CN112010390B - Method for self-cleaning arsenic removal in waste acid through ultrasonic waves - Google Patents

Method for self-cleaning arsenic removal in waste acid through ultrasonic waves Download PDF

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CN112010390B
CN112010390B CN201910457332.5A CN201910457332A CN112010390B CN 112010390 B CN112010390 B CN 112010390B CN 201910457332 A CN201910457332 A CN 201910457332A CN 112010390 B CN112010390 B CN 112010390B
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arsenic
waste acid
ultrasonic
acid
waste
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CN112010390A (en
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张利波
李静
罗永光
邹景田
曲洪涛
席云浩
张侯文
付光
李云
张特
保佳懿
张宏
廖天棋
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Kunming University of Science and Technology
Yunnan Chihong Zinc and Germanium Co Ltd
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Kunming University of Science and Technology
Yunnan Chihong Zinc and Germanium Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal 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

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

Abstract

The invention relates to a method for removing arsenic by ultrasonic self-cleaning in waste acid, which can achieve the aim of efficiently removing arsenic by only utilizing an ultrasonic device which is independently developed to carry out ultrasonic strengthening treatment on the waste acid without adding any reagent, and comprises the following specific steps: adding ultrasonic wave into the waste acid for strengthening, reacting for a certain time to generate precipitate, and performing solid-liquid separation to obtain filtered solution and precipitate impurities. According to the arsenic removal method provided by the invention, arsenic impurities in the waste acid can be efficiently removed, the process is simple, the cost is greatly reduced, and meanwhile, the treated acid and water can be recycled to a zinc oxide smoke dust recovery working section, so that the pollution to the environment is reduced; meanwhile, waste of a large amount of acid and water in the waste acid is avoided, no arsenic removal reagent is added, the treatment cost is reduced, other impurities are not introduced, and the method is energy-saving and environment-friendly.

Description

Method for self-cleaning arsenic removal in waste acid through ultrasonic waves
Technical Field
The invention relates to the field of wet metallurgy, in particular to a method for strengthening treatment of arsenic in a waste acid solution by ultrasonic waves.
Background
In the non-ferrous metal smelting process, a large amount of flue gas containing sulfur dioxide is generated, and the sulfur dioxide is recycled to prepare sulfuric acid, so that the smoke harm is eliminated, and the value is created. However, in the process of preparing sulfuric acid by using flue gas, arsenic, cadmium, chlorine and the like in the flue gas are transferred to 'waste acid' generated by washing the flue gas.
And arsenic, chlorine, fluorine and other impurities are harmful to the environment, and are necessary to be separated from the comprehensive utilization resources, so that the waste acid solution can be recycled.
For removing arsenic impurities, the existing lead-iron-zinc smelting enterprises mainly adopt a terminal treatment mode, and particularly adopt a lime neutralization iron salt method to carry out waste acid treatment. In the current waste acid treatment operation of enterprises, lime under the condition of normal temperature (room temperature) is added into waste acid to adjust the pH of the solution, a large amount of gypsum residues are generated, ferric salt and the like are added into the solution to achieve the purpose of precipitating arsenic, and the obtained solution needs to be subjected to secondary treatment to reach the national standard and then is discharged.
The existing arsenic removal process of the contaminated acid has high cost, serious resource waste and complex process operation; the treatment cost of the generated gypsum slag is high; the acid consumption and the water consumption of enterprises are large. There is an urgent need for a method to solve the above problems.
The invention aims to overcome the defects in the prior art and provide a method for self-cleaning and removing arsenic in waste acid by ultrasonic waves, which has the advantages of simple process flow, easy implementation, no need of adding any reagent, reduced energy consumption, reduced resource waste, avoidance of gypsum slag generation and capability of greatly improving economic benefits and environmental benefits.
Disclosure of Invention
In order to solve the problems, the inventor of the present invention has conducted intensive research and provides a method for self-cleaning arsenic removal in contaminated acid by ultrasonic waves, specifically comprising: and optionally stirring the waste acid, then adding ultrasonic waves to carry out an enhanced reaction, carrying out the enhanced reaction for a certain time by the ultrasonic waves to separate out solids, and finally carrying out solid-liquid separation to obtain a filtered solution and precipitated impurities. According to the ultrasonic self-cleaning arsenic removal method provided by the invention, arsenic can be removed efficiently without adding any reagent, the treatment cost is remarkably reduced, the generation of lime slag is completely avoided, the arsenic removal time is greatly shortened, the power consumption and the energy consumption are saved, the treated acid can be recycled, and the pollution to the environment is reduced, thereby completing the invention.
