CN110550786A - Waste liquid treatment process - Google Patents

Waste liquid treatment process Download PDF

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Publication number
CN110550786A
CN110550786A CN201910995731.7A CN201910995731A CN110550786A CN 110550786 A CN110550786 A CN 110550786A CN 201910995731 A CN201910995731 A CN 201910995731A CN 110550786 A CN110550786 A CN 110550786A
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waste liquid
agent
iron
copper
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CN110550786B (en
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刘新
阙山东
夏国春
李少元
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Guangxi Senhe High Technology Co Ltd
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Guangxi Senhe High Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/24Treatment of water, waste water, or sewage by flotation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/26Treatment of water, waste water, or sewage by extraction
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62Heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/70Treatment of water, waste water, or sewage by reduction
    • C02F1/705Reduction by metals
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/103Arsenic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/203Iron or iron compound
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/02Temperature
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The invention relates to the technical field of non-cyanide beneficiation waste liquid treatment, and particularly relates to a waste liquid treatment process. The waste liquid treatment process is used for treating the waste liquid with strong acidity, and comprises the following steps: adding an oxidant into the waste liquid to change low-valence ions in the waste liquid into high-valence ions; then, removing iron ions; then, adding an impurity removing agent into the waste liquid to remove Pb ions, Zn ions and Sb ions; then, adding an anthrax forming agent into the waste liquid to form anthrax from pentavalent arsenic ions. The method can effectively treat the strongly acidic waste liquid, effectively remove arsenic in the waste liquid, and recycle metal ions such as lead ions, iron ions, antimony ions and the like.

Description

waste liquid treatment process
Technical Field
the invention relates to the technical field of non-cyanide beneficiation waste liquid treatment, and particularly relates to a waste liquid treatment process.
Background
the existing gold extraction process and method are always the main method due to high cyanidation leaching efficiency, relatively simple process, convenient operation and relatively low cost. And cyaniding leaching is surrounded, so that the leachability of the ore is improved, and a combined gold extraction process of various pretreatments, namely cyaniding leaching, is developed. Greatly improves the utilization rate of gold resources. However, the use of cyanide is limited in many countries or regions because of the great toxicity of cyanide, which brings great safety risk to the environment and human and livestock; meanwhile, cyaniding leaching is influenced by a plurality of factors, and less oxidized ore and easily-selected ore which are suitable for cyaniding leaching are available, more difficultly-selected ore or multiple difficultly-selected ore which are not suitable for cyaniding leaching are available, so people research a plurality of non-cyanogen leaching production processes in order to protect the environment and improve the utilization rate of resources. The basic performance and the process of the medicament are the same as those of a cyanide base, and the leaching of refractory and multiple refractory ores is still to be verified and developed.
In the prior art, the waste liquid after screening ores by using a non-cyanide leaching agent is large in amount, heavy metal ions are not completely removed, repeated treatment is needed, the process is too long, the consumed time is large, and when the heavy metal ions are removed, multiple heavy metal ions are simultaneously removed, so that each metal ion cannot be singly recovered, and the resource utilization cannot be realized.
In view of this, the invention is particularly proposed.
Disclosure of Invention
the invention aims to provide a waste liquid treatment process, which can effectively treat a strongly acidic waste liquid, effectively remove arsenic ions, iron ions, antimony ions and other ions in the waste liquid, and can recycle metal ions such as lead ions, iron ions, antimony ions and the like independently.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a waste liquid treatment process, where the waste liquid treatment process is used to treat a waste liquid with strong acidity, where the waste liquid includes trivalent arsenic ions, trivalent antimony ions, ferrous ions, ferric ions, pentavalent arsenic ions, and pentavalent antimony ions,
The waste liquid treatment process comprises the following steps: adding an oxidant into the waste liquid to change low-valence ions in the waste liquid into high-valence ions;
Then, removing iron ions;
Then, adding an impurity removing agent into the waste liquid, and then carrying out flotation to remove Pb ions, Zn ions and Sb ions;
Then, adding an anthrax forming agent into the waste liquid to form anthrax from pentavalent arsenic ions.
