CN112194279B - Method for adsorbing arsenic in arsenic-containing wastewater - Google Patents

Method for adsorbing arsenic in arsenic-containing wastewater Download PDF

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CN112194279B
CN112194279B CN202010936978.4A CN202010936978A CN112194279B CN 112194279 B CN112194279 B CN 112194279B CN 202010936978 A CN202010936978 A CN 202010936978A CN 112194279 B CN112194279 B CN 112194279B
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arsenic
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nickel disulfide
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CN112194279A (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

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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 used, 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 with strong carcinogenicity and mutagenicity in natural water. As the activity of air is low, the process of oxidizing As (III) into As (V) is extremely slow, and the half-life period is about one year, so that the As (III) with stronger toxicity can stably exist for a long time in the aerobic surface water body. And arsenic-containing pyrite (FeS) as the arsenic-containing primary mineral with geological motion or human mining activities 2 ) Hen yellow (As) 4 S 4 ) Realgar (As) 2 S 3 ) 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 of 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, the reaction rate and efficiency are low, and therefore a method for efficiently oxidizing As (III) in arsenic-containing wastewater and efficiently adsorbing the As (III) needs to be found. Common As (III) removal methods include physical methods, chemical oxidation, microbial oxidation, and catalytic oxidation, among others.
The method is a physical method, namely arsenic in a water body is removed through a physical effect, for example, chinese patent CN108393494B prepares a porous electro-adsorption arsenic removal material generated on the surface of porous metal tin and metal tin in situ, arsenic is adsorbed and desorbed through a method of applying voltage, but the method has lower selectivity on adsorbed ions, does not generate oxidation effect on arsenic, and does not reduce toxicity. Chinese patent CN110075782A uses honeycomb briquette cinder selected from solid waste as a main raw material, combines alum, a stabilizer, an organic ligand, an adhesive and a solvent, and obtains a novel arsenic adsorption material through reaction steps of soaking, sieving, stirring and the like, but the material has a complex manufacturing process and cannot be reused.
Chemical oxidation, i.e. direct oxidation of As (III) to As (V) by adding strong oxidants to the wastewater, commonly used oxidants being KMnO 4 And O 3 Etc., for example, chinese patent CN1609021 adopts KMnO 4 Removing underground water As (III), patent CN102614841A utilizes KMnO 4 Modified eggshells remove arsenic from water, however, in water treatment, KMnO 4 The dosage is large, the price is expensive, excessive manganese ions and potassium ions can be introduced in the treatment process, the requirement of the oxidation process on the temperature is high, the temperature needs to be controlled at 10-20 ℃, and the concentration of the arsenic oxide which can be oxidized is low and is 3-6mg/L. Another O 3 The As (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 ferruginous bacteria, temperature-resistant oxidized bacillus thiooxidans, ferrous oxide leptospira, and acidophilic oxidized ferrous thiobacillus thiooxidans to oxidize As (III), but only the condition of pH is acidity, the pH value is 1.6-2.8, the reaction time is up to 3-5 days, and the amount of trivalent arsenic oxide only reaches 3.56-7.57mg/L. Chinese patent CN107099299B, which is a method for preparing a mixed bacterial solution, is prepared by uniformly mixing a Bacillus licheniformis fermentation solution, a Pseudomonas mendocina fermentation solution, a Nocardia coralline fermentation solution, an Arthrobacter crystallopoiensis fermentation solution, a Pseudomonas aeruginosa fermentation solution and a Clostridium paphioicum fermentation solution according to a certain volume ratio; 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 step and is only limited in soil environment. As the tolerance of the microorganisms to As (III) is still relatively low at present, the time for achieving a 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 used for treating 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 is required to be high and needs to reach 600-700 ℃, and 0.5g/L of the adsorbent can only adsorb about 10mg/L of arsenic, so that 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, an iron salt solution and a sulfate solution, transferring the mixed solution into a reaction kettle, and removing precipitates generated by reaction at the temperature of 135-200 ℃. 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 solve 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 method firstly adjusts the pH value of the arsenic-containing wastewater 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 to ensure that dissolved oxygen in the arsenic-containing wastewater is at a certain value, contacting the added nickel disulfide minerals with the dissolved oxygen to react to generate a large amount of hydrogen peroxide, and respectively performing Fenton reaction on the generated hydrogen peroxide, ferric oxide and nickel disulfide to generate hydroxyl radicals with strong oxidizing property, so that medium-trivalent arsenic in the wastewater is oxidized into pentavalent arsenic, and meanwhile, ferric iron has an excellent adsorption effect on the pentavalent arsenic, thereby 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 500r/min. The stirring speed is set within the range, so that on one hand, the uniform mixing of all 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 m 2 (iv) 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 a 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 also 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. Iron sesquioxide can be obtained from commercial sources, and is not described herein.