The invention aims to provide the following technical scheme:
in a first aspect, the invention provides a method for removing arsenic from contaminated acid, which comprises the steps of carrying out enhanced arsenic removal on the contaminated acid by using ultrasonic waves;
wherein the ultrasonic power is 60-160W, preferably 90-130W;
wherein the ultrasonic reaction time is 5-60 minutes, preferably 10-45 minutes.
Wherein, according to the method, the method comprises the following steps:
step 1, optionally preheating the waste acid;
step 2, carrying out ultrasonic wave reinforced reaction on the waste acid obtained in the step 1 to obtain a solid-liquid mixture;
and 3, carrying out solid-liquid separation on the solid-liquid mixture obtained in the step 2.
According to the method, the waste acid is a solution obtained by making acid from smelting flue gas, and the smelting flue gas comprises copper, lead, zinc and pyrite smelting flue gas, preferably lead and zinc smelting flue gas, more preferably zinc smelting flue gas, and further preferably zinc sulfide concentrate smelting flue gas.
According to the method for self-cleaning and removing arsenic in the waste acid by ultrasonic waves, the method has the following beneficial effects:
(1) the method of the invention removes arsenic in the waste acid by ultrasonic reinforcement, the speed of generating precipitate is fast, the reaction time is greatly shortened, the pH value of the treated acid is basically unchanged, and the improvement of economic benefit and environmental benefit is comprehensively realized;
(2) the method can obtain granular arsenic-containing precipitate, is easy to filter and reduces the treatment time;
(3) the waste acid is not neutralized in the method, so that the generation of lime mud is reduced, the time is saved, and the environmental pollution is reduced;
(4) the acid treated by the method can be reused in a zinc oxide smoke dust recovery working section, so that the environmental pollution is reduced, and the energy is saved;
(5) the method can realize high-efficiency arsenic removal only by using ultrasonic polluted acid without adding any reagent, so that the arsenic removal process is simpler and the cost is greatly reduced.
Drawings
FIG. 1 shows a flow diagram of self-cleaning arsenic removal in ultrasonically enhanced contaminated acid provided by the present invention;
FIG. 2 shows the XRD patterns measured after drying of the precipitate obtained in example 1;
FIG. 3 shows an SEM image of the dried precipitate obtained in example 1.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
As mentioned in the background, the current conventional methods for arsenic removal from contaminated acids are the ferrous sulfate-lime process and the sulfidation process.
The slag amount generated by the ferrous sulfate-lime method is large, heavy metals such as arsenic and the like are distributed in the slag in a scattered manner, the resources such as arsenic, cadmium and the like are difficult to recycle, the leakage-free permanent storage of the waste slag is difficult to realize, and secondary pollution can occur at any time.
In the sulfurization method, soluble sulfide reacts with heavy metal to generate insoluble sulfide, and the insoluble sulfide is removed from waste acid. The contents of arsenic, cadmium and the like in the sulfide slag are greatly improved, the toxic heavy metals in the waste acid are removed, the heavy metals are recycled, and the reactions can occur under the condition of low pH value. However, the effect of removing arsenic and cadmium by a vulcanization method is not obvious, and some methods firstly remove most of arsenic by the vulcanization method and then remove the rest arsenic by an iron salt-lime method.
Therefore, a method with high arsenic removal efficiency, simple and easy process flow, low energy consumption and less resource waste is needed to solve the above problems.
In order to solve the problems, the invention provides a method for self-cleaning arsenic removal in polluted acid by ultrasonic waves, which can achieve the purpose of efficiently removing arsenic by only carrying out ultrasonic strengthening treatment on the polluted acid by using the ultrasonic waves without adding any reagent.
Generally, ultrasonic waves refer to sound waves with a frequency higher than 20000 hz, which have good directivity and strong penetration ability, are easy to obtain more concentrated sound energy, and propagate in water for a long distance. Furthermore, ultrasonic oscillation is generally used in chemistry (chemical engineering) to make the solid dispersion more uniform.
