CN114634220A - Method for photodegrading organic arsenide - Google Patents
Method for photodegrading organic arsenide Download PDFInfo
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- CN114634220A CN114634220A CN202210053197.XA CN202210053197A CN114634220A CN 114634220 A CN114634220 A CN 114634220A CN 202210053197 A CN202210053197 A CN 202210053197A CN 114634220 A CN114634220 A CN 114634220A
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- resorcinol
- rox
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- 238000000034 method Methods 0.000 title claims abstract description 29
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229960003052 roxarsone Drugs 0.000 claims abstract description 74
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical compound OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 claims abstract description 72
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 59
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 27
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000011068 loading method Methods 0.000 claims abstract description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 14
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000001632 sodium acetate Substances 0.000 claims abstract description 14
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 12
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 31
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 150000001495 arsenic compounds Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000593 degrading effect Effects 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000003647 oxidation Effects 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 238000011065 in-situ storage Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 244000144972 livestock Species 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 244000144977 poultry Species 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- LVKZSFMYNWRPJX-UHFFFAOYSA-N benzenearsonic acid Natural products O[As](O)(=O)C1=CC=CC=C1 LVKZSFMYNWRPJX-UHFFFAOYSA-N 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- -1 phenylarsonic acid compound Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003674 animal food additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a method for effectively treating organic arsenic compound- -Rocarsone (ROX). The method comprises the steps of placing ferroferric oxide loaded resorcinol-formaldehyde resin with specific loading capacity into a photocatalysis tube, adding ROX solution, adjusting the pH value of mixed solution to be below 3, continuously stirring the mixed solution under the dark condition to achieve adsorption-desorption balance, then turning on a lamp for irradiation, and degrading ROX, wherein Fe is used for degrading ROX3O4The resorcinol-formaldehyde-loaded resin is prepared by dispersing resorcinol-formaldehyde resin with the weight ratio of 100:120.75:696.6, crystalline ferric chloride hexahydrate and sodium acetate into ethylene glycol containing CTAB (cetyl trimethyl ammonium bromide) for hydrothermal reactionAccording to the method, the removal rate of Roxarsone (ROX) in 2h reaches 75%.
Description
Technical Field
The invention relates to a method for photodegrading organic arsenide.
Background
The phenylarsonic acid compound is used as a feed additive capable of improving the feed conversion rate and improving the animal fur color, and is widely applied to the livestock and poultry breeding industry. The phenylarsonic acid compound is difficult to be metabolized by animals, and over 90 percent of ROX is discharged into water and soil along with livestock and poultry manure. The Roxarsone (ROX) is frequently detected in livestock and poultry breeding wastewater as a common feed additive, the concentration of Roxarsone (ROX) detected in the livestock and poultry breeding wastewater is as high as 14-54mg/kg, and the roxarsone is easily decomposed into high-toxicity inorganic arsenic species (iAs) in a natural environment, and the roxarsone is prepared from the following raw materials: arsenous acid and arsenic acid, thereby polluting water and soil. iAs can pass through the food chain and thus be harmful to human health. In the traditional treatment technology of phenylarsonic acid compounds, the retention time of the adsorption technology for treating organic arsenic pollutants is long, and the total arsenic removal rate of the chemical oxidation technology is poor. The Fenton oxidation technology is widely used for water pollution treatment due to the advantages of simple operation, low cost, high degradation efficiency and the like. The traditional homogeneous Fenton technology can generate a large amount of iron mud, so that the operation cost is increased; further, hydrogen peroxide (H) as an oxidizing agent in the Fenton reaction2O2) Has higher safety risk in production, transportation and storage. In this regard, heterogeneous in situ self-production H was developed2O2The fenton technique can effectively solve the above problems.
H2O2The oxidant is a clean oxidant, can react with organic substances which are difficult to degrade in the nature to generate oxygen and water, and does not cause secondary pollution. H2O2The production process is complex, the cost is high, and the transportation and storage safety risk is high. In this regard, photocatalytic in situ reduction of molecular oxygen (O)2) Generation of H2O2The technology is a new economic and environment-friendly strategy, and the technology has a very promising application prospect. Yasuhiro Shiraishi et al prepared m-phenylenedi by a simple hydrothermal reactionPhenol-formaldehyde Resin (RF) and found to be a semiconductor photocatalyst with high efficiency in the presence of water molecules and with O being produced from broad spectrum sunlight2Conversion to H2O2. The preparation method of the resin is simple, and the preparation raw materials are cheap; catalytic preparation of H2O2The reaction of (a) can be carried out at normal temperature and pressure; h2O2The yield of (A) is higher.
