CN113697931A - Self-doped bismuth tungstate (Bi)2.15WO6) Method for efficiently removing bisphenol A by Persulfate (PS) system - Google Patents

Self-doped bismuth tungstate (Bi)2.15WO6) Method for efficiently removing bisphenol A by Persulfate (PS) system Download PDF

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CN113697931A
CN113697931A CN202111042360.4A CN202111042360A CN113697931A CN 113697931 A CN113697931 A CN 113697931A CN 202111042360 A CN202111042360 A CN 202111042360A CN 113697931 A CN113697931 A CN 113697931A
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bisphenol
solution
suspension
solid
efficiently removing
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CN113697931B (en
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刘勇
刘天宇
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Tianjin University of Technology
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/31Chromium, molybdenum or tungsten combined with bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/023Reactive oxygen species, singlet oxygen, OH radical
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
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Abstract

The invention provides self-doped bismuth tungstate (Bi)2.15WO6) The method for efficiently removing the bisphenol A by a non-free radical mechanism through a Persulfate (PS) system comprises the following steps: s1: bi to be prepared2.15WO6Placing the solid in water to obtain a suspension, and adjusting the pH of the suspension to be more than 7.0 by using acid or alkali; s2: to Bi2.15WO6Respectively adding PS solution and bisphenol A solution with the same pH value into the suspension and starting to stir at a constant speed; s3: timing is started when the bisphenol A solution is added and the sample is taken for detection at regular timeThe concentration of bisphenol A. The invention states that Bi2.15WO6The method for efficiently removing the bisphenol A through a non-free radical mechanism in the absence of light in the PS system obtains a certain amount of phenolic polymers in the reaction process, and realizes resource utilization while removing the bisphenol A.