The inventor feels that the invention is surprising and surprised that the invention can generate arsenic-containing sediment only by using ultrasonic waves to perform strengthened oscillation on the contaminated acid solution, and the aim of efficiently removing arsenic can be achieved. So far, the method provided by the invention has not been reported at home and abroad.
The detailed contents of the method provided by the invention are as follows:
in a first aspect, the invention provides a method for removing arsenic from contaminated acid, which comprises the steps of carrying out enhanced arsenic removal on the contaminated acid by using ultrasonic waves;
in one embodiment, the ultrasonic power is 60W to 160W, preferably 90W to 130W, such as 100W;
in one embodiment, the ultrasonic reaction time is 5 to 60 minutes, preferably 10 to 45 minutes, such as 30 minutes;
in a preferred embodiment, the ultrasonic power is 100W and the ultrasonic wave is intensified for 30 minutes.
The inventor finds that the temperature of the waste acid is not particularly limited, and the experiment is generally carried out at room temperature, and the temperature of the solution is increased after the ultrasonic wave is acted, so the experiment temperature is 30-95 ℃, and preferably 35-80 ℃.
The invention provides a method for removing arsenic from waste acid, which comprises the following steps:
step 1, optionally preheating the waste acid;
step 2, carrying out ultrasonic wave reinforced reaction on the waste acid obtained in the step 1 to obtain a solid-liquid mixture;
and 3, carrying out solid-liquid separation on the solid-liquid mixture obtained in the step 2.
In a preferred embodiment of the present invention,
in the step 1, the preheating temperature is 30-95 ℃, and more preferably 35-80 ℃;
in step 2, the ultrasonic power is 60W to 160W, more preferably 90W to 130W,
the ultrasonic reaction time is 5-60 minutes, and more preferably 10-45 minutes;
in step 3, the solid-liquid separation is filtration.
In the step 1, the waste acid is optionally heated to 30-95 ℃.
The inventors have found that the contaminated acid may optionally be subjected to a heat treatment; that is, the heat treatment may be performed or may not be performed. Can effectively remove arsenic when the subsequent steps are carried out.
In the actual production, the temperature of the waste acid discharged by a factory is generally not more than 95 ℃, the waste acid to be treated is not particularly heated or cooled, and if the temperature of the waste acid discharged in the actual production is slightly high, the arsenic can be directly removed by the method without cooling; if the temperature of the waste acid discharged in the actual production is slightly low, the arsenic can be removed by directly using the method of the invention without heating; in conclusion, the arsenic removal method has no special requirement on the treatment temperature of the waste acid, so the arsenic removal method can simplify the process and reduce the energy consumption.
In a preferred embodiment, the contaminated acid is added to the reaction vessel and heated to a temperature of from 35 to 80 ℃, for example 35 ℃.
In the step 2, carrying out ultrasonic wave reinforced reaction on the waste acid obtained in the step 1 to obtain a solid-liquid mixture;
in a preferred embodiment, the ultrasonic power is 90W to 130W;
in a further preferred embodiment, the ultrasonic power is 100W to 130W;
the inventor finds that the arsenic concentration in the treated waste acid is gradually reduced along with the increase of the ultrasonic power, namely the arsenic removal efficiency is improved; after the power reaches a certain value, the arsenic removal capacity reaches the limit, and the arsenic removal efficiency tends to be stable and does not change any more.
The inventors have found that ultrasound of different frequencies has substantially no effect on the arsenic removal results.
In a preferred embodiment, the ultrasonic reaction time is 5-60 minutes;
in a further preferred embodiment, the ultrasonic reaction time is 10 to 45 minutes;
in a still further preferred embodiment, the sonication reaction time is 30 minutes.
The inventor finds that the ultrasonic time is too short, and the arsenic removal efficiency is low; the ultrasonic reaction time is more preferably 30 minutes because the ultrasonic reaction time is too long, the arsenic removal efficiency is not improved much, and energy is wasted.
Through a great deal of exploration and research, the inventor surprisingly discovers that arsenic in the waste acid solution can be almost completely precipitated and removed by ultrasonic oscillation directly under the original acidic condition without neutralizing the waste acid, and the obtained precipitate is granular, has good dispersibility, good filtration and high filtration speed.
