CN115069744A - Process for treating arsenic-containing waste residues through micro-electrolysis-Fenton combination - Google Patents
Process for treating arsenic-containing waste residues through micro-electrolysis-Fenton combination Download PDFInfo
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- CN115069744A CN115069744A CN202210653320.1A CN202210653320A CN115069744A CN 115069744 A CN115069744 A CN 115069744A CN 202210653320 A CN202210653320 A CN 202210653320A CN 115069744 A CN115069744 A CN 115069744A
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- arsenic
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- electrolysis
- fenton
- containing waste
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 33
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 description 6
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 5
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 150000001495 arsenic compounds Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 229940093920 gynecological arsenic compound Drugs 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- -1 As 2 S 3 Chemical class 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of solid waste treatment, and discloses a process for treating arsenic-containing waste residues through micro-electrolysis-Fenton combination. The invention can degrade the organic arsenic in the waste residue into inorganic arsenic, oxidize and adsorb the inorganic arsenic which is degraded and originally exists in the waste residue, and the micro-electrolysis provides cheap Fe for Fenton reaction 2+ And an adsorbent is not required to be added, so that the reaction efficiency is high, the operation is simple, and the cost is low.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination.
Background
Arsenic is widely found in nature, and currently known arsenates and related minerals are over three hundred, and arsenic is one of the earliest recognized carcinogens by the international cancer research institute. More typical of arsenic compounds, e.g. As 2 S 3 、As 2 O 3 、AsH 3 The arsenic compounds can damage the nerves of people, stimulate respiratory system zones, even cause canceration and seriously threaten the health of people after entering the human body. However, arsenic does not disappear in natural environment with time, but is enriched, and the food chain is enriched in organisms, so that serious effects are caused to the environment and the organismsAnd (4) harming. According to statistics, currently, the arsenic-containing waste residue generated in China is over 50 ten thousand tons every year, and a simple stacking method causes secondary pollution, so that harmless recycling of the arsenic-containing waste residue is one of the environmental problems which need to be solved urgently.
At present, resource utilization and stable solidification are main treatment methods for arsenic-containing waste residues at home and abroad, wherein the resource utilization treatment is mainly divided into a fire treatment process and a wet treatment process.
The main method is to carry out oxidizing roasting on arsenic-containing waste residue at high temperature, the arsenic content in the process can be removed to 40-70%, and if a vulcanizing agent is added into the arsenic-containing waste residue under the vacuum condition, the removal rate of the arsenic can reach 98%. Although the process is simple to operate, the process is not widely used because of high energy consumption and easy secondary pollution to the environment. The wet dearsenization is to perform acid leaching or salt leaching treatment on the waste residue, and then remove the arsenic in the waste residue through a vulcanization method or other reduction harmless treatment modes. The main components of the arsenic-containing waste residue after treatment in the chemical industry comprise ferric arsenate, calcium arsenate and arsenic sulfide.
Therefore, the problem to be solved by the technical personnel in the field is how to provide a treatment process of arsenic-containing waste residue, which has simple process, economical operation, energy saving and environmental protection.
Disclosure of Invention
In view of this, the invention provides a process for treating arsenic-containing waste residues by micro-electrolysis and Fenton combination.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination comprises the following steps:
(1) dissolving arsenic-containing waste residues in water to obtain mixed slurry;
(2) adding the mixed slurry into a micro-electrolysis reactor, adjusting the pH value to 2-4, and then adding activated carbon and scrap iron to carry out micro-electrolysis reaction;
(3) the effluent of the micro-electrolysis reactor enters a Fenton reactor, hydrogen peroxide is added for Fenton reaction,
(4) and (4) enabling the effluent of the Fenton reactor to enter a pH adjusting tank, adjusting the pH value to 7-9, precipitating and filtering to obtain the Fenton reaction product.
In the invention, the active carbon and the scrap iron form a micro-electrolysis electrode, organic arsenic is converted into inorganic arsenic through micro-electrolysis reaction, and the formed Fe 2+ Can be used as the raw material of the subsequent Fenton reaction. Added hydrogen peroxide and Fe 2+ Form Fenton's reagent, which can degrade organic arsenic and oxidize trivalent arsenic into pentavalent arsenic, and Fe 2+ Is oxidized into Fe 3+ The ferric arsenate which is extremely insoluble with arsenic is formed, and the ferric hydroxide colloid formed under the alkaline regulation can also be used as a high-efficiency adsorbent of arsenic salt to effectively adsorb the generated high-toxicity arsenic salt.
