CN113880220A - Method for removing arsinic acid in water by using cerium-manganese bimetallic catalyst to activate persulfate and synchronously adsorb and degrade - Google Patents
Method for removing arsinic acid in water by using cerium-manganese bimetallic catalyst to activate persulfate and synchronously adsorb and degrade Download PDFInfo
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- CN113880220A CN113880220A CN202111281770.4A CN202111281770A CN113880220A CN 113880220 A CN113880220 A CN 113880220A CN 202111281770 A CN202111281770 A CN 202111281770A CN 113880220 A CN113880220 A CN 113880220A
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- cerium
- water
- persulfate
- arsanilic acid
- bimetallic catalyst
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- YOSLGHBNHHKHST-UHFFFAOYSA-N cerium manganese Chemical compound [Mn].[Mn].[Mn].[Mn].[Mn].[Ce] YOSLGHBNHHKHST-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
- VJWWIRSVNSXUAC-UHFFFAOYSA-N arsinic acid Chemical compound O[AsH2]=O VJWWIRSVNSXUAC-UHFFFAOYSA-N 0.000 title claims abstract description 8
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229950002705 arsanilic acid Drugs 0.000 claims abstract description 92
- 150000000703 Cerium Chemical class 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 133
- 239000011259 mixed solution Substances 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000001360 synchronised effect Effects 0.000 claims description 11
- 239000012425 OXONE® Substances 0.000 claims description 7
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 abstract description 15
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 15
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 238000005406 washing Methods 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 238000003828 vacuum filtration Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
- 239000012452 mother liquor Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000000703 high-speed centrifugation Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 238000001994 activation Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- DDPGACIVVDXPCY-UHFFFAOYSA-N [As].[AsH3] Chemical compound [As].[AsH3] DDPGACIVVDXPCY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000008236 biological pathway Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- -1 metal oxide persulfate Chemical class 0.000 description 1
- 230000001394 metastastic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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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
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to the technical field of water treatment, in particular to a method for efficiently controlling the pollution of arsanilic acid in water by activating persulfate through a cerium-manganese bimetallic catalyst. The cerium-manganese bimetallic catalyst is prepared from potassium permanganate and cerium salt, and is combined with persulfate to remove arsinic acid in water. The invention provides a method for removing arsinic acid in water by catalyzing persulfate through a cerium-manganese bimetallic catalyst for the first time. In the method, the cerium-manganese bimetallic catalyst/persulfate system has good degradation capability of arsanilic acid under the condition of acidity to alkalescence, and meanwhile, cerium ferrite and manganese ferrite in the catalyst have strong adsorption capability on inorganic arsenic, so that the released inorganic arsenic can be adsorbed and fixed while the arsanilic acid is degraded. The cerium-manganese bimetallic catalyst prepared by the method can be recycled for multiple times, and the operation cost is reduced.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for efficiently controlling the pollution of arsanilic acid in water by activating persulfate through a cerium-manganese bimetallic catalyst.
Background
The arsanilic acid (p-ASA) is taken as a common feed additive, is hardly metabolized after being ingested by livestock and poultry, more than 90 percent of the arsanilic acid can be directly discharged out of a body along with excrement, and is easily discharged into a water environment along with culture wastewater after being irrigated in a farmland and washed by rainwater. Research shows that p-ASA is detected in environment media such as underground water, surface water, soil and the like near a farm. Although p-ASA is essentially harmless to the human body at low doses, in aqueous environments they can be transformed by biological and non-biological pathways to produce inorganic arsenic with strong toxicity, high carcinogenicity and strong metastatic properties. Therefore, there is a need to find an effective method for solving the pollution problem of the arsanilic acid in the water environment.