In alternative embodiments, the oxidizing agent comprises at least one of an acidic media oxidizing agent and a basic media oxidizing agent;
Preferably, the acidic medium oxidizing agent comprises at least one of potassium permanganate and hydrogen peroxide;
Preferably, the alkaline medium oxidizing agent comprises at least one of chlorate and nitrite;
more preferably, the chlorate salt comprises sodium chlorate and the nitrite salt comprises sodium nitrite.
In alternative embodiments, the molar ratio of the oxidant to the total amount of lower valent ions is from 1 to 1.1: 1;
Preferably, the oxidation time is 0.5 to 1.0 hour.
in an alternative embodiment, removing iron ions comprises: extracting by using an iron ion extracting agent, and then separating liquid to obtain an extract liquid and an raffinate liquid;
preferably, the iron ion removal comprises the step of carrying out acid recovery treatment on the raffinate obtained by removing the iron ions;
More preferably, the acid recovery process comprises: and carrying out reduced pressure evaporation on the raffinate.
in an optional embodiment, after removing the iron ions, before adding the impurity removing agent, removing the copper ions is further included;
preferably, the removal of copper ions comprises separating copper by reacting the liquid after acid recovery with a reagent;
more preferably, removing the copper ions comprises removing the copper ions by a displacement reaction using a metal having higher reducibility than copper, more preferably, the metal having higher reducibility than copper is iron;
More preferably, removing copper ions comprises extracting the solution after recovering the acid with an extractant.
in an alternative embodiment, the trash removal agent is a sulfide, preferably sodium sulfide;
Preferably, before the impurity removing agent is added, the pH of the waste liquid is adjusted;
preferably, the pH is adjusted to a pH of the waste liquid of 1.0 or less, preferably 0.5 to 1.0.
in an optional embodiment, the addition amount of the impurity removing agent is 1.0-1.2 times of the chemical amount of the total ions of the impurities in the waste liquid;
preferably, the pH end point of the solution after the reaction by adding the impurity-removing agent is controlled to be 3.4 or less, preferably 3.2 to 3.4.
In an alternative embodiment, the anthracene forming agent comprises a ferrous salt and/or a calcium containing compound;
preferably, the ferrous salt is ferrous sulfate;
preferably, the calcification comprises lime or limestone.
in an alternative embodiment, the amount of the anthracene forming agent is 150%.
In an optional embodiment, before adding oxidant, analyzing the components of the waste liquor to determine the ion components and concentration contained in the waste liquor, and determining the oxidant, the impurity removing agent and the anthrax forming agent according to the analysis result;
Preferably, the temperature of the waste liquid in the waste liquid treatment process is always between 85 and 95 ℃;
Preferably, the pH of the strongly acidic waste liquid is less than 0.5.
The invention has the following beneficial effects: according to the invention, low-valence ions in the waste liquid are changed into high-valence ions by using the oxidant, particularly ferrous ions and trivalent arsenic and antimonic acid ions are changed into iron ions and pentavalent arsenic and antimonic acid ions, so that the iron ions, the arsenic ions and the antimonic ions can form stable precipitates in subsequent operation, and are not subjected to back dissolution under an acidic condition, and the removal effect of the iron ions, the arsenic ions and the antimonic ions is further ensured. Then, the iron ions are removed independently, so that the iron can be effectively and independently recovered, and the content of the iron ions in the waste liquid is reduced; then, an impurity removing agent is added to form precipitates with Pb ions, Zn ions and Sb ions, and then flotation is carried out to obtain solids containing each metal independently, so that the ions are effectively removed. Finally adding anthrax forming agent to form stable pentavalent arsenic ions, which are not anti-soluble under acidic conditions, and effectively remove arsenic ions.
Drawings
in order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flow chart of a waste liquid treatment process provided in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
the features and properties of the present invention are described in further detail below with reference to examples.