The Fenton oxidation technology is a water treatment process with simple operation and good performance, and is widely applied to sewage treatment. However, the conventional fenton oxidation technology has low iron ion circulation efficiency, is easy to generate a large amount of iron-containing sludge, and needs continuous addition of ferrous ions to maintain the oxidation performance, which increases the operation cost of the oxidation technology. In contrast, the invention designs and prepares a heterogeneous ferroferric oxide loaded RF resin photo-synergetic in-situ Fenton oxidation system, and is applied to the treatment of a high-risk organic arsenic compound- -Roxarsone (ROX).
Ferroferric oxide is loaded on resorcinol formaldehyde resin particles, photogenerated holes and electrons are generated by utilizing the excellent photocatalytic performance of the resorcinol formaldehyde resin, pollutants are degraded by the photogenerated holes through oxidation, oxygen is reduced by the photogenerated electrons to generate hydrogen peroxide, and the hydrogen peroxide and the ferroferric oxide are subjected to heterogeneous Fenton reaction to cooperatively degrade organic pollutants.
However, the application of the ferroferric oxide-supported resorcinol-formaldehyde resin in the field of photocatalysis ROX has not been found in the prior art.
Zhejiang university of industry and commerce proposes a new material for producing hydrogen peroxide and removing pollutants, and a preparation method and application thereof (CN 113318793A), which adopts the following steps: (1) stirring and mixing resorcinol, formaldehyde and ammonia water, then carrying out hydrothermal reaction, washing and forming a solid after the hydrothermal reaction, and drying to obtain resorcinol-formaldehyde resin; (2) adding the prepared resorcinol formaldehyde resin powder into a mixed solution of ferrous salt and ferric salt, stirring uniformly, heating, dropwise adding ammonia water, reacting, washing and forming a solid, and drying to obtain a resorcinol formaldehyde resin-ferroferric oxide novel catalytic material; when the material is used for photocatalysis of ROX, the degradation rate of ROX in 2h is only 15.6%.
Through a great deal of research, the inventor of the invention finds that the resorcinol-formaldehyde resin, the crystalline ferric chloride hexahydrate and the sodium acetate with specific mass ratios are dispersed into ethylene glycol containing CTAB, the ferroferric oxide loaded resorcinol-formaldehyde resin with specific loading capacity is prepared through hydrothermal reaction, and a photo-synergetic in-situ Fenton oxidation system under the condition that the pH value is 3 can generate H in situ under photocatalysis2O2Plays an important role in the Fenton oxidation process, and the degradation rate of 2h on ROX is as high as 75%. .
Disclosure of Invention
The invention provides a method for effectively treating organic arsenic compound- -Rocarsone (ROX). The method comprises the steps of placing ferroferric oxide loaded resorcinol-formaldehyde resin with specific loading capacity into a photocatalysis tube, adding ROX solution, adjusting the pH value of mixed solution to be below 3, continuously stirring the mixed solution under the dark condition to achieve adsorption-desorption balance, then turning on a lamp for irradiation, and degrading ROX, wherein Fe is used for degrading ROX3O4The supported resorcinol-formaldehyde resin is prepared by dispersing resorcinol-formaldehyde resin with the weight ratio of 100:120.75:696.6, crystalline ferric chloride hexahydrate and sodium acetate into ethylene glycol containing CTAB for hydrothermal reaction, and the removal rate of Roxarsone (ROX) in 2h by using the method disclosed by the invention reaches 75%.