The inventor also finds that the technical effect of the invention can not be achieved when all ultrasonic oscillators ultrasonically strengthen the waste acid, and the ultrasonic instrument designed by the inventor has high ultrasonic power density and can convert electric energy into ultrasonic energy to the maximum extent so as to realize and achieve the technical effect of the invention; for example, the technical effects of the present invention can be obtained by using the following ultrasonic devices: chinese patent CN206872893U, an anti-corrosion ultrasonic enhanced leaching device; and chinese patent CN206762870U, an ultrasonic enhanced leaching device; and chinese patent CN207187170U, an ultrasonic enhanced leaching experimental apparatus.
The present inventors found that, As shown in FIG. 2, arsenic sulfide (As) is the main component of the precipitate obtained by removing arsenic from the XRD pattern of the obtained precipitate2S3) Arsenic oxide (As)2O3) Lead sulfate (PbSO)4) (ii) a This is probably because the water molecules are cleaved under the action of ultrasonic waves to produce ■ H having a strong reducing property, ■ H having a strong reducing property and H dissolved in the waste acid2SO3Reaction is carried out, SO is put into acid solution3 2-Reduction to S2-S generated2-With HAsO in solution2/H3AsO3Reaction for producing As2S3And (4) precipitating. And because original Pb ions in the contaminated acid may be PbCl in the acidic solution4 2-、PbCl3 -、PbCl2 0、PbCl+The original complex balance of Pb ions is broken under the action of ultrasonic wave, so that Pb exists2+By PbSO4Is precipitated into the slag (i.e., precipitation). However, the above is only a possibility of the present invention, and the present invention is not limited thereto.
In the invention, the obtained precipitate is granular, has good dispersibility, good filtering performance and high filtering speed. Compared with the arsenic removal method in the prior art, the method has the following great advantages: the waste acid solution does not need pretreatment, does not need pH adjustment, does not generate gypsum slag, and saves time and labor; no reagent is needed to be added for removing arsenic, so that the cost is saved; the sediment generated by arsenic removal is filtered, and the arsenic removal efficiency is high; the arsenic removal process is simple and easy to operate.
Optionally stirring in the step 1 and the step 2.
In step 3, the solid-liquid mixture of step 2 is subjected to solid-liquid separation.
In the present invention, the filtration method is not particularly limited, and in the present invention, reduced pressure filtration is employed.
In the invention, the waste acid is a solution obtained by making acid from smelting flue gas, and the smelting flue gas comprises copper, lead, zinc and pyrite smelting flue gas, preferably lead and zinc smelting flue gas, more preferably zinc smelting flue gas, and further preferably zinc sulfide concentrate smelting flue gas;
more preferably, the contaminated acid contains Cl in addition to sulfuric acid and arsenic-、F-And containing one or more metal ions, e.g. Pd2+、Cd2+、Cu2+。
The inventor finds that the method is suitable for lead, zinc and copper smelting to generate waste acid, preferably for lead and zinc smelting to generate waste acid, and the pH value is not particularly limited.
According to the method for removing arsenic in the waste acid by ultrasonic self-cleaning, provided by the invention, no reagent is added, and the waste acid solution is subjected to an enhanced treatment reaction by using ultrasonic waves, so that arsenic can be efficiently removed, the arsenic removal efficiency is more than 99.8%, the process is simple, the cost is greatly reduced, and the method is favorable for popularization and application.
FIG. 1 shows the specific operation steps of the ultrasonic self-cleaning arsenic removal in the contaminated acid according to a preferred embodiment of the invention:
preheating the contaminated acid, stirring, maintaining the temperature of the solution at 35 ℃, adding ultrasonic waves for enhancing reaction, wherein the ultrasonic wave power is 100W, taking out after 30 minutes of ultrasonic wave enhanced reaction, filtering to obtain filtrate and filter residue, measuring the arsenic content in the filtrate, and enabling the arsenic content to reach the standard, thereby achieving the enterprise recycling standard. The measuring method of the arsenic content adopts an ICP measuring method.