The waste liquid obtained by the gold beneficiation process in the prior art is generally alkaline cyanide waste liquid, arsenic antimony compounds removed from the waste liquid are a mixture of trivalent and pentavalent, the arsenic antimony compounds are easy to dissolve back under a weak acid condition, and precipitates formed by reaction are not in a stable scorodite state, so that arsenic ions and antimony ions are not completely removed. The content of ions such as copper, lead and zinc in the cyanide waste liquid is low, and the cyanide waste liquid exists in a cyanide complexing form, and the cyanide waste liquid becomes waste slag along with cyanide removal, so that the ions such as copper, lead and zinc cannot be recycled independently, and good recycling cannot be realized. Meanwhile, the waste liquid obtained by the prior art is alkaline cyanidation waste liquid, namely the waste liquid treatment process in the prior art generally aims at alkaline waste liquid, but the process waste liquid treated by the embodiment of the invention is strong-acid waste liquid, the waste liquid is recycled waste liquid, low-price arsenic, antimony and other ions are contained in the waste liquid, and the prior art for treating the gold dressing alkaline waste liquid cannot well treat the acidic waste liquid provided by the embodiment of the invention.
specifically, the source of the waste liquid is the waste liquid formed by recovering resources of a solution generated after gold beneficiation, wherein the gold beneficiation is to perform a chemical reaction on a raw material and a medicament, gold and silver and other non-ferrous metal impurity ions enter a leachate, then obtain gold from the leachate, and generate a solution containing a large amount of iron ions and a small amount of non-ferrous metal ions. And the iron ions have high concentration in the solution, an iron product can be obtained through crystallization, and then a waste liquid after resource recovery is formed, but copper-lead-zinc-antimony-arsenic impurities are accumulated in the solution, when the concentration reaches a certain concentration, the waste liquid after the resource recovery formed after crystallization and filtration must be treated with harmful impurities, and the waste liquid also contains high-concentration iron salt, and copper, lead, zinc and antimony metal ions can be recycled, so that the resource utilization rate is increased. Therefore, the application aims at carrying out secondary treatment on waste liquid formed by waste water which is recycled. Accordingly, an embodiment of the present invention provides a waste liquid treatment process, referring to fig. 1, including the following steps:
the waste liquid provided by the embodiment of the invention is strongly acidic, and the pH of the waste liquid is less than 0.5.
the waste liquid contains not only the above-mentioned heavy metal ions but also other heavy metal ions, for example, copper ions, lead ions, zinc ions, and the like.
Firstly, analyzing the components of the waste liquid, determining the ion components and concentration contained in the waste liquid, and determining the dosage of the oxidant, the impurity removing agent and the anthrax forming agent according to the analysis result to ensure the removal effect of each ion.
And secondly, adding an oxidant into the waste liquid to change low-valence ions in the waste liquid into high-valence ions, specifically, because the waste liquid contains low-valence ions such as ferrous ions, trivalent arsenic ions and antimonic acid ions, when the low-valence ions form precipitates in the subsequent process, the low-valence ions are easy to dissolve reversely in an acidic solution, so that the ion removal efficiency is reduced, the low-valence ions are oxidized to form high-valence ions, the precipitates formed in the subsequent process can be ensured to exist stably under an acidic condition, the phenomenon of dissolving reversely can not occur, and the removal effect of the arsenic ions, the ferric ions and the antimony ions is ensured.
The oxidizing agent comprises at least one of an acidic medium oxidizing agent and a basic medium oxidizing agent;
Preferably, the acidic medium oxidizing agent comprises at least one of potassium permanganate and hydrogen peroxide;
Preferably, the alkaline medium oxidizing agent comprises at least one of chlorate and nitrite;
More preferably, the chlorate salt comprises sodium chlorate and the nitrite salt comprises sodium nitrite. By adopting the oxidant, the oxidation effect can be ensured, so that low-valence ions are completely oxidized into high-valence ions, the reverse dissolution of the subsequently formed precipitate is effectively avoided, and the removal effect of ions is improved.
in alternative embodiments, the molar ratio of the oxidant to the total amount of lower valent ions is from 1 to 1.1: 1;
Preferably, the oxidation time is 0.5 to 1.0 hour. The oxidation effect can be ensured by adopting the conditions for oxidation.
Thirdly, removing iron ions; the reason why the iron ions are removed separately is that the iron sulfide formed by the impurity removing agent added subsequently and the iron ions cannot be separated from zinc sulfide, antimony sulfide, lead sulfide and the like well, and then the metal containing only iron cannot be obtained, so that the iron ions need to be removed separately.
