CN110252239B - Method for efficiently controlling organic arsine pollution in water - Google Patents
Method for efficiently controlling organic arsine pollution in water Download PDFInfo
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- CN110252239B CN110252239B CN201910401024.0A CN201910401024A CN110252239B CN 110252239 B CN110252239 B CN 110252239B CN 201910401024 A CN201910401024 A CN 201910401024A CN 110252239 B CN110252239 B CN 110252239B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 44
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 30
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000000703 high-speed centrifugation Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 36
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 claims description 33
- 229950002705 arsanilic acid Drugs 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000011109 contamination Methods 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 150000004679 hydroxides Chemical class 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 abstract description 2
- 231100000086 high toxicity Toxicity 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 5
- 238000005349 anion exchange Methods 0.000 description 4
- VJWWIRSVNSXUAC-UHFFFAOYSA-N arsinic acid Chemical compound O[AsH2]=O VJWWIRSVNSXUAC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010871 livestock manure Substances 0.000 description 4
- 238000006385 ozonation reaction Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 244000144972 livestock Species 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 210000003608 fece Anatomy 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical compound OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 2
- 229960003052 roxarsone Drugs 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010027476 Metastases Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- -1 arsinic acid (p-amino phenylarsonic acid) Chemical compound 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000009401 metastasis Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000009374 poultry farming Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing organic arsine in water by using Layered Double Hydroxides (LDHs) to catalyze ozone, which can efficiently control organic arsine pollution in water. The invention aims to solve the problem of removing high-toxicity organic arsine in water and search for an efficient, green and economic method. The invention is realized by the following steps: firstly, preparing MnFe-LDHs; secondly, purifying raw water; and thirdly, recovering MnFe-LDHs by adopting a high-speed centrifugation or filtration method, thus finishing the method for removing organic arsine in water by using LDHs to catalyze ozone. The MnFe-LDHs can not only effectively catalyze ozone to remove organic arsine compounds in water (the removal rate is over 98 percent), but also can effectively enrich inorganic arsenic released in the degradation process (the removal rate is over 99.9 percent), and realize the safe control of organic arsine pollution in water. The metal ion leaching rate is extremely low in the using process, and secondary pollution is avoided; the solid catalyst used in the invention can be separated by filtration and recycled, and the operation cost is reduced.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing organic arsine in water by using Layered Double Hydroxides (LDHs) to catalyze ozone, which can efficiently control organic arsine pollution in water.
Background
Aromatic organic arsine compounds (AOCs) have long been used extensively as feed additives in livestock and poultry farming and have not been adequately regarded and strictly managed. After being taken into livestock and poultry, AOCs are hardly metabolized, and more than 90 percent of AOCs are discharged out of the body through feces in the original form. Because livestock manure is rich in nutrients, the livestock manure is generally accumulated and then applied to nearby farmlands as fertilizer. However, AOCs have relatively high water solubility, and with field irrigation and rain wash, AOCs in fertilizers can be transferred to ground water and surface water by leaching. It has been reported that about 57% of arsenic in livestock manure can pass through field runoff into natural waters. The concentration of the arsanilic acid (p-ASA) detected from a surface water sample near a certain pig farm in Zhujiang Delta reaches 0.53-2.6 mu g/L. The concentration of Roxarsone (ROX) detected in runoff flowing through the livestock and poultry manure improved soil is as high as 1.07 mg/L. Although AOCs have low toxicity and low dose and are not harmful to human body, they can generate inorganic arsenic with strong toxicity, high carcinogenicity and strong metastasis by biotransformation pathways in water environment. Therefore, it is necessary to find an effective treatment method to solve the problem of organic arsine pollution in the environment.
The catalytic ozone oxidation technology is a technology for removing hot spots of refractory organic pollutants by oxidation, and has an application prospect, namely, a plurality of hydroxyl free radicals (OH) with high oxidation activity are generated in a reaction system by adding a plurality of catalysts, so that the purpose of degrading the organic pollutants in water is achieved. The technology is divided into homogeneous catalytic ozonation and heterogeneous catalytic ozonation according to different catalysts. Commonly used catalysts for homogeneously catalyzed ozonation are typically transition metal ions such as: mn2+、Fe2+、Fe3+、Cu2+、Zn2+、Co2+And the like. The homogeneous catalyst has the advantages of high reaction speed, high reaction activity and the like, but after the reaction, metal ions are dissolved in water, so that the catalyst is greatly lost, and economic loss and environmental pollution are caused. Compared with homogeneous catalysis ozone oxidation, heterogeneous catalysis ozone oxidation can improve the removal efficiency of organic matters, and has the characteristics of simple operation, convenient maintenance, no secondary pollution and the like, so that the method has wide application prospect and development potential in the water treatment process. The Layered Double Hydroxides (LDHs) have unique layered structure, acid-base property, strong adsorbability and interlayer anion exchange capacity, and have wide application prospect in the field of catalysis.