Description

Self-doped bismuth tungstate (Bi)2.15WO6) Method for efficiently removing bisphenol A by Persulfate (PS) system
Technical Field
The invention belongs to the field of bisphenol A-containing wastewater environmental treatment, and particularly relates to a non-free radical mechanism self-doped bismuth tungstate (Bi)2.15WO6) A method for removing bisphenol A by a Persulfate (PS) system.
Background
Bisphenol A is an important chemical substance and is widely applied to synthesis of materials such as polycarbonate, epoxy resin and the like. Bisphenol a can interact with a variety of biological receptors, such as Estrogen Receptor (ER), Androgen Receptor (AR), Thyroid Hormone Receptor (THR), interfering with human endocrine. In recent years, some countries have also established sewage discharge standards. The emission limits for bisphenol A in Japan and the United states are 2.5mg/L and 0.5mg/L, respectively, with the highest emission limit in China being 1 mg/L. When bisphenol a contaminants enter the aqueous environment, they interfere with human endocrine and have a serious impact on the human reproductive, neurological and immune systems.
Advanced Oxidation Processes (AOPs) are a pollutant treatment technology that has emerged in the 80 s of the 20 th century. The conventional AOPs technology degrades organic pollutants in wastewater by generating strong oxidizing OH to mineralize the organic matters. However, this technique has not been effective in removing refractory organics in the face of these. In recent years, the AOPs technology based on PS has attracted attention from a large number of researchers. PS exhibits high oxidation reactivity towards many organic contaminants. Oxidized SO generated during PS activation under acidic conditions4 ·-And OH exhibits high reactivity to organic contaminants. With hydrogen peroxide (H)2O2) Compared with Peroxymonosulfate (PMS), PS has the advantages of more stable chemical property, lower transportation cost, lower price and the like. But SO4 ·-And OH has low selectivity to pollutants and can cause certain damage to the primary environment.
Bi2.15WO6Widely used as a photocatalyst in the field of photocatalysis, in Bi2.15WO6In the research of photocatalytic oxidation pollutants, various active oxygen species (ROS) such as holes (h +) and superoxide radical (O)2-) And hydroxyl radicals (. OH) as the main oxidizing species. However, Bi2.15WO6The main role in the process of catalytic oxidation of pollutants is to generate radicals with strong oxidizing property, so Bi is used2.15WO6The removal pathway as a catalyst is a free radical mechanism.
In conclusion, Bi2.15WO6the/PS system is efficient and economical in removing pollutants, so that Bi is applied2.15WO6The PS system can efficiently remove the wastewater containing the bisphenol A, and the reaction is carried out through a non-free radical mechanism, and the resource recycling of the oxidation product is a great technical innovation.
Disclosure of Invention
In view of the above, the present invention states Bi2.15WO6The method for efficiently removing the bisphenol A through a non-free radical mechanism in the absence of light in the PS system obtains a certain amount of phenolic polymers in the reaction process, and realizes resource utilization while removing the bisphenol A.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
Bi2.15WO6the method for efficiently removing bisphenol A by a non-free radical mechanism in the absence of light by the aid of the PS system is characterized by comprising the following steps:
in the first step, the prepared Bi2.15WO6The solid is placed in water to give a suspension, which is adjusted to a pH of greater than 7.0 using an acid or base.
And secondly, adding Persulfate (PS) solution and bisphenol A solution with the same pH value into the obtained suspension respectively and starting to stir at a constant speed.
And thirdly, timing when the bisphenol A solution is added, and sampling at regular time to detect the concentration of the bisphenol A.
Further, the solid Bi is prepared by a hydrothermal method2.15WO6
Further, mixing a bismuth nitrate solution and a sodium tungstate solution in proportion at normal temperature, adjusting the pH to 1.0 by using acid or alkali, uniformly stirring, placing the mixture in an oven to start reaction, cooling, and cleaning, drying and grinding the obtained solid to obtain the solid Bi2.15WO6
Further, uniformly stirring a bismuth nitrate solution dissolved in a 1M nitric acid solution and a sodium tungstate solution dissolved in a 1M sodium hydroxide solution according to the proportion of Bi to W being 2.15 to 1, placing the mixture in an oven for reaction after the mixture is completely uniform, and cleaning, drying and grinding the obtained solid after cooling to obtain the solid Bi2.15WO6
Further, reacting the uniformly mixed bismuth nitrate solution and sodium tungstate solution in an oven at 180 ℃ for 24 hours.
Further, in the first step, Bi to be prepared2.15WO6The solid is placed in waterA suspension is obtained, which is adjusted to a pH of more than 7.0 using 1M sodium hydroxide solution or 1M hydrochloric acid solution.
Further, 1M methanol and 20mM chloroform are respectively added into the solution obtained in the second step, the uniform stirring is started, and the time is counted along with the addition of the bisphenol A solution, and the bisphenol A concentration is periodically sampled and detected to carry out the free radical masking experiment.
Further, collecting insoluble solids in the system after reaction, washing with deionized water, drying to obtain insoluble products, and performing FTIR analysis on the insoluble products to obtain the phenolic polymer as the product.
Compared with the prior art, the invention uses the self-doped bismuth tungstate (Bi)2.15WO6) The method for efficiently removing the bisphenol A by the Persulfate (PS) system has the following advantages:
(1) use of Bi2.15WO6In the process of removing the bisphenol A-containing wastewater by the PS system, the bisphenol A is removed by a non-free radical mechanism, so that not only are pollutants removed, but also the phenolic polymer is obtained, the reaction is efficient, and the resource utilization is realized.
(2) Under the condition of being more than neutral, Bi2.15WO6The way of removing bisphenol A by the PS system is a non-free radical mechanism, and is completely different from the free radical way of the traditional AOPs technology.
(3) The common degradation path of bisphenol A-containing wastewater usually uses photocatalytic oxidation or strong oxidizing free radicals for degradation, which increases the cost and destroys the original environment, while Bi2.15WO6The removal of bisphenol A by the PS system does not need an additional light source and does not generate a large amount of free radicals, thereby reducing the cost of wastewater treatment.
(4) The insoluble phenolic polymer is obtained in the process of removing the pollutants, the polymer can be obtained while the bisphenol A is removed, the resource treatment of the bisphenol A wastewater is realized, and a new thought is provided for efficiently removing the bisphenol A pollutants at low cost.
Drawings
FIG. 1 shows Bi obtained in example 12.15WO6XRD pattern of (a);
FIG. 2 is a schematic view of an embodimentBi of examples 1 and 22.15WO6Degradation diagram of bisphenol A by PS system;
FIG. 3 shows Bi of example 12.15WO6Radical masking experimental plot for the/PS system;
FIG. 4 is an FTIR chart of insoluble matter after reaction obtained in example 1.
Detailed Description
1. Preparation of Bi2.15WO6The process is as follows:
uniformly stirring a bismuth nitrate solution dissolved in a 1M nitric acid solution and a sodium tungstate solution dissolved in a 1M sodium hydroxide solution according to the proportion of Bi to W being 2.15 to 1, putting the mixture into an oven to react for 24 hours at 180 ℃ in the oven after the mixture is completely uniform, and cleaning, drying and grinding the obtained solid after cooling to obtain the solid Bi2.15WO6After being ground into uniform powder using an agate mortar, the powder was put into a dry box for standby, and XRD analysis was performed on the prepared sample, and the results are shown in fig. 1.
2.Bi2.15WO6Experiment for removing bisphenol A by PS system
Weighing a certain amount of Bi2.15WO6The suspension was placed in a 100mL beaker containing a quantity of deionized water and adjusted to greater than 7.0 using 1M sodium hydroxide solution or hydrochloric acid solution. Then, a certain volume of PS and bisphenol A solution with the same pH value is added into the suspension liquid in sequence, and the suspension liquid is placed in a stirrer to be mixed uniformly. The timing is started at the same time of adding the bisphenol A solution, and the sampling is timed.
The bisphenol A concentration was measured by high performance liquid chromatography.
(1) Determination reagent:
bisphenol a standard stock solution: 100mg of bisphenol A was completely dissolved in a 1L volumetric flask.
(2) Drawing a standard curve: taking 5 bisphenol A (5, 10, 20, 25, 40mg L) with different concentrations-1) The detection was carried out at a wavelength of 276nm in a mobile phase of a mixed solution (50: 50) of acetonitrile and water.
(3) And (3) determination of a water sample: taking a small amount of reaction liquid at a certain time, filtering out clear liquid by a filter for testing, and calculating the content of bisphenol A in the solution according to a standard curve.
Under alkaline condition Bi2.15WO6The removal efficiency of the/PS system for bisphenol A is shown in FIG. 2.
(3) Radical masking experiments
Weighing a certain amount of Bi2.15WO6Placed in a 100mL beaker containing a quantity of deionized water and the suspension adjusted to greater than 7.0 using 1M sodium hydroxide solution. Then, a certain volume of PS and bisphenol A solutions with the same pH value are sequentially added into the suspension, 1M methanol and 20mM chloroform are respectively added into the system to be uniformly mixed, and the mixture is placed in a stirrer to be uniformly mixed. The timing is started at the same time of adding the bisphenol A solution, and the sampling is timed.
Under alkaline condition Bi2.15WO6the/PS system radical masking experiment chart is shown in FIG. 3.
(4) Characterization of post-reaction insolubles
Insoluble solid in the system after reaction is collected, washed by deionized water and dried to obtain insoluble product, FTIR analysis is carried out on the insoluble product, and the analysis result is shown in figure 4.

