CN112194279A - Method for adsorbing arsenic in arsenic-containing wastewater - Google Patents

Method for adsorbing arsenic in arsenic-containing wastewater Download PDF

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CN112194279A
CN112194279A CN202010936978.4A CN202010936978A CN112194279A CN 112194279 A CN112194279 A CN 112194279A CN 202010936978 A CN202010936978 A CN 202010936978A CN 112194279 A CN112194279 A CN 112194279A
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arsenic
containing wastewater
reaction
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nickel
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CN112194279B (en
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韩煦
王世杰
孙世玮
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Tianjin University
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The invention provides a method for adsorbing arsenic in arsenic-containing wastewater, which comprises the steps of adjusting the pH value of the arsenic-containing wastewater to be 4-11, introducing oxygen into the arsenic-containing wastewater, putting a nickel disulfide mineral and ferric oxide into the arsenic-containing wastewater under the condition of keeping out of the sun, stirring, keeping out of the sun, and reacting at constant temperature, wherein the reaction temperature is 22-27 ℃, and the reaction time is 10-80 min. Compared with the prior art, the adsorption quantity of trivalent arsenic is greatly improved, no by-product is generated in the adsorption process, and secondary pollution in water is avoided; in addition, the nickel disulfide as a catalyst can be repeatedly utilized, so that the method is environment-friendly and realizes effective treatment of the arsenic-containing wastewater. The invention solves the problems of high price and complex process of the existing treatment technology.

Description

Method for adsorbing arsenic in arsenic-containing wastewater
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for adsorbing arsenic in arsenic-containing wastewater.
Background
Trivalent arsenic as (iii) and pentavalent arsenic as (v) are toxic pollutants in natural water bodies that are highly carcinogenic and mutagenic. Due to the low activity of air, the process of oxidizing As (III) into As (V) is very slow, and the half-life period is about one year, so that in the aerobic surface water body, the As (III) with stronger toxicity can stably exist for a long time. And arsenic-containing pyrite (FeS) as the arsenic-containing primary mineral with geological motion or human mining activities2) Hen yellow (As)4S4) Realgar (As)2S3) Sulfide minerals such as arsenopyrite (FeAsS) and the like are transferred to an oxygen-enriched water body and are oxidized and dissolved, so that mine wastewater is formed. As arsenic in minerals is released into a water body along with the formation of mine wastewater, 180 samples of acid mine wastewater in the United states are counted, and the arsenic content is found to be between 1 mu g/L and 340 mg/L. Arsenic-containing wastewater causes serious pollution to surface water and underground water around a mining area, and seriously threatens the health of surrounding residents.
As (III) is difficult to be adsorbed in an aerobic system, the toxicity of As (III) is hundreds times that of As (V), thermodynamic data predict that Dissolved Oxygen (DO) can quantitatively oxidize As (III), but the reaction time can reach months or even half a year, and the reaction rate and efficiency are low, so that a method for efficiently oxidizing As (III) in arsenic-containing wastewater and efficiently adsorbing the As (III) is required to be found. Common as (iii) removal methods include physical methods, chemical oxidation, microbial oxidation, and catalytic oxidation.
The physical method, namely removing arsenic in water body by physical action, for example, chinese patent CN108393494B prepares a porous electro-adsorption arsenic removal material generated in situ on the surface of porous metallic tin and metallic tin, and arsenic is adsorbed and desorbed by applying voltage, but the method has low selectivity to adsorbed ions, does not produce oxidation effect on arsenic, and has no reduction in toxicity. Chinese patent CN110075782A adopts honeycomb briquette cinder selected from solid waste as main raw material, combines alum, stabilizer, organic ligand, adhesive and solvent, and obtains novel arsenic adsorption material through reaction steps of soaking, sieving, stirring and the like, but the material has complex manufacturing process and can not be reused.
Chemical oxidation, i.e. direct oxidation of As (III) to As (V) by adding strong oxidant, such as KMnO4And O3Etc. for example, CN1609021 in Chinese patent adopts KMnO4Removal of groundwater As (III), patent CN102614841A using KMnO4Modified eggshells remove arsenic from water, however, in water treatment, KMnO4The dosage is large, the price is expensive, excessive manganese ions and potassium ions can be introduced in the treatment process, the requirement on the temperature in the oxidation process is high, the temperature needs to be controlled at 10-20 ℃,the concentration of the arsenic oxide is lower and is 3-6 mg/L. Another O3As (III) oxide has the problems of difficult operation, high cost and the like in the pollution remediation process. The Chinese patent CN111072176A uses hydrogen peroxide to oxidize arsenic and uses liquid polymeric ferric sulfate to carry out arsenic precipitation reaction to realize liquid-solid separation, the amount of the hydrogen peroxide required by the method is large, and the requirement on the pH value of the arsenic precipitation reaction is strict.
The microbial oxidation method is the most common method in sewage treatment, and Chinese patent CN106698821B adopts thermophilic iron bacteria, temperature-resistant oxidized thiobacillus, ferrous oxide leptospirillum and acidophilic ferrous oxide thiobacillus to oxidize As (III), but the condition of pH is only acidic, the pH value is 1.6-2.8, the reaction time is 3-5 days, and the amount of trivalent arsenic oxide only reaches 3.56-7.57 mg/L. Chinese patent CN107099299B uniformly mixing Bacillus licheniformis fermentation liquor, Pseudomonas mendocina fermentation liquor, Nocardia corallina fermentation liquor, Arthrobacter crystallopoiensis fermentation liquor, Pseudomonas aeruginosa fermentation liquor and Clostridium paphioparvum fermentation liquor according to a certain volume ratio to obtain a mixed bacterial liquor; and then mixing the mixed bacterial liquid and the carrier according to the mass ratio of 2:3 to prepare the biological agent for repairing the arsenic-polluted soil, wherein the method is complex in steps and is only limited to the soil environment. Until now, the tolerance of the microorganisms to As (III) is still relatively low, the time for achieving better As (III) oxidation effect is longer, and the application of the microorganisms to the treatment of high-concentration arsenic-containing wastewater is greatly limited.
The catalytic oxidation is mainly to treat As (III) by using a transition metal mineral catalytic oxidation technology at present. Chinese patent CN107159100B provides a ferro-manganese modified natural mineral composite material, a preparation method and an arsenic adsorbent, the baking temperature of the method needs to be higher, 600-700 ℃ needs to be achieved, 0.5g/L of the adsorbent can only adsorb about 10mg/L of arsenic, and the adsorption efficiency is low. Chinese patent CN108483690A relates to a method for treating high-arsenic wastewater, which comprises the steps of uniformly mixing wastewater to be treated containing trivalent arsenic, ferric salt solution and sulfate solution, transferring the mixed solution into a reaction kettle, and reacting at the temperature of 135 ℃ and 200 ℃ to generate precipitate for removal. The method has complex process, various generated precipitates and low reusability.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
The invention aims to: the method for adsorbing arsenic in arsenic-containing wastewater provided by the invention solves the problems of high treatment price, complex process and the like in the prior art, and can be used for efficiently and environmentally oxidizing and adsorbing high-concentration arsenic-containing wastewater within hours, so that the arsenic-containing wastewater can be effectively treated.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for adsorbing arsenic in arsenic-containing wastewater comprises the steps of adjusting the pH value of the arsenic-containing wastewater to be 4-11, introducing oxygen into the arsenic-containing wastewater, putting a nickel disulfide mineral and ferric oxide into the arsenic-containing wastewater under the condition of keeping out of the sun, stirring, keeping out of the sun, and reacting at constant temperature, wherein the reaction temperature is 22-27 ℃, and the reaction time is 10-80 min.
The pH value of the arsenic-containing wastewater is adjusted to a certain range, and under the pH value, the synergistic oxidation adsorption effect of the nickel disulfide minerals and the ferric oxide on arsenic is better and excellent. The method comprises the steps of firstly introducing certain oxygen into arsenic-containing wastewater, ensuring that dissolved oxygen in the arsenic-containing wastewater is at a certain value, enabling added nickel disulfide minerals to be in contact with the dissolved oxygen and then react to generate a large amount of hydrogen peroxide, enabling the generated hydrogen peroxide to respectively perform Fenton reaction with ferric oxide and nickel disulfide to generate hydroxyl radicals with strong oxidizing property, further oxidizing medium trivalent arsenic in the wastewater into pentavalent arsenic, enabling ferric iron to have an excellent adsorption effect on the pentavalent arsenic, and realizing oxidation and adsorption treatment of the trivalent arsenic wastewater.