Disclosure of Invention
The invention aims to solve the problem of safety control of organic arsine pollution in water, and provides a method for removing organic arsine in water by using LDHs to catalyze ozone for the first time.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for efficiently controlling organic arsine contamination in water, the method comprising the steps of:
the first step is as follows: preparation of MnFe-LDHs
S1, adding Mn (NO)3)2·4H2O and Fe (NO)3)3·9H2Adding O into deionized water, and stirring until the O is completely dissolved;
s2, NaOH and Na are added under the condition of stirring2CO3Dropwise adding the mixed solution into the mixed solution obtained in the step S1 to adjust the pH value to 9.8-10.1;
s3, aging the mixed solution obtained in the step S2 in a water bath at 60 ℃ for 4 hours, and maintaining the pH of the mixed solution at 9.8-10.1;
s4, filtering the mixed solution obtained in the step S3, washing the filtered precipitate with ethanol and deionized water for a plurality of times in sequence, and placing the washed precipitate in a 60 ℃ drying oven for vacuum drying overnight to obtain MnFe-LDHs;
the second step: purification of raw water
S5, placing raw water containing the arsanilic acid into a reactor, adding the MnFe-LDHs prepared in the step S4 into the reactor, fully stirring the mixture for 20-40 min by using a magnetic stirrer to achieve adsorption balance, and then introducing ozone into the reactor to react for 5-30 min, so that the high-efficiency removal of the arsanilic acid in the raw water and the high-efficiency enrichment of released inorganic arsenic can be realized;
the third step: recovery of MnFe-LDHs
S6, recovering MnFe-LDHs by a high-speed centrifugation or filtration method, washing the MnFe-LDHs for a plurality of times by ethanol and deionized water in sequence, and placing the cleaned MnFe-LDHs in a 60 ℃ oven for vacuum drying.
Preferably, the Mn (NO) in step S13)2·4H2O and Fe (NO)3)3·9H2The molar ratio of O is 1 to 1.5:1 to 1.5, more preferably 1: 1.
Preferably, the NaOH and Na are used in step S22CO3The molar ratio of (a) to (b) is 3 to 4:1, more preferably 3.5: 1.
Preferably, in step S5, the ratio of the amount mg of MnFe-LDHs added to the volume L of raw water is 10-500: 1.
Preferably, the ozone is prepared by pure oxygen in step S5, the ozone is introduced from the bottom of the reactor through a sand core aeration head, the temperature in the reactor is kept at 15-45 ℃, and the pH value of the solution in the reactor is 3-11.
Preferably, the flow rate of the ozone is 0.1-1.0L/min.
Preferably, the rotating speed of the centrifuge is 13000-16000 r/min, more preferably 15000r/min when MnFe-LDHs are recovered by adopting a high-speed centrifugation method.
The principle of the invention is as follows: at present, the methods for removing organic arsine in water mainly comprise an adsorption method and some advanced oxidation technologies including UV/H2O2、UV/TiO2、UV/O3Fenton oxidation, etc., but these techniques only achieve the oxidative conversion of organic arsine to inorganic arsenic and do not completely remove the arsenic contaminants from the water body. LDHs are a large class of important novel inorganic functional materials with supermolecular intercalation structures, unique spatial structures and higher ionsCapacity is exchanged. The interlayer anion exchange characteristic of MnFe-LDHs is favorable for ozone and inorganic arsenic to enter the interlayer, and the catalytic decomposition of ozone and the enrichment of released inorganic arsenic are accelerated; the high specific surface area can provide a large number of catalytic and adsorption active sites, which is beneficial to the catalysis of ozone and the adsorption of released inorganic arsenic; the regular and ordered open pore canals and the pore diameter with adjustable size can provide a substance transmission path for catalytic and adsorption reactions, and are beneficial to the diffusion of the AOCs and the released inorganic arsenic to active sites. The developed MnFe-LDHs is a green, efficient and stable multifunctional solid material, and can realize the safety control of the AOCs in water.