The specific content comprises the following steps:
a method for treating Rocarsone (ROX), an organic arsenic compound, characterized in that heterogeneous Fe is used3O4Supported resorcinol-formaldehyde resin as a photocatalyst for photocatalytic degradation of Roxarsone (ROX) in an environment with a pH value of 3, comprising heterogeneous phase Fe3O4Loading resorcinol-formaldehyde resin into a photocatalytic tube, adding ROX solution, adjusting the pH value of the mixed solution to be below 3, continuously stirring the mixed solution under a dark condition to achieve adsorption-desorption balance, and then turning on a lamp to irradiate to degrade ROX; the above-mentionedHeterogeneous Fe3O4The resorcinol-formaldehyde loaded resin is prepared by the following method:
1) weighing resorcinol-formaldehyde resin, crystalline ferric chloride hexahydrate and sodium acetate in a mass ratio of 100:120.75:696.6, dispersing into ethylene glycol with a predetermined volume, and heating and stirring under an oil bath until the resorcinol-formaldehyde resin, the crystalline ferric chloride hexahydrate and the sodium acetate are dissolved;
2) transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for a preset time at a preset temperature, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin.
Further, said heterogeneous phase of Fe3O4The resorcinol-formaldehyde loaded resin is prepared by the following method: 10mg of CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 120.75mg of crystalline ferric chloride hexahydrate and 696.6mg of sodium acetate were weighed out and dispersed in 50mL of the ethylene glycol, heated under an oil bath with stirring until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin.
Further, the oil bath temperature was 60 ℃.
Further, the resorcinol is prepared by the following method:
1) weighing 0.116mL of ammonia water, 0.3969g of resorcinol and 0.547mL of formaldehyde, dispersing into 40mL of deionized water, and stirring in a sealed manner on a stirrer with a constant rotating speed for a certain time until the ammonia water, the 0.3969g of resorcinol and the formaldehyde are dissolved;
2) and transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24 hours at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain the resorcinol-formaldehyde resin.
Further, 50mg of heterogeneous Fe was weighed3O4Loading resorcinol-formaldehyde resin into a photocatalysis tube, adding 50mL ROX solution, and stirring the mixed solution for 30min in darkSo as to achieve the adsorption-desorption equilibrium, and then turn on the lamp to irradiate, so as to degrade the ROX.
The invention has the following beneficial effects:
1.Fe3O4successful preparation of @ RF
As can be seen from FIG. 1, Fe is supported as compared with RF3O4The material of (2) is in the presence of Fe3O4Characteristic diffraction peak of (1), with Fe3O4Increase in the amount of Fe3O4The characteristic signal peak of (a) is enhanced. As can be seen from FIG. 2, the RF pellet is a uniform sphere with a particle size of about 600-800 nm. In addition, the RF surface was successfully loaded with nano-Fe3O4Pellets, nano Fe without CTAB3O4The grain diameter is about 150-200nm, and when the surfactant CTAB is added, the nano Fe3O4The particle size is reduced to 50 nm. This is because CTAB can reduce Fe3O4The surface energy of the unit cell thereby limiting Fe3O4The particle size of (a).
2.Fe3O4Photocatalytic Properties of @ RF
FIG. 3 examines Fe3The oxidation performance of the photo-synergetic in-situ Fenton oxidation system on ROX under different pH conditions when the O loading is 25 wt%. During a dark adsorption period of 30 min: at pH 3, 47% of ROX is replaced by Fe3O4@ RF-25 material adsorption; at pH 6, 26% of ROX is replaced by Fe3O4@ RF-25 material adsorption; at pH 9, only 18% of ROX is replaced by Fe3O4The @ RF-25 material adsorbs. This indicates that the pH of the reaction solution affects the presence of ROX in the solution and Fe3O4@ RF-25 surface charge, thereby influencing ROX at Fe3O4The adsorption state of the @ RF surface, ROX is positively charged due to protonation under acidic conditions, and can be adsorbed on Fe by electrostatic adsorption3O4@ RF-25 surface. Fe under 2h simulated sunlight irradiation under the conditions of pH 3, 6 and 93O4The ROX removal rates of @ RF-25 were 75%, 28% and 13%, respectively. It can be seen that the photocatalytic in-situ Fenton oxidation is carried out under the condition of pH 3The system has adsorption and catalytic oxidation performances far higher than other pH values, can efficiently degrade the target organic pollutant ROX, and achieves unexpected technical effects.