The inventor surprisingly found that compared with the previous research of adding zinc powder and copper sulfate solution into contaminated acid and then adding ultrasonic wave to enhance arsenic removal (application No. 2018111722758), the invention can remove arsenic efficiently by only ultrasonic wave enhancement treatment without adding any reagent, and has high arsenic removal efficiency. The invention has greater advantages.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
Example 1
Adding 100mL of waste acid solution into a reaction kettle, stirring and preheating to 35 ℃, wherein the main component of the waste acid is As (H)3AsO3Form) 735mg/L, Cl (as Cl)-Form) 1320mg/L, Pb (as Pb)2+Form) 116mg/L, Cd (as Cd)2+Form) 101.7mg/L, Cu (as Cu)2+Form) 2.86mg/L, F (as F)-Form exists) 456mg/L, pH is 1.2;
the method comprises the following steps of (1) performing ultrasonic strengthening treatment on waste acid by using an ultrasonic device, wherein the ultrasonic power is 100W, the temperature of the waste acid is maintained at 35 ℃, and the ultrasonic strengthening reaction is finished for 30 minutes to obtain a solid-liquid mixture;
filtering the solid-liquid mixture to obtain filtrate and residue, and measuring arsenic content in the filtrate, wherein the arsenic content is As (expressed As H)3AsO3Form) 0.44 mg/L; in the above reaction process, the removal rate of arsenic was 99.94%.
Example 2
Adding 100mL of waste acid solution into a reaction kettle, stirring and preheating to 35 ℃, wherein the main component of the waste acid is As (H)3AsO3Form) 790mg/L, Cl (as Cl)-Form) 1025mg/L, Pb (as Pb)2+Form(s) 198mg/L, Cd: (With Cd2 +Form) 98mg/L, Cu (as Cu)2+Form) 4.57mg/L, F (as F)-Form exists) 502mg/L, pH 1.0;
the method comprises the following steps of (1) performing ultrasonic strengthening treatment on waste acid by using an ultrasonic device, wherein the ultrasonic power is 100W, the temperature of the waste acid is maintained at 35 ℃, and the ultrasonic strengthening reaction is finished for 30 minutes to obtain a solid-liquid mixture;
filtering the solid-liquid mixture to obtain filtrate and residue, and measuring arsenic content in the filtrate, wherein the arsenic content is As (expressed As H)3AsO3Form) 1.3 mg/L; in the above reaction process, the removal rate of arsenic was 99.83%.
Example 3
Adding 100mL of waste acid solution into a reaction kettle, stirring and preheating to 35 ℃, wherein the main component of the waste acid is As (H)3AsO3Form) 525mg/L of Cl (as Cl)-Form) 1103mg/L, Pb (as Pb)2+Form) 156mg/L, Cd (as Cd)2+Form) 86.5mg/L, Cu (as Cu)2+Form) 0.86mg/L, F (as F)-Form exists) 598mg/L, pH 1.5;
ultrasonic waves are added into the ultrasonic device to strengthen the waste acid, the power of the ultrasonic waves is 100W, the temperature of the waste acid is maintained at 35 ℃, and the ultrasonic strengthening reaction is finished for 30 minutes to obtain a solid-liquid mixture;
filtering the solid-liquid mixture to obtain filtrate and residue, and measuring arsenic content in the filtrate, wherein the arsenic content is As (expressed As H)3AsO3Form exists) 0.37 mg/L; in the above reaction process, the removal rate of arsenic was 99.93%.
Example 4
Adding 100mL of waste acid solution into a reaction kettle, stirring and preheating to 35 ℃, wherein the main component of the waste acid is As (H)3AsO3Form) 619mg/L, Cl (as Cl)-Form) 1258mg/L, Pb (as Pb)2+Form) 121mg/L, Cd (as Cd)2+Form) 89.6mg/L, Cu (as Cu)2+Form) 4.39mg/L, F (as F)-Form exists) 495mg/L, pH 1.6;
ultrasonic waves are added into the ultrasonic device to strengthen the waste acid, the power of the ultrasonic waves is 100W, the temperature of the waste acid is maintained at 35 ℃, and the ultrasonic strengthening reaction is finished for 30 minutes to obtain a solid-liquid mixture;
filtering the solid-liquid mixture to obtain filtrate and residue, and measuring arsenic content in the filtrate, wherein the arsenic content is As (expressed As H)3AsO3Form) 1.23 mg/L; in the above reaction process, the removal rate of arsenic was 99.8%.
Example 5
Adding 100mL of waste acid solution into a reaction kettle, stirring and preheating to 35 ℃, wherein the main component of the waste acid is As (H)3AsO3Form) 1134mg/L, Cl (as Cl)-Form) 1225mg/L, Pb (as Pb)2+Form) 136mg/L, Cd (as Cd)2+Form) 115.6mg/L, Cu (as Cu)2+Form) 5.12mg/L, F (as F)-Form) 498mg/L, pH 0.9;
ultrasonic waves are added into the ultrasonic device to strengthen the waste acid, the power of the ultrasonic waves is 100W, the temperature of the waste acid is maintained at 35 ℃, and the ultrasonic strengthening reaction is finished for 30 minutes to obtain a solid-liquid mixture;
filtering the solid-liquid mixture to obtain filtrate and residue, and measuring arsenic content in the filtrate, wherein the arsenic content is As (expressed As H)3AsO3The form exists) 1.8mg/L, which reaches the enterprise recycling standard; in the above reaction process, the removal rate of arsenic was 99.84%.
Comparative example
Comparative example 1
Adding 100mL of waste acid solution into a reaction kettle, stirring and preheating to 35 ℃, wherein the main component of the waste acid is As (H)3AsO3Form) 1134mg/L, Cl (as Cl)-Form) 1225mg/L, Pb (as Pb)2+Form) 136mg/L, Cd (as Cd)2+Form) 115.6mg/L, Cu (as Cu)2+Form) 5.12mg/L, F (as F)-Form) 498mg/L, pH 0.9;
ultrasonic waves are added into the ultrasonic device to strengthen the waste acid, the power of the ultrasonic waves is 100W, the temperature of the waste acid is maintained at 35 ℃, and the ultrasonic strengthening reaction is finished for 10 minutes to obtain a solid-liquid mixture;
filtering the solid-liquid mixture to obtain filtrate and residue, and measuring arsenic content in the filtrate, wherein the arsenic content is As (expressed As H)3AsO3Form exists) 32.9mg/L, which reaches the enterprise recycling standard; in the above reaction process, the removal rate of arsenic was 97.1%.
Comparative example 2
Adding 100mL of waste acid solution into a reaction kettle, stirring and preheating to 35 ℃, wherein the main component of the waste acid is As (H)3AsO3Form) 1134mg/L, Cl (as Cl)-Form) 1225mg/L, Pb (as Pb)2+Form) 136mg/L, Cd (as Cd)2+Form) 115.6mg/L, Cu (as Cu)2+Form) 5.12mg/L, F (as F)-Form) 498mg/L, pH 0.9;
meanwhile, 0.393g of zinc powder and 13.1mL of 50g/L copper sulfate solution are added into the dirty acid, and stirring is carried out;
adding ultrasonic waves to strengthen the waste acid, wherein the ultrasonic power is 100W, the temperature of the waste acid is maintained at 35 ℃, and the ultrasonic strengthening reaction is finished for 10 minutes to obtain a solid-liquid mixture;
filtering the solid-liquid mixture to obtain filtrate and residue, and measuring arsenic content in the filtrate, wherein the arsenic content is As (expressed As H)3AsO3Form exists) 31.7mg/L, which reaches the enterprise recycling standard; in the above reaction process, the removal rate of arsenic was 97.2%.
Comparative example 3
The same procedure As in example 1, except that in comparative example 3, instead of the contaminated acid of example 1, a sulfuric acid solution containing only arsenic, in which As (As H) is used3AsO3Form exists) 735mg/L, pH 1.2;
finally, the arsenic content of the filtrate, As (in H), is determined3AsO3Form) 724 mg/L; in the above reaction process, the removal rate of arsenic was 1.4%.
Comparative example 4
Same as in example 1, except forIn this comparative example 4, the contaminated acid of example 1 was not used, but a sulfuric acid solution containing arsenic, chlorine and fluorine, in which As (As H)3AsO3Form) 735mg/L, Cl (as Cl)-Form) 1320mg/L, F (as F)-Form exists) 456mg/L, pH is 1.0;
finally, the arsenic content of the filtrate, As (in H), is determined3AsO3Form) 728 mg/L; in the above reaction process, the removal rate of arsenic was 0.9%.
Comparative example 5
The same procedure As in example 1, except that in comparative example 4, instead of the contaminated acid of example 1, a sulfuric acid solution containing arsenic, chlorine, fluorine, lead, cadmium, in which As is (in H), was used3AsO3Form) 735mg/L, Cl (as Cl)-Form) 1320mg/L, Pb (as Pb)2+Form) 116mg/L, Cd (as Cd)2+Form) 101.7mg/L, F (as F)-Form exists) 456mg/L, pH is 1.0;
finally, the arsenic content of the filtrate, As (in H), is determined3AsO3Form) 10.25 mg/L; in the above reaction process, the removal rate of arsenic was 98.60%.
Comparative example 6
The same procedure As in example 1, except that in comparative example 6, instead of the contaminated acid of example 1, a sulfuric acid solution containing arsenic, chlorine, fluorine, lead, cadmium, copper, in which As is (As H), was used3AsO3Form) 735mg/L, Cl (as Cl)-Form) 1320mg/L, Pb (as Pb)2+Form) 116mg/L, Cd (as Cd)2+Form) 101.7mg/L, Cu (as Cu)2+Form) 2.86mg/L, F (as F)-Form exists) 456mg/L, pH is 1.0;
finally, the arsenic content of the filtrate, As (in H), is determined3AsO3Form) 1.05 mg/L; in the above reaction process, the removal rate of arsenic was 99.85%.
Comparative example 7
The same procedure and materials as in example 1 were followed, except that the ultrasonic device of the present invention was not used, but a commercially available ultrasonic oscillator (model No. Gute ultrasonic GT SONIC-P13) was used; finally, the arsenic removal rate was 15.3%.
Comparing the examples with the comparative example 1, the ultrasonic time has influence on the arsenic removal result, and the ultrasonic time is preferably not less than 30 min;
as can be seen from the comparison between the example and the comparative example 2, the application can achieve the purpose of efficiently removing arsenic only by adopting the ultrasonic device of the invention without adding any reagent, thereby saving time and reducing cost;
as can be seen from the comparison between the examples and the comparative examples 3 to 6, the sulfuric acid solution contains some specific substances in addition to arsenic, and the technical effect of the present invention can be obtained only by the self-cleaning of the ultrasonic device according to the present invention.
As can be seen from comparison between example and comparative example 7, the technical effects of the present invention can be obtained only by the ultrasonic device having the functions of the ultrasonic apparatus according to the present invention.
In summary, the present invention does not need to add any reagent, and the waste acid of the present invention can be treated with the ultrasonic device of the present invention to remove arsenic in the waste acid with high efficiency.
Examples of the experiments
XRD analysis of sample of Experimental example 1
The solid precipitate obtained in example 1 was dried and analyzed by XRD scanning using a Bruker D8Advance type X-ray diffractometer (XRD), a copper target (Cu K α (λ ═ 0.154nm)) ray, a Ni filter, an operating voltage of 40kV, a current of 40mA, a scanning range of 2 θ ═ 10 to 90 °, and the crystal phase structure of the sample was analyzed. The results are shown in FIG. 2.
As can be seen from FIG. 2, the solid precipitate obtained was mainly composed of arsenic sulfide (As)2S3) Arsenic oxide (As)2O3) Lead sulfate (PbSO)4)。
Experimental example 2 SEM analysis of sample
The solid precipitate obtained in example 1 was dried and analyzed by SEM scanning electron microscope (Hitachi S-4700), and the result is a photograph showing the surface morphology of the product in FIG. 3.
As can be seen from FIG. 3, the precipitate contained a large amount of flocculent matter. It is analyzed As2S3Mainly comprises the following steps.
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 technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (4)

1. A method for removing arsenic from waste acid is characterized by comprising the following steps:
step 1, preheating waste acid, wherein the preheating temperature is 30-95 ℃;
step 2, carrying out ultrasonic wave strengthening reaction on the waste acid obtained in the step 1 to obtain a solid-liquid mixture, wherein the ultrasonic wave power is 90-130W, and the ultrasonic reaction time is 5-60 minutes;
step 3, carrying out solid-liquid separation on the solid-liquid mixture obtained in the step 2;
the waste acid is a solution obtained by preparing acid from smelting flue gas, the smelting flue gas is zinc smelting flue gas, and the waste acid contains Cl in addition to sulfuric acid and arsenic-、F-And containing one or more Pd2+、Cd2+、Cu2+A metal ion.
2. The method according to claim 1, wherein the ultrasonic reaction time is 10 to 45 minutes.
3. The method of claim 1,
in the step 1, the preheating temperature is 35-80 ℃;
in step 3, the solid-liquid separation is filtration.
4. The method according to any one of claims 1 to 3, wherein the smelting flue gas is zinc sulphide concentrate smelting flue gas.
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