The invention has the beneficial effects that:
the MnFe-LDHs have interlayer anion exchange characteristics and hydroxide groups contained on a laminate thereof, and are favorable for catalyzing the decomposition of ozone and the adsorption of released inorganic arsenic;
secondly, the MnFe-LDHs can be recycled after being used, so that the operation cost is reduced;
thirdly, the invention is simple to operate and easy to realize;
the method adopted by the invention has extremely low metal ion dissolution concentration and extremely low secondary pollution;
fifthly, the method can effectively remove arsinic acid (p-amino phenylarsonic acid) in water, the removal rate is as high as more than 95%, and meanwhile, inorganic arsenic is basically not detected.
Drawings
FIG. 1 is a graph showing the effect of various processes on the removal of arsanilic acid;
FIG. 2 is a diagram showing the effect of MnFe-LDHs catalytic ozonation for degrading arsanilic acid in ten times in example 7 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the embodiment in combination with the attached drawings.
Example 1:
a method for efficiently controlling organic arsine contamination in water, said method comprising the steps of:
the first step is as follows: preparation of MnFe-LDHs
S1, mixing Mn (NO) with a molar ratio of 1:13)2·4H2O and Fe (NO)3)3·9H2Adding O into deionized water, and stirring until the O is completely dissolved;
s2, mixing NaOH and Na with a molar ratio of 3.5:1 under the condition of stirring2CO3Dropwise adding the mixed solution into the mixed solution obtained in the step S1 to adjust the pH value to 9.8-10.1;
s3, aging the mixed solution obtained in the step S2 in a water bath at 60 ℃ for 4 hours, and maintaining the pH of the mixed solution at 9.8-10.1;
s4, filtering the mixed solution obtained in the step S3, washing the filtered precipitate with ethanol and deionized water for a plurality of times in sequence, and placing the washed precipitate in a 60 ℃ drying oven for vacuum drying overnight to obtain MnFe-LDHs;
the second step is that: purification of raw water
S5, placing raw water into a reactor, wherein the volume of the raw water is 500mL, the concentration of arsanilic acid in the raw water is 1.2mg/L, adding 10mg of MnFe-LDHs prepared in the step S4 into the raw water, fully stirring the mixture for 30min by using a magnetic stirrer to achieve adsorption balance, preparing ozone by using pure oxygen, introducing the ozone from the bottom of the reactor through a sand core aeration head, reacting the mixture for 30min under the conditions of keeping the reaction temperature at 45 ℃ and the pH value at 7, and ensuring the flow rate of the ozone to be 0.5L/min, so that the high-efficiency removal of arsanilic acid in the raw water and the high-efficiency enrichment of released inorganic arsenic can be realized;
the third step: recovery of MnFe-LDHs
S6, recovering MnFe-LDHs by a high-speed centrifugation method, wherein the rotation speed of the centrifuge is 15000r/min, washing the MnFe-LDHs for a plurality of times by using ethanol and deionized water in sequence, and placing the cleaned MnFe-LDHs in an oven at 60 ℃ for vacuum drying.
In this example, the arsanilic acid removal rate was 96.2%, and no inorganic arsenic was detected.
Example 2:
a method for efficiently controlling organic arsine contamination in water, said method comprising the steps of:
the first step is as follows: preparation of MnFe-LDHs
S1, mixing Mn (NO) with a molar ratio of 1:13)2·4H2O and Fe (N)O3)3·9H2Adding O into deionized water, and stirring until the O is completely dissolved;
s2, mixing NaOH and Na with a molar ratio of 3.5:1 under the condition of stirring2CO3Dropwise adding the mixed solution into the mixed solution obtained in the step S1 to adjust the pH value to 9.8-10.1;
s3, aging the mixed solution obtained in the step S2 in a water bath at 60 ℃ for 4 hours, and maintaining the pH of the mixed solution at 9.8-10.1;
s4, filtering the mixed solution obtained in the step S3, washing the filtered precipitate with ethanol and deionized water for a plurality of times in sequence, and placing the washed precipitate in a 60 ℃ drying oven for vacuum drying overnight to obtain MnFe-LDHs;
the second step is that: purification of raw water
S5, placing raw water into a reactor, wherein the volume of the raw water is 500mL, the concentration of arsanilic acid in the raw water is 6mg/L, adding 30mg of MnFe-LDHs prepared in the step S4 into the raw water, fully stirring the mixture for 20min by using a magnetic stirrer to achieve adsorption balance, preparing ozone by using pure oxygen, introducing the ozone from the bottom of the reactor through a sand core aeration head, reacting the ozone for 20min under the conditions that the reaction temperature is 15 ℃ and the pH value is 9, and the flow rate of the ozone is 0.1L/min, so that the high-efficiency removal of arsanilic acid in the raw water and the high-efficiency enrichment of released inorganic arsenic can be realized;
the third step: recovery of MnFe-LDHs
S6, recovering MnFe-LDHs by adopting a filtering method, sequentially washing the MnFe-LDHs for a plurality of times by using ethanol and deionized water, and placing the cleaned MnFe-LDHs in an oven at 60 ℃ for vacuum drying.