Preferably, the stirring speed is 400-550 r/min. More preferably, the stirring rate is 500 r/min. The stirring speed is set within the range, so that on one hand, the uniform mixing of all the substances can be ensured, and the uniform reaction is facilitated; on the other hand, the method is also beneficial to the constant temperature of the whole reaction, and the large influence of the temperature fluctuation on the reaction is avoided.
Preferably, the pH value of the arsenic-containing wastewater is 7-11; during the reaction, the pH of the arsenic-containing wastewater is kept constant. Specifically, the pH can be adjusted with sodium hydroxide and hydrochloric acid. Before the reaction, the pH value is adjusted to a certain pH value, the pH value is kept to fluctuate near the pH value in the reaction process, preferably, the pH value is kept constant, and the maintenance of the pH value in the reaction process can ensure that the nickel disulfide mineral and the ferric oxide have good adsorption performance on arsenic in the wastewater, and particularly, the reaction is facilitated when the pH value is maintained under a slightly alkaline condition. More preferably, the arsenic-containing wastewater has a pH of 9.
Preferably, the nickel disulfide mineral is cubic ore with purity of more than 98%. The nickel disulfide with higher purity is adopted, so that secondary pollution to the wastewater is avoided as much as possible, and side reactions are increased; on the other hand, the nickel disulfide mineral is used as a catalyst, the high-purity nickel disulfide can prolong the service life of the nickel disulfide mineral in recycling, and the production cost is reduced.
Preferably, the diameter of the nickel disulfide mineral is 300-500 nm, and the specific surface area is 6-8 m2(ii) in terms of/g. By adopting the nano-particle nickel disulfide mineral, on one hand, the contact area between the nano-particle nickel disulfide mineral and dissolved oxygen in water is increased, the release amount and release efficiency of hydrogen peroxide are increased, and further the oxidation rate of trivalent arsenic is accelerated; on the other hand, the synergistic effect of the nickel disulfide minerals and the ferric oxide under the diameter is more excellent, and the oxidation adsorption rate of arsenic in water is higher.
Preferably, the nickel disulfide mineral is synthesized by a hydrothermal method, and the hydrothermal temperature can be 130-150 ℃.
Preferably, the nickel disulfide mineral is synthesized by hydrothermal reaction of nickel salt and sulfur-containing compound. Specifically, nickel chloride and sodium thiosulfate can be adopted to prepare in a hydrothermal reaction kettle, and the prepared product has high purity and meets the requirement on nickel disulfide minerals.
Preferably, the concentration of trivalent arsenic in the arsenic-containing wastewater is 20-100 mg/L.
Preferably, the input amount of the nickel disulfide mineral is 0.01-1.2 g/L, and the input amount of the ferric oxide is 0.01-1.2 g/L. For treating wastewater with high content of trivalent arsenic, the amount of the added nickel disulfide minerals and ferric oxide is increased, and is not limited to the concentration limit.
Preferably, the concentration of dissolved oxygen in the arsenic-containing wastewater is 3-9 mg/L. The dissolved oxygen content may increase with increasing arsenic concentration and nickel disulfide mineral concentration in the wastewater.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the adsorption method provided by the invention, nickel disulfide is used as an active transition metal sulfide, and the nickel disulfide can generate a large amount of hydrogen peroxide active species through contact reaction with oxygen, and can stably exist under different pH values, so that the adsorption method is more suitable for arsenic purification treatment of different waste water, and the use range of the adsorption method is increased; the generated hydrogen peroxide and ferric oxide generate Fenton reaction and generate synergistic effect with nickel disulfide, so that the oxidation reaction is further promoted, and the reaction in the wastewater is carried out towards positive reaction. Compared with the prior art, the adsorption quantity of trivalent arsenic is greatly improved, no by-product is generated in the adsorption process, and secondary pollution in water is avoided; in addition, the nickel disulfide as a catalyst can be repeatedly utilized, so that the method is environment-friendly and realizes effective treatment of the arsenic-containing wastewater. The invention solves the problems of high price and complex process of the existing treatment technology.
2) The ferric oxide and the nickel disulfide adopted by the invention have synergistic effect, on one hand, the adsorption reaction is promoted, and on the other hand, the adsorption performance of iron ions on arsenic is reused, so that the integral adsorption efficiency and the adsorption quantity of arsenic can be greatly improved.
