CN114314798B - Method for removing organic pollutants by activating persulfate through diatomite composite loaded with iron and manganese - Google Patents
Method for removing organic pollutants by activating persulfate through diatomite composite loaded with iron and manganese Download PDFInfo
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- CN114314798B CN114314798B CN202111665617.1A CN202111665617A CN114314798B CN 114314798 B CN114314798 B CN 114314798B CN 202111665617 A CN202111665617 A CN 202111665617A CN 114314798 B CN114314798 B CN 114314798B
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- persulfate
- manganese
- diatomite
- iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 21
- 239000011572 manganese Substances 0.000 title claims abstract description 21
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 19
- 230000003213 activating effect Effects 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002689 soil Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 16
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- JDLKFOPOAOFWQN-VIFPVBQESA-N Allicin Natural products C=CCS[S@](=O)CC=C JDLKFOPOAOFWQN-VIFPVBQESA-N 0.000 claims description 5
- JDLKFOPOAOFWQN-UHFFFAOYSA-N allicin Chemical compound C=CCSS(=O)CC=C JDLKFOPOAOFWQN-UHFFFAOYSA-N 0.000 claims description 5
- 235000010081 allicin Nutrition 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005909 Kieselgur Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 3
- 150000004820 halides Chemical class 0.000 claims 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 19
- 230000004913 activation Effects 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 8
- 235000018417 cysteine Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000007725 thermal activation Methods 0.000 description 2
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- PTEOIAOTEKGIFV-UHFFFAOYSA-N [Fe].[K].[K].[K] Chemical compound [Fe].[K].[K].[K] PTEOIAOTEKGIFV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000935 antidepressant agent Substances 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 229940074360 caffeic acid Drugs 0.000 description 1
- 235000004883 caffeic acid Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 1
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 description 1
- 235000007746 carvacrol Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for removing organic pollutants by activating persulfate through a diatomite composite material loaded with iron and manganese, which comprises the following steps of: (S1) modifying pretreated diatomite by using a mercaptosilane coupling agent, soaking the modified diatomite in a mixed solution of ferrous salt and manganese salt, adding an alkaline solution, stirring to obtain slurry, drying the slurry, washing, drying again, and grinding to obtain an iron and manganese loaded diatomite composite material; and (S2) adding the persulfate aqueous solution and the composite material obtained in the step (S1) into the water body or soil to be repaired, fully mixing, and degrading and removing the organic pollutants in the object to be repaired. The composite material prepared by the invention can effectively activate persulfate and quickly degrade refractory organic matters in a system to be repaired. The method is green, safe, environment-friendly and low in cost, does not need to additionally implement measures such as heating, light irradiation and the like, and saves energy and related equipment.
Description
Technical Field
The invention relates to the field of environmental remediation, in particular to a method for removing organic pollutants by activating persulfate through a diatomite composite loaded with iron and manganese.
Background
In recent years, the problem of water and soil environmental pollution in China is gradually outstanding, and people pay more attention to the pollution. According to the report, shallow groundwater in most cities in China is polluted by organic pollutants in different degrees, about hundreds of thousands of fields exist when industrial plots are shut down and moved, most soil and groundwater have organic pollution, and meanwhile, wastewater discharged by some chemical enterprises contains a certain amount of organic pollutants. The economical and rapid removal of organic contamination from these contaminations is a major and difficult point of remediation.
In recent years, an oxidation technology based on activated persulfate has the advantages of strong oxidation capacity, basically no secondary pollution, easiness in control, low cost and the like, and becomes a hotspot of organic pollution removal research and application, the mechanism of the oxidation technology is that persulfate generates sulfate radicals (formula 1) with strong oxidation property under the activation action of an activator, so that organic pollutants are oxidized and degraded into small molecular substances and finally mineralized into carbon dioxide and water.