In this example, the arsanilic acid removal rate was 95.4%, and no inorganic arsenic was detected.
Example 3:
in this example, the mass of MnFe-LDHs added to raw water was 100mg, and the other conditions were the same as in example 1.
In this example, the arsanilic acid removal rate was 98.4%, and no inorganic arsenic was detected.
Example 4:
the flow rate of ozone in this example was 1.0L/min, and the other conditions were the same as in example 2.
In this example, the arsanilic acid removal rate was 97.2%, and no inorganic arsenic was detected.
Example 5:
a method for efficiently controlling organic arsine contamination in water, said method comprising the steps of:
the first step is as follows: preparation of MnFe-LDHs
S1, mixing Mn (NO) with a molar ratio of 1:13)2·4H2O and Fe (NO)3)3·9H2Adding O into deionized water, and stirring until the O is completely dissolved;
s2, mixing NaOH and Na with a molar ratio of 3.5:1 under the condition of stirring2CO3Dropwise adding the mixed solution into the mixed solution obtained in the step S1 to adjust the pH value to 9.8-10.1;
s3, aging the mixed solution obtained in the step S2 in a water bath at 60 ℃ for 4 hours, and maintaining the pH of the mixed solution at 9.8-10.1;
s4, filtering the mixed solution obtained in the step S3, washing the filtered precipitate with ethanol and deionized water for a plurality of times in sequence, and putting the washed precipitate in a drying oven at 60 ℃ for vacuum drying overnight to obtain MnFe-LDHs;
the second step is that: purification of raw water
S5, placing raw water into a reactor, wherein the volume of the raw water is 500mL, the concentration of arsanilic acid in the raw water is 3.2mg/L, adding 20mg of MnFe-LDHs prepared in the step S4 into the raw water, fully stirring the mixture for 20min by using a magnetic stirrer to achieve adsorption balance, preparing ozone by using pure oxygen, introducing the ozone from the bottom of the reactor through a sand core aeration head, reacting the mixture for 30min under the conditions of keeping the reaction temperature at 15 ℃ and the pH value at 3, and ensuring the flow rate of the ozone to be 0.5L/min, so that the high-efficiency removal of arsanilic acid in the raw water and the high-efficiency enrichment of released inorganic arsenic can be realized;
the third step: recovery of MnFe-LDHs
S6, recovering MnFe-LDHs by a high-speed centrifugation method, wherein the rotation speed of the centrifuge is 15000r/min, washing the MnFe-LDHs for a plurality of times by using ethanol and deionized water in sequence, and placing the cleaned MnFe-LDHs in an oven at 60 ℃ for vacuum drying.
In this example, the arsanilic acid removal rate was 98.3%, and no inorganic arsenic was detected.
Example 6:
in this example, the reaction temperature was kept at 45 ℃ in step S5, and the other conditions were the same as in example 5.
In this example, the arsanilic acid removal rate was 98.5%, and no inorganic arsenic was detected.
Example 7:
the other conditions are the same as example 5, the used MnFe-LDHs are the MnFe-LDHs recovered in example 5, the test is repeated for 9 times, the used MnFe-LDHs are the MnFe-LDHs recovered last time each time, the total recycling time is 10 times, and the effect of catalyzing, ozonizing and degrading the arsanilic acid by using the MnFe-LDHs for ten times is shown in figure 2.