3) According to the invention, a large number of experimental researches prove that under the conditions of pH of 7-11 and alkalescence, the synergistic effect of the hydrogen peroxide, the ferric oxide and the nickel disulfide on the arsenic is more excellent, the oxidation rate of trivalent arsenic can reach more than 96%, and the highest adsorption rate can reach more than 88%.
Drawings
FIG. 1 is a catalytic oxidation diagram of example 1 of the present invention.
FIG. 2 is a graph showing the adsorption effect in example 1 of the present invention.
FIG. 3 is a catalytic oxidation diagram of example 2 of the present invention.
FIG. 4 is a graph showing the adsorption effect in example 2 of the present invention.
FIG. 5 is a catalytic oxidation diagram of example 3 of the present invention.
FIG. 6 is a graph showing the adsorption effect in example 3 of the present invention.
FIG. 7 is a catalytic oxidation diagram of example 4 of the present invention.
FIG. 8 is a graph showing the adsorption effect in example 4 of the present invention.
FIG. 9 is a catalytic oxidation diagram of example 5 of the present invention.
FIG. 10 is a graph showing the adsorption effect in example 5 of the present invention.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A method for adsorbing arsenic in arsenic-containing wastewater comprises the following steps:
(1) and (3) reacting 0.2M of nickel chloride and 0.4M of sodium thiosulfate solution in an oven at 145 ℃ for 12 hours to synthesize the nickel disulfide mineral, and washing and drying to obtain the nickel disulfide mineral. The ferric oxide can be obtained from the market, and is not described herein.
(2) A50 mg/L arsenic-containing wastewater was prepared in 3 groups (group a, group b, and group c) by 100ml, and adjusted to pH 4 with sodium hydroxide and hydrochloric acid.
(3) Under the dark condition, 1g/L of nickel disulfide mineral powder and 0g/L of ferric oxide powder are simultaneously added into a group a, 0g/L of nickel disulfide mineral powder and 1g/L of ferric oxide powder are simultaneously added into a group b, 0.5g/L of nickel disulfide mineral powder and 0.5g/L of ferric oxide powder are simultaneously added into a group c, the pH value is adjusted to be 4 by sodium hydroxide and hydrochloric acid at the moment of the whole reaction process, the reaction is kept unchanged, the reaction is carried out in a constant temperature incubator at 25 ℃, the concentration of dissolved oxygen in wastewater is 3-7 mg/L, the stirring, the dark and the reaction are kept to be carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) And after the reaction is carried out for 20-80 min, the adsorption of arsenic in the arsenic-containing wastewater is completed.
Example 2
A method for adsorbing arsenic in arsenic-containing wastewater comprises the following steps:
(1) and (3) reacting 0.2M of nickel chloride and 0.4M of sodium thiosulfate solution in an oven at 145 ℃ for 12 hours to synthesize the nickel disulfide mineral, and washing and drying to obtain the nickel disulfide mineral. The ferric oxide can be obtained from the market, and is not described herein.
(2) A50 mg/L arsenic-containing wastewater was prepared in 3 groups (group a, group b, and group c) by 100ml, and adjusted to pH 7 with sodium hydroxide and hydrochloric acid.
(3) Under the dark condition, 1g/L of nickel disulfide mineral powder and 0g/L of ferric oxide powder are simultaneously added into a group a, 0g/L of nickel disulfide mineral powder and 1g/L of ferric oxide powder are simultaneously added into a group b, 0.5g/L of nickel disulfide mineral powder and 0.5g/L of ferric oxide powder are simultaneously added into a group c, the pH value is adjusted to be 7 by sodium hydroxide and hydrochloric acid at the moment of the whole reaction process, the reaction is kept unchanged, the reaction is carried out in a constant temperature incubator at 25 ℃, the concentration of dissolved oxygen in wastewater is 3-7 mg/L, the stirring, the dark and the reaction are kept to be carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) And after the reaction is carried out for 20-80 min, the adsorption of arsenic in the arsenic-containing wastewater is completed.
Example 3
A method for adsorbing arsenic in arsenic-containing wastewater comprises the following steps:
(1) and (3) reacting 0.2M of nickel chloride and 0.4M of sodium thiosulfate solution in an oven at 145 ℃ for 12 hours to synthesize the nickel disulfide mineral, and washing and drying to obtain the nickel disulfide mineral. The ferric oxide can be obtained from the market, and is not described herein.
