CN108249550A - A kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation - Google Patents
A kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation Download PDFInfo
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- CN108249550A CN108249550A CN201711459139.2A CN201711459139A CN108249550A CN 108249550 A CN108249550 A CN 108249550A CN 201711459139 A CN201711459139 A CN 201711459139A CN 108249550 A CN108249550 A CN 108249550A
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- repair materials
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- 239000000463 material Substances 0.000 title claims abstract description 89
- 230000008439 repair process Effects 0.000 title claims abstract description 50
- 239000003673 groundwater Substances 0.000 title claims abstract description 31
- 238000005067 remediation Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000011109 contamination Methods 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000001301 oxygen Substances 0.000 claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 60
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011787 zinc oxide Substances 0.000 claims abstract description 28
- 239000003610 charcoal Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000006174 pH buffer Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 35
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 claims description 30
- 239000004343 Calcium peroxide Substances 0.000 claims description 15
- 235000019402 calcium peroxide Nutrition 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002028 Biomass Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000008172 hydrogenated vegetable oil Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 3
- 244000105624 Arachis hypogaea Species 0.000 claims description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 3
- 235000018262 Arachis monticola Nutrition 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 240000000560 Citrus x paradisi Species 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000020232 peanut Nutrition 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229940080314 sodium bentonite Drugs 0.000 claims description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000010718 Oxidation Activity Effects 0.000 abstract description 2
- 235000013399 edible fruits Nutrition 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 2
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000009973 maize Nutrition 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000005445 natural material Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 235000013904 zinc acetate Nutrition 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation method of the multiple-effect repair materials for organic contamination groundwater remediation, which is formed by ecological restoration material, oxygen-release material, additive, charcoal, modified superfine zinc oxide, pH buffer through certain process combining.Multiple-effect repair materials property prepared by the present invention is stablized, and surface area is big, has preferable absorption and catalytic oxidation activity；The oxygen release duration is long, and release efficiency is high, can ensure the sustainability of the biological prosthetic effect of underground water；Realize absorption, chemical oxidation, catalysis oxidation and the collaboration of biological prosthetic multiple-effect fruit, it is single to overcome existing groundwater remediation chemicals treatment function, treatment effect control difference and generation secondary pollution problems are a kind of multi-functional groundwater remediation medicaments for meeting green suslainability and repairing theory.
Description
Technical field
The invention belongs to groundwater remediation technical fields, and in particular to a kind of multiple-effect for organic contamination groundwater remediation
The preparation method of repair materials.
Background technology
Underground water is the important component of freshwater resources, and very important effect is played in human social development.But
Be industrial waste is arbitrarily stacked, a large amount of uses of agriculture chemical, oil exploitation, transport, handling, storage, processing and using process
In leakage, all cause serious water and soil pollution, grave danger caused to public health.It is rapid with China's industrial or agricultural
Development, more and more organic chemical pollutants enter natural environment, and are seeped into soil environment as rainwash enters, Jin Erjin
Enter in groundwater environment, the quality of groundwater for making China is worsening, and underground water pollution area constantly expands, show from point to
Face develops, aggravates from part to the trend of regional diffusion, pollution level, and harm is on the rise.Organic Contamination of Groundwater it is main
Leakage of the source for oil and oil product.Petroleum hydrocarbon（PHCs）The complex being made of hundreds of compounds, complicated component,
And it with bioaccumulation, can for a long time retain in the environment.Once underground water, by petroleum hydrocarbon contaminated, general decades are all difficult to
Restore water quality in its natural state.
The restorative procedure of organic contamination underground water generally comprises showering and in-situ remediation method.Ex-situ remediation method master
Refer to carry out the conventional process mode of dystopy processing after polluted underground water is extracted out.This method is larger to underground water disturbance,
The diffusion of pollutant is easily formed, and is relatively inaccessible to repair target.It is organic that efficient based technique for in-situ remediation is increasingly becoming underground water
The new direction that pollution amelioration is administered.For in-situ immobilization, corresponding repair materials are added（Medicament）, such as it is used for direct oxidation
The oxidant of organic pollution, the oxygen release agent for enhanced biological processing are the key that then to carry out in-situ immobilization.It is applied at present
The repair materials function of in-situ immobilization is single, and the activity of reparation is urgently promoted with efficiency, and expensive, usage amount is greatly, instead
It should relatively slow, easily formation secondary pollution etc..Research about repair materials become the research of domestic and international groundwater remediation hot spot and
Difficult point.
