CN112093947B - Method for removing heavy metals by cyanogen breaking of high-concentration cyanide-containing wastewater in gold production - Google Patents

Method for removing heavy metals by cyanogen breaking of high-concentration cyanide-containing wastewater in gold production Download PDF

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CN112093947B
CN112093947B CN202010994986.4A CN202010994986A CN112093947B CN 112093947 B CN112093947 B CN 112093947B CN 202010994986 A CN202010994986 A CN 202010994986A CN 112093947 B CN112093947 B CN 112093947B
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breaking
cyanide
cyanogen
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containing wastewater
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CN112093947A (en
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李俊杰
李雪林
刘娟
林健
江秀东
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Zhaojin Mining Industry 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
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
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Abstract

The invention relates to a method for removing heavy metals by cyanogen-containing wastewater with high concentration in gold production, belonging to the technical field of cyanogen-containing wastewater treatment. Which comprises the following steps: s1, flocculating and precipitating; s2, electrolysis; s3, primary natural precipitation; s4, primary cyanogen breaking; s5, secondary natural precipitation; s6, removing iron; s7, secondary cyanogen breaking; and S8, carrying out precipitation treatment. The invention can separate the heavy metal solid generated in the electrolytic process through one-time precipitation, which is beneficial to the recovery treatment of heavy metal; according to the invention, the third supernatant is subjected to iron removal treatment by using an iron removal catalyst after secondary precipitation, so that iron elements in cyanide-containing wastewater can be effectively removed, and the pollution load of subsequent secondary cyanide breaking treatment is reduced; the invention can further remove the untreated CN by the primary cyanogen breaking by adopting the secondary cyanogen breaking ‑ And the difficulty of subsequent treatment is reduced. Compared with other methods for removing cyanogen to obtain heavy metal, the method is simple and easy to implement, the reaction process is stable, and no secondary pollution is caused.