Specifically, an iron ion extracting agent is used for extraction, and then liquid separation is carried out to obtain an extraction liquid and a raffinate; the iron ions are extracted into the extraction liquid to realize effective recovery and separation of the iron ions, the content of the iron ions in the waste liquid is reduced, and meanwhile, the iron ions are independently recovered, so that the resource recovery of the metal ions is realized.
removing iron ions comprises the step of carrying out acid recovery treatment on the raffinate obtained by removing iron ions;
more preferably, the acid recovery process comprises: and carrying out reduced pressure evaporation on the raffinate. And the acid in the raffinate is recycled, so that the influence of the acid on the subsequent ion removal is reduced, and the ion removal effect is ensured. Meanwhile, the reduced pressure evaporation provided by the embodiment of the invention is a conventional technical means, and the invention is not described in detail.
step four, after removing iron ions, removing copper ions before adding an impurity removing agent; if the waste liquid contains copper ions and the copper ions are more than 50mg/mL, the operation of removing the copper ions is needed.
Preferably, the removal of copper ions comprises separating copper by reacting the liquid after acid recovery with a reagent;
More preferably, removing the copper ions comprises removing the copper ions by a displacement reaction using a metal having higher reducibility than copper, more preferably, the metal having higher reducibility than copper is iron; although iron ions are introduced here, the content of copper ions is smaller than the amount of the original iron ions, and in this case, the amount of iron ions introduced is also smaller, and a large amount of iron contamination is not caused. The introduced iron ions can react with sulfate radical and arsenic ions to form anthrax, and then remove iron ions.
More preferably, removing copper ions comprises extracting the solution after recovering the acid with an extractant.
And fifthly, adjusting the pH value of the waste liquid to be less than 1.0, preferably 0.5-1.0, controlling the pH value of the solution, and ensuring that each ion can be effectively removed after an impurity removing agent is added subsequently. Specifically, the pH of the waste liquid is adjusted, if copper ions are removed by using iron, the iron ions do not form precipitates with the impurity removing agent, and lead ions, zinc ions and antimony ions can form precipitates with the impurity removing agent, so that Pb ions, Zn ions and Sb ions are removed.
Then, adding an impurity removing agent into the waste liquid to remove Pb ions, Zn ions and Sb ions; the impurity removing agent can not only remove Pb, Zn and Sb ions, but also properly remove copper ions, and when the content of the copper ions is less and can not be independently recovered, the impurity removing agent can also remove the copper ions, so that the content of each ion in the waste liquid is reduced.
Further, the impurity removing agent is sulfide, preferably sodium sulfide;
The addition amount of the impurity removing agent is 1.2 times of the chemical amount of the total ions of the impurities in the waste liquid;
preferably, the pH end point of the solution after the reaction by adding the impurity-removing agent is controlled to be 3.4 or less, preferably 3.2 to 3.4. The removal effect of antimony, lead and other ions can be ensured by adopting the conditions.
Sixth step, adding anthrax forming agent into the waste liquid to allow pentavalent arsenic ions to form anthrax. The oxidation of low-valence arsenic ions into high-valence arsenic ions can stabilize the formed anthrax precipitate, prevent re-dissolution, and ensure the removal effect of arsenic ions.
The process for forming anthrax requires that the anthrax forming agent and waste liquor have an action time of more than 8 hr, and ensures complete formation of anthrax and removal effect of arsenic ions.
The anthrax forming agent comprises ferrous salt and/or calcium-containing compound;
preferably, the ferrous salt is ferrous sulfate;
preferably, the calcification comprises lime or limestone.
In an alternative embodiment, the amount of the anthracene forming agent is 150%. The above odor anthrax and the dosage are adopted to ensure the removal effect of arsenic ions. Here, the addition amount of the ozone anthracene stone forming agent is 120-150%, which refers to the theoretical formed ozone stone with the molar amount of 120-150%.
Further, in the whole waste liquid treatment process, it is necessary to ensure that the temperature of the waste liquid is always between 85-95 deg.C, so as to ensure formation of stable odor-causing stones, and ensure separation effect of each ion, and further ensure treatment effect of the waste liquid.
Example 1
Taking the leaching waste liquid, detecting the concentration of copper ions of 50mg/L, lead ions of 23mg/L, zinc ions of 2mg/L, arsenic ions of 45mg/L (trivalent arsenic ion concentration of 16mg/L), antimony ions of 2.5mg/L (trivalent antimony ion concentration of 1.0mg/L) and ferrous ions of 5g/L, and the pH value of the waste liquid is 0.1.
Taking 500g of sample, adding 8g of 50% hydrogen peroxide (the molar ratio of the oxidant to the total amount of the low-valence ions is 1.3:1.0) by mass percent, and stirring and oxidizing for 1.0 hour. Then 25ml of P204 iron ion extracting agent is added to extract iron ions, liquid separation is carried out after the mixture is kept stand for 2.0 hours, and the raffinate after the liquid separation is decompressed and evaporated to recover acid. Then adjusting the pH value of the waste liquid to 2.0-3.0, adding 0.1g of sodium sulfide (the adding amount of an impurity removing agent is 1.2 times of the chemical amount of the total ions of the impurities in the waste liquid), after the reaction is finished, adjusting the pH value of the solution to 3.3, then filtering, adding 0.24 g of ferric sulfate (containing crystal water) into the filtrate, stirring and reacting for about 8 hours, and carrying out precipitation and filtration in the whole treatment process, wherein the temperature of the waste liquid is kept between 90 ℃ and 95 ℃. Because the copper content is not high and is small, the iron powder is not added, and the sodium sulfide can precipitate copper, so that the copper ion content is reduced.
The content of impurities such as copper, lead, zinc, antimony and arsenic in the filtrate is analyzed to be 0.5mg/L, 0.2mg/L, 0.3mg/L, 0.1mg/L and 0.2mg/L respectively, and the arsenic removal rate is 99.56 percent.
Example 2
taking the leaching waste liquid, and detecting the concentration of copper ions of 150mg/L, lead ions of 63mg/L, zinc ions of 24mg/L, arsenic ions of 58mg/L (wherein trivalent arsenic ions of 12mg/L), antimony ions of 12.5mg/L (trivalent antimony ions of 5.3mg/L) and ferrous ions of 7.6g/L, wherein the pH value of the waste liquid is 0.15.
Taking 500g of sample, adding 12g of 50% hydrogen peroxide (the molar ratio of the hydrogen peroxide to the total amount of the low-valence ions is 1.3:1) in percentage by mass into the waste liquid, and stirring and oxidizing for 1.0 hour; then 25ml of P204 iron ion extracting agent is added to extract iron ions, liquid separation is carried out after the mixture is kept stand for 3.0 hours, and the raffinate after the liquid separation is decompressed and evaporated to recover acid. Then, 0.2g of iron powder was added to the liquid phase after liquid separation, and filtration was carried out. And then adjusting the pH value of the waste liquid to 2.5-3.0, adding 0.1g of sodium sulfide (the addition amount of an impurity removing agent is 1.2 times of the chemical amount of the total ions of the impurities in the waste liquid), after the reaction is finished, adjusting the pH value of the solution to 3.5, then filtering, adding 0.28 g of a mixture of ferric sulfate and limestone into the filtrate, stirring and reacting for about 8 hours, and carrying out precipitation and filtration in the whole treatment process, wherein the temperature of the waste liquid is kept between 85 ℃ and 95 ℃.
The content of copper, lead, zinc, antimony and arsenic in the filtrate was analyzed to be 0.8mg/L, 0.5mg/L, 0.2mg/L, 0.5mg/L and 0.23mg/L, respectively. The arsenic removal rate is 99.60 percent.
Example 3
taking the leaching waste liquid, detecting the concentration of 95mg/L copper-containing ions, 42mg/L lead ions, 18mg/L zinc ions, 84mg/L arsenic ions (wherein the concentration of trivalent arsenic ions is 20mg/L), 5.5mg/L antimony ions (trivalent antimony ions is 2.3mg/L) and 8.2g/L ferrous ions, and the pH value of the waste liquid is 0.20.