As shown in the attached figure 2, the MnFe-LDHs has good recycling performance, the removal rate of the catalytic ozone to the arsanilic acid is still higher than 96% after being recycled for ten times, and in addition, no inorganic arsenic is detected in the recycling process for ten times, which indicates that the MnFe-LDHs shows good recycling performance. In conclusion, the MnFe-LDHs not only can efficiently catalyze the arsinic acid in the water to be degraded by the ozone, but also can efficiently enrich the inorganic arsenic released in the degradation process of the arsinic acid, has the advantages of high efficiency, greenness, economy and the like, and is suitable for removing the organic arsine compounds in the water.
Example 8:
this example discusses the adsorption performance of MnFe-LDHs alone on arsinic acid:
the first step is as follows: preparation of MnFe-LDHs
S1, mixing Mn (NO) with a molar ratio of 1:13)2·4H2O and Fe (NO)3)3·9H2Adding O into deionized water, and stirring until the O is completely dissolved;
s2, mixing NaOH and Na with a molar ratio of 3.5:1 under the condition of stirring2CO3Dropwise adding the mixed solution into the mixed solution obtained in the step S1 to adjust the pH value to 9.8-10.1;
s3, aging the mixed solution obtained in the step S2 in a water bath at 60 ℃ for 4 hours, and maintaining the pH of the mixed solution at 9.8-10.1;
s4, filtering the mixed solution obtained in the step S3, washing the filtered precipitate with ethanol and deionized water for a plurality of times in sequence, and placing the washed precipitate in a 60 ℃ drying oven for vacuum drying overnight to obtain MnFe-LDHs;
the second step is that: purification of raw water
S5, placing raw water into a reactor, wherein the volume of the raw water is 500mL, the concentration of arsanilic acid in the raw water is 10mg/L, adding 50mg of MnFe-LDHs prepared in the step S4 into the raw water, and fully stirring the mixture for 20min by using a magnetic stirrer to achieve adsorption balance.
Example 9:
this example discusses the performance of ozone oxidation of arsinic acid alone:
the volume of raw water in the reactor is 500mL, and the concentration of arsanilic acid in the raw water is 10 mg/L;
and (3) introducing ozone into the reactor to perform reaction: ozone is prepared by pure oxygen, the ozone is introduced from the bottom of the reactor through a sand core aeration head at the flow rate of 0.5L/min, and the reaction is carried out for 30min under the conditions that the reaction temperature is kept at 25 ℃ and the pH value is 7, so that the partial removal of the arsanilic acid in the water can be realized.
Example 10:
this example discusses the performance experiment of MnFe-LDHs catalyzing ozone oxidation arsanilic acid:
the first step is as follows: preparation of MnFe-LDHs
S1, mixing Mn (NO) with a molar ratio of 1:13)2·4H2O and Fe (NO)3)3·9H2Adding O into deionized water, and stirring until the O is completely dissolved;
s2, mixing NaOH and Na with a molar ratio of 3.5:1 under the condition of stirring2CO3Dropwise adding the mixed solution into the mixed solution obtained in the step S1 to adjust the pH value to 9.8-10.1;
s3, aging the mixed solution obtained in the step S2 in a water bath at 60 ℃ for 4 hours, and maintaining the pH of the mixed solution at 9.8-10.1;
s4, filtering the mixed solution obtained in the step S3, washing the filtered precipitate with ethanol and deionized water for a plurality of times in sequence, and placing the washed precipitate in a 60 ℃ drying oven for vacuum drying overnight to obtain MnFe-LDHs;
the second step is that: purification of raw water
S5, placing raw water into a reactor, wherein the volume of the raw water is 500mL, the concentration of arsanilic acid in the raw water is 10mg/L, adding 50mg of MnFe-LDHs prepared in the step S4 into the raw water, fully stirring the mixture for 20min by using a magnetic stirrer to achieve adsorption balance, preparing ozone by using pure oxygen, introducing the ozone from the bottom of the reactor through a sand core aeration head, reacting for 30min under the conditions that the reaction temperature is 25 ℃ and the pH value is 7, and the flow rate of the ozone is 0.5L/min, so that the high-efficiency removal of the arsanilic acid in the raw water and the high-efficiency enrichment of released inorganic arsenic can be realized.
Examples 8, 9 and 10 discuss comparative experiments of MnFe-LDHs, ozone and MnFe-LDHs catalyzing ozone oxidation arsanilic acid respectively, and the comparative effect picture is shown in figure 1.
