained-release agent, and the OD600 value of the microorganism is increased from 0.01 to 0.23.
(4) The calcium peroxide composite sustained-release agent prepared in example 1 is subjected to a degradation experiment for enhancing pseudomonas fluorescens to benzene series.
The experimental method comprises the following steps: the pseudomonas fluorescens with the strain number of 1.15059 is purchased from the China general microbiological culture Collection center, LB culture medium is selected for strain revival according to the method suggested by the management center, then 1ml of microbial inoculum is inoculated into a glass bottle filled with inorganic salt culture medium, wherein the content of benzene series is 0.5mg/L respectively, certain mass of the calcium peroxide composite sustained-release agent prepared in the embodiment 1 is added into the glass bottle, the initial concentration of calcium peroxide is 0.8g/L, and the concentration of the benzene series in the solution and the growth condition of the microbes are respectively monitored by a gas phase mass spectrometer and an ultramicro spectrophotometer after 3 days. The results show that the addition of the calcium peroxide composite sustained-release agent prepared in example 1 improves the removal rates of benzene, toluene, ethylbenzene and xylene by 21.1%, 27.5%, 31.8% and 26.6% respectively, and the OD600 value of the microorganism is increased from 0.01 to 0.22.
(5) The calcium peroxide composite sustained release agent prepared in example 1 and comparative examples 3 and 4 is subjected to degradation experiments of benzene series by indigenous microorganisms of intensified polluted underground water.
The experimental method comprises the following steps: collecting underground water of a certain gas station, wherein benzene, toluene, ethylbenzene and xylene all exceed standards, selecting an LB culture medium to amplify indigenous microorganisms in the underground water, performing induced acclimation on the indigenous microorganisms by taking benzene series as a unique carbon source under aerobic conditions, then inoculating 1ml of acclimated microorganism liquid into a glass bottle filled with an inorganic salt culture medium, wherein the content of the benzene series is 0.5mg/L of each of the benzene, the toluene, the ethylbenzene and the xylene, respectively adding certain mass of the calcium peroxide composite sustained-release agents prepared in the example 1 and the comparative examples 3-5 into the glass bottle to enable the initial concentration of calcium peroxide to be 0.8g/L, and monitoring the concentration of the benzene series in the solution and the growth condition of the microorganisms by using a gas phase mass spectrometer and an ultramicro spectrophotometer after 3 days. The results are shown in FIG. 4. The calcium peroxide composite slow-release agent obviously improves the removal efficiency of benzene series, and the repair effect of the embodiment 1 is superior to that of the comparative examples 3, 4 and 5. The addition of the calcium peroxide composite sustained-release agent prepared in example 1 improves the removal rate of benzene, toluene, ethylbenzene and xylene by 22.3%, 21.5%, 26.9% and 16.0% respectively, and the OD600 value of the microorganism is increased from 0.01 to 0.74.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A preparation method of a calcium peroxide composite sustained-release agent is characterized by comprising the following steps:
s1, mixing polyvinyl alcohol, sodium alginate and water to prepare a mixed solution; wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the water is 2-5: 1: 30-50, the preparation condition is that the mixture is stirred for 4-5 hours at the temperature of 60-80 ℃ and the speed of 80-120 rpm;
s2, adding calcium peroxide, glucose, biochar and a pH regulator into the mixed solution, and uniformly stirring to obtain a mixture, wherein the stirring time is 5-10min and the temperature is 2-5 ℃; wherein, the mass ratio of calcium peroxide: glucose: biochar: the pH regulator is 1: 0.5-2.5: 0.1-0.2: 0.1-0.12;
and S3, pouring the mixture into a mold, freezing, thawing, performing freeze-thaw cycles for a plurality of times, taking out, and drying to obtain the product.
2. The preparation method of the calcium peroxide composite sustained-release agent according to claim 1, wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the water in the mixed solution is 3: 1: 40, stirring at the speed of 100rpm for 4-5h at the temperature of 70 ℃.
3. The preparation method of the calcium peroxide composite sustained-release agent according to claim 1, which is characterized in that the weight ratio of calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: sodium alginate is 1: 0.5-2.5: 0.1-0.2: 0.1-0.12: 7.5-8.5: 2.5-2.8.
4. The preparation method of the calcium peroxide composite sustained-release agent according to claim 3, wherein the weight ratio of the calcium peroxide: glucose: biochar: pH regulator: polyvinyl alcohol: sodium alginate is 1: 2.5: 0.10: 0.11: 7.5: 2.5.
5. the preparation method 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 chip; 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.
6. The method for preparing the calcium peroxide composite sustained-release agent according to claim 1, wherein the pH regulator comprises citric acid and/or potassium dihydrogen phosphate.
7. The preparation method of the calcium peroxide composite sustained-release agent according to claim 1, wherein in the process of freeze-thaw 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.
8. The method for preparing the calcium peroxide composite sustained-release agent according to claim 1, wherein the number of freeze-thaw cycles is 2 to 3.
9. The calcium peroxide composite sustained-release agent prepared by the preparation method of the calcium peroxide composite sustained-release agent according to any one of claims 1 to 8, wherein the particle size of the calcium peroxide composite sustained-release agent is 1cm3Wherein the particle diameter of the embedded calcium peroxide particles is 0.2-1 mm.
10. The application of the calcium peroxide composite slow-release agent prepared by the preparation method of the calcium peroxide composite slow-release agent according to any one of claims 1 to 8 in groundwater pollution remediation.
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