The invention discloses a kind of preparation method of the multiple-effect repair materials for organic contamination groundwater remediation, to make
It is standby it is a kind of collect aoxidize, absorption, oxygen release and the multiple repair function such as biological prosthetic composite repairing material, oxygen release ingredient therein can
A kind of long-term, efficient solid oxygen source is provided for polluted underground water reparation, promotes underground water biological prosthetic；Utilizing simultaneously has
The natural cryptomelane material of nano aperture good absorption and oxidability to organic pollution；Modified nano zinc oxide have pair
The catalytic capability of organic pollution oxidation reaction can further strengthen the processing procedure of organic pollution.
Invention content
The purpose of the present invention is to provide a kind of preparation sides of the multiple-effect repair materials for organic contamination groundwater remediation
Method can realize the sustainability reparation of underground water pollution using the multiple-effect repair materials prepared, improve environmental improvement efficiency.
To achieve these goals, technical scheme is as follows：It is a kind of to be used for the more of organic contamination groundwater remediation
Imitate the preparation method of repair materials, it is characterised in that this method includes the following steps：
A, it is screened to obtain grain size 80-150 mesh after natural cryptomelane is put into ball mill ball milling, have pore passage structure, aperture is
The natural cryptomelane particle of 0.46-50.00 nm；
B, prepared by charcoal：It is put into KOH solution and impregnates after biomass is cleaned, after taking-up cleaning air-dries, be put into baking oven
Drying, by the biomass medium temperature anaerobic pyrolysis after drying, obtains charcoal, and charcoal crushing 50-80 mesh is sealed up for safekeeping for use；
C, prepared by modified superfine zinc oxide：
1. zinc acetate and sodium acetate are placed in ball milling in ball mill, it is transferred in crucible after clear viscous shape is presented in powder；
2. crucible is moved in micro-wave oven and limits oxygen heating, natural cooling is to get superfine zinc oxide particle in inert gas；
3. adding in copper source in superfine zinc oxide particle, after being grinded with a mortar, it is placed again into micro-wave oven and limits oxygen heating, in inertia
Natural cooling in gas；
4. then adding partially hydrogenated vegetable oil and isobutanol, stir evenly, and be washed with deionized, then vacuum is dried
Dry, ball milling is to get modified superfine zinc oxide particle；
D, oxygen-release material is first taken to be adsorbed in biological carbon surface, then with natural cryptomelane particle, additive, modified superfine zinc oxide
Particle, pH buffer mixing are compressed into tablet form mixture；
E, by flaky mixture under inert atmosphere protection, 4-6 h is calcined at 150-200 DEG C, are cooled down under inert gas shielding,
Then it crushes to get multiple-effect composite repairing material.
Preferably, in step D, the weight of the multiple-effect composite repairing material each component of the organic contamination groundwater remediation
Measuring part is：10~35 parts of natural cryptomelane particle, 20~45 parts of oxygen-release material, 5~18 parts of additive, 10~25 parts of charcoal,
Modified 5~20 parts of superfine zinc oxide particle, 15~30 parts of pH buffer.
Further, the natural cryptomelane in step A uses [MnO6] the octahedron double-strand corner-sharing top oxygen shape that side forms altogether
Into the natural cryptomelane of 2 × 2 types, after crushing and screening after, obtain the natural cryptomelane of nano aperture.
Further, the oxygen-release material includes one or both of calper calcium peroxide, peromag both base-materials
Arbitrary combination.
Further, the additive is one or more of arbitrary in natural sodium bentonite, zeolite or calcium carbonate
Combination.
Further, the biomass is agricultural crop straw, the one or more of of peanut shell, pomelo peel, cocoanut shell appoint
Meaning combination.
Further, the pH buffer be potassium dihydrogen phosphate, potassium hydrogen phosphate, two kinds of diammonium hydrogen phosphate and ammonium sulfate
Or several arbitrary combination.
A kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation provided by the invention, is prepared into
The multiple-effect repair materials arrived, the groundwater remediation available for organic pollution, it can also be used to which the surface water body of organic pollution is repaiied
It is multiple.