(2) A50 mg/L arsenic-containing wastewater was prepared in 3 groups (group a, group b, and group c) by 100ml, and adjusted to pH 9 with sodium hydroxide and hydrochloric acid.
(3) Under the dark condition, 1g/L of nickel disulfide mineral powder and 0g/L of ferric oxide powder are simultaneously added into a group a, 0g/L of nickel disulfide mineral powder and 1g/L of ferric oxide powder are simultaneously added into a group b, 0.5g/L of nickel disulfide mineral powder and 0.5g/L of ferric oxide powder are simultaneously added into a group c, the pH value is adjusted to be 9 by sodium hydroxide and hydrochloric acid at the moment of the whole reaction process, the reaction is kept unchanged, the reaction is carried out in a constant temperature incubator at 25 ℃, the concentration of dissolved oxygen in wastewater is 3-7 mg/L, the stirring, the dark and the reaction are kept to be carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) And after the reaction is carried out for 20-80 min, the adsorption of arsenic in the arsenic-containing wastewater is completed.
Example 4
A method for adsorbing arsenic in arsenic-containing wastewater comprises the following steps:
(1) and (3) reacting 0.2M of nickel chloride and 0.4M of sodium thiosulfate solution in an oven at 145 ℃ for 12 hours to synthesize the nickel disulfide mineral, and washing and drying to obtain the nickel disulfide mineral. The ferric oxide can be obtained from the market, and is not described herein.
(2) A50 mg/L arsenic-containing wastewater was prepared in 3 groups (group a, group b, and group c) by 100ml, and adjusted to pH 11 with sodium hydroxide and hydrochloric acid.
(3) Under the dark condition, 1g/L of nickel disulfide mineral powder and 0g/L of ferric oxide powder are simultaneously added into a group a, 0g/L of nickel disulfide mineral powder and 1g/L of ferric oxide powder are simultaneously added into a group b, 0.5g/L of nickel disulfide mineral powder and 0.5g/L of ferric oxide powder are simultaneously added into a group c, the pH value is adjusted to 11 by using sodium hydroxide and hydrochloric acid at the moment of the whole reaction process, the reaction is kept unchanged, the reaction is carried out in a constant temperature incubator at 25 ℃, the concentration of dissolved oxygen in wastewater is 3-7 mg/L, the stirring, the dark and the reaction are kept to be carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) And after the reaction is carried out for 20-80 min, the adsorption of arsenic in the arsenic-containing wastewater is completed.
Example 5
A method for adsorbing arsenic in arsenic-containing wastewater comprises the following steps:
(1) and (3) reacting 0.2M of nickel chloride and 0.4M of sodium thiosulfate solution in an oven at 145 ℃ for 12 hours to synthesize the nickel disulfide mineral, and washing and drying to obtain the nickel disulfide mineral. The ferric oxide can be obtained from the market, and is not described herein.
(2) 100ml of arsenic-containing wastewater containing 20, 50 and 100mg/L was prepared in 3 groups (group a, group b and group c), and the pH was adjusted to 9 with sodium hydroxide and hydrochloric acid.
(3) Under the condition of keeping out of the sun, 0.5g/L of nickel disulfide mineral powder and 0.5g/L of ferric oxide powder are simultaneously added into the groups a, b and c, the pH value is adjusted to be 9 by using sodium hydroxide and hydrochloric acid at the moment in the whole reaction process, the reaction is kept unchanged, the reaction is carried out in a constant-temperature incubator at 25 ℃, the concentration of dissolved oxygen in wastewater is 3-7 mg/L, the reaction is uniformly carried out under stirring and keeping out of the sun at the speed of 500r/min, and the influence of illumination is avoided.
(4) And after the reaction is carried out for 20-80 min, the adsorption of arsenic in the arsenic-containing wastewater is completed.
Example 6
Different from the embodiment 5, the added nickel disulfide mineral powder in the three groups of a, b and c is 0.3g/L, and the added ferric oxide powder is 0.7 g/L.
The rest is the same as embodiment 5, and the description is omitted here.
Example 7
Unlike example 6, the pH of the arsenic-containing wastewater during the reaction of this example was 4.
The rest is the same as embodiment 6, and the description is omitted here.