(2) Set 3 (a, b and c) 100ml arsenic wastewater containing 50mg/L was prepared and adjusted to pH =4 with sodium hydroxide and hydrochloric acid.
(3) Under the light-tight 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 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 light-tight and the reaction are kept to be carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) 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) Set 3 (a, b and c) 100ml arsenic wastewater containing 50mg/L was prepared and adjusted to pH =7 with sodium hydroxide and hydrochloric acid.
(3) Under the condition of keeping out of the sun, 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, keeping out of the sun and the reaction are carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) 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) Set 3 (a, b and c) 100ml arsenic wastewater containing 50mg/L was prepared and adjusted to pH =9 with sodium hydroxide and hydrochloric acid.
(3) Under the condition of keeping out of the sun, 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, keeping out of the sun and the reaction are carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) 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) Set 3 (a, b and c) 100ml arsenic wastewater containing 50mg/L was prepared and adjusted to pH =11 with sodium hydroxide and hydrochloric acid.
(3) Under the condition of keeping out of the sun, 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, keeping out of the sun and the reaction are carried out uniformly at the speed of 500r/min, and the influence of illumination is avoided.
(4) 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) 3 groups (a group, b group and c group) of 100ml arsenic-containing wastewater containing 20, 50 and 100mg/L respectively were prepared and adjusted to pH =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 9 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 reaction is uniformly carried out under the stirring, keeping out of the sun and keeping the reaction at the speed of 500r/min, and the influence of illumination is avoided.
(4) 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 0.7g/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 0.3g/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 in the reaction process 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
The difference from the embodiment 5 is that 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 1g/L.
The rest is the same as embodiment 5, and the description is omitted here.
In the course of the reactions of the above examples 1 to 13, every other stageTaking 0.5ml of reaction system solution, centrifuging the sample solution by a high-speed centrifuge, measuring the arsenic concentration of the supernatant by an arsenic molybdenum blue method, measuring the absorbance at the position of 880nm of wavelength by using an ultraviolet visible spectrophotometer, and measuring the concentration C of the residual pentavalent arsenic in the reaction system solution 1 mg/L and Total arsenic concentration C 2 mg/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 M 1 And M 2 The percent oxidation and percent adsorption of arsenic were calculated.
The specific calculation formula is as follows:
total arsenic oxide mass =0.1C in the reaction system 1 +M 1
Oxidation rate =100% total arsenic oxide mass/(2, 5, 10) mg
Total arsenic adsorbed mass = M 1 +M 2
Adsorption rate =100% total adsorption content/(2, 5, 10) mg
Examples 1-13 the percent oxidation and percent adsorption of arsenic obtained during the 80min test 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 of the above examples 1 to 4, it can be seen that if nickel disulfide or ferric oxide is used alone for adsorption, although a certain adsorption effect is obtained, 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 during the reaction also has a large influence on the adsorption effect, and it can be easily found from the test results in examples 1 to 4, 6 to 9, and 10 to 12 that the effect is more excellent under the slightly alkaline condition than under the acidic condition. 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 (9)

1. A method for adsorbing arsenic in arsenic-containing wastewater is characterized by adjusting the pH of the arsenic-containing wastewater to be 4 to 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 to 27 ℃, and the reaction time is 10 to 80min; the concentration of trivalent arsenic in the arsenic-containing wastewater is 20 to 100mg/L.
2. The method according to claim 1, characterized in that the stirring rate is 400 to 550r/min.
3. The method according to claim 1, wherein the arsenic-containing wastewater has a pH of 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 as claimed in claim 4, wherein the diameter of the nickel disulfide mineral is 300 to 500nm, and the specific surface area is 6 to 8m 2 /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 input amount of the nickel disulfide mineral is 0.01 to 1.2g/L, and the input amount of the ferric oxide is 0.01 to 1.2g/L.
9. The method as claimed in claim 8, wherein the concentration of dissolved oxygen in the arsenic-containing wastewater is 3 to 9mg/L.
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