Claims (7)

1.Bi2.15WO6The method for removing the bisphenol A by the PS system is characterized by comprising the following steps:
(1) bi to be prepared2.15WO6Placing in water to obtain suspension, and adjusting pH to more than 7.0 with alkali; and starting stirring the PS solution and the bisphenol A solution with the same pH value at a constant speed.
(2) And timing when the bisphenol A solution is added and sampling at regular time to detect the concentration of the bisphenol A.
2. The Bi according to claim 12.15WO6The method for removing the bisphenol A by the PS system is characterized in that: preparation of the solid Bi Using a hydrothermal method2.15WO6
3. The Bi according to claim 12.15WO6The method for removing the bisphenol A by the PS system is characterized in that: using bismuth nitrate solution and sodium tungstateMixing the solutions at normal temperature in proportion, adjusting pH to 1.0 with acid or alkali, stirring, placing in an oven for reaction at 180 deg.C for 24h, cooling, and collecting the obtained solid to obtain solid Bi2.15WO6
4. The Bi according to claim 32.15WO6The method for removing the bisphenol A by the PS system is characterized in that: mixing uniformly in the ratio of Bi to W being 2.15 to 1.
5. The Bi according to claim 12.15WO6The method for removing the bisphenol A by the PS system is characterized in that: in the step (1), the prepared Bi2.15WO6The suspension was placed in water and its pH adjusted to greater than 7.0 with 1M sodium hydroxide solution.
6. The Bi according to claim 12.15WO6The method for removing the bisphenol A by the PS system is characterized in that: in the step (1), 1M methanol and 20mM chloroform are respectively added, timing is started when the bisphenol A solution is added, sampling and detection are carried out at regular time, and a masking experiment is carried out.
7. The Bi according to claim 12.15WO6The method for removing the bisphenol A by the PS system is characterized in that: infrared spectroscopy (FTIR) analysis of the insoluble solids in the system gave the product as a phenolic polymer.
CN202111042360.4A 2021-09-07 2021-09-07 Self-doping bismuth tungstate (Bi)2.15WO6) Method for efficiently removing bisphenol A by Persulfate (PS) system Active CN113697931B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109126835A (en) * 2018-07-26 2019-01-04 中国电建集团成都勘测设计研究院有限公司 Photochemical catalyst La3+The method of/BiOI and bisphenol AF of degrading
CN112062258A (en) * 2020-09-16 2020-12-11 天津理工大学 Method for degrading aniline by using copper oxide persulfate system without free radical mechanism

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109126835A (en) * 2018-07-26 2019-01-04 中国电建集团成都勘测设计研究院有限公司 Photochemical catalyst La3+The method of/BiOI and bisphenol AF of degrading
CN112062258A (en) * 2020-09-16 2020-12-11 天津理工大学 Method for degrading aniline by using copper oxide persulfate system without free radical mechanism

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LIU TY, ET AL: "Oxidative polymerization of bisphenol A (BPA) via H-abstraction by Bi2.15WO6 and persulfate: Importance of the surface complexes", CHEMICAL ENGINEERING JOURNAL, vol. 435, 28 February 2022 (2022-02-28), pages 134816 *
WANG CONG, WT AL: "Catalytic reactivity of Co3O4 with different facets in the hydrogen abstraction of phenol by persulfate", APPLIED CATALYSIS B-ENVIRONMENTAL, vol. 270, 30 April 2020 (2020-04-30), pages 118819 *
WEI, Y ET AL: "Efficient peroxodisulfate activation by iodine vacancy rich bismuth oxyiodide: A vacancy induced mechanism", CHEMICAL ENGINEERING JOURNAL, 1 November 2019 (2019-11-01), pages 121971 *
王正昊: "非自由基路线活化过硫酸盐的研究现状", 广州化工, vol. 47, no. 17, 30 September 2019 (2019-09-30), pages 40 - 43 *

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