Example 8
Unlike example 6, the pH of the arsenic-containing wastewater during the reaction of this example was 7.
The rest is the same as embodiment 6, and the description is omitted here.
Example 9
Unlike example 6, the pH of the arsenic-containing wastewater during the reaction of this example was 11.
The rest is the same as embodiment 6, and the description is omitted here.
Example 10
Different from the embodiment 5, the added nickel disulfide mineral powder in the three groups of a, b and c is 0.7g/L, and the added ferric oxide powder is 0.3 g/L.
The rest is the same as embodiment 5, and the description is omitted here.
Example 11
Unlike example 10, the pH of the arsenic-containing wastewater during the reaction of this example was 7.
The rest is the same as embodiment 10, and the description is omitted here.
Example 12
Unlike example 10, the pH of the arsenic-containing wastewater during the reaction of this example was 11.
The rest is the same as embodiment 10, and the description is omitted here.
Example 13
Different from the embodiment 5, the added nickel disulfide mineral powder in the three groups of a, b and c is 1g/L, and the added ferric oxide powder is 1 g/L.
The rest is the same as embodiment 5, and the description is omitted here.
In the reaction processes of the above examples 1 to 13, 0.5ml of the reaction system solution was taken at regular intervals, the sample solution was centrifuged by a high-speed centrifuge, the arsenic concentration in the supernatant was measured by the arsenic molybdenum blue method, the absorbance was measured at a wavelength of 880nm by an ultraviolet visible spectrophotometer, and the concentration C of the residual pentavalent arsenic in the reaction system solution was measured1mg/L and Total arsenic concentration C2mg/L and the reaction system is 0.1L, centrifugally separated ferric oxide and nickel disulfide are subjected to acid cleaning, the concentration of pentavalent arsenic and the total arsenic in acid cleaning solution are measured, and the mass of pentavalent arsenic adsorbed on the surface of the mineral is calculated to be M1And M2The percent oxidation and percent adsorption of arsenic were calculated.
The specific calculation formula is as follows:
total arsenic oxide mass of 0.1C1+M1
Oxidation rate 100% total arsenic oxide mass/(2, 5, 10) mg
Total adsorbed arsenic mass as M1+M2
Adsorption rate of 100%. Total adsorption content/(2, 5, 10) mg
The percent oxidation and percent adsorption of arsenic obtained from examples 1-13 tested over 80min are shown in Table 1.
TABLE 1
Figure BDA0002672302240000101
From the test results, it can be seen that the effect of performing adsorption treatment on arsenic by using nickel disulfide and ferric oxide together is more excellent, particularly, the pH is controlled to be 9, and the nickel disulfide and ferric oxide are in a proper concentration range, the synergistic effect of nickel disulfide and ferric oxide is more remarkable, the oxidation rate in example 5 can reach over 99%, and the adsorption rate can also reach over 95%, even in high-concentration arsenic-containing wastewater, under the condition that the contents of nickel disulfide and ferric oxide are insufficient, the oxidation rate can also reach over 86%, and the adsorption rate can reach 79.2%.
From the test results of the three groups a, b and c in the above examples 1-4, it can be seen that if nickel disulfide or ferric oxide is used alone for adsorption, although a certain adsorption effect is achieved, the adsorption effect is far inferior to the effect of the mixed adsorption of the two. This is mainly because if only nickel disulfide is added, although it and oxygen can generate a certain amount of hydrogen peroxide to oxidize trivalent arsenic, the oxidation effect is effective, the reaction cannot move continuously in the forward direction, and finally, the excellent adsorption effect cannot be achieved. If only ferric oxide is added, hydrogen peroxide and hydroxyl radicals with strong oxidizing property are lacked in the system, trivalent arsenic cannot be oxidized firstly, and ferric oxide has limited adsorption effect on trivalent arsenic and can not achieve excellent adsorption effect. In conclusion, the test results of a plurality of tests show that the excellent effect of the invention is that the excellent adsorption effect is finally achieved by virtue of the synergistic effect of the nickel disulfide and the ferric oxide and controlling the reaction conditions.