In recent years, based on sulfate radicals (SO)4 -High-grade oxidation technology has received wide attention from researchers. According to different catalysts, the method can be divided into a homogeneous catalysis persulfate technology and a heterogeneous catalysis persulfate technology. Transition metal ions, e.g. Mn2+、Fe2+、Fe3+、Cu2+、Zn2+、Co2+The catalyst is a common homogeneous persulfate catalyst, but has the problems of poor stability, difficult recovery, easy secondary pollution and the like. Compared with the homogeneous catalysis persulfate technology, the heterogeneous catalysis persulfate technology can improve the removal efficiency of organic matters, and has the characteristics of simple operation, convenient maintenance, no secondary pollution and the like, so the method has wide application prospect and development potential in the water treatment process. Wherein the metal oxide is a relatively common persulfate heterogeneous catalyst, such as Fe2O3，Co3O4，MnO2And the like. However, the rate limiting step in the reduction of high valence metal species greatly limits the ability of single metal oxidation to activate persulfate. Meanwhile, the single metal oxide is not high in inorganic arsenic enrichment efficiency, so that the cost of the single metal oxide persulfate activation process is high in the actual application process, and the feasibility is reduced. Aiming at the problems, the cerium-manganese bimetallic Catalyst (CMO) is prepared by a coprecipitation method, and the catalytic performance is further improved on the basis of utilizing the bimetal to accelerate the oxidation-reduction cycle, so that the pollution of the arsanilic acid in water is efficiently controlled.
Disclosure of Invention
The invention aims to solve the problem of arsine (arsenic) pollution related to arsine in water, and provides a method for removing arsine in water by catalyzing persulfate through a cerium-manganese bimetallic catalyst for the first time.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for removing arsinic acid in water by using a cerium-manganese bimetallic catalyst to activate persulfate and synchronously adsorb and degrade, which comprises the following steps:
(1) preparing a cerium-manganese bimetallic catalyst:
s1, adding cerium salt into water to dissolve to obtain a cerium salt solution A;
s2, mixing KMnO4Dissolving the mixed solution and NaOH by using water to obtain a mixed solution B;
s3, under the stirring condition, mixing the KMnO4Dropwise adding the mixed solution B of NaOH into the cerium salt solution A obtained in the step S1 to adjust the pH value of the mixed solution A to 7.0-8.0, so as to obtain a mixed solution C;
s4, stirring the mixed solution C obtained in the step S3, standing, filtering, and carrying out post-treatment on the solid to obtain a cerium-manganese bimetallic catalyst CMO;
(2) removing arsanilic acid in water: adding the cerium-manganese bimetallic catalyst CMO obtained in the step (1) into an aqueous solution containing the arsanilic acid, and then adding a persulfate or persulfate solution for reaction for a certain time to remove the arsanilic acid in the water.
Preferably, the concentration of the cerium salt solution in S1 in step (1) is 5mM in terms of cerium.
Preferably, the cerium salt in the step (1) in the S1 is cerium nitrate or cerium sulfate; more preferably, the cerium nitrate is Ce (NO)3)3·6H2O, cerium sulfate being Ce2(SO4)3·8H2O。
Preferably, KMnO in the step (1)4The molar ratio of the cerium element in the cerium salt to the cerium salt is 1: (2-10).
Preferably, KMnO in the mixed solution B in S2 in the step (1)4The concentration is 0.5-2.5 mM, and the concentration of NaOH is 1-5 mM.
Preferably, the stirring time in the step (1) S4 is 30-45 min.
Preferably, the standing time in the step (1) in S4 is 4-6 h.
Preferably, the post-treatment in S4 in step (1) includes washing and drying; more preferably, the washing is washing the solid with ethanol and pure water several times, preferably 3-5 times; and the drying is to dry the solid at the temperature of 55-75 ℃ for 12-24 h.
Preferably, the concentration of CMO in the aqueous solution containing arsanilic acid in the step (2) is 100-500 mg/L.
Preferably, the concentration of the arsanilic acid in the water solution containing the arsanilic acid in the step (2) is 5-20 mg/L.
Preferably, in the step (2), the cerium-manganese bimetallic catalyst CMO is added into the aqueous solution containing the arsanilic acid and then is oscillated or stirred for 20-40min to reach the adsorption equilibrium of the CMO on the arsanilic acid.
Preferably, the persulfate in the step (2) is potassium peroxymonosulfate, sodium persulfate or potassium persulfate.
Preferably, the molar ratio of the persulfate to the arsanilic acid in the step (2) is (5-100): 1.
preferably, the concentration of the persulfate in the aqueous solution containing the arsanilic acid (i.e. in the reaction system) in the step (2) is 0.1-10 mM.
Preferably, the step (2) is carried out at a temperature of 20-50 ℃.
Preferably, the step (2) is carried out at a pH of 3 to 11.
Preferably, the reaction time in the step (2) is 30-120min, and more preferably 60 min.
Preferably, the method further comprises: and (3) recovering the cerium-manganese bimetallic catalyst CMO: after the reaction in the step (2) is finished, recovering the CMO by adopting a vacuum filtration or high-speed centrifugation method, and washing and drying the CMO; more preferably, the washing is to sequentially wash the CMO with ethanol and pure water for a plurality of times, preferably 3 to 5 times, and the drying is to dry the washed CMO at 55 to 75 ℃; more preferably, when high speed centrifugation is used, the centrifuge is at least 10000 r/min.
The invention solves the problem that the inorganic arsenic in the water body can not be synchronously controlled when various advanced oxidation processes remove the organic arsine in the water body at present; solves the problem that the catalytic capability of the prior heterogeneous catalyst is greatly reduced in neutral or alkalescent environment. The CMO prepared by the invention has good activation effect on persulfate, and can quickly catalyze persulfate to oxidize and degrade arsanilic acid in water. Meanwhile, the material contains rich cerium element, manganese element and surface hydroxyl, so that the material has strong adsorption capacity on inorganic arsenic and can realize synchronous and efficient enrichment of inorganic arsenic in water. Can be repeatedly recycled.
Compared with the prior art, the invention has the beneficial effects that:
(1) cerium ferrite and manganese ferrite in the cerium-manganese bimetallic catalyst CMO have strong adsorption capacity on inorganic arsenic, and are beneficial to catalyzing persulfate and adsorbing and fixing released inorganic arsenic;
(2) the CMO can be recycled after being used, the effect is better, and the operation cost is effectively reduced;
(3) the CMO/persulfate system still has good degradation capability of the arsanilic acid under the neutral or weak alkaline condition;
(4) the method is simple to operate and easy to realize.
Drawings
FIG. 1 is a graph showing the variation of the percentage of arsanilic acid concentration with time under the conditions of experiment one, experiment two and experiment three of the present invention;
FIG. 2 is a graph of the percent arsanilic acid concentration versus time at four different pH conditions tested in accordance with the present invention;
FIG. 3 shows the arsanilic acid removal rate of 60min after each CMO recovery under the conditions of experiment five of the present invention.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
The first embodiment is as follows:
the embodiment provides a method for removing arsinic acid in water by catalyzing persulfate through a cerium-manganese bimetallic catalyst, which comprises the following steps:
preparation of cerium-manganese bimetallic catalyst
S1, adding cerium salt into 30mL of deionized water, and stirring for 20min at room temperature;
the cerium salt in step S1 is Ce (NO)3)3·6H2O or Ce2(SO4)3·8H2O, the concentration of cerium salt is 5mM calculated by cerium element;
s2, under the condition of keeping stirring, adding KMnO4Gradually dropwise adding the mixed solution of NaOH and NaOH into the mixed solution obtained in the step S1 at a dropwise adding speed of 2mL/min to adjust the pH value of the mixed solution to 7.0-8.0;
the KMnO in step S24The volume of the mixed solution of NaOH and NaOH is 30 mL;
the KMnO in step S24KMnO contained in the mixed solution with NaOH4The concentration is 0.5-2.5 mM;
the KMnO in step S24The concentration of NaOH contained in the mixed solution of NaOH and NaOH is 1-5 mM;
the KMnO in step S24The molar ratio of the cerium element in the cerium salt to the cerium salt is 1:(2～10)；
s3, continuously stirring the mixed solution in the step S2 for 30-45 min, and standing and aging at room temperature for 4-6 h;
s4, carrying out vacuum filtration on the mixed solution, and washing the obtained gray black precipitate with ethanol and pure water for a plurality of times in sequence;
s5, drying the washed precipitate in an oven at 55 ℃ for 12-24 h to obtain CMO;
secondly, removing the arsanilic acid in the water
S6, placing raw water containing the arsanilic acid into a reactor, adding the CMO prepared in the step S5 into the reactor, oscillating the reactor in a water bath oscillator for 20-40min to achieve adsorption balance, and then adding persulfate or persulfate solution into the reactor to react for 5-60min, so that the high-efficiency removal of the arsanilic acid in the raw water and the synchronous high-efficiency enrichment of released inorganic arsenic can be realized;
the addition amount of the CMO in the step S6 is 100-500 mg/L;
the concentration of the aqueous solution containing the arsanilic acid in the step S6 is 5-20 mg/L;
the volume of the aqueous solution containing arsanilic acid in the step S6 is 100 mL;
in the step S6, the persulfate is potassium peroxymonosulfate, sodium persulfate or potassium persulfate; the concentration of the persulfate in the aqueous solution containing the arsanilic acid (namely in the reaction system) is 0.1-10 mM;
the molar ratio of the persulfate to the arsanilic acid in the aqueous solution in the step S6 is (5-100): 1;
in step S6, the temperature is kept at 20-50 ℃, and the pH is kept at 3-11;
the reaction time is 5-60 min;
III, recovery of CMO
S7, recovering the CMO by adopting a vacuum filtration or high-speed centrifugation method, sequentially washing the CMO by using ethanol and deionized water for a plurality of times, and drying the washed CMO in an oven at 55 ℃.
And step S7, washing the CMO with ethanol and deionized water for not less than 5 times.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the concentration of the target pollutant arsanilic acid in step S6 is 5-10 mg/L, and other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: the difference between the second embodiment and the first to the second embodiments is that the concentration of the target pollutant arsanilic acid in the second step is 10-20 mg/L, and other steps and parameters are the same as those in the first to the second embodiments.
The fourth concrete implementation mode: the difference between this embodiment and the first to the third embodiment is that the amount of CMO added in the second step is 200-300 mg/L. Other steps and parameters are the same as those in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to the fourth embodiments is that the amount of CMO added in the second step is 300-400 mg/L. Other steps and parameters are the same as those in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between the first embodiment and the fifth embodiment is that the initial pH of the water-contaminated arsanilic acid solution is 3 to 10. Other steps and parameters are the same as those in one of the first to fifth embodiments.
To verify the beneficial effects of the present invention, the following experiments were performed:
experiment one: a method for removing arsinic acid in water by catalyzing persulfate through a cerium-manganese bimetallic catalyst comprises the following steps:
preparation of cerium-manganese bimetallic catalyst
S1, adding Ce (NO)3)3·6H2Adding O into 30mL of deionized water, and stirring for 20min at room temperature;
ce (NO) described in step S13)3·6H2The mass of O is 2.171 g;
s2, under the condition of keeping stirring, adding KMnO4Gradually dropwise adding the mixed solution of NaOH and the mixed solution of NaOH into the mixed solution obtained in the step S1 to adjust the pH value of the mixed solution to 7.0-8.0;
the KMnO in step S24The volume of the mixed solution of NaOH and NaOH is 30 mL;
the KMnO in step S24And NaOH in the mixed solutionKMnO contained4The mass is 0.158 g;
the KMnO in step S24The mass of NaOH contained in the mixed solution of NaOH and NaOH was 1.000 g;
s3, continuously stirring the mixed solution in the step S2 for 30min, and standing and aging at room temperature for 4 h;
s4, carrying out vacuum filtration on the mixed solution, and washing the obtained gray black precipitate with ethanol and pure water for a plurality of times in sequence;
s5, drying the washed precipitate in an oven at 55 ℃ for 24 hours to obtain CMO;
secondly, removing the arsanilic acid in the water
S6, placing raw water containing the arsanilic acid into a reactor, adding the CMO prepared in the step S5 into the reactor, oscillating the reactor in a water bath oscillator for 30min to achieve adsorption balance, and then adding persulfate solution into the reactor to react for 60min, 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 addition amount of the CMO in the step S6 is 200 mg/L;
the concentration of the aqueous solution containing the arsanilic acid in the step S6 is 10 mg/L;
the volume of the aqueous solution containing arsanilic acid in the step S6 is 100 mL;
in the step S6, the persulfate solution is a potassium peroxymonosulfate solution;
the volume of the persulfate mother liquor added in the step S6 is 1mL, the concentration of the persulfate mother liquor is 30mM, and the concentration of persulfate in the arsanilic acid aqueous solution is 0.3 mM;
the temperature of the reaction solution in step S6 is 25 ℃;
the initial pH of the reaction solution in step S6 was 7.0;
III, recovery of CMO
S7, recovering the CMO by adopting a vacuum filtration or high-speed centrifugation method, sequentially washing the CMO by using ethanol and deionized water for a plurality of times, and drying the washed CMO in an oven at 55 ℃.
And step S7, washing the CMO with ethanol and deionized water for not less than 5 times.