Description

Method for removing heavy metals by cyanogen breaking of high-concentration cyanide-containing wastewater in gold production
Technical Field
The invention relates to the technical field of cyanide-containing wastewater treatment, in particular to a method for removing heavy metals by removing cyanide from high-concentration cyanide-containing wastewater in gold production.
Background
Cyanide-containing wastewater can be generated in the gold production process, heavy metals are carried in the cyanide-containing wastewater, and particularly, gold, silver and the like are discharged along with the wastewater, so that resource waste is easily caused.
At present, the main methods for treating the high-concentration cyanogen-containing waste liquid generated in the gold production process at home and abroad comprise a chlorination method, an acidification method, a sulfur dioxide-air oxidation method, an activated carbon adsorption method and a precipitation method. The following disadvantages exist respectively:
the disadvantages of the chlorination process are: firstly, if the sealing of the equipment is not good in the wastewater treatment process, CNCI (cyanogen chloride) escapes into the air, so that the operation environment is easily polluted; secondly, cyanide in the ferrocyanide complex and the ferricyanide complex cannot be destroyed, and cannot be removed by forming precipitates, so that the total cyanide is high, and especially when barren solution of a gold concentrate cyaniding plant is treated, the barren solution is high in iron content, the releasable cyanide is difficult to reduce to below 0.5mg/L, and the total cyanide content is higher; and thirdly, when the bleaching powder or bleaching powder is used for treating the high-concentration cyanide-containing wastewater, the use amount is large, and the chloride ion concentration in the wastewater is high, so that a complex is formed with copper, and the copper exceeds the standard.
The disadvantages of the sulfur dioxide-air oxidation process are: firstly, the thiocyanide in the wastewater can not be eliminated, and when the wastewater containing the thiocyanide is treated, the residual toxicity of the wastewater is still high; II, exceeding the standard of copper ions at a discharge port of a workshop; the method belongs to a method for destroying cyanide, has no economic benefit, and can not recover noble metals and heavy metals in the wastewater.
The disadvantages of the acidification method are: firstly, when the concentration of cyanide is low, the treatment cost is too high; secondly, the wastewater treated by the acidification recovery method needs to be treated for the second time before being discharged; third, SCN in waste water - The COD can not be completely removed, so the COD is probably higher, and the COD of the discharged water can exceed the standard; IV, SO 4 2- Higher concentration of ions if to SO 4 2- The discharge has special requirements, and the wastewater should be further treated.
The disadvantages of the activated carbon method are: firstly, only clear water can be treated, and wastewater and ore pulp with more impurities cannot be treated; secondly, the treatment effect of high-concentration cyanogen-containing heavy metal is not good enough.
At present, heavy metals in cyanide-containing wastewater cannot be effectively removed or recovered by adopting a chlorination method, an acidification method, a sulfur dioxide-air oxidation method, an activated carbon adsorption method and a precipitation method, and the problems of resource waste and high energy consumption exist. In view of this, it is necessary to provide a new method for removing heavy metals by breaking cyanogen in high-concentration cyanide-containing wastewater in gold production, so as to solve the deficiencies of the prior art.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method for removing heavy metals by cyanogen-containing wastewater with high concentration in gold production, wherein CN in the cyanogen-containing wastewater - The treatment rate reaches 99.97 percent, and the heavy metal Cu 2+ The treatment rate of the method reaches 99.94 percent, the method is simple and easy to implement, the reaction process is stable, and no secondary pollution is caused.
The technical scheme for solving the technical problems is as follows:
a method for removing heavy metals by cyanide-breaking of high-concentration cyanide-containing wastewater in gold production comprises the following steps:
s1, flocculating and precipitating: adding polyaluminium chloride into high-concentration cyanogen-containing wastewater to be treated, and flocculating and precipitating to obtain a first supernatant;
s2, electrolysis: electrolyzing the first supernatant obtained in the step S1 to remove heavy metal Cu 2+ Obtaining electrolyte;
s3, primary natural precipitation: adjusting the electrolyte obtained in the step S2 to be alkaline, and performing natural precipitation to obtain a second supernatant;
s4, primary cyanogen breaking: respectively adding a primary cyanogen breaking agent and a primary cyanogen breaking catalyst into the second supernatant obtained in the step S3, and performing a primary cyanogen breaking reaction to obtain a primary cyanogen breaking solution;
s5, secondary natural precipitation: naturally precipitating the primary cyanogen breaking solution obtained in the step S4 to obtain a third supernatant;
s6, iron removal: removing iron element from the third supernatant obtained in the step S5 to obtain filtrate;
s7, secondary cyanogen breaking: respectively adding a secondary cyanogen breaking agent and a secondary cyanogen breaking catalyst into the filtrate obtained in the step S6 under an alkaline condition, and performing a secondary cyanogen breaking reaction to obtain a secondary cyanogen breaking solution;
s8, precipitation treatment: precipitating and filtering the secondary cyanogen breaking solution obtained in the step S7 to obtain the heavy metal Cu removed 2+ And (3) solution.
The invention has the beneficial effects that: the invention can separate the heavy metal solid generated in the electrolytic process through one-time precipitation, which is beneficial to the recovery treatment of heavy metal; according to the invention, after secondary precipitation, the third supernatant is subjected to iron removal treatment by using an iron removal catalyst, so that the iron element in cyanide-containing wastewater can be effectively removed, and the pollution load of subsequent secondary cyanide breaking treatment is reduced; the invention can further remove the untreated CN by the primary cyanogen breaking by adopting the secondary cyanogen breaking - And the difficulty of subsequent treatment is reduced. Compared with other methods for removing cyanogen to obtain heavy metal, CN - The treatment rate of (2) was 99.97%, heavy metal Cu 2+ The treatment rate of the method is 99.94 percent, which is superior to that of CN treatment in the prior art - And Cu 2+ The method is simple and easy to implement, the reaction process is stable, and no secondary pollution is caused.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step 1, CN in the high-concