CN115340228A - Arsenic removal method under acidic condition - Google Patents

Arsenic removal method under acidic condition Download PDF

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CN115340228A
CN115340228A CN202210816838.2A CN202210816838A CN115340228A CN 115340228 A CN115340228 A CN 115340228A CN 202210816838 A CN202210816838 A CN 202210816838A CN 115340228 A CN115340228 A CN 115340228A
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arsenic
content
agent
acid solution
measured
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李静
张利波
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
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  • Removal Of Specific Substances (AREA)

Abstract

The invention discloses an arsenic removal method under acidic conditions, which comprises the following steps: step 1, adding a vulcanizing agent into arsenic-containing wastewater; step 2, adding a reinforcing agent into the system in the step 1, and then carrying out ultrasonic treatment; and 3, removing cations of the introduced vulcanizing agents. The method for removing arsenic under acidic condition disclosed by the invention has low treatment cost of introduced cationsCan prevent local S caused by the aggregation of the vulcanizing agent 2‑ Excessive, promote the vulcanization medicament utilization ratio, reduce environmental pollution, and can show reduction reaction time, promote and remove arsenic efficiency.

Description

Arsenic removal method under acidic condition
Technical Field
The invention belongs to the technical field of arsenic-containing wastewater treatment, and particularly relates to an arsenic removal method under an acidic condition.
Background
In the fields of metallurgy, mineral separation, chemical industry, materials and the like, a large amount of arsenic-containing waste water is generated, particularly in the smelting process of nonferrous metals, smelting flue gas needs to be purified and washed for producing sulfuric acid products meeting the national standard, and a large amount of acidic waste water containing harmful impurities, namely waste acid, is generated in the purifying and washing process. The contaminated acid is mainly free acid and contains high-concentration arsenic, so that the contaminated acid is easy to cause great harm to the environment if not treated properly.
For removing arsenic impurities, the existing lead-iron smelting enterprises mainly adopt a terminal treatment mode, and particularly adopt a lime neutralization iron salt method to carry out waste acid treatment. Generally, lime under the condition of normal temperature (room temperature) is added into a waste acid solution to adjust the pH value of the solution, a large amount of gypsum residues are generated, iron salt and the like are added into the solution to achieve the purpose of precipitating arsenic, and the obtained solution is discharged after being subjected to secondary treatment to reach the national standard. This process consumes a large amount of H in the solution + The waste of acid resources is caused, and according to the difference of arsenic content of raw materials, the arsenic content in the gypsum slag fluctuates, so that the property of the produced gypsum slag is unstable, the arsenic in the solid slag exceeds the standard or partially exceeds the standard, the common solid waste slag is changed into dangerous waste slag, and the environment is damaged.
Therefore, it is necessary to provide a method for removing arsenic under acidic conditions, which can significantly improve the arsenic removal efficiency, reduce the cost, reduce the environmental pollution, and save the energy consumption.
Disclosure of Invention
In order to overcome the problems, the inventor of the present invention has made intensive studies to design a method for removing arsenic under acidic conditions, which uses a non-sodium salt sulfide agent in combination with enhanced ultrasonic action to treat arsenic-containing wastewater under acidic conditions, and can significantly reduce reaction time, improve arsenic removal efficiency, reduce treatment cost and reduce environmental pollution, thereby completing the present invention.
In particular, the invention aims to provide a method for removing arsenic under acidic conditions, comprising the following steps:
step 1, adding a vulcanizing agent into arsenic-containing wastewater;
step 2, adding a reinforcing agent into the system in the step 1, and then carrying out ultrasonic treatment;
and 3, removing cations of the introduced vulcanizing agents.
The invention has the advantages that:
(1) The arsenic removal method under the acidic condition provided by the invention is simple to operate, easy to control the condition and wide in application range;
(2) According to the arsenic removal method under the acidic condition, the added vulcanizing agent does not introduce sodium ions into the system, so that the system load can be reduced, the introduced iron ions are convenient to remove, and the treatment cost is low;
(3) The arsenic removal method under the acidic condition provided by the invention adopts ultrasonic wave to assist in arsenic removal, and can prevent local S caused by aggregation of vulcanizing agents 2- The excessive vulcanization agent improves the utilization rate of the vulcanization agent and reduces the environmental pollution;
(4) According to the arsenic removal method under the acidic condition, the reinforcing agent is added to enhance the ultrasonic effect, so that the reaction time can be obviously shortened, and the arsenic removal efficiency is improved.
Drawings
FIG. 1 shows a schematic diagram of the arsenic removal process according to a preferred embodiment of the present invention.
Detailed Description
The present invention is described in further detail below by way of preferred embodiments and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
The inventor researches and discovers that the sulfuration method has a good effect of removing arsenic under an acidic condition, and the sulfuration method is to react soluble sulfide with heavy metal to generate insoluble sulfide and remove the insoluble sulfide from polluted acid. Commonly used sulfidizing agents are sodium sulfide, sodium hydrosulfide or hydrogen sulfide gas. When sodium sulfide and sodium hydrosulfide are used for removing arsenic, na is introduced in the process + The burden is caused to the production system, and the subsequent sodium removal method has higher cost and is not suitable for large-scale use; when the arsenic is removed by using the hydrogen sulfide gas, although other impurity ions are not introduced into the system, the retention time of the system in the solution is short, and in order to ensure the arsenic removal effect, enough excess of the hydrogen sulfide gas needs to be ensured, so that the unreacted hydrogen sulfide gas in the arsenic removal process is released into the surrounding environmentEnvironmental pollution is caused, and the preparation of hydrogen sulfide gas requires a large amount of equipment investment and has high requirements on safe treatment.
The ultrasonic wave has a vibration frequency higher than 20000Hz and a very high vibration frequency (frequency) per second, and when the ultrasonic wave is transmitted in a medium, a mechanical effect, a cavitation effect and a thermal effect can generate a series of effects of mechanics, thermal, chemistry and the like, particularly, the acoustic cavitation effect generates a local high-temperature high-pressure environment at the moment of cavitation nuclear explosion and generates strong impact and high-speed micro-jet erosion on the medium, thereby providing a very special physical environment for chemical reactions which are difficult to realize under general conditions, opening a channel of the chemical reactions and accelerating the chemical reactions.
In view of the above, the present inventors have conducted extensive experiments and found that the above problems can be solved by using a non-sodium salt vulcanizing agent in combination with enhanced ultrasonic waves, and therefore, the present inventors have provided a method for removing arsenic under acidic conditions, as shown in fig. 1, the method comprising the steps of:
step 1, adding a vulcanizing agent into arsenic-containing wastewater;
step 2, adding a reinforcing agent into the system in the step 1, and then carrying out ultrasonic treatment;
and 3, removing cations of the introduced vulcanizing agents.
The arsenic removal process under acidic conditions is described in further detail below:
step 1, adding a vulcanizing agent into the arsenic-containing wastewater.
According to a preferred embodiment of the invention, the arsenic-containing waste water is acidic, wherein H is + The concentration of (B) is 0.1mol/L to 4mol/L.
In a further preferred embodiment, the arsenic content in the arsenic-containing wastewater is from 100mg/L to 30000mg/L, preferably from 200mg/L to 20000mg/L, more preferably from 300mg/L to 10000mg/L, and may be, for example, 300mg/L, 312mg/L, 932mg/L or 28700mg/L.
In the invention, the arsenic in the arsenic-containing wastewater under the acidic condition is H 3 AsO 3 Or H 3 AsO 4 The form exists.
According to a preferred embodiment of the invention, the sulphiding agent includes, but is not limited to, sodium sulphide, calcium sulphide, phosphorus sulphide, iron sulphide.
Preferably, the sulphiding agent is selected from one or more of sodium sulphide, calcium sulphide, phosphorus sulphide and iron sulphide.
More preferably, the sulfurising agent is iron sulfide.
The inventor considers that the adoption of sodium sulfide or sodium hydrosulfide reagent to remove arsenic can introduce Na + The inventor finds that the problem can be avoided by adopting the non-sodium sulfide to remove arsenic through a large number of tests, particularly, the arsenic removal efficiency is high by adopting the iron sulfide as a vulcanizing agent, and the subsequent iron removal method is simple to operate and low in removal cost.
In a further preferred embodiment, the sulfurizing agent is FeS and/or FeS 2 。
In the present invention, feS and/or FeS is selected 2 As a vulcanizing agent, feS and/or FeS can be used without introducing sodium ions into the system to reduce the burden on the system 2 Added into arsenic-containing wastewater, the dissolution needs a certain time, and S can be slowly released in the arsenic removal process 2- So that most of S is released 2- Reacts with arsenic to achieve the aim of removing arsenic, improves the utilization efficiency of a vulcanizing agent, and simultaneously reduces a large amount of S which can not react with arsenic in the arsenic removing process of the existing vulcanizing method 2- Reacting with hydrogen ions in the system to generate hydrogen sulfide gas to be released into the environment, thereby causing environmental threat.
In a further preferred embodiment, the molar ratio of sulfur in the added sulfidizing agent to arsenic in the arsenic-containing wastewater is (2-4): 2, preferably (2.5 to 3.5): 2, more preferably 3:2.
preferably, when the vulcanizing agent added is FeS, the addition amount of FeS is 2-6 g/L, preferably 2.5-5 g/L, more preferably 3-4 g/L, such as 3.5g/L, based on 300mg/L of arsenic;
the amount of FeS added is 8 to 16g/L, preferably 9 to 15g/L, more preferably 10 to 14g/L, such as 12g/L, based on 932mg/L of arsenic;
the added vulcanizing agent is FeS 2 Based on 312mg/L arsenic, feS 2 Is added in an amount of 7 to 13g/L, preferably 8 to 12g/L, more preferably 9 to 11g/L, such as 10g/L.
932mg/L arsenic, feS based 2 The amount of (B) is 20 to 40g/L, preferably 25 to 35g/L, for example 30g/L.
And 2, adding a reinforcing agent into the system in the step 1, and then carrying out ultrasonic treatment.
The inventor discovers that the arsenic-containing wastewater added with the vulcanizing agent can be rapidly and uniformly dispersed into the arsenic-containing wastewater by adopting ultrasonic treatment to prevent the vulcanizing agent from gathering to cause local S 2- The excessive sulfur is avoided to overflow by hydrogen sulfide gas, the utilization rate of the vulcanizing agent is improved, and the environment is improved; in addition, a large amount of hydrogen free radicals with reducibility are generated during the action of ultrasonic waves, the oxidation-reduction potential of a system is reduced, and the sulfuration arsenic removal reaction is easier and faster carried out rightwards (arsenic removal reaction principle: me) x S y (sulfurized agent) + H 3 AsO 3＝＝＝＝ As 2 S 3 +Me n+ (ii) a Or Me x S y (sulfurized agent) + H 3 AsO 4＝＝＝＝ As 2 S 5 +Me n+ ) The efficiency of the reaction for removing arsenic by sulfuration is improved, the reaction time is shortened, and the arsenic sulfide precipitate generated in the long-time arsenic removal process is prevented from being dissolved back to reduce the arsenic removal effect.
Further, the inventor researches and discovers that if the treated arsenic-containing wastewater belongs to a strong acid, acidic or weak acidic environment, namely under an acidic condition, hydrogen radicals are more favorably generated, so that the effect of ultrasonic waves is more obvious. Therefore, the ultrasonic wave is more suitable for treating the arsenic-containing wastewater under the acidic condition, and the vulcanizing agent and the ultrasonic wave are preferably combined to treat the arsenic-containing wastewater under the acidic condition.
According to a preferred embodiment of the invention, the enhancer is an agent with a reducing effect so as to reduce the oxidation-reduction potential of the system and improve the arsenic removal efficiency.
In a further preferred embodiment, the enhancer is selected from one or more of 2-propanol, ascorbic acid, tert-butanol, ethanol, tert-butanol, methanol;
preferably, the enhancer is selected from one or more of 2-propanol, ascorbic acid, tert-butanol, preferably 2-propanol and/or ascorbic acid, more preferably 2-propanol.
The inventor researches and discovers that in the ultrasonic treatment process, by adding 2-propanol and/or ascorbic acid and other medicaments, the ultrasonic effect can be obviously enhanced, the oxidation-reduction potential of the system is reduced, the arsenic removal efficiency is further improved, and the reaction time is shortened. The main reason is that the reinforcing agents such as 2-propanol and/or ascorbic acid can remove hydroxyl radicals of the system and further enable hydrogen radicals to play a role, and in addition, the ascorbic acid also has a reduction effect so as to further reduce the oxidation-reduction potential of the system and promote the arsenic removal reaction.