As shown in the attached figure 1, MnFe-LDHs can realize the removal of a small part of arsanilic acid (14.37%) through adsorption within 30 minutes; whereas ozone oxidation alone for 30 minutes was able to remove 37.22% of the arsanilic acid. When MnFe-LDHs and ozone are used together, the effect of removing the arsanilic acid in the water is obvious, and the removal rate reaches 98.04 percent within 30 minutes. In the oxidation process using ozone alone, 0.752mg/L inorganic arsenic is released in MnFe-LDHs/O by HPLC-inductively coupled plasma mass spectrometer3In the process, inorganic arsenic is not detected, which shows that MnFe-LDHs has good enrichment effect on inorganic arsenic released in the process of arsanilic acid degradation.
In conclusion, the MnFe-LDHs have interlayer anion exchange characteristics and hydroxide groups contained on the laminates thereof, and are favorable for catalyzing the decomposition of ozone and the adsorption of released inorganic arsenic; the MnFe-LDHs can be recycled after being used, so that the operation cost is reduced; the method is simple to operate and easy to realize; the method adopted by the invention has extremely low metal ion dissolution concentration and extremely low secondary pollution; the method can effectively remove the arsanilic acid in the water, the removal rate is up to more than 95%, and meanwhile, inorganic arsenic is basically not detected.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (7)
1. A method for efficiently controlling organic arsine pollution in water is characterized by comprising the following steps:
the first step is as follows: preparation of MnFe-LDHs
S1, adding Mn (NO)3)2·4H2O and Fe (NO)3)3·9H2Adding O into deionized water, and stirring until the O is completely dissolved;
s2, NaOH and Na are added under the condition of stirring2CO3The mixed solution is dropwise added into the mixed solution obtained in the step S1 to adjust the pH value of the mixed solution to 9.8-10.1;
s3, aging the mixed solution obtained in the step S2 in a water bath at 60 ℃ for 4 hours, and maintaining the pH of the mixed solution at 9.8-10.1;
s4, filtering the mixed solution obtained in the step S3, washing the filtered precipitate with ethanol and deionized water for a plurality of times in sequence, and placing the washed precipitate in a 60 ℃ drying oven for vacuum drying overnight to obtain MnFe-LDHs;
the second step is that: purification of raw water
S5, placing raw water containing arsanilic acid into a reactor, adding the MnFe-LDHs prepared in the step S4 into the reactor, fully stirring the raw water for 20-40 min by using a magnetic stirrer to achieve adsorption balance, introducing ozone into the reactor for reacting for 5-30 min, introducing the ozone from the bottom of the reactor through a sand core aeration head, keeping the temperature in the reactor at 15-45 ℃, and the pH of a solution in the reactor at 3-11, so that the high-efficiency removal of the arsanilic acid in the raw water and the high-efficiency enrichment of released inorganic arsenic can be realized;
the third step: recovery of MnFe-LDHs
S6, recovering MnFe-LDHs by a high-speed centrifugation or filtration method, washing the MnFe-LDHs for a plurality of times by ethanol and deionized water in sequence, and placing the cleaned MnFe-LDHs in a 60 ℃ oven for vacuum drying.
2. The method for efficiently controlling organic arsine contamination in water of claim 1, wherein the Mn (NO) in step S13)2·4H2O and Fe (NO)3)3·9H2The molar ratio of O is 1-1.5: 1-1.5.
3. The method for efficiently controlling organic arsine contamination in water of claim 1, wherein the NaOH and Na are added in step S22CO3The molar ratio of (A) to (B) is 3-4: 1.
4. The method for efficiently controlling organic arsine pollution in water according to claim 1, wherein the ratio of the dosage mg of MnFe-LDHs to the volume L of raw water in step S5 is 10-500: 1.
5. The method for efficiently controlling organic arsine contamination in water of claim 4, wherein in step S5, the ozone is prepared as pure oxygen.
6. The method for efficiently controlling organic arsine contamination in water as recited in claim 5, wherein the flow rate of said ozone is 0.1-1.0L/min.
7. The method for efficiently controlling organic arsine pollution in water according to claim 1, wherein the rotation speed of a centrifuge is 13000-16000 r/min when MnFe-LDHs are recovered by a high-speed centrifugation method.
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Application publication date: 20190920 Assignee: Tongxiang Tujian Intelligent Technology Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980037543 Denomination of invention: An Efficient Method for Controlling Organic Arsenic Pollution in Water Granted publication date: 20220617 License type: Common License Record date: 20230705 |
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