The data results are shown in fig. 1, which shows that the arsanilic acid removal rate can reach 95.69% when persulfate is used in combination with CMO, and no inorganic arsenic is detected in the residual solution. Therefore, the CMO not only can effectively activate persulfate, but also has good enrichment effect on inorganic arsenic.
Experiment two: the adsorption experiment of the arsanilic acid by independently adding CMO is carried out according to the following method:
preparation of cerium-manganese bimetallic catalyst
S1, adding Ce (NO)3)3·6H2Adding O into 30mL of deionized water, and stirring for 20min at room temperature;
ce (NO) described in step S13)3·6H2The mass of O is 2.171 g;
s2, under the condition of keeping stirring, adding KMnO4Gradually dropwise adding the mixed solution of NaOH and the mixed solution of NaOH into the mixed solution obtained in the step S1 to adjust the pH value of the mixed solution to 7.0-8.0;
the KMnO in step S24The volume of the mixed solution of NaOH and NaOH is 30 mL;
the KMnO in step S24KMnO contained in the mixed solution with NaOH4The mass is 0.158 g;
the KMnO in step S24The mass of NaOH contained in the mixed solution of NaOH and NaOH was 1.000 g;
s3, continuously stirring the mixed solution in the step S2 for 30min, and standing and aging at room temperature for 4 h;
s4, carrying out vacuum filtration on the mixed solution, and washing the obtained gray black precipitate with ethanol and pure water for a plurality of times in sequence;
s5, drying the washed precipitate in an oven at 55 ℃ for 24 hours to obtain CMO;
secondly, removing the arsanilic acid in the water
S6, placing raw water containing arsanilic acid into a reactor, adding the CMO prepared in the step S5 into the reactor, and oscillating the reactor in a water bath oscillator for 60 min;
the addition amount of the CMO in the step S6 is 200 mg/L;
the concentration of the aqueous solution containing the arsanilic acid in the step S6 is 10 mg/L;
the volume of the aqueous solution containing arsanilic acid in the step S6 is 100 mL;
the temperature of the reaction solution in step S6 is 25 ℃;
the initial pH of the reaction solution in step S6 was 7.0;
recovery of CMO
S7, recovering the CMO by adopting a vacuum filtration or high-speed centrifugation method, sequentially washing the CMO by using ethanol and deionized water for a plurality of times, and drying the washed CMO in an oven at 55 ℃.
And step S7, washing the CMO with ethanol and deionized water for not less than 5 times.
The results are shown in figure 1 and the data indicate that CMO can remove 19.35% of the arsanilic acid by adsorption within 60 min.
Experiment three: the oxidation experiment of arsanilic acid by adding persulfate alone is carried out according to the following method:
firstly, preparing an arsanilic acid aqueous solution: preparing an arsanilic acid aqueous solution with a certain concentration and transferring the arsanilic acid aqueous solution into a reactor;
the concentration of the arsanilic acid-containing aqueous solution in the first step is 10 mg/L;
the volume of the aqueous arsanilic acid solution transferred to the reactor in step one was 100 mL.
Secondly, persulfate is added: adding a persulfate solution into the reactor in the step one, maintaining the temperature of the reaction solution at 25 ℃, and carrying out oscillation reaction for 60min to finish an oxidation experiment of the monodisperse acid by independently adding persulfate;
in the second step, the persulfate solution is a potassium peroxymonosulfate solution;
in the second step, the volume of the persulfate mother liquor added is 1mL, the concentration of the persulfate mother liquor is 30mM, and the concentration of persulfate in the arsanilic acid aqueous solution is 0.3 mM;
in the second step, the temperature of the reaction solution is 25 ℃;
the initial pH of the reaction solution in step two was 7.0.
The data results are shown in fig. 1 and show that persulfate alone removed 29.78% of the arsanilic acid in 60 min.