The present invention creatively proposes a kind of " absorption+chemical oxidation+catalysis oxygen for organic contamination groundwater remediation
The preparation method of change+biological prosthetic " multiple-effect composite repairing material.The repair materials are by ecological restoration material, oxygen-release material, addition
Agent, charcoal, modified superfine zinc oxide, pH buffer are combined.Ecological restoration material natural cryptomelane is because of its special crystalline substance
Body structure and chemical feature and show good environment attribute, such as surface reconditioning, Hole bottom cavity blast, nano effect, can adsorb
And aoxidize organic pollution；Oxygen-release material is capable of providing solid oxygen source, promotes underground water biological prosthetic；Additive, it is such as natural
Sodium bentonite has absorption property, and is the layer structure that natural octahedral sheet is formed, and is one good between layers
Chemical reaction place, and it can slow down contact of the oxygen-release material with water after water swelling, extend the oxygen release time；Biology
Charcoal has absorption property, and plays peptizaiton, inhibits powder reuniting；Modified ultra micro oxidisability, which can be catalyzed, accelerates organic matter
Degradation；PH buffer can inhibit the alkaline environment generated due to oxygen release functional material, buffered pH value, maintain the suitable ring of microorganism
Border, while also nutrition is provided for microorganism.Multiple-effect repair materials property prepared by the present invention is stablized, and surface area is big, has preferable
Absorption and catalytic oxidation activity；The oxygen release duration is long, and release efficiency is high, and can ensure the biological prosthetic effect of underground water can
Duration；Absorption, chemical oxidation, catalysis oxidation and the collaboration of biological prosthetic multiple-effect fruit are realized, existing underground water is overcome and repaiies
Multiple chemicals treatment function is single, treatment effect control difference and generates secondary pollution problems, and it is sustainable to be that one kind meets green
Property repair theory multi-functional groundwater remediation medicament.
Compared with prior art, the present invention it has the following advantages:
（1）Existing repair materials function is single, and the activity of reparation is urgently promoted with efficiency.The present invention is by the way that a variety of differences are repaiied
The Combinatorial Optimization of multiple functional material is, it can be achieved that absorption to organic contamination underground water（Enrichment）, catalysis/chemical oxidation, oxygen supply with
Biological prosthetic multiple repair function strengthens repair process, promotes repairing effect.
（2）In multiple-effect repair materials there is the cryptomelane ingredient of nano aperture, belong to natural material, cost is more cheap, system
It is standby easy, have the functions such as thermal stability, absorption property, nano effect and catalysis oxidation, there is good reparation to underground water
Effect.
（3）Oxygen-release material in multiple-effect repair materials, by by calper calcium peroxide or peromag and additive and charcoal
It is compound, the problem of solving current oxygen release agent and be difficult to control oxygen release rate, cause effective oxygen waste in oxygen-releasing compound；And pH
The addition of buffer can improve the underground water pH caused by calper calcium peroxide oxygen release and increase.The composite material is promoting oxygen release efficiency
Simultaneous buffering pH changes, and is capable of the biological treatment process of efficient hardening underground water.
（4）The preparation method of multiple-effect repair materials provided by the invention, required abundant raw material and cheap, material therefor
Mostly natural material, the multiple-effect repair materials being prepared, which introduce soil and groundwater environment, will not cause potential secondary dirt
Dye meets the sustainable reparation theory of green.
Description of the drawings
Fig. 1 is the preparation technology figure of multiple-effect repair materials in the present invention.
Fig. 2 is the multiple-effect repair materials-water solution system DO variation diagrams.
Fig. 3 is the multiple-effect repair materials-water solution system pH variation diagrams.
Specific embodiment
The following examples are the further explanations to the present invention rather than limit the scope of the invention.
A kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation, it is characterised in that multiple-effect reparation
The preparation method of material, includes the following steps：
A, it is screened to obtain grain size 80-150 mesh after natural cryptomelane is put into 8~12 h of ball mill ball milling, have pore passage structure,
Aperture is the natural cryptomelane particle of 0.46-50.00 nm；
B, prepared by charcoal：It is put into after biomass is cleaned in 3.5-5.5 mgg-1 KOH solution and impregnates 30 h, taken out
After cleaning air-dries, it is put into 50-60 DEG C of baking oven and dries overnight, the biomass medium temperature anaerobic pyrolysis 3-8 h after drying are obtained
Charcoal seals charcoal crushing 50-80 mesh for use up for safekeeping；
C, prepared by modified superfine zinc oxide：
1. zinc acetate and sodium acetate are placed in ball mill, 15 min of ball milling, earthenware is transferred to after clear viscous shape is presented in powder
In crucible（More preferably, the mol of zinc acetate and sodium acetate ratios are 1:1~1.4）；
20 min are heated 2. crucible is moved in micro-wave oven and limits oxygen, natural cooling is to get superfine zinc oxide in inert gas
Grain；
3. copper source is added in superfine zinc oxide particle（Mass ratio 1：0.08~0.2）, with 10 min of mortar grinder, it is placed again into
It limits oxygen in micro-wave oven to heat in 10 min, natural cooling in inert gas；
4. and then add a certain amount of partially hydrogenated vegetable oil and isobutanol（More preferably, partially hydrogenated vegetable oil and isobutanol
Volume ratio 3；2）, it stirs evenly at a certain temperature, and be washed with deionized, vacuum drying, ball milling at 80-100 DEG C,
Up to modified superfine zinc oxide particle.
D, oxygen-release material is first taken to be adsorbed in biological carbon surface, is then aoxidized with ecological restoration material, additive, modified ultra micro
Zinc particle, pH buffer mixing are compressed into tablet form；
E, by flaky mixture under inert atmosphere protection, 4-6 h is calcined at 150-200 DEG C, are cooled down under inert gas shielding,
Then it crushes to get multiple-effect repair materials.
In terms of 100 parts of total number, the parts by weight of each component are the multiple-effect repair materials：Natural cryptomelane particle 10~35
Part, 20~45 parts of oxygen-release material, 5~18 parts of additive, 10~25 parts of charcoal, modified 5~20 parts of superfine zinc oxide, pH bufferings
15~30 parts of agent.
Further, the natural cryptomelane particle is [MnO6] the double-strand corner-sharing top oxygen of the octahedra composition of side altogether formed
The natural cryptomelane of 2 × 2 types, after crushing and screening after, obtain the natural cryptomelane material of nano aperture.The oxygen-release material
Include the arbitrary combination of one or both of calper calcium peroxide, peromag both base-materials.The additive is natural sodium
One or more of arbitrary combination in base bentonite, zeolite or calcium carbonate.The charcoal is anoxic heat after biomass drying
Solution obtains, and the biomass is agricultural crop straw, one or more of arbitrary combinations of peanut shell, pomelo peel, cocoanut shell.It is described
Modified oxidized property catalyst be Copper-cladding Aluminum Bar superfine zinc oxide particle.The pH buffer for potassium dihydrogen phosphate, potassium hydrogen phosphate,
The arbitrary combination of two or more of diammonium hydrogen phosphate and ammonium sulfate.
In embodiment, the buying such as calper calcium peroxide, potassium dihydrogen phosphate, ammonium sulfate, zinc acetate, sodium acetate and copper chloride is in upper
Extra large Sinopharm Chemical Reagent Co., Ltd.；Natural cryptomelane comes from Guangxi county manganese ore；Additive derives from Sichuan province；
Maize straw comes from Qingpu Shanghai area.
Ecological restoration material, charcoal, modified ultra micro Nano-Zinc particle etc. are prepared by the following method.
It is prepared by ecological restoration material：2000 g of natural cryptomelane is taken, it is screened to obtain grain after being put into 12 h of ball mill ball milling
The particle of diameter 80-150 mesh is washed particle and is dried overnight at 80 DEG C, and natural cooling is to get nanometer natural cryptomelane
Grain.BET characterizations are carried out to the natural cryptomelane particle after ball milling, measure its specific surface area as 20.23--116.45 m2/g,
Grain aperture is 0.56-46.32 nm.