S 2 O 8 2- + activator → SO 4 ·- +(SO 4 ·- or SO 4 2- ) (1)
The activators are associated with the cost of the technical application and the presence of secondary pollution to the environment. Therefore, the search for effective activators is an important element for the development of the persulfate advanced oxidation technology. At present, the main activation modes of persulfate mainly comprise thermal activation, light radiation activation, alkali activation and transition metal activation. The thermal activation and the light irradiation activation need extra heating and irradiation equipment, the operation cost is high, the energy consumption is high, the method is only suitable for small-scale soil and water body repair, and the large-area popularization and application cannot be realized at present; the pH needs to be increased to more than 12 for alkali activation, so that the alkali pollution of the soil or water body is repaired; the activation of the transition metal is most commonly performed by ferrous ions, which have high activation efficiency but easily generate a large amount of iron mud, thereby affecting the reutilization of soil or water. And ferrous iron is easily oxidized into ferric iron in the activation process, and then the activity is lost. The biggest defects of the above activation modes are high energy consumption or secondary pollution to the environment caused by the added activating agent. For removing trace organic matters, important is not only that the non-activation effect generates free radicals, but also that the secondary pollution is not generated when removing light-polluted organic matters, and the original state of water or soil is recovered to the greatest extent. Therefore, it is necessary to develop an activating agent for activating persulfate, which has the advantages of low cost, little influence on water or soil environment, easy operation and convenient use, and is used for removing trace organic pollutants.
In the prior art, cysteine and ferrous salt are used together to prolong the activity of the ferric salt.
CN110422922A discloses a method for removing organic pollution by cysteine reinforced iron/persulfate, wherein a mixture of iron ions and cysteine is added into a system to be repaired, and persulfate is oxidized and degraded by the action of the iron ions and the cysteine. However, this method is not economical and requires the consumption of large amounts of cysteine for large scale remediation of water or soil.
CN112023949 discloses a method for degrading printing and dyeing wastewater in monopersulfate, which requires the addition of metal molybdenum salt and metal cobalt salt, even if the lower concentration of cobalt ions is harmful to human bodies and is not easy to discharge in soil, a new pollution source is introduced.
CN112279355A discloses a method for removing antidepressant drugs in water by activating persulfate, which is to add cysteine, ferrous salt and persulfate to oxidize and degrade drug components in water.
The method utilizes the reducibility of cysteine, can improve the utilization rate of ferric salt, and quickly degrades organic substances in a system to be repaired. However, the treatment system has the disadvantages that although the organic pollutant content in the system can be rapidly reduced in a short time, the treatment system has weak effect on the sustained efficacy, often loses activity within a few days, and when new pollution is generated, the treatment system also needs to be added with a medicament again, so that the treatment system is neither economical nor environment-friendly.
In the prior art, carrier-supported iron or an oxide thereof is used as an activating substance, and CN111111741A discloses a porous boron nitride-supported iron nano material, which is prepared by calcining a precursor of cyanuric acid and boric acid at 1400-1600 ℃ in an ammonia atmosphere to obtain porous boron nitride as a carrier, stirring the porous boron nitride with tripotassium iron salt at 80-90 ℃, drying, grinding and calcining at 600-800 ℃. The material has high catalytic activity on persulfate, and the magnetic material can be conveniently separated. On the one hand, the method of the patent needs a plurality of times of calcination, particularly needs calcination at the temperature of more than 1400 ℃, and has serious energy consumption; the material obtained in this patent can be recovered magnetically, but is difficult to recycle and is not economical.
Therefore, the method can not only clear the refractory organic matters of the system to be repaired by using the persulfate-based oxidation technology with high efficiency, but also maintain the efficacy for a long time, and is more convenient for the technical popularization and large-scale application of the persulfate advanced oxidant to practice.
Disclosure of Invention
In view of the above, the implementation of the present invention provides a method for removing organic pollutants in water or soil by using an iron and manganese loaded diatomite composite material to activate persulfate, wherein the method has characteristics of low cost, convenient use and easy operation, and has strong feasibility for repairing organic polluted water or soil. According to the invention, cheap and easily available diatomite is used as a carrier, the modification of the mercaptosilane coupling agent is carried out, the loaded metallic iron is used as an activating substance, the loaded manganese is used as an auxiliary activating substance, and the obtained diatomite loaded with bimetallic iron/manganese is used as a component for activating persulfate, so that persulfate can be efficiently activated, the purpose of long-acting activation is achieved, and the cost is reduced.
The invention provides a method for removing organic pollutants by activating persulfate through a diatomite composite material loaded with iron and manganese, which comprises the following steps of:
(S1) modifying the pretreated diatomite by a mercaptosilane coupling agent, soaking the modified diatomite in a mixed solution of ferrous salt and manganese salt, adding an alkaline solution, stirring to obtain a slurry, drying and washing the slurry, drying again, and grinding to obtain the diatomite composite material loaded with iron and manganese;
and (S2) adding the persulfate aqueous solution and the composite material obtained in the step (S1) into the water body or soil to be repaired, fully mixing, and degrading and removing the organic pollutants in the object to be repaired.