Preferably, in the above process for treating arsenic-containing waste residue by micro-electrolysis-fenton combination, the mass ratio of the arsenic-containing waste residue to water in step (1) is 1: (1-2).
The beneficial effects of the above technical scheme are: the arsenic-containing waste residue is formed into waste salt slurry, and solid salt and dissolved salt are in a dissolving-crystallizing equilibrium state, so that arsenic in the waste residue is fully dispersed in water.
Preferably, in the above process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination, the mass ratio of the activated carbon to the scrap iron in step (2) is 1: (1-2).
The beneficial effects of the above technical scheme are: iron is used as a cathode, carbon is used as an anode, and a microelectrode is fully formed to carry out micro-electrolysis reaction.
Preferably, in the above process for treating arsenic-containing waste residue by micro-electrolysis-Fenton combination, the time of the micro-electrolysis reaction in the step (2) is 0.5-2 h.
The beneficial effects of the above technical scheme are: the micro-electrolysis reaction is fully carried out, the organic arsenic is fully degraded, and sufficient Fe is provided for the subsequent Fenton reaction 2+ 。
Preferably, in the above process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination, the amount of hydrogen peroxide added in step (3) is 2-6mL/L based on the total amount of liquid in the Fenton reactor.
The beneficial effects of the above technical scheme are: adding hydrogen peroxide and micro-electricityFe formed by decomposition 2+ A Fenton reaction takes place, the arsenic is oxidized to pentavalent arsenic and reacts with the Fe formed 3+ The reaction produces ferric arsenate which is extremely insoluble.
Preferably, in the above process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination, the Fenton reaction time in step (3) is 0.5-2 h.
The beneficial effects of the above technical scheme are: the Fenton reaction is fully carried out, and simultaneously Fe 3+ Forming ferric hydroxide adsorbent under alkaline condition to adsorb and remove arsenic salt.
According to the technical scheme, compared with the prior art, the invention discloses and provides a process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination, and the process has the following beneficial effects:
(1) the invention couples micro-electrolysis and Fenton reaction, improves the degradation efficiency of organic arsenic, and the micro-electrolysis also provides Fe for the Fenton reaction 2+ A good catalytic oxidation system is formed with hydrogen peroxide, the system is stable, and the treatment efficiency is high;
(2) the method utilizes hydroxyl free radicals in Fenton reaction to deeply degrade organic arsenic and oxidize inorganic trivalent arsenic into pentavalent arsenic so as to react with Fe 3+ Ferric arsenate which is extremely insoluble is formed, so that the treatment capacity of arsenic with different forms is improved;
(3) the invention adjusts the pH value to be alkaline, so that Fe in Fenton reaction 3+ The ferric hydroxide colloid is formed, the generated arsenic salt is efficiently adsorbed, an adsorbent is not required to be added, and the operation cost is saved;
(4) the invention uses the combined mode of micro-electrolysis and Fenton reaction, has simple process, economic operation and higher efficiency, does not generate other pollutants in the degradation and adsorption process, and is an environment-friendly treatment process.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The principle of micro-electrolysis in the invention is that an infinite number of fine galvanic cells are formed due to the potential difference between iron-carbon particles. In these fine cells, iron is at a lower potential as the cathode and carbon is at a higher potential as the anode; the electrochemical reaction takes place in an aqueous solution containing an acidic electrolyte. One of the results of the micro-electrolysis process reaction is that iron is corroded and becomes ferrous ions, and the ferrous ions catalyze hydrogen peroxide to form a catalytic oxidation system, so that a good coupling effect is formed with Fenton reaction. The micro-electrolysis-Fenton combined process can convert organic arsenic into inorganic arsenic and utilize Fe 3+ The high-efficiency adsorbability of insoluble ferric arsenate and ferric hydroxide formed with arsenic can adsorb arsenic salt, and arsenic in different forms in waste residue can be effectively removed without adding an adsorbent.
Example 1
A process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination comprises the following steps: dissolving arsenic-containing waste residues and water according to the mass ratio of 1:1.5, feeding the obtained mixed slurry into a micro-electrolysis reactor, adding HCl to adjust the pH value of the slurry to 2-4, and adding the mixture according to the mass ratio of 1: 2, feeding water into the iron chips and the activated carbon for 10min, opening an air pipeline valve, opening a fan for aeration, controlling the air-water ratio to be 4:1, and reacting for 1 h. The effluent of the micro-electrolysis reactor enters a Fenton reactor, and hydrogen peroxide is added into the reactor according to the proportion of 4 mL/L; and opening an air pipeline valve, feeding air and stirring, and reacting for 2 h. And (4) enabling the effluent of the Fenton reactor to enter a pH adjusting tank, adding sodium carbonate to adjust the pH value to 7-9, precipitating for 2h, and filtering. The supernatant in the sedimentation tank can be continuously utilized and enters a subsequent treatment system, and the obtained precipitate can be used for subsequent resource recycling of arsenic.
Example 2
A process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination comprises the following steps: dissolving arsenic-containing waste residues and water according to the mass ratio of 1:1.2, feeding the obtained mixed slurry into a micro-electrolysis reactor, and adding H 2 SO 4 Adjusting the pH value of the slurry to 2-4, and adding the slurry in a mass ratio of 1:1 iron chips andand (3) after 15min of water inflow of the activated carbon, opening an air pipeline valve, opening a fan for aeration, controlling the air-water ratio to be 3:1, and reacting for 1.5 h. The effluent of the micro-electrolysis reactor enters a Fenton reactor, and hydrogen peroxide is added into the reactor according to the proportion of 3 mL/L; and opening an air pipeline valve, feeding air and stirring, and reacting for 1.5 h. And (4) enabling the effluent of the Fenton reactor to enter a pH adjusting tank, adding lime milk to adjust the pH value to 7-9, precipitating for 3 hours and filtering. The supernatant of the sedimentation tank can be discharged outwards or flows into other treatment units, and the sediment can be further treated to realize the resource treatment of arsenic.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A process for treating arsenic-containing waste residues by micro-electrolysis-Fenton combination is characterized by comprising the following steps:
(1) dissolving arsenic-containing waste residues in water to obtain mixed slurry;
(2) adding the mixed slurry into a micro-electrolysis reactor, adjusting the pH value to 2-4, and then adding activated carbon and scrap iron to carry out micro-electrolysis reaction;
(3) the effluent of the micro-electrolysis reactor enters a Fenton reactor, hydrogen peroxide is added to carry out Fenton reaction,
(4) and (4) enabling the effluent of the Fenton reactor to enter a pH adjusting tank, adjusting the pH value to 7-9, precipitating and filtering to obtain the final product.
2. The process for micro-electrolysis-Fenton combined treatment of arsenic-containing waste residue according to claim 1, wherein the mass ratio of the arsenic-containing waste residue to water in the step (1) is 1: (1-2).
3. The process for treating arsenic-containing waste residue by virtue of microelectrolysis-Fenton combination according to claim 1, wherein the mass ratio of the activated carbon to the scrap iron in the step (2) is 1: (1-2).
4. The process for treating arsenic-containing waste residue by micro-electrolysis-Fenton combination according to claim 1, wherein the time of the micro-electrolysis reaction in the step (2) is 0.5-2 h.
5. The process for micro-electrolysis-Fenton combined treatment of arsenic-containing waste residue according to claim 1, wherein in the step (3), the addition amount of the hydrogen peroxide is 2-6mL/L based on the total liquid amount in the Fenton reactor.
6. The process for micro-electrolysis-Fenton combined treatment of arsenic-containing waste residue according to claim 1, wherein the Fenton reaction time in the step (3) is 0.5-2 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210653320.1A CN115069744A (en) | 2022-06-09 | 2022-06-09 | Process for treating arsenic-containing waste residues through micro-electrolysis-Fenton combination |
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| CN202210653320.1A CN115069744A (en) | 2022-06-09 | 2022-06-09 | Process for treating arsenic-containing waste residues through micro-electrolysis-Fenton combination |
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| CN202210653320.1A Pending CN115069744A (en) | 2022-06-09 | 2022-06-09 | Process for treating arsenic-containing waste residues through micro-electrolysis-Fenton combination |
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| CN111470671A (en) * | 2020-04-16 | 2020-07-31 | 山东省科学院激光研究所 | Method for treating arsenic-containing organic wastewater |
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