As can be seen from FIG. 4, Fe3O4Fe at lower loading3O4The decomposition efficiency of @ RF is not high, and the decomposition efficiency and Fe3O4The load quantity is positively correlated. Fe3O4The 2h final ROX degradation rates of 2.5 wt%, 5 wt%, 7.5 wt% loading were only 22%, 25%, 32%, respectively. Fe3O4The low loading is not sufficient to catalyze the decomposition of H generated in situ2O2The concentration of active species such as hydroxyl radical (. OH) in the system is low, so that the oxidative degradation capability on ROX is weak. Increase of Fe3O4After a loading ratio, Fe3O4The degradation efficiency of @ RF is significantly improved. Fe3O4@RF-20、Fe3O4@RF-25、 Fe3O4The degradation rate of ROX in 120min of @ RF-30 is 59%, 75% and 70%, respectively, wherein Fe3O4The degrading activity of @ RF-25 is highest. This is attributed to Fe3O4Catalytic decomposition of H2O2Ability of (C) and Fe3O4Adsorption capacity for ROX. However, too high Fe3O4The loading can cause the RF surface active sites to be covered, and limit Fe3O @ RF absorption of light to suppress Fe3O @ RF photocatalytic conversion of O2Generation of H2O2。
FIG. 5 shows that RF degrades 20% of ROX within 2H of light, since RF can be converted to high concentration of H during light irradiation2O2However H2O2The self-decomposition rate is slow, and the generated OH is not enough to realize the efficient degradation of ROX. In addition, Fe in the absence of light3O4@ RF-25 is capable of removing 45% ROX by electrostatic force adsorption. Under the condition of illumination, Fe3O4@ RF-25 enables in situ generation and utilization of H2O2And high concentration OH is generated to realize rapid degradation of ROX, so that 75% of ROX is removed.
3.Fe3O4Resorcinol-Formaldehyde Supported resin (Fe)3O4@ RF) photocatalytic mechanism
As shown in FIG. 6, the Fe load3O4Front and back OH,1O2And O2 -Paramagnetic signal spectra were captured. Fe can be observed in FIG. 6(a)3O4The system @ RF-25 has a quadruple characteristic OH peak, and the signal is stronger than that of the RF system. In FIG. 6(b) it can be seen clearly in both systems1O2Triple characteristic peak of (1), and Fe3O4The peak intensity in the @ RF-25 system is significantly stronger. In FIG. 6(c), Fe3O4The interference of the spectral line of the @ RF-25 system by Fe is too obvious, no obvious peak intensity appears, and near-O can be observed in the RF system2 -Six characteristic peaks of (a). Proves that the main active substances of the photocatalysis synergistic in-situ Fenton oxidation system are OH,1O2And O2 -。
As can be seen in fig. 7. Fe3O4In the solution before the reaction of the @ RF-25 photocatalysis synergistic in-situ Fenton oxidation system, except ROX, inorganic arsenic is mainly As (III), and As (V) only accounts for a small part. After the reaction is finished, ROX in the system is oxidized and degraded into inorganic arsenic species, wherein As (V) is taken As the main species, and the concentration of the As (V) is greatly increased. This is due to the degradation of ROX during oxidation to As (III) and subsequent further oxidation to As (V).
The synergistic mechanism of the photo-synergetic in-situ Fenton oxidation system is as follows: fe3O4@ RF-25 photo-excited to generate photo-generated e-，e-O is reduced through a double electron reduction path2Conversion to H2O2. Simultaneous surface nano-Fe3O4Can efficiently decompose H2O2Generating high concentration OH which participates in the oxidation of ROX, the degradation of ROX molecules to generate As (III) and further deep oxidation to As (V). Inorganic arsenic species by adsorption on Fe3O4Surface removal is achieved. In conclusion, the light-synergetic in-situ Fenton oxidation system realizes the efficient removal of the target pollutant ROX through the synergistic effect of pre-oxidation-adsorption.
Drawings
FIG. 1 different Fe loadings Fe3O4XRD spectrogram of @ RF
FIG. 2 two Fe without and with CTAB3O4Load of Fe3O4TEM photograph of @ RF: (a) fe3O4@ RF-5, (b) Fe3O4@RF-5+CTAB，(c)Fe3O4@RF-25，(d)Fe3O4@RF-25+CTAB
FIG. 3 effect of different pH values on ROX degradation. (according to the conditions that the amount of the catalyst is 1g/L, the concentration of the ROX solution is 20mg/L, a light source is 300W, a xenon lamp AM1.5 filter is adopted, and the temperature is 25℃.)
Figure 4 effect of different Fe loadings on ROX degradation. (reaction conditions: amount of catalyst 1g/L, concentration of ROX solution 20mg/L, pH 3, light source 300W xenon lamp AM1.5 filter, temperature 25 ℃ C.)
FIG. 5 Experimental necessities. (reaction conditions: amount of catalyst 1g/L, concentration of ROX solution 20mg/L, pH 3, light source 300W xenon lamp AM1.5 filter, temperature 25 ℃ C.)
Figure 6 free radical trapping EPR profiles in different systems: (a) OH, (b)1O2，(c)·O2 -
FIG. 7 concentration of inorganic arsenic in solution before and after reaction
FIG. 8 Fe before reaction3O4@ RF-25 with Fe after reaction involved in degradation of ROX3O4XPS spectrum for @ RF-25: (a) fe 2p, (b) C1 s, (C) O1 s.
FIG. 9 Fe before reaction3O4@ RF-25 with Fe after reaction involving degradation of ROX3O4XPS spectra of @ RF-25: as 3d
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example Fe3O4Preparation of Resorcinol-Formaldehyde Supported resin
Examples
Weighing 0.116mL of ammonia, 0.3969g of resorcinol, and 0.547mL of formaldehyde dispersionTo 40mL of deionized water. Hermetically stirring the mixture for a certain time on a stirrer with constant rotating speed until the mixture is dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24 hours at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain resorcinol-formaldehyde resin; 10mg CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 120.75mg of crystalline ferric chloride hexahydrate and 696.6mg of sodium acetate were weighed out and dispersed in 50mL of the ethylene glycol, heated under an oil bath with stirring until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin. The final sample was labeled as Fe3O4@RF-25。
Comparative example 1
0.116mL of aqueous ammonia, 0.3969g of resorcinol, and 0.547mL of formaldehyde were weighed out and dispersed into 40mL of deionized water. Hermetically stirring the mixture for a certain time on a stirrer with constant rotating speed until the mixture is dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24 hours at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain resorcinol-formaldehyde resin; 10mg of CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 12.07mg of crystalline ferric chloride hexahydrate and 69.66mg of sodium acetate were weighed out and dispersed in 50mL of the ethylene glycol, heated under an oil bath with stirring until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4The resorcinol-formaldehyde resin is loaded. The final sample was marked as Fe3O4@RF-2.5。
Comparative example 2
Weigh 0.116mL of ammonia, 0.3969g of resorcinol, and 0.547mL of formaldehyde into 40mL of deionized water. Hermetically stirring the mixture for a certain time on a stirrer with constant rotating speed until the mixture is dissolved; transferring the obtained solution into a hydrothermal kettle, and placing the hydrothermal kettle in a drying ovenHeating the sample in a box at 250 ℃ for 24h, naturally cooling the sample to room temperature, washing the sample with water and alcohol for a plurality of times, and drying to obtain resorcinol-formaldehyde resin; 10mg CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 24.15mg of crystalline ferric chloride hexahydrate and 139.32mg of sodium acetate were weighed out and dispersed in 50mL of the ethylene glycol, heated under an oil bath with stirring until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin. The final sample was labeled as Fe3O4@RF-5。
Comparative example 3
Weigh 0.116mL of ammonia, 0.3969g of resorcinol, and 0.547mL of formaldehyde into 40mL of deionized water. Hermetically stirring the mixture on a stirrer with constant rotating speed for a certain time until the mixture is dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24 hours at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain resorcinol-formaldehyde resin; 10mg of CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 36.23mg of crystalline ferric chloride hexahydrate, and 208.98mg of sodium acetate were weighed out and dispersed in 50mL of the ethylene glycol, heated under an oil bath with stirring until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin. The final sample was labeled as Fe3O4@RF-7.5。
Comparative example 4
0.116mL of aqueous ammonia, 0.3969g of resorcinol, and 0.547mL of formaldehyde were weighed out and dispersed into 40mL of deionized water. Hermetically stirring the mixture for a certain time on a stirrer with constant rotating speed until the mixture is dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24 hours at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain resorcinol-formaldehyde resin; will be provided with10mg CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 96.6mg of crystalline ferric chloride hexahydrate and 557.28mg of sodium acetate were weighed and dispersed in 50mL of the ethylene glycol, heated and stirred under an oil bath until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin. The final sample was labeled as Fe3O4@RF-20。
Comparative example 5
Weigh 0.116mL of ammonia, 0.3969g of resorcinol, and 0.547mL of formaldehyde into 40mL of deionized water. Hermetically stirring the mixture on a stirrer with constant rotating speed for a certain time until the mixture is dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24 hours at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain resorcinol-formaldehyde resin; 10mg of CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 144.9mg of crystalline ferric chloride hexahydrate and 835.92mg of sodium acetate were weighed out and dispersed in 50mL of the ethylene glycol, heated under an oil bath with stirring until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin. The final sample was labeled as Fe3O4@RF-30。
Comparative example 6
Weigh 0.116mL of ammonia, 0.3969g of resorcinol, and 0.547mL of formaldehyde into 40mL of deionized water. Hermetically stirring the mixture on a stirrer with constant rotating speed for a certain time until the mixture is dissolved; and transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24h at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain resorcinol-formaldehyde resin which is marked as RF.
Experiments and data
1. Photocatalytic degradation
The photocatalytic performance of each catalyst was evaluated by the degradation rate of ROX under simulated sunlight conditions. 50mg of Fe3O4Putting the loaded resorcinol-formaldehyde resin into a photocatalytic tube, adding a 50mLROX solution, ultrasonically dispersing and uniformly mixing in an ultrasonic machine, continuously stirring the mixed solution under a dark condition to achieve adsorption-desorption balance, and then turning on a lamp for irradiation to degrade ROX. In the experiment, 1.2mL of sample was taken out at regular intervals by a dropper, and put into a syringe equipped with a 0.22 μm hydrophilic PTEE needle filter, and quickly injected into a centrifuge tube, and 1mL of sample was transferred to a liquid phase vial containing 1mL of methanol by a pipette, and the ROX concentration therein was measured by a high-resolution liquid chromatograph/mass spectrometer. The detection conditions are as follows: the injection volume was 1 μ L, and the mobile phase consisted of 15% methanol and 85% deionized water at a rate of 0.3 mL/min. Wherein, the filter used for simulating the sunlight is AM 1.5.
2.Fe3O4Physicochemical Properties of @ RF
In the preparation of series Fe3O4In the process of @ RF, a traditional post-alkalization method is tried, wherein the post-alkalization method is to directly prepare NaOH or KOH solution with a certain concentration, disperse a sample into the solution, continuously stir, heat to 120 ℃ by using an oil bath until the water in the solution is completely evaporated, then centrifuge and wash the sample for a plurality of times, and dry the sample.
As shown in fig. 1. As can be seen from the figure, as the Fe load mass ratio increases in order, Fe3O4@ RF Material apparent presence of Fe3O4Is determined as a characteristic diffraction peak of Fe3O4Successfully loaded on the surface of the RF material. At a lower loading mass ratio (less than or equal to 7.5 wt%), Fe3O4Is less RF shielded and therefore does not exhibit significant Fe3O4Characteristic peak.
As shown in fig. 2, we can see that the RF pellets are in a uniform spherical shape, indicating that the preparation of RF nanomaterials is successful. And Fe is clearly shown in the picture3O4Has been successfully loaded on the RF surface, and 25 wt% of Fe is loaded3O4@ RF with a lot of free Fe around3O4. In the preparation of Fe3O4The CTAB surfactant is added in the process of @ RF to effectively reduce Fe3O4Surface energy of Fe to thereby control3O4Particle size of nanoparticles and prevention of Fe3O4The particles aggregate. From FIGS. 2a and 2b, Fe in the former diagram can be seen3O4The particle diameter is about 150nm, while the latter figure shows Fe3O4The particle size of the particles is controlled to be about 50 nm. In FIG. 2c Fe3O4The agglomeration phenomenon of the particles is relatively obvious, Fe3O4The particle size of the particles is mostly about 200 nm; in FIG. 2b Fe3O4The agglomeration of the particles is reduced, Fe3O4The particle size is mostly 100-150 nm. From the above results, CTAB was used for Fe3O4The purpose of modifying the particles is achieved
In XPS characterization of materials, FIG. 8 is Fe before reaction3O4@ RF-25 with Fe after reaction involving degradation of ROX3O4XPS spectra of @ RF-25. C1 s 284.6eV represents a C ═ C double bond, 286.1eV represents a C — O bond, and 288.2eV represents a C ═ O double bond, derived from the benzene type C and the quinone type C in the resorcinol-formaldehyde resin beads. 530.4eV and 532.8eV in O1 s correspond to O ═ C and O — C bonds, respectively. The XPS characteristic peaks of C and O elements have no obvious displacement before and after the reaction, which shows that H is generated in situ by photocatalysis2O2The process RF maintains a high chemical stability. In the spectrum of Fe 2p, the peaks of 710.8eV and 715.1eV correspond to Fe2+And Fe3+The characteristic peak of Fe 2p3/2, and the peaks at 724.6eV and 727.7eV respectively correspond to Fe2+And Fe3+Fe 2p1/2 characteristic peak of Fe after reaction2+/Fe3+The ratio decreases, which indicates Fe3O4Participate in H2O2In which Fe is present2 +Is oxidized into Fe3+。
FIG. 9 shows Fe before reaction3O4@ RF-25 with Fe after reaction involving degradation of ROX3O4The As 3d XPS spectrum of @ RF-25 reflects the valence distribution of As indicated by the catalyst before and after the reaction. In FIG. 943.4eV is As (III) and 45.2eV is As (V). This indicates that As is removed by in situ adsorption.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.