The pretreatment of diatomaceous earth is well known in the art, i.e., diatomaceous earth is soaked in acid, washed with deionized water, and dried, and the acid is not particularly limited, and hydrochloric acid or sulfuric acid is generally used.
Further, the mercaptosilane coupling agent is selected from at least one of KH-580 and KH-590.
Further, the mass ratio of the diatomite to the mercaptosilane coupling agent is 100:4-7. The method for modifying the diatomite by the mercaptosilane coupling agent comprises the following steps: soaking diatomite in an alcoholic solution of a mercaptosilane coupling agent under the reflux condition of 50-60 ℃, taking out, washing with water, and drying to obtain modified diatomite; preferably, the alcoholic solution of mercaptosilane coupling agent has a concentration of 2 to 5% by weight.
The iron and manganese salts are not particularly limited, such as nitrates, halogen salts, and specifically include, but are not limited to, ferrous sulfate, ferrous chloride, ferrous nitrate, manganese chloride. Further, the molar ratio of the ferric salt to the manganese salt is 5-8:1, and the molarity of the ferric salt is 0.2-0.3mol/L.
Preferably, the mass ratio of the modified diatomite to the mixed solution of ferrous salt and manganese salt is 1:3-5.
Further, the alkaline solution is at least one of ammonia water, sodium hydroxide and potassium hydroxide. When the ammonia water is used, the concentration of the ammonia water is 20-30wt%, and when the ammonia water is sodium hydroxide or potassium hydroxide, the mass concentration is 3-5wt%. The addition amount of the alkaline solution is to fully precipitate the ferric salt and the manganese salt.
The washing is with 60-80% ethanol water solution, and the grinding is to 100-200 μm particle size.
Further, the persulfate is selected from the group consisting of sodium peroxodisulfate, potassium peroxodisulfate, and/or ammonium peroxodisulfate, which is selected from the group consisting of sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate.
The system to be repaired is a body of water or soil, such as groundwater, surface water, wastewater, agricultural soil, industrial contaminated soil, and the like.
Further, in the step (S2), the dosage of the diatomite composite material loaded with iron and manganese is determined according to the system to be repaired and the pollution source therein, and a person skilled in the art can flexibly select the diatomite composite material according to actual needs. For example, for a water body to be treated, 10-30g of diatomite composite material loaded with iron and manganese can be added into each liter of water; the addition amount of the persulfate is 5 to 15 times, preferably 7 to 10 times, the molar amount of the hardly degradable organic pollutant in the object to be treated.
Preferably, a reducing agent can be further added in the step (S2), wherein the reducing agent is at least one of vitamin C, allicin, tea polyphenol, gallic acid, carvacrol, caffeic acid and cysteine, and the adding amount of the reducing agent is 10-20% of the molar amount of the persulfate; the reducing agent is preferably a compound of vitamin C and allicin according to the mass ratio of 1-2:1-2.
The beneficial effects after the implementation of the invention are as follows:
1. compared with the prior art, the invention provides the composite material which utilizes cheap diatomite to load iron and manganese and is used for removing organic matters in water or soil by matching with persulfate. The composite material prepared by the invention can effectively activate persulfate and quickly degrade refractory organic matters in a system to be repaired.
2. According to the invention, the kieselguhr is modified by the mercaptosilane coupling agent, so that the activation capability of the composite material is improved, probably because the loading capability and stability of the kieselguhr to metal are enhanced after the mercaptosilane coupling agent is modified, and also because the mercapto group has certain reducibility, the method is beneficial to the conversion of ferric iron generated in the system back to ferrous iron.
3. The inventor unexpectedly discovers that the addition of a certain amount of manganese and iron can generate a synergistic effect, the durability of the activation performance of the composite material can be obviously improved, and the persulfate is added into the system to be repaired again within a test time of 10 days, so that the composite material still has strong activation performance,
4. the method is green, safe, environment-friendly and low in cost, does not need to additionally implement measures such as heating, light irradiation and the like, saves energy and related equipment, can effectively remove organic pollutants which are difficult to degrade in a system to be repaired, and does not generate secondary pollution to the environment; the application range is wide.
Detailed Description
The present application is further illustrated by the following examples.
Unless otherwise specified, "parts" in the examples of the present invention are parts by mass.
The chlorobenzene concentration in the solution in the embodiment of the invention is obtained by adopting a high performance liquid chromatography test.
Example 1
(S1) soaking 100 parts of diatomite in 10wt% of dilute hydrochloric acid for 1 hour under the stirring condition, centrifuging, drying to finish the pretreatment of the diatomite, soaking the pretreated diatomite in 200 parts of 2wt% KH-580 ethanol solution under the reflux stirring condition at 50 ℃, soaking for 5 hours, taking out, washing with water, and drying to obtain the diatomite modified by the mercaptosilane coupling agent; the modified diatomaceous earth was impregnated with 300 parts of Fe (NO) 3 ) 2 And MnCl 2 In the mixed solution of (1), wherein Fe (NO) 3 ) 2 The molar concentration is 0.2mol/L, mnCl 2 Adding 100 parts of 30wt% ammonia water into the solution with the molar concentration of 0.04mol/L, stirring the solution to form slurry, washing the slurry for 2 times by using deionized water after drying, then washing the slurry for 2 times by using ethanol, drying the slurry, and grinding and sieving the dried slurry to obtain the diatomite composite material loaded with iron and manganese and having the average particle size of about 120 mu m;
(S2) in a 200. Mu.M chlorobenzene brown reagent bottle containing 100mL, 1g of the iron and manganese-loaded diatomite composite obtained in step (S1) and 0.048g of sodium persulfate (molar ratio of sodium persulfate to chlorobenzene is approximately 10: 1) are added to the brown reagent bottle, the bottle is capped and sealed, the reaction bottle is placed on a constant temperature oscillator, and the reaction is started for 1h at 20 ℃ with the chlorobenzene concentration being tested every 15 min.
Example 2
The other conditions and operation were the same as in example 1 except that in step (S1), fe (NO) 3 ) 2 The molar concentration is 0.24mol/L, mnCl 2 The molar concentration is 0.03mol/L.
Example 3
Other conditionsThe same operation as in example 1 was conducted except that in step (S1), fe (NO) 3 ) 2 The molar concentration is 0.24mol/L, mnCl 2 The molar concentration is 0.02mol/L.
Example 4
The other conditions and operation were the same as in example 1 except that in step (S1), fe (NO) 3 ) 2 The molar concentration is 0.16mol/L, mnCl 2 The molar concentration is 0.08mol/L.
Example 5
The other conditions and operation were the same as in example 1 except that in the step (S1), the concentration of the ethanol solution of KH-580 was 3.5wt%.
Example 6
The other conditions and operation were the same as in example 1 except that in the step (S1), the concentration of the ethanol solution of KH-580 was 1.5% by weight.
Example 7
The other conditions and operation were the same as in example 1 except that in the step (S1), the ethanol solution of KH-580 was used in a concentration of 5wt%.
Example 8
The other conditions and operation were the same as in example 1 except that in step (S2), 20. Mu. Mol of vitamin and 20. Mu. Mol of allicin were further added.
Example 9
The other conditions and operations were the same as in example 1 except that in step (S2), 40. Mu. Mol of vitamin was further added.
Example 10
The other conditions and operation were the same as in example 1 except that in step (S2), 40. Mu. Mol of allicin was further added.
Comparative example 1
The other conditions and operation were the same as in example 1 except that in the step (S1), diatomaceous earth was directly impregnated with Fe (NO) without modification with mercaptosilane coupling agent KH-580 3 ) 2 And MnCl 2 In the mixed solution of (1).
Comparative example 2
The other conditions and operation were the same as in example 1 except that in step (S1), mercaptosilane coupling agent KH-580 was replaced with aminosilane coupling agent KH-550 of equal mass.
Comparative example 3
The other conditions and operation were the same as in example 1 except that the modified diatomaceous earth was impregnated with 300 parts of 0.24mol/LFe (NO) 3 ) 2 In solution, i.e. without addition of MnCl 2 。
Comparative example 4
The other conditions and operation were the same as in example 1 except that the modified diatomaceous earth was impregnated with 300 parts of 0.2mol/L Fe (NO) 3 ) 2 And 0.04mol/L of CuCl 2 In solution.
