CN116986703A - Method for removing halogenated organic pollutants in water by reduction of carbon-based catalyst - Google Patents
Method for removing halogenated organic pollutants in water by reduction of carbon-based catalyst Download PDFInfo
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- CN116986703A CN116986703A CN202211037291.2A CN202211037291A CN116986703A CN 116986703 A CN116986703 A CN 116986703A CN 202211037291 A CN202211037291 A CN 202211037291A CN 116986703 A CN116986703 A CN 116986703A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000002957 persistent organic pollutant Substances 0.000 title abstract description 15
- 230000009467 reduction Effects 0.000 title abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 230000001603 reducing effect Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 238000005695 dehalogenation reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 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 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 6
- 239000003673 groundwater Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003651 drinking water Substances 0.000 claims description 5
- 235000020188 drinking water Nutrition 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 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 description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 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 description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000011550 stock solution Substances 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- -1 trichloroethylene, tetrachloroethylene Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000006042 reductive dechlorination reaction Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- GBCQLYRFIUILDL-UHFFFAOYSA-N 1-chlorocyclohexa-2,4-dien-1-ol Chemical compound OC1(Cl)CC=CC=C1 GBCQLYRFIUILDL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/36—Organic compounds containing halogen
Abstract
The invention discloses a method for removing halogenated organic pollutants in water by reduction with a carbon-based catalyst. The method comprises the following specific steps: (1) adjusting the pH value of water to be treated to 5.0 to 12.0; (2) adding a reducing agent into the water to be treated; (3) And (3) introducing the pretreated water into a reactor containing a catalyst for reaction, and separating the catalyst to obtain effluent. The method can utilize various cheap reducing agents, has higher electron utilization efficiency of the reducing agents, has lower investment compared with the prior art, can rapidly remove halogenated organic matters, has little interference by coexisting ions, and can keep long-term activity without regeneration of the catalyst, thereby realizing the efficient removal of halogenated organic pollutants in water.
Description
Technical Field
The invention belongs to the technical field of water treatment. And more particularly to a method for removing halogenated organic contaminants from water.
Background
The halogenated organic matters are basic raw materials of organic chemical industry and are widely applied to the industries of chemical industry, electronics, printing and the like. However, during its application, such substances enter the natural environment in large quantities. It is often difficult to degrade naturally, and is toxic, carcinogenic, and bioaccumulative, posing an environmental hazard. The oxidation method, biological method and chemical reduction method can realize harmless conversion of halogenated organic matters. In the application process of the oxidation method, byproducts with higher toxicity are possibly generated, dehalogenation bacteria which are depended on by the biological method slowly grow, and the biological method is difficult to be applied to engineering. The halogenated organic matters have strong toxicity and degradation resistance due to the existence of halogenated groups, and can be removed by a chemical reduction method, so that the halogenated organic matters are harmless. Thus, chemical reduction is considered to be one of the most effective methods for removing halogenated organic contaminants from water.
Existing halogenated organic chemical reduction dehalogenation technologies include zero-valent metal methods, photocatalysis, electrocatalysis, noble metal catalytic hydrogenation methods and the like. In these processes, electrons are transferred from an electron donor to a halogenated organic compound to effect dehalogenation. Because the chemical property of halogenated organic matters is stable, the halogenated organic matters are difficult to be efficiently catalyzed and reduced, and for a zero-valent metal method represented by a zero-valent iron technology, the lower electron utilization efficiency leads the dosage of the halogen organic matters to generally need far exceeding the dosage of pollutants, so that the high material cost is caused; the dechlorination technology taking light energy and electric energy as necessary reaction conditions needs to rely on a great deal of energy consumption to ensure the effect of reducing pollutants; in the hydrogenation technology taking a noble metal catalyst as a core, the catalyst is expensive and easy to deactivate, and the continuous hydrogen or the hydrogen-containing reducing agent further increases the technical cost. In summary, the existing reduction dechlorination technology relies on a large amount of strong reducing agents, light energy, electric energy and the like to provide electrons required by the reaction, and the excessive material and energy input is not matched with the environment and economic benefits of the technology, so that the wide application of the technology is hindered. Therefore, development of an economical and efficient reductive dechlorination technology is needed to meet the technical benefit principle.
If the dehalogenation reaction of halogenated organic substances can be realized by using a cheap and easily available reducing agent as an electron donor without needing a large amount of energy, a more economical reductive dehalogenation technology can be constructed than the prior art. Most halogenated organics have low redox potentials, such as standard redox potentials of-0.67V for trichloroethylene and-0.66V for 1-chlorophenol (Aquatic Redox Chemistry, american Chemical Society, 2011), and typically the reducing agent is much higher than these values, such as about 0.1V for EDTA complexed ferrous iron (chem. Rev.2021,121, 8161-8233.). Therefore, most reducing agents cannot directly realize dechlorination reaction, and the use of a catalyst becomes a necessary choice. The carbon-based catalyst has wide raw material sources, simple preparation, large-scale production prospect (environ. Sci. Technology.2017, 51 (16), 8893-8908), and capability of catalyzing electron transfer, and is one of potential catalysts for constructing a novel reduction dehalogenation system. In summary, the development of a reductive dechlorination technology based on a carbon-based catalyst, which uses a cheap and easily available reducing agent as an electron donor, can solve the bottleneck problem of insufficient economy in the prior art, and promotes the application of the technology in the field of water treatment.
Disclosure of Invention
In order to solve the problem of high investment in the existing chemical reduction dehalogenation technology, the invention aims to provide a novel method for realizing dehalogenation reaction by utilizing a plurality of cheap and easily available reducing agents. The electron of the reducing agent is transferred to the catalyst by adding the reducing agent, cobalt and nitrogen doped carbon-based catalyst into water, and the electron of the catalyst is transferred to the halogenated organic molecules through the active center of the cobalt-nitrogen coordination structure, so that dehalogenation reaction is realized. The dehalogenated organic matter has less environmental hazard, and can be used for subsequent treatment with other non-biological toxic organic matters by a microbiological method. The dehalogenation method in the method can utilize various reducing agents, especially cheap reducing agents, and meanwhile, the system has higher utilization efficiency of electrons of the reducing agents, compared with the prior art, the method has lower investment, can rapidly remove halogenated organic matters, has little interference by coexisting ions, can keep long-term activity without regeneration, can still keep original activity after being repeatedly used for a plurality of weeks in a packed column experiment, and can realize the efficient removal of halogenated organic pollutants in a water body.
The invention provides a method for removing halogenated organic pollutants in water by reduction of a carbon-based catalyst, wherein a system of the method consists of the carbon-based catalyst and a reducing agent, the method promotes the electron transfer effect of the reducing agent to halogenated organic matters by the carbon-based catalyst, so that the halogenated organic matters undergo dehalogenation reaction, and the method specifically comprises the following steps:
(1) Adjusting the pH value of water to be treated to 5.0 to 12.0;
(2) Then adding a reducing agent into the water to be treated;
(3) The water sample treated by the method enters a reactor containing a carbon-based catalyst for reaction, and the catalyst is separated after the reaction to obtain effluent.
In the step (1) of the invention, alkaline agents such as lime, sodium hydroxide, ammonia water and the like can be adopted to adjust the pH value of water to be treated to be 5.0 or more.
In the present invention, if the reducing agent is added in the step (2) to cause the pH of the water to be treated to decrease, the step (1) may be performed after the step (2), and the principle is that the pH of the water is 5.0 or more before the step (3), so as to facilitate the halogen atom removal reaction.
In the present invention, steps (1) and (2) may be performed in a jet mixer, a cyclone mixer, a pipe mixer or other complete mixing equipment.
In the invention, the reactor in the step (3) comprises a packed column, a fluidized bed, a stirring pool, an underground water infiltration reaction wall and the like.
In the invention, the reducing agent in the step (2) comprises a reducing inorganic salt and a reducing organic substance. Wherein the reducing inorganic salt comprises, but is not limited to, soluble ferrous salts (such as ferrous chloride, ferrous sulfate, etc.), divalent manganese salts or other reducing metal inorganic salts, metal salt organic complexes prepared from the metal inorganic salts, other inorganic salts with reducing property (such as sodium sulfite, sodium borohydride, hydroxylamine hydrochloride, etc.); the reducing organic matters comprise ascorbic acid, dithiothreitol and other organic matters with reducing property. In addition, the reducing agent can be a medicament compounded by one or more of the reducing agents, can be solid or pre-dissolved ferrous salt stock solution, and is distilled water or tap water.
In the invention, the carbon-based catalyst in the step (3) is a cobalt and nitrogen co-doped carbon-based material. The catalyst is synthesized by high-temperature pyrolysis of cobalt metal salt, nitrogen source and carbon source in inert gas.
Wherein the cobalt metal salts include, but are not limited to, inorganic salts, organic salts (including formulated organic complex salts) of cobalt in each valence state; nitrogen sources include, but are not limited to, ammonium salts, melamine, dicyandiamide, cyanuric acid, urea or other nitrogen-containing substances having a nitrogen content of more than 20% by mass; carbon sources include, but are not limited to, glucose, activated carbon, biomass or other substances having carbon content above 10% by mass.
The preparation method of the catalyst comprises the following specific steps:
(1) Mixing cobalt metal salt, nitrogen source and carbon source, wherein the mass of the carbon source accounts for more than 20% of the mass of the three substances, and the mixing mode comprises stirring raw material solids, ball milling the raw material solids, dissolving the raw material in water or evaporating the raw material in an organic solvent, and combining the above modes;
(2) The mixture prepared by the steps is placed in a pyrolysis furnace such as a tube furnace, a converter and the like, calcined in inert gases such as nitrogen, argon and the like, the temperature is 300-1200 ℃, preferably 800-900 ℃, and the catalyst is obtained after the calcination and cooling.
The invention adds reducing agent into water to be treated, the dosage of which increases with the increase of the concentration of halogenated organic pollutants, the mol ratio of the reducing agent to the pollutants is controlled to be more than 5, and is generally not more than 1000 based on cost consideration, and the reducing agent is adjusted according to the removal effect.
In the step (2), the mol ratio of the reducing agent to the pollutants in the water to be treated is 5-1000:1; preferably 75 to 100:1.
In the step (3), the mass ratio of the carbon-based catalyst to the water sample can be adjusted according to the form of a reactor, and the dosage of the carbon-based catalyst in a batch stirring reactor (a stirring tank) is 0.05-0.5 kg/ton, preferably 0.2 kg/ton; in a continuous flow stirred reactor (stirred tank), the ratio of the carbon-based catalyst dosage to the reactor volume is between 0.05 and 0.5 kg/cubic meter, preferably 0.2 kg/cubic meter; in a column reactor (packed column), the dosage of the carbon-based catalyst is calculated as the effective volume of the column reactor, and the effective volume is the water volume of 6-12 hours; preferably, the water volume is 8 hours.
In the step (3), the temperature of the reaction is 5-30 ℃, and the reaction can be operated under the normal temperature condition within the range without adjusting the temperature.
In the step (3), the reaction time is 0.5 to 48 hours, and is adjusted according to the kind of the reducing agent.
The pollutant mentioned in the invention can be trichloroethylene, tetrachloroethylene, tetrachloromethane, pentachlorobenzene or other organic matters needing to be reduced and dehalogenated for removal; the water to be treated in the invention is groundwater, drinking water or industrial wastewater.
The following is a mechanism analysis of the present invention:
in the cobalt and nitrogen co-doped carbon-based catalyst prepared by the method, an active site is a structure of cobalt and nitrogen atoms connected, wherein cobalt is a central atom and is surrounded by a plurality of (usually 4) nitrogen atoms, and a substrate of the catalyst is a nitrogen-doped carbon substrate. In the catalytic reduction process, the carbon-based part of the catalyst plays a role in accepting electrons of the reducing agent, so that the catalytic system utilizes various reducing agents, especially cheap reducing agents; after the active site accepts electrons, the active site can react with halogen atoms on halogenated organic matters and carbon atoms connected with the halogen atoms to attack carbon halogen bonds connected with the halogen atoms, so that the halogen atoms are separated from the organic matters.
Because the affinity of the carbon-based material and various reducing agents is strong, the surface of the carbon-based material is easy to adsorb various reducing agents, and the substrate has strong absorption capacity to electrons of the reducing agents, the system shows higher electron utilization efficiency. Since most of the inorganic ions in the water have no influence on the process, the efficiency of the system is little interfered by coexisting ions. The reaction rate gradually rises along with the rising of the pH value, the pH value of the water to be treated is controlled to be more than 5.0, the environment favorable for the reaction can be generated, and most of underground water and drinking water can meet the conditions without adjustment. Meanwhile, the reaction is an electron transfer process, the reaction process is mild, and all reactants and products do not cause irreversible damage to the catalyst components and structures, so that the catalyst can keep long-term activity without regeneration.
After the reaction is finished, halogenated organic matters in the water are removed, and the catalyst is separated by precipitation and other methods to obtain the treated water. Some reducing agent remained in the treated water can be removed synchronously through precipitation, such as ferrous iron, etc., if the reducing agent can not be removed through precipitation, the reducing agent which can be removed through a subsequent treatment process is preferably selected.
The invention has the following beneficial effects: in the method, the medicaments used in the preparation process of the catalyst are all green, safe and low-cost reagents, and the preparation method is simple and low in cost; the reducing agent has wide selectable range, and can be conveniently transported and has low price according to actual needs. The method can avoid using expensive strong reducing agent, and the electron utilization efficiency of the reducing agent is higher; the method does not need to use noble metal catalysis or other high-energy consumption methods to promote the electron transfer process, so that compared with the prior art, the method has obvious cost advantages. The reaction needs mild conditions, can be practically applied in various forms, is suitable for the existing facilities of most water treatment processes, and does not need process transformation. The invention has important economic and environmental significance.
Drawings
FIG. 1 is a scanning electron microscope topography characterization of a cobalt-nitrogen co-doped carbon-based material made according to an exemplary method of preparation of the present invention (example 3);
FIG. 2 is a graph showing the results of far-edge XAFS characterization of cobalt-nitrogen co-doped carbon-based materials prepared according to the typical preparation method of the present invention (example 3), wherein the schematic diagram is a catalyst molecular structure and the central atom is cobalt atom;
FIG. 3 is a graph showing the concentration of chloroform over time in a stirred tank reactor over 12 hours (example 7);
FIG. 4 is a schematic diagram of a packed column reactor (example 10);
FIG. 5 shows the concentration of trichloroacetic acid in effluent over time in a packed column reactor (example 10)
FIG. 6 shows the concentration of trichloroethylene in effluent over time in a fluidized bed reactor (example 11).
Detailed Description
The following specific embodiments further describe the technical solution of the present invention, but are not limited thereto, and all modifications and equivalents of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be included in the protection scope of the present invention. The following examples illustrate the effectiveness of the process of the present invention with respect to partially halogenated organics as target contaminants, with comparable results for other contaminants. The method for removing halogenated organic pollutants uses cobalt and nitrogen co-doped carbon-based material as a catalyst to catalyze electrons of a reducing agent in water to transfer to halogenated organic matters, so that the halogenated organic matters are reduced and removed. The method comprises the following steps: adjusting the pH value of water to be treated to 5.0 or above; adding a reducing agent into water to be treated, wherein the dosage of the reducing agent is increased along with the increase of the concentration of halogenated organic pollutants, the mol ratio of the reducing agent to the pollutants is controlled to be more than 5, and the reducing agent is adjusted according to the removal effect; the water sample treated by the method enters a reactor containing a catalyst for reaction, and the catalyst is separated after the reaction to obtain effluent, wherein the reactor can be a stirring tank, a packed column, a fluidized bed reactor or various reactors such as a groundwater infiltration reaction wall. When a stirred tank reactor is used, the stirrer rotation speed is 100 to 400rpm. The reactor should be closed as much as possible, isolate air, reduce the loss of reducing agent.
Several specific examples are given further below.
Examples 1 to 6: preparation of carbon-based catalysts
(1) Mixing cobalt metal salt, nitrogen source and carbon source, wherein the mass of the carbon source accounts for more than 20% of the mass of the three substances, and the mixing mode comprises stirring raw material solids, ball milling the raw material solids, dissolving the raw material in water or evaporating the raw material in an organic solvent, and combining the above modes;
(2) And (3) placing the mixture prepared by the steps into a pyrolysis furnace such as a tube furnace, a converter and the like, calcining in inert gases such as nitrogen, argon and the like at the temperature of 300-1200 ℃, and cooling after calcining to obtain the carbon-based catalyst.
Wherein, each reaction parameter is shown in the following table 1:
TABLE 1 parameters for the preparation of carbon-based catalysts in examples 1-6
Example 7: method for removing halogenated organic pollutants in water by reduction of carbon-based catalyst
This example was carried out in a stirred tank reactor, comprising the following steps:
the pH of the industrial wastewater containing 0.1mmol/L tetrachloromethane was adjusted to 8.0, and 1mmol/L sodium thiosulfate was added, the wastewater flow rate was 1m 3 And/h, the stirring reaction tanks are provided with two groups which are alternately operated, each group of reactors contains 0.2 kg/ton of the carbon-based catalyst prepared in the embodiment 4 of the invention, the stirring speed is 300rpm during operation, the hydraulic retention time is 12 hours, the reactors are switched every 12 hours during operation, the original reactors are stopped to be stirred, the reaction is kept stand for 10 hours, the supernatant is discharged after the carbon-based catalyst is precipitated, and the reaction is carried out in the other group of reactors during the standing time, so that the operation is repeated. The supernatant fluid is the treated water, the change of the concentration of the tetrachloromethane with time is shown in figure 3, and the concentration of the tetrachloromethane in the effluent water for 12 hours is reduced to 0.0001mmol/L.
Example 8 method for reduction removal of halogenated organic pollutants from Water Using carbon-based catalysts
This example differs from example 7 in that the wastewater was contaminated with 0.05mmol/L pentachlorophenol, the stirred tank residence time was 24 hours, the settling time per set was 10 hours, and the remaining conditions were the same. The concentration of pentachlorophenol in the effluent is reduced to 0.00002mmol/L. The effluent enters a subsequent microorganism treatment unit to further remove phenol generated by reduction of pentachlorophenol.
Example 9 reduction of halogenated organic pollutants in Water Using carbon-based catalysts
This example differs from example 7 in that the reducing agent used is ascorbic acid, the remaining conditions being the same. The concentration of tetrachloromethane in the effluent was reduced to 0.00001mmol/L. The effluent enters a subsequent microorganism treatment unit to further remove organic matters generated by oxidation of the ascorbic acid.
Example 10 method for reduction removal of halogenated organic pollutants from Water Using carbon-based catalysts
This example was carried out in a packed column reactor, and the specific steps are as follows:
adding 0.5mmol/L ferrous chloride into drinking water containing 1mg/L trichloroacetic acid, continuously injecting sodium hydroxide solution to adjust pH to 8.0, and adjusting drinking water flow to 50m 3 And (3) continuously entering a catalyst filling column from bottom to top, wherein the schematic diagram of the filling column is shown in fig. 4, the filling column is a mixture of the carbon-based catalyst prepared in the embodiment 6 of the invention and quartz sand, the mixture contains 10kg of the catalyst, the filling column is sealed, only a water inlet and a water outlet can be contacted with air, the hydraulic retention time is 2 hours, the trichloroacetic acid concentration in the effluent is stabilized below 0.02mg/L, and the change of the effluent concentration with time is shown in fig. 5. The added ferrous iron is converted to ferric iron, part is trapped in the packed column, and the other part is removed by subsequent sand filtration.
Example 11 method for reduction removal of halogenated organic pollutants from Water Using carbon-based catalysts
This example was carried out in a fluidized bed reactor, and the specific steps are as follows:
pumping underground water containing 0.01mmol/L trichloroethylene to the ground surface, adding 0.5mmol/L ferrous sulfide, adjusting pH to 8.0, and water flow to 10m 3 And (3) continuously entering a fluidized bed from bottom to top, wherein 1kg of the carbon-based catalyst prepared in the embodiment 2 of the invention is contained in the fluidized bed, only the water inlet and the water outlet of the whole process flow can be contacted with air, the hydraulic retention time is 10 hours, water is discharged from the upper part of the fluidized bed, and the carbon-based catalyst is positioned below the reactor under the action of gravity and does not flow out along with the discharged water. The trichloroethylene concentration in the effluent can be stably kept at about 0.00002mmol/L, and the change of the effluent concentration with time is shown in FIG. 6. The added ferrous iron is converted into three in the fluidized bed or after contacting with oxygen along with effluentThe iron value is removed by a subsequent precipitation process.
Example 12 method for reduction removal of halogenated organic pollutants from Water Using carbon-based catalysts
The embodiment is carried out in an underground water infiltration reaction wall, and the specific steps are as follows:
the carbon-based catalyst prepared in example 6 of the present invention was mixed with quartz sand, buried underground in the form of a permeable reactive barrier, and placed in the direction of the groundwater runoff of the contaminated groundwater, the permeable reactive barrier having a thickness of 1m, a height of 10m, and a width of 3m. The polluted underground water contains 0.01mmol/L tetrachloroethylene, when the ferrous salt content in the underground water is lower than 0.5mmol/L, ferrous sulfate is injected into the underground water to supplement the ferrous sulfate to 0.5mmol/L, and after the water flows through the reaction wall, the concentration of the tetrachloroethylene can be as low as 0.0001mmol/L. The added ferrous iron is harmless to the natural environment, and special treatment is not needed.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that would occur to one skilled in the art are included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is defined by the appended claims.
Claims (11)
1. A method for reducing halogenated organic contaminants in water using a carbon-based catalyst, the method comprising the steps of:
(1) Adjusting the pH value of water to be treated to 5.0 to 12.0;
(2) Then adding a reducing agent into the water to be treated;
(3) After the steps (1) and (2), the water sample enters a reactor containing a carbon-based catalyst for reaction, and the catalyst is separated after the reaction to obtain effluent.
2. The method of claim 1, wherein in step (2), the reducing agent comprises a reducing inorganic salt and a reducing organic substance, wherein the reducing inorganic salt comprises a soluble ferrous salt, a divalent manganese salt or other reducing metal inorganic salt, a metal salt organic complex prepared from the metal inorganic salt, sodium sulfite, sodium borohydride, and hydroxylamine hydrochloride; the reducing organic matters comprise ascorbic acid, dithiothreitol and other organic matters with reducing property.
3. The method of claim 1, wherein in step (2), the reducing agent is a solid or a pre-dissolved ferrous salt stock solution, and the solvent is distilled water or tap water.
4. The method according to claim 1, wherein in step (2), the molar ratio of the reducing agent to the contaminants in the water to be treated is from 5 to 1000:1.
5. The method of claim 1, wherein steps (1) and (2) are performed in a jet mixer, a cyclone mixer, a pipe mixer, or other complete mixing device.
6. The method of claim 1, wherein if step (2) results in a decrease in the pH of the water, step (1) is performed after step (2), in that the pH of the water is above 5.0 prior to step (3).
7. The method according to claim 1, wherein in the step (3), the carbon-based catalyst is synthesized by pyrolysis of cobalt metal salt, nitrogen source and carbon source in inert gas; wherein the cobalt metal salt comprises inorganic salt and organic salt of cobalt in each valence state; the nitrogen source comprises ammonium salt, melamine, dicyandiamide, cyanuric acid, urea or other nitrogen-containing substances with the nitrogen content mass ratio higher than 20%; the carbon source comprises glucose, activated carbon, biomass or other substances with a carbon content of more than 10% by mass.
8. The method according to claim 7, wherein the synthesis of the carbon-based catalyst is performed as follows:
a) Mixing cobalt metal salt, nitrogen source and carbon source, wherein the mass of the carbon source accounts for more than 20% of the mass of the three substances, and the mixing mode comprises stirring raw material solids, ball milling the raw material solids, dissolving the raw material in water or evaporating the raw material in an organic solvent, and combining the above modes;
b) Placing the mixture prepared in the step a) into a pyrolysis furnace, calcining in inert gas at 300-1200 ℃, and cooling after calcining to obtain the carbon-based catalyst.
9. The method of claim 1, wherein in step (3), the reactor comprises a packed column, a fluidized bed, a stirred tank, a groundwater permeable reactive wall; the temperature of the reaction is 5-30 ℃.
10. The method according to claim 1, wherein the contaminant is trichloroethylene, tetrachloroethylene, tetrachloromethane, pentachlorobenzene or other organic matter that requires reductive dehalogenation; the water to be treated is groundwater, drinking water or industrial wastewater.
11. The method according to claim 1, wherein in the step (3), the mass ratio of the carbon-based catalyst to the water sample is adjustable according to the form of a reactor, and the dosage of the carbon-based catalyst in the stirred tank reactor is 0.05-0.5 kg/ton; in the packed column reactor, the dosage of the carbon-based catalyst is calculated as the effective volume of the packed column reactor, and the effective volume is the water volume of 6-12 hours.
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