Claims (5)
1. A method for treating Rocarsone (ROX), an organic arsenic compound, characterized in that heterogeneous Fe is used3O4Supported resorcinol-formaldehyde resin as a photocatalyst for photocatalytic degradation of Roxarsone (ROX) in an environment with a pH value of 3, comprising heterogeneous phase Fe3O4Loading resorcinol-formaldehyde resin into a photocatalytic tube, adding ROX solution, adjusting the pH value of the mixed solution to be below 3, continuously stirring the mixed solution under a dark condition to achieve adsorption-desorption balance, and then turning on a lamp to irradiate to degrade ROX; said heterogeneous phase of Fe3O4The resorcinol-formaldehyde loaded resin is prepared by the following method:
1) weighing resorcinol-formaldehyde resin, crystalline ferric chloride hexahydrate and sodium acetate at a mass ratio of 100:120.75:696.6, dispersing into ethylene glycol containing CTAB with a predetermined volume, heating and stirring under oil bath until dissolving;
2) transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for a preset time at a preset temperature, naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin.
2. The method of claim wherein said heterogeneous Fe is used as a treatment for Rocarsone (ROX), an organic arsenic compound3O4The resorcinol-formaldehyde loaded resin is prepared by the following method: 10mg CTAB was dispersed in 50mL of ethylene glycol, and then 100mg of resorcinol-formaldehyde resin, 120.75mg of crystalline ferric chloride hexahydrate and 696.6mg of sodium acetate were weighed out and dispersed in 50mL of the ethylene glycol, heated under an oil bath with stirring until dissolved; transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating at 180 ℃ for 12h, and waiting forNaturally cooling to room temperature, washing the obtained sample with water and alcohol for several times, and drying to obtain heterogeneous Fe3O4Carrying the resorcinol-formaldehyde resin.
3. The method for treating Roxarsone (ROX) as an organoarsenic compound in accordance with any of the preceding claims, wherein the oil bath temperature is 60 ℃.
4. The method of treating an organic arsenic compound- -Roxarsone (ROX) according to the above claim, wherein the resorcinol is prepared by the following method:
1) weighing 0.116mL of ammonia water, 0.3969g of resorcinol and 0.547mL of formaldehyde, dispersing into 40mL of deionized water, and stirring in a sealed manner on a stirrer with a constant rotating speed for a certain time until the ammonia water, the 0.3969g of resorcinol and the formaldehyde are dissolved;
2) and transferring the obtained solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven, heating for 24 hours at 250 ℃, after naturally cooling to room temperature, sequentially washing the obtained sample with water and alcohol for a plurality of times, and drying to obtain the resorcinol-formaldehyde resin.
5. The method of claim wherein 50mg of heterogeneous Fe is weighed out to obtain a 50mg solution3O4The loaded resorcinol-formaldehyde resin is placed in a photocatalysis tube, 50mL of ROX solution is added, the mixed solution is continuously stirred for 30min under the dark condition to achieve adsorption-desorption balance, and then the mixed solution is turned on to irradiate, so that ROX is degraded.
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