It is prepared by charcoal：Maize straw after acquisition is cleaned 5 times repeatedly, and is rinsed with deionized water, places into 3.5
mg·g-130 h are impregnated in KOH solution, after taking-up cleaning air-dries, is put into 50 ~ 60 DEG C of baking ovens and dries overnight, will dry
Biomass medium temperature anaerobic pyrolysis 3-8 h afterwards, obtain charcoal, and charcoal crushing 50-80 mesh is sealed up for safekeeping for use；
Modified superfine zinc oxide particle：By zinc acetate（0.1mol）With sodium acetate（0.12 mol）It is placed in ball mill, ball milling 15
Min is transferred to after clear viscous shape is presented in powder in crucible；Crucible is moved in micro-wave oven and limits oxygen 20 min of heating, lazy
Natural cooling is to get superfine zinc oxide particle in property gas；3g copper chlorides are added in superfine zinc oxide particle, use mortar
10 min are ground, is placed again into micro-wave oven and limits in 10 min of oxygen heating, natural cooling in inert gas；Then 50 are added
The partially hydrogenated vegetable oil and isobutanol of ml（The volume ratio 3 of partially hydrogenated vegetable oil and isobutanol；2）, stirred at 60-80 DEG C
It mixes uniformly, and is washed with deionized, vacuum drying, ball milling are to get modified superfine zinc oxide particle at 80-100 DEG C.
Embodiment 1
According to 20 parts of natural cryptomelane particle, 35 parts of oxygen-release material, 8 parts of additive, 15 parts of charcoal, modified superfine zinc oxide 5
Part, the preparation ratio preparation multiple-effect repair materials of 17 parts of pH buffer.
The multiple-effect composite repairing material and calper calcium peroxide medicament are weighed respectively, and the dosage for ensureing calper calcium peroxide ingredient is 1
g/L.Two kinds of materials are respectively placed in 50 mL anaerobic waters, and in confined conditions, the dissolved oxygen DO concentration that timing measures solution becomes
Change, the results are shown in Figure 2.At oxygen release initial stage, calper calcium peroxide and water fast reaction, the dissolved oxygen concentration after 10 h in water reach
Nearly 6 mg/L, later the dissolved oxygen in water be basically stable at 6 mg/L or so.And the multiple-effect repair materials that prepare of the present invention its release
The oxygen release rate at oxygen initial stage is substantially less than pure calper calcium peroxide, and oxygen in water is about 3.5 mg/L after 10 h are reacted with water；Reaction
After 36 h, oxygen in water concentration is about 6 mg/L.The oxygen release curve of multiple-effect repair materials is more gentle compared with calper calcium peroxide, explanation
Multiple-effect composite repairing material prepared by the present invention can regulate and control the oxygen release process of oxygen release agent, reduce the waste of effective oxygen, have more
Stable oxygen release effect.
Embodiment 2
According to 20 parts of natural cryptomelane particle, 35 parts of oxygen-release material, 8 parts of additive, 15 parts of charcoal, modified superfine zinc oxide 5
Part, the preparation ratio preparation multiple-effect repair materials of 17 parts of pH buffer.The multiple-effect repair materials and calper calcium peroxide medicament are weighed, are protected
The dosage for demonstrate,proving calper calcium peroxide ingredient is 1 g/L.Two kinds of materials are respectively placed in 50 mL anaerobic waters, in confined conditions, timing
The pH variations of solution are measured, the results are shown in Figure 3.Solution of the calper calcium peroxide as oxygen release agent is added, pH is rapid in 10 min
Raising, reaches 11.0, and in 5 h later, pH reaches stable, and about 11.2.And after adding the multiple-effect repair materials of the present invention, it is molten
Liquid pH after 1 h rises to 8.5, then basicly stable later, and about 8.8.Multiple-effect composite repairing material has buffered calper calcium peroxide and has caused
PH variation, reflect the multiple-effect composite repairing material preferably pH abilities of regulation and control.
Embodiment 3
According to 20 parts of natural cryptomelane particle, 35 parts of oxygen-release material, 8 parts of additive, 15 parts of charcoal, modified superfine zinc oxide 5
Part, the preparation ratio preparation multiple-effect repair materials of 17 parts of pH buffer.Multiple-effect repair materials made above are placed in 100 mg/
In L phenol anaerobic solution, pharmaceutical quantities are 5 g/L.After reacting 24 h, phenol concentration and TOC in solution are measured.The results show that
The removal efficiency of phenol reaches 95.3%, TOC removal rates up to 92.1% after 24 hours.