In addition, the pH value in the reaction process also has a great influence on the adsorption effect, and the test results in examples 1-4, 6-9 and 10-12 can be easily obtained, so that the effect is more excellent under alkaline conditions compared with acidic conditions. In the conventional fenton reaction, the oxidation potential of hydroxyl radicals is high under an acidic condition, but the inventor verifies through a large number of test results that the nickel disulfide and the ferric oxide show excellent adsorption effect on arsenic adsorption under a slightly alkaline condition, and the excellent adsorption effect is finally obtained because multiple reactions in a reaction system are mutually influenced and mutually promoted.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. The method for adsorbing arsenic in arsenic-containing wastewater is characterized by adjusting the pH value of the arsenic-containing wastewater to 4-11, introducing oxygen into the arsenic-containing wastewater, putting a nickel disulfide mineral and ferric oxide into the arsenic-containing wastewater under a light-proof condition, stirring, keeping the temperature away from light, and reacting for 10-80 min at a constant temperature, wherein the reaction temperature is 22-27 ℃.
2. The method of claim 1, wherein the stirring is at a rate of 400 to 550 r/min.
3. The method according to claim 1, wherein the pH of the arsenic-containing wastewater is 7 to 11; during the reaction, the pH of the arsenic-containing wastewater is kept constant.
4. The method according to claim 1, wherein the nickel disulfide mineral is cubic ore with a purity greater than 98%.
5. The method according to claim 4, wherein the nickel disulfide mineral has a diameter of 300 to 500nm and a specific surface area of 6 to 8m2/g。
6. The method according to claim 4, wherein the nickel disulfide mineral is synthesized by a hydrothermal method.
7. The method according to claim 6, wherein the nickel disulphide mineral is synthesized by hydrothermal reaction of a nickel salt and a sulphur containing compound.
8. The method according to claim 1, wherein the concentration of trivalent arsenic in the arsenic-containing wastewater is 20-100 mg/L.
9. The method according to claim 8, wherein the amount of the nickel disulfide mineral added is 0.01 to 1.2g/L, and the amount of the iron sesquioxide added is 0.01 to 1.2 g/L.
10. The method of claim 9, wherein the concentration of dissolved oxygen in the arsenic-containing wastewater is 3-9 mg/L.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115193449A (en) * 2022-07-08 2022-10-18 深水海纳水务集团股份有限公司 Porous iron-based catalyst and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103332768A (en) * 2013-06-27 2013-10-02 同济大学 Method for synchronously removing arsenite and arsenate from water
CN106277278A (en) * 2016-10-14 2017-01-04 合肥工业大学 A kind of method utilizing iron oxides multiphase Fenton system to process arsenic-containing waste water
US20190015818A1 (en) * 2017-07-13 2019-01-17 Board Of Trustees Of The University Of Arkansas Doped carbonaceous materials for photocatalytic removal of pollutants under visible light, making methods and applications of same
CN110142051A (en) * 2019-05-28 2019-08-20 广州大学 A kind of zinc sulphide load molybdenum sulfide catalyst and its preparation method and application
CN111320241A (en) * 2020-02-28 2020-06-23 同济大学 Carbon aerogel for improving divalent Fe reducibility and hydrogen peroxide yield in electrode and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103332768A (en) * 2013-06-27 2013-10-02 同济大学 Method for synchronously removing arsenite and arsenate from water
CN106277278A (en) * 2016-10-14 2017-01-04 合肥工业大学 A kind of method utilizing iron oxides multiphase Fenton system to process arsenic-containing waste water
US20190015818A1 (en) * 2017-07-13 2019-01-17 Board Of Trustees Of The University Of Arkansas Doped carbonaceous materials for photocatalytic removal of pollutants under visible light, making methods and applications of same
CN110142051A (en) * 2019-05-28 2019-08-20 广州大学 A kind of zinc sulphide load molybdenum sulfide catalyst and its preparation method and application
CN111320241A (en) * 2020-02-28 2020-06-23 同济大学 Carbon aerogel for improving divalent Fe reducibility and hydrogen peroxide yield in electrode and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PENGZHANG等: "Mechanisms of hydroxyl radical production from abiotic oxidation of pyrite under acidic conditions", 《GEOCHIMICA ET COSMOCHIMICA ACTA》 *
YONG-LINGLIU: "Oxidation reactivity of As(III)-containing pyrites: Differences between structurally-incorporated and adsorbed As(III)", 《CHEMICAL GEOLOGY》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115193449A (en) * 2022-07-08 2022-10-18 深水海纳水务集团股份有限公司 Porous iron-based catalyst and preparation method thereof

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