Taking 500g of sample, adding 2.5g of potassium permanganate (the molar ratio of the oxidant to the total amount of the low-valence ions is 1.02:1) into the waste liquid, and stirring and oxidizing for 1.0 hour; then 25ml of P204 iron ion extracting agent is added to extract iron ions, liquid separation is carried out after the mixture is kept stand for 3.0 hours, and the raffinate after the liquid separation is decompressed and evaporated to recover acid. Then, 0.13g of iron powder was added to the liquid phase after liquid separation, followed by filtration. And then adjusting the pH value of the waste liquid to 2.5-3.0, adding 0.05g of sodium sulfide (the addition amount of an impurity removing agent is 1.2 times of the chemical amount of the total ions of the impurities in the waste liquid), after the reaction is finished, adjusting the pH value of the solution to 3.3, then filtering, adding 0.18 g of a mixture of ferric sulfate and limestone into the filtrate, stirring and reacting for about 8 hours, and carrying out precipitation and filtration in the whole treatment process, wherein the temperature of the waste liquid is kept between 85 ℃ and 95 ℃.
the content of copper, lead, zinc, antimony and arsenic in the filtrate was analyzed to be 0.71mg/L, 0.64mg/L, 0.20mg/L, 0.40mg/L and 0.30mg/L, respectively. The arsenic removal rate is 99.64 percent.
example 4
the same leaching waste liquid in example 3 was taken and tested for copper ion content of 95mg/L, lead ion content of 42mg/L, zinc ion content of 18mg/L, arsenic ion content of 84mg/L (wherein the trivalent arsenic ion content is 20mg/L), antimony ion content of 5.5mg/L (trivalent antimony ion content of 2.3mg/L) and ferrous ion content of 8.2g/L, and the pH of the waste liquid was 0.20.
Taking 500g of sample, adding 3.2g of sodium chlorate (the molar ratio of the sodium chlorate to the total amount of low-valence ions is 1.07:1) into the waste liquid, and stirring and oxidizing for 1.0 hour; then 25ml of P204 iron ion extracting agent is added to extract iron ions, liquid separation is carried out after the mixture is kept stand for 3.0 hours, and the raffinate after the liquid separation is decompressed and evaporated to recover acid. Then, 0.13g of iron powder was added to the liquid phase after liquid separation, followed by filtration. And then adjusting the pH value of the waste liquid to 2.5-3.0, adding 0.05g of sodium sulfide (the addition amount of an impurity removing agent is 1.2 times of the chemical amount of the total ions of the impurities in the waste liquid), after the reaction is finished, adjusting the pH value of the solution to 3.3, then filtering, adding 0.18 g of a mixture of ferric sulfate and limestone into the filtrate, stirring and reacting for about 8 hours, and carrying out precipitation and filtration in the whole treatment process, wherein the temperature of the waste liquid is kept between 85 ℃ and 95 ℃.
The content of copper, lead, zinc, antimony and arsenic in the filtrate was analyzed to be 0.75mg/L, 0.61mg/L, 0.32mg/L, 0.50mg/L and 0.34mg/L, respectively. The arsenic removal rate is 99.60 percent.
Example 5
The same leaching waste liquid in example 3 was taken and tested for copper ion content of 95mg/L, lead ion content of 42mg/L, zinc ion content of 18mg/L, arsenic ion content of 84mg/L (wherein the trivalent arsenic ion content is 20mg/L), antimony ion content of 5.5mg/L (trivalent antimony ion content of 2.3mg/L) and ferrous ion content of 8.2g/L, and the pH of the waste liquid was 0.20.
Taking 500g of sample, adding 2g of sodium nitrite (the molar ratio of sodium nitrite to the total amount of low-valence ions is 1.1:1) into the waste liquid, and filling air, stirring and oxidizing for 1.0 hour; then 25ml of P204 iron ion extracting agent is added to extract iron ions, liquid separation is carried out after the mixture is kept stand for 3.0 hours, and the raffinate after the liquid separation is decompressed and evaporated to recover acid. Then, 0.13g of iron powder was added to the liquid phase after liquid separation, followed by filtration. And then adjusting the pH value of the waste liquid to 2.5-3.0, adding 0.05g of sodium sulfide (the addition amount of an impurity removing agent is 1.2 times of the chemical amount of the total ions of the impurities in the waste liquid), after the reaction is finished, adjusting the pH value of the solution to 3.3, then filtering, adding 0.18 g of a mixture of ferric sulfate and limestone into the filtrate, stirring and reacting for about 8 hours, and carrying out precipitation and filtration in the whole treatment process, wherein the temperature of the waste liquid is kept between 85 ℃ and 95 ℃.