Experiment four: the experiment of degrading the arsanilic acid by the CMO activated persulfate in different pH ranges is carried out according to the following steps:
preparation of cerium-manganese bimetallic catalyst
S1, adding Ce (NO)3)3·6H2Adding O into 30mL of deionized water, and stirring for 20min at room temperature;
ce (NO) described in step S13)3·6H2The mass of O is 2.171 g;
s2, under the condition of keeping stirring, adding KMnO4Gradually dropwise adding the mixed solution of NaOH and the mixed solution of NaOH into the mixed solution obtained in the step S1 to adjust the pH value of the mixed solution to 7.0-8.0;
the KMnO in step S24The volume of the mixed solution of NaOH and NaOH is 30 mL;
the KMnO in step S24KMnO contained in the mixed solution with NaOH4The mass is 0.158 g;
the KMnO in step S24The mass of NaOH contained in the mixed solution of NaOH and NaOH was 1.000 g;
s3, continuously stirring the mixed solution in the step S2 for 30min, and standing and aging at room temperature for 4 h;
s4, carrying out vacuum filtration on the mixed solution, and washing the obtained gray black precipitate with ethanol and pure water for a plurality of times in sequence;
s5, drying the washed precipitate in an oven at 55 ℃ for 24 hours to obtain CMO;
secondly, adjusting the pH value of the arsanilic acid aqueous solution
S6, using NaOH or H2SO4Adjusting the initial pH value of the arsanilic acid aqueous solution by the solution;
NaOH or H in step S62SO4The concentration of the solution is 0.1 mol/L;
the initial pH values of the adjusted arsanilic acid aqueous solution in step S6 are 11, 9, 7, 5, 3;
thirdly, removing arsanilic acid in water
S7, placing raw water containing the arsanilic acid into a reactor, adding the CMO prepared in the step S5 into the reactor, oscillating the reactor in a water bath oscillator for 30min to achieve adsorption balance, and then adding persulfate stock solution into the reactor to react for 60min, 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 addition amount of the CMO in the step S7 is 200 mg/L;
the concentration of the aqueous solution containing the arsanilic acid in the step S7 is 10 mg/L;
the volume of the arsanilic acid polluted water solution in the step S7 is 100 mL;
in the step S7, the persulfate solution is a potassium peroxymonosulfate solution;
the volume of the persulfate-added persulfate mother liquor in the step S7 is 1mL, the concentration of the persulfate mother liquor is 30mM, and the concentration of persulfate in the arsanilic acid aqueous solution is 0.3 mM;
the temperature of the reaction solution in step S7 is 25 ℃;
recovery of CMO
S8, recovering the CMO by adopting a vacuum filtration or high-speed centrifugation method, sequentially washing the CMO by using ethanol and deionized water for a plurality of times, and drying the washed CMO in an oven at 55 ℃.
And step S8, washing the CMO with ethanol and deionized water for not less than 5 times.
The results are shown in FIG. 2, which is a graph of the arsanilic acid concentration in a CMO/persulfate system as a function of time at various initial pH conditions. The system has better degradation capability under the condition that the pH value is 3.0-7.0, the removal rate of the arsanilic acid is always kept above 90%, and even under the alkaline condition that the pH value is 9.0 and 11.0, the system still has better removal effect which is more than 80%.
Experiment five: the CMO recovery and repeated use of the activated persulfate to degrade the arsanilic acid experiment were carried out according to the following steps:
preparation of cerium-manganese bimetallic catalyst
S1, adding Ce (NO)3)3·6H2Adding O into 30mL of deionized water, and stirring for 20min at room temperature;
ce (NO) described in step S13)3·6H2The mass of O is 2.171 g;
s2, under the condition of keeping stirring, adding KMnO4Gradually dropwise adding the mixed solution of NaOH and the mixed solution of NaOH into the mixed solution obtained in the step S1 to adjust the pH value of the mixed solution to 7.0-8.0;
the KMnO in step S24The volume of the mixed solution of NaOH and NaOH is 30 mL;
the KMnO in step S24KMnO contained in the mixed solution with NaOH4The mass is 0.158 g;
the KMnO in step S24The mass of NaOH contained in the mixed solution of NaOH and NaOH was 1.000 g;
s3, continuously stirring the mixed solution in the step S2 for 30min, and standing and aging at room temperature for 4 h;
s4, carrying out vacuum filtration on the mixed solution, and washing the obtained gray black precipitate with ethanol and pure water for a plurality of times in sequence;
s5, drying the washed precipitate in an oven at 55 ℃ for 24 hours to obtain CMO;
secondly, removing the arsanilic acid in the water
S6, placing raw water containing the arsanilic acid into a reactor, adding the CMO prepared in the step S5 into the reactor, oscillating the reactor in a water bath oscillator for 30min to achieve adsorption balance, and then adding persulfate stock solution into the reactor to react for 60min, 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 addition amount of the CMO in the step S6 is 200 mg/L;
the concentration of the aqueous solution containing the arsanilic acid in the step S6 is 10 mg/L;
the volume of the aqueous solution containing arsanilic acid in the step S6 is 100 mL;
in the step S6, the persulfate solution is a potassium peroxymonosulfate solution;
the volume of the persulfate mother liquor added in the step S6 is 1mL, the concentration of the persulfate mother liquor is 30mM, and the concentration of persulfate in the arsanilic acid aqueous solution is 0.3 mM;
the temperature of the reaction solution in step S6 is 25 ℃;
the initial pH of the reaction solution in step S6 was 7.0;
III, recovery of CMO
S7, recovering the CMO by adopting a vacuum filtration or high-speed centrifugation method, sequentially washing the CMO by using ethanol and deionized water for a plurality of times, and drying the washed CMO in an oven at 55 ℃.
And step S7, washing the CMO with ethanol and deionized water for not less than 5 times.
Four, CMO repeated use of activated persulfate to degrade arsanilic acid
S7, weighing a certain amount of recovered, cleaned and dried CMO for activating persulfate to degrade arsanilic acid, and the rest is the same as the step S6.
The data result is shown in fig. 3, and shows that after five times of recycling, the repeatedly used CMO and persulfate still have good degradation capability on the arsanilic acid, and the removal rate of the arsanilic acid is always kept above 85%. Indicating that the CMO has better stability.
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 (10)
1. A method for removing arsinic acid in water by using a cerium-manganese bimetallic catalyst to activate persulfate and synchronously adsorb and degrade the persulfate is characterized by comprising the following steps of:
(1) preparing a cerium-manganese bimetallic catalyst:
s1, adding cerium salt into water to dissolve to obtain a cerium salt solution A;
s2, mixing KMnO4Dissolving the mixed solution and NaOH by using water to obtain a mixed solution B;
s3, under the stirring condition, dropwise adding the mixed solution B into the cerium salt solution A to adjust the pH value to 7.0-8.0, so as to obtain a mixed solution C;
s4, stirring and standing the mixed solution C, filtering, and post-treating the solid to obtain a cerium-manganese bimetallic catalyst;
(2) removing arsanilic acid in water: and (2) adding the cerium-manganese bimetallic catalyst in the step (1) into an aqueous solution containing the arsanilic acid, and then adding persulfate or persulfate solution for reaction for a certain time to remove the arsanilic acid in the water.
2. The method for removing the arsanilic acid in the water by the synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate according to claim 1, wherein the cerium salt in the step (1) in the step S1 is cerium nitrate or cerium sulfate.
3. The method for removing the arsanilic acid in the water by the synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate according to claim 1, wherein the KMnO in the step (1)4The molar ratio of the cerium element in the cerium salt to the cerium salt is 1: (2-10).
4. The method for removing the arsanilic acid in the water by the synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate according to claim 1, wherein the KMnO in the mixed solution B in S2 in the step (1)4The concentration is 0.5-2.5 mM, and the concentration of NaOH is 1-5 mM.
5. The method for removing the arsanilic acid in the water through synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate according to claim 1, wherein in the step (1), the stirring time in S4 is 30-45 min, and the standing time is 4-6 h.
6. The method for removing the arsanilic acid in the water by synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate according to claim 1, wherein the concentration of the arsanilic acid in the water solution containing the arsanilic acid in the step (2) is 5-20 mg/L.
7. The method for removing the arsanilic acid in the water by the synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate as claimed in claim 1, wherein the concentration of the cerium-manganese bimetallic catalyst in the water solution containing the arsanilic acid in the step (2) is 100-500 mg/L.
8. The method for removing the arsanilic acid in the water by the synchronous adsorption and degradation of the double-metal cerium-manganese catalyst activated persulfate according to claim 1, wherein the persulfate in the step (2) is potassium peroxymonosulfate, sodium persulfate or potassium persulfate.
9. The method for removing the arsanilic acid in the water by synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate according to claim 1, wherein the molar ratio of the persulfate to the arsanilic acid in the step (2) is (5-100): 1.
10. the method for removing the arsanilic acid in the water by the synchronous adsorption and degradation of the cerium-manganese bimetallic catalyst activated persulfate according to claim 1, wherein the reaction time in the step (2) is 30-120 min.
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