In a further preferred embodiment, the mass fraction of the reinforcing agent in the system is between 0.5% and 10%, preferably between 0.5% and 8%, for example 1%.
According to a preferred embodiment of the present invention, the power of the ultrasonic wave is 100W to 2000W, and the action time is 5min to 90min.
In the power range, a better strengthening effect can be achieved, and meanwhile, the energy consumption is reduced. The ultrasonic action time is set, so that the arsenic removal effect can be ensured.
In a further preferred embodiment, the ultrasonic treatment is performed by using a probe type ultrasonic generator and is power ultrasound.
Preferably, the frequency of the ultrasonic waves is 20kHz.
In the invention, after ultrasonic treatment for a period of time, the content of arsenic in the arsenic-containing wastewater is measured.
And 3, removing cations of the introduced vulcanizing agents.
In the present invention, the inventors consider that the added sulfuration agents introduce cations, which need to be removed.
According to a preferred embodiment of the invention, the cations in the thionating agent are removed according to a method comprising the following steps:
and 3-1, adding an alkaline solution into the arsenic-removed solution to adjust the pH value to be between 2 and 4.
Wherein, the alkaline solution is preferably sodium hydroxide solution or concentrated ammonia water.
And 3-2, aerating air or ozone into the solution to perform oxidation and iron removal.
According to a preferred embodiment of the invention, the solution is exposed to ozone for oxidative iron removal.
In a further preferred embodiment, the ozone gas flow is 3g/h, the reaction temperature is 40 to 80 ℃ and the treatment time is 10 to 40min.
Preferably, in the cation removing process, ultrasonic wave strengthening is adopted, and the ultrasonic wave power is 100W-500W.
Wherein, fe 2+ Mainly in the form of FeOOH, and precipitates are generated, and the residue-liquid separation can be realized through filtration, so that cations introduced into the vulcanizing agent are removed.
According to the arsenic removal method under the acidic condition, the iron sulfide is added to serve as a vulcanizing agent, so that the problem of high cost of subsequent sodium removal caused by the existing sodium sulfide is effectively solved, meanwhile, the ultrasonic waves and the reinforcing agent are used in a combined mode to assist in arsenic removal, the arsenic removal efficiency is remarkably improved by utilizing the enhanced ultrasonic effect, and the reaction time is shortened.
Examples
The present invention is further described below by way of specific examples, which are merely illustrative and do not limit the scope of the present invention in any way.
Example 1
Placing 3L of waste acid with arsenic content of 312mg/L in a container, H + The concentration is 1mol/L, 10g/L of FeS is added into a container 2 Adding reinforcing agent 2-propanol with mass percent of 1% in the system, then carrying out ultrasonic treatment by adopting an ultrasonic device, wherein the power of ultrasonic is 150W, the action time is 75min, and reacting respectively for 15minSampling at min, 30min, 45min, 60min, 75min and 90min, and measuring the content of arsenic in the waste acid solution by using an inductively coupled plasma spectrometer, wherein the results are shown in table 1:
watch (A) 1. The following examples of the present invention
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 25 91.99
30 17 94.55
45 14 95.51
60 13 95.83
75 11 96.47
90 8 97.44
As is clear from Table 1, the removal rate of arsenic reached 97.44% after 90min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 0.71g, and the content of dry slag is 0.46g.
Example 2
The arsenic removal process described in this example is similar to that of example 1, except that FeS is added to the contaminated acid 2 Is 50g/L.
The arsenic content in the contaminated acid was measured and the results are shown in table 2:
TABLE 2
Figure BDA0003742756480000081
Figure BDA0003742756480000091
As can be seen from Table 2, the removal rate of arsenic reached 97.33% after 30min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 51g, and the content of dry slag is 37.2g.
Example 3
Placing 3L of waste acid of melting furnace with arsenic content of 300mg/L in a container, and H + The concentration is 1mol/L, feS of 3.5g/L is added into a container, reinforcing agent tert-butyl alcohol is added, the mass fraction of the FeS in the system is 1%, then ultrasonic treatment is carried out by adopting an ultrasonic device, the power of ultrasonic is 150W, the action time is 35min, samples are taken when the FeS reacts for 5min, 10min, 15min, 20min, 25min, 30min and 35min respectively, the content of arsenic in the contaminated acid solution is measured by adopting an inductively coupled plasma spectrometer, and the results are shown in Table 3:
TABLE 3
Time (min) Arsenic content (mg/L) Removal Rate (%)
5 215 28.33
10 106 64.67
15 48 84.00
20 17 94.33
25 15 95.00
30 14 95.33
35 14 95.33
As is clear from Table 3, the removal rate of arsenic reached 95.33% after 30min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 0.71g, and the content of dry slag is 0.41g.
Example 4
Placing 3L of waste acid with arsenic content of 932mg/L in a container, and H + At a concentration of 1mol/L, 30g/L of FeS was added to the vessel 2 Adding a reinforcing agent 2-propanol with the mass fraction of 1% in the system, then carrying out ultrasonic treatment by using an ultrasonic device, wherein the power of ultrasonic waves is 150W, the action time is 75min, sampling is carried out when the reaction is carried out for 15min, 30min, 45min, 60min, 75min and 90min respectively, and the content of arsenic in the waste acid solution is measured by using an inductively coupled plasma spectrometer, wherein the results are shown in Table 4:
TABLE 4
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 62 93.35
30 32 96.57
45 22 97.64
60 18 98.07
75 14 98.50
90 11 98.82
As can be seen from Table 4, the removal rate of arsenic reached 98.82% after 90min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 21.2g, and the content of dry slag is 12g.
Example 5
The arsenic removal process used in this example was similar to that used in example 4, except that 12g/L FeS was added to the contaminated acid.
The arsenic content in the contaminated acid was measured and the results are shown in table 5:
TABLE 5
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 61 93.45
30 32 96.57
45 23 97.53
60 16 98.28
75 14 98.50
90 11 98.82
As shown in Table 5, the removal rate of arsenic reached 98.82% after 90min treatment
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 14.1g, and the content of dry slag is 7.3g.
Example 6
Placing 3L of waste acid with the arsenic content of 28700mg/L in a container, and H + Adding 87g/L FeS into a container with the concentration of 1mol/L, adding an enhancer of 2-propanol with the mass fraction of 1% in the system, performing ultrasonic treatment by using an ultrasonic device with the ultrasonic power of 150W and the action time of 75min, respectively sampling at the time of reaction for 15min, 30min, 45min, 60min and 75min, and adopting inductively coupled plasmaThe content of arsenic in the contaminated acid solution was measured by a spectral generator and the results are shown in table 6:
TABLE 6
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 14823 48.71
30 5650 80.45
45 1214 95.80
60 592 97.95
75 318 98.90
As is clear from Table 6, the removal rate of arsenic reached 98.90% by 75min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 171g, and the content of dry slag is 96g.
Example 7
Placing 3L of waste acid with arsenic content of 932mg/L in a container, and H + The concentration is 1mol/L, 3.8g/L of CaS is added into a container 4 Adding a reinforcing agent 2-propanol, wherein the mass fraction of the reinforcing agent in the system is 1%, then carrying out ultrasonic treatment by using an ultrasonic device, the power of ultrasonic waves is 150W, the action time is 75min, sampling is carried out when the reaction is carried out for 15min, 30min, 45min, 60min and 75min respectively, and the content of arsenic in the contaminated acid solution is measured by using an inductively coupled plasma spectrometer, wherein the results are shown in Table 7:
TABLE 7
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 43 95.39
30 27 97.10
45 14 98.50
60 14 98.50
75 14 98.50
As is clear from Table 7, the removal rate of arsenic reached 98.50% by 75min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 8.24g, and the content of dry slag is 4.27g.
Example 8
Placing 3L of waste acid with arsenic content of 932mg/L in a container, and H + At a concentration of 1mol/L, 1.3g/L of P was added to the vessel 2 S 5 Adding a reinforcing agent 2-propanol with the mass fraction of 1% in the system, then carrying out ultrasonic treatment by using an ultrasonic device, wherein the power of ultrasonic waves is 150W, the action time is 60min, sampling is carried out when the reactions are carried out for 15min, 30min, 45min and 60min respectively, and the content of arsenic in the contaminated acid solution is measured by using an inductively coupled plasma spectrometer, wherein the results are shown in Table 8:
TABLE 8
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 36 96.13
30 33 96.45
45 18 98.07
60 18 98.07
As is clear from Table 8, the removal rate of arsenic reached 98.07% after 60min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 3.6g, and the content of dry slag is 1.7g.
Example 9
Restlessness
Adding concentrated ammonia water into the arsenic-removed solution obtained in the embodiment 1 to adjust the pH value to 2-4, exposing ozone into the solution to oxidize and remove iron, wherein the flow rate of the ozone gas is 3g/h, the reaction temperature is 40-80 ℃, the treatment time is 30min, ultrasonic strengthening is adopted in the cation removal process, the ultrasonic power is 100-500W,
detection of Fe after filtration 2+ The concentration was 0.16g/L.
Comparative example
Comparative example 1
The arsenic-containing contaminated acid treated by the comparative example was the same as the arsenic-containing contaminated acid treated in example 1, and the arsenic-containing contaminated acid was treated by ultrasonic waves alone without adding any chemical agent, and the power and time of the ultrasonic waves were the same as those of example 1.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 9:
TABLE 9
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 48 84.6
30 37 87.7
45 28 91.0
60 28 91.0
75 28 91.0
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 0.74g, and the content of dry slag is 0.42g.
Comparative example 2
The arsenic-containing contaminated acid treated by the comparative example was the same as the arsenic-containing contaminated acid treated in example 3, and the arsenic-containing contaminated acid was treated by ultrasonic waves alone without adding any chemical agent, and the power and time of the ultrasonic waves were the same as those of example 3.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 10:
watch 10
Time (min) Arsenic content (mg/L) Removal Rate (%)
5 239 20.33
10 121 59.67
15 57 81.00
20 24 92.00
25 21 93.00
30 21 93.00
35 20 93.33
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 0.68g, and the content of dry slag is 0.37g.
Comparative example 3
The arsenic-containing contaminated acid treated in this comparative example was the same as the arsenic-containing contaminated acid treated in example 4, and the power and time of ultrasonic treatment were the same as those of example 4, except that the arsenic-containing contaminated acid was treated with ultrasonic waves alone without adding any chemical agent.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 11:
TABLE 11
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 102 89.06
30 67 92.81
45 35 96.24
60 34 96.35
75 34 96.35
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 3.1g, and the content of dry slag is 1.3g.
Comparative example 4
The arsenic-containing contaminated acid treated in this comparative example was the same as the arsenic-containing contaminated acid treated in example 1, and only FeS was added to the vessel in the same concentration and total amount as in example 1 2 (10 g/L of FeS 2 ) Ultrasonic treatment is not employed.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 12:
TABLE 12
Figure BDA0003742756480000151
Figure BDA0003742756480000161
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 9.6g, and the content of dry slag is 4.8g.
Comparative example 5
The contaminated arsenic-containing acid treated in this comparative example was the same as the contaminated arsenic-containing acid treated in example 3, except that FeS (FeS of 3.5 g/L) was added to the vessel in the same concentration and total amount as in example 3, and that ultrasonic treatment was not carried out.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 13:
watch 13
Time (min) Arsenic content (mg/L) Removal Rate (%)
5 215 28.33
10 119 61.9
15 76.8 75.4
20 96 69.2
25 73 76.6
30 73 76.6
35 61.5 80.3
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 1.3g, and the content of dry slag is 0.56g.
Comparative example 6
The arsenic-containing contaminated acid treated in this comparative example was the same as the arsenic-containing contaminated acid treated in example 4, and only FeS was added to the vessel in the same concentration and total amount as in example 4 2 (30 g/L of FeS 2 ) Ultrasonic treatment is not employed.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 14:
TABLE 14
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 341 63.41
30 262 71.89
45 241 74.14
60 224 75.97
75 190 79.61
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 32.2g, and the content of dry slag is 17.4g.
Comparative example 7
The contaminated acid containing arsenic treated in this comparative example was the same as the contaminated acid containing arsenic treated in example 5, and only FeS (FeS of 12 g/L) was added to the vessel in the same concentration and total amount as in example 5, without ultrasonic treatment.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 15:
watch 15
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 362 61.16
30 288 69.10
45 263 71.78
60 241 74.14
75 362 61.16
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 17.2g, and the content of dry slag is 10g.
Comparative example 8
The arsenic removal method used in this comparative example was similar to that of example 1, except that no strengthening agent was added during the sonication.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 16:
TABLE 16
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 31 89.67
30 16 94.67
45 14 95.33
60 14 95.33
75 14 95.33
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 0.69g, and the content of dry slag is 0.46g.
Comparative example 9
The arsenic removal method used in this comparative example was similar to that of example 3, except that no enhancer was added during the ultrasonic treatment.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 17:
TABLE 17
Time (min) Arsenic content (mg/L) Removal Rate (%)
5 234 22.00
10 127 57.67
15 61 79.67
20 24 92.00
25 21 93.00
30 17 94.33
35 17 94.33
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 0.69g, and the content of dry slag is 0.41g.
Comparative example 10
The arsenic removal process used in this comparative example was similar to that of example 4, except that no strengthening agent was added during the sonication.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 18:
watch 18
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 69 92.60
30 38 95.92
45 21 97.75
60 15 98.39
75 14 98.50
90 13 98.61
105 11 98.82
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 20.3g, and the content of dry slag is 11.9g.
Comparative example 11
The arsenic removal method used in this comparative example was similar to that of example 6, except that no strengthening agent was added during the sonication.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 19:
watch 19
Figure BDA0003742756480000191
Figure BDA0003742756480000201
As is clear from Table 19, the removal rate of arsenic reached 98.83% by 75min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 171g, and the content of dry slag is 96g.
Comparative example 12
This comparative example used an arsenic removal process similar to that of example 7, except that no strengthening agent was added during the sonication.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 20:
watch 20
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 48 94.8
30 28.8 96.9
45 19.2 97.9
60 15.4 98.3
75 15.4 98.3
As is clear from Table 20, the removal rate of arsenic reached 98.3% by 75min of treatment.
Further, the content of the solid waste residue in the waste acid after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 8.24g, and the content of dry slag is 4.27g.
Comparative example 13
The arsenic removal method used in this comparative example was similar to that of example 8, except that no strengthening agent was added during the sonication.
The arsenic content of the contaminated acid solution was measured and the results are shown in table 21:
TABLE 21
Time (min) Arsenic content (mg/L) Removal Rate (%)
15 38.4 95.9
30 38.4 95.9
45 34.5 96.3
60 28.8 96.9
As can be seen from Table 21, after 60min of treatment, the arsenic content in the contaminated acid was reduced from 932mg/L to 28.8mg/L, and the removal rate reached 96.9%.
Further, the content of the solid waste residue in the waste acid solution after the reaction is measured, and the result shows that: in each liter of the waste acid solution, the content of wet slag is 3.6g, and the content of dry slag is 1.7g.
By combining the above examples and comparative examples, it can be seen that the arsenic removal method under acidic conditions described herein can achieve synergistic effects by combining the use of a vulcanizing agent, a reinforcing agent, and ultrasonic waves, significantly improve arsenic removal efficiency, and reduce reaction time
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention.

Claims (8)

1. A method for removing arsenic under acidic conditions, comprising the steps of:
step 1, adding a vulcanizing agent into arsenic-containing wastewater;
step 2, adding a reinforcing agent into the system in the step 1, and then carrying out ultrasonic treatment;
and 3, removing cations of the introduced vulcanizing agents.
2. The method according to claim 1, wherein in step 1, the arsenic content in the arsenic-containing wastewater is 100mg/L to 30000mg/L.
3. The method of claim 1, wherein in step 1, the sulfidizing agent is iron sulfide;
preferably, the sulfurizing agent is FeS and/or FeS 2 。
4. The method according to claim 1, wherein in step 1, the ratio of the sulfur in the added sulfurating agent to the arsenic content in the arsenic-containing wastewater is (2-4): 2.
5. the method as claimed in claim 1, wherein in step 2, the enhancer is an agent with reducing action to reduce the oxidation-reduction potential of the system and improve the arsenic removal efficiency;
preferably, the enhancer is selected from one or more of 2-propanol, ascorbic acid, tert-butanol, ethanol, tert-butanol and methanol.
6. The method according to claim 5, wherein in the step 2, the mass fraction of the reinforcing agent is 0.5-10%.
7. The method according to claim 1, wherein in step 2, the power of the ultrasonic wave is 50W to 2000W.
8. The method according to claim 1, wherein in step 2, the ultrasonic wave is applied for 5-90 min.
CN202210816838.2A 2022-07-12 2022-07-12 Arsenic removal method under acidic condition Pending CN115340228A (en)

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