According to 22 parts of natural cryptomelane particle, 38 parts of oxygen-release material, 5 parts of additive, 10 parts of charcoal, modified ultra micro oxidation
The preparation ratio preparation multiple-effect repair materials of 6 parts of zinc, 19 parts of pH buffer.Multiple-effect repair materials made above are placed in 100
In mg/L phenol anaerobic solution, pharmaceutical quantities are 5 g/L.After reacting 24 h, phenol concentration and TOC in solution are measured.As a result it shows
Show, the removal efficiency of phenol reaches 100%, TOC removal rates up to 95.7% after 24 hours.
Although present disclosure is discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (8)
1. the preparation method of a kind of multiple-effect repair materials for organic contamination groundwater remediation, it is characterised in that this method includes
Following steps：
A, it is screened to obtain grain size 80-150 mesh after natural cryptomelane is put into ball mill ball milling, have pore passage structure, aperture is
The natural cryptomelane particle of 0.46-50.00 nm；
B, prepared by charcoal：It is put into KOH solution and impregnates after biomass is cleaned, after taking-up cleaning air-dries, be put into baking oven
Drying, by the biomass medium temperature anaerobic pyrolysis after drying, obtains charcoal, and charcoal crushing 50-80 mesh is sealed up for safekeeping for use；
C, prepared by modified superfine zinc oxide：
1. zinc acetate and sodium acetate are placed in ball milling in ball mill, it is transferred in crucible after clear viscous shape is presented in powder；
2. crucible is moved in micro-wave oven and limits oxygen heating, natural cooling is to get superfine zinc oxide particle in inert gas；
3. adding in copper source in superfine zinc oxide particle, after being grinded with a mortar, it is placed again into micro-wave oven and limits oxygen heating, in inertia
Natural cooling in gas；
4. then adding partially hydrogenated vegetable oil and isobutanol, stir evenly, and be washed with deionized, then vacuum is dried
Dry, ball milling is to get modified superfine zinc oxide particle；
D, oxygen-release material is first taken to be adsorbed in biological carbon surface, then with natural cryptomelane particle, additive, modified superfine zinc oxide
Particle, pH buffer mixing are compressed into tablet form mixture；
E, by flaky mixture under inert atmosphere protection, 4-6 h is calcined at 150-200 DEG C, are cooled down under inert gas shielding,
Then it crushes to get multiple-effect composite repairing material.
2. a kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation as described in claim 1,
It is characterized in that, the natural cryptomelane in step A uses [MnO6] octahedron double-strand corner-sharing top oxygen 2 × 2 types of formation that side forms altogether
Natural cryptomelane, after crushing and screening after, obtain the natural cryptomelane of nano aperture.
3. a kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation as described in claim 1,
It is characterized in that, in step D, the parts by weight of the multiple-effect composite repairing material each component of the organic contamination groundwater remediation
For：10~35 parts of natural cryptomelane particle, 5~18 parts of additive, 10~25 parts of charcoal, is modified 20~45 parts of oxygen-release material
5~20 parts of superfine zinc oxide particle, 15~30 parts of pH buffer.
4. a kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation as described in claim 1,
Be characterized in that in step B, the biomass is agricultural crop straw, peanut shell, pomelo peel, cocoanut shell it is one or more of arbitrary
Combination.
5. a kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation as described in claim 1,
It is characterized in that the oxygen-release material includes arbitrary group of one or both of calper calcium peroxide, peromag both base-materials
It closes.
6. a kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation as described in claim 1,
It is characterized in that, the additive is arbitrary combinations one or more of in natural sodium bentonite, zeolite or calcium carbonate.
7. a kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation as described in claim 1,
It is two or more of potassium dihydrogen phosphate, potassium hydrogen phosphate, diammonium hydrogen phosphate and ammonium sulfate to be characterized in that the pH buffer
Arbitrary combination.
8. a kind of preparation method of multiple-effect repair materials for organic contamination groundwater remediation as described in claim 1,
The multiple-effect composite repairing material being prepared is characterized in that, for the groundwater remediation of organic pollution or for organic matter dirt
The surface water body reparation of dye.
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