The concentrations of the chlorobenzene solutions treated with the modified diatomaceous earth and the persulfate in the above examples and comparative examples were measured to calculate the degradation rates. In addition, in order to test the durability of the iron and manganese loaded diatomite composite material of the present invention, the materials were put in batches, specifically, the iron and manganese loaded diatomite composite material was put in the simulated polluted water body first, and was stored away from light, and after 10 days, other reagents, i.e., sodium persulfate, were put in, and in examples 8 to 10, a reducing agent was additionally put in, and the degradation rate after 1 hour of reaction was tested under the same conditions, with the results as shown in table 1 below:
TABLE 1
Note: -means that no such test was performed.
As can be seen from the data analysis in Table 1, the diatomite composite material loaded with iron and manganese, which is prepared by the invention, is used as an active substance for activating persulfate, can efficiently activate sodium persulfate so as to degrade organic matters in a water body, purify water quality, and can maintain the effect for a long time, and when the water body needs to be purified again, only persulfate needs to be added again. Or after the purification is finished, the diatomite composite material loaded with iron and manganese and the water system are heterogeneous, so that the diatomite composite material can be taken out for recycling.
According to the invention, the diatomite is modified by the mercaptosilane coupling agent, and then loaded with iron and manganese, so that the synergistic effect can be achieved, the activation capability of the composite material is enhanced together, the stability of the activation capability of the composite material is strong, the composite material is durable, the strong activation capability can be maintained for a long time, and persulfate can be added when the water quality or soil needs to be restored after being polluted again, so that the actual operation is facilitated, and the cost is saved.
Claims (8)
1. A method for removing organic pollutants by activating persulfate through a diatomite composite material loaded with iron and manganese comprises the following steps:
(S1) modifying pretreated diatomite by using a mercaptosilane coupling agent, soaking the modified diatomite in a mixed solution of ferrous salt and manganese salt, adding an alkaline solution, stirring to obtain slurry, drying the slurry, washing, drying again, and grinding to obtain an iron and manganese loaded diatomite composite material; the mass ratio of the diatomite to the mercaptosilane coupling agent is 100:4-7; the molar ratio of the ferrous salt to the manganese salt is 5-8:1, and the molarity of the ferric salt is 0.2-0.3mol/L; the mass ratio of the modified diatomite to the mixed solution of ferrous salt and manganese salt is 1:3-5; the mercaptosilane coupling agent is selected from at least one of KH-580 and KH-590;
(S2) adding the persulfate aqueous solution and the composite material obtained in the step (S1) into the water body or soil to be repaired, fully mixing, and degrading and removing the organic pollutants in the object to be repaired;
and (S2) adding a reducing agent, wherein the reducing agent is a compound of vitamin C and allicin according to a mass ratio of 1-2:1-2, and the adding amount of the reducing agent is 10-20% of the molar amount of persulfate.
2. The method of claim 1, wherein the diatomaceous earth is modified with a mercaptosilane coupling agent by: soaking the diatomite in an alcoholic solution of a mercaptosilane coupling agent under the reflux condition of 50-60 ℃, taking out, washing with water, and drying to obtain modified diatomite; the concentration of the alcoholic solution of the mercaptosilane coupling agent is 2 to 5% by weight.
3. The method according to claim 1, wherein the ferrous and manganese salts are selected from the group consisting of nitrates, halides of the metals.
4. The method according to claim 3, wherein the ferrous salt is selected from the group consisting of ferrous chloride, ferrous nitrate; the manganese salt is selected from manganese nitrate and manganese chloride.
5. The method of claim 1, wherein the alkaline solution is at least one of ammonia, sodium hydroxide, potassium hydroxide; the washing is with 60-80% ethanol water solution, and the grinding is to 100-200 μm particle size.
6. The method according to claim 1, wherein the persulfate is selected from the group consisting of sodium persulfate, potassium persulfate, and ammonium persulfate and/or the persulfate is selected from the group consisting of sodium persulfate, potassium persulfate, and ammonium persulfate and the persulfate is selected from the group consisting of at least one of sodium persulfate, potassium persulfate, and ammonium persulfate.
7. The method according to claim 1, wherein in the step (S2), 1-10g of the diatomite composite loaded with iron and manganese is added per liter of water for the water body to be treated; the addition amount of the persulfate is 10 to 30 times of the molar amount of the organic pollutants difficult to degrade in the object to be treated.
8. The method according to claim 7, wherein in the step (S2), 3-5g of the diatomite composite loaded with iron and manganese is added per liter of water for the water body to be treated; the addition amount of the persulfate is 15 to 20 times of the molar amount of the organic pollutants difficult to degrade in the object to be treated.
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