the content of copper, lead, zinc, antimony and arsenic in the filtrate was analyzed to be 0.85mg/L, 0.65mg/L, 0.30mg/L, 0.40mg/L and 0.45mg/L, respectively. The arsenic removal rate is 99.46 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A waste liquid treatment process is characterized in that the waste liquid treatment process is used for treating a strongly acidic waste liquid, wherein the waste liquid comprises trivalent arsenic ions, trivalent antimony ions, ferrous ions, ferric ions, pentavalent arsenic ions and pentavalent antimony ions,
The waste liquid treatment process comprises the following steps: adding an oxidant into the waste liquid to change low-valence ions in the waste liquid into high-valence ions;
Then, removing iron ions;
then, adding an impurity removing agent into the waste liquid, and then carrying out flotation to remove Pb ions, Zn ions and Sb ions;
Then, adding an anthrax forming agent into the waste liquid to form anthrax from pentavalent arsenic ions.
2. The waste liquid treatment process according to claim 1, wherein the oxidizing agent comprises at least one of an acidic medium oxidizing agent and a basic medium oxidizing agent;
Preferably, the acidic medium oxidizing agent comprises at least one of potassium permanganate and hydrogen peroxide;
Preferably, the alkaline medium oxidizing agent comprises at least one of chlorate and nitrite;
More preferably, the chlorate salt comprises sodium chlorate and the nitrite salt comprises sodium nitrite.
3. The process of claim 1, wherein the molar ratio of the oxidant to the total amount of the lower valent ions is 1-1.1: 1;
preferably, the oxidation time is 0.5 to 1.0 hour.
4. the waste liquid treatment process according to claim 1, wherein removing iron ions comprises: extracting by using an iron ion extracting agent, and then separating liquid to obtain an extract liquid and an raffinate liquid;
preferably, the iron ion removal comprises the step of carrying out acid recovery treatment on the raffinate obtained by removing the iron ions;
More preferably, the acid recovery process comprises: and carrying out reduced pressure evaporation on the raffinate.
5. The waste liquid treatment process according to claim 4, wherein after removing iron ions, before adding an impurity removing agent, copper ions are removed;
Preferably, the removal of copper ions comprises separating copper by reacting the liquid after acid recovery with a reagent;
More preferably, removing the copper ions comprises removing the copper ions by a displacement reaction using a metal having higher reducibility than copper, more preferably, the metal having higher reducibility than copper is iron;
More preferably, removing copper ions comprises extracting the solution after recovering the acid with an extractant.
6. the waste liquid treatment process according to any one of claims 1 to 5, wherein the impurity removing agent is a sulfide, preferably sodium sulfide;
preferably, before the impurity removing agent is added, the pH of the waste liquid is adjusted;
preferably, the pH is adjusted to a pH of the waste liquid of 1.0 or less, preferably 0.5 to 1.0.
7. the waste liquid treatment process according to any one of claims 1 to 5, wherein the amount of the impurity removing agent added is 1.0 to 1.2 times of the chemical amount of the total ions of the impurities in the waste liquid;
preferably, the pH end point of the solution after the reaction by adding the impurity-removing agent is controlled to be 3.4 or less, preferably 3.2 to 3.4.
8. the process of claim 7, wherein the anthracene-forming agent comprises a ferrous salt and/or a calcium-containing compound;
preferably, the ferrous salt is ferrous sulfate;
Preferably, the calcification comprises lime or limestone.
9. The process as claimed in claim 8, wherein the anthrax forming agent is added in an amount of 120-150%.
10. the process of claim 1, wherein the components of the waste liquid are analyzed before adding oxidant to determine the ionic components and concentration of the waste liquid, and then the oxidant, the impurity removing agent and the odor-causing agent are determined according to the analysis result;
Preferably, the temperature of the waste liquid in the waste liquid treatment process is always between 85 and 95 ℃;
Preferably, the pH of the strongly acidic waste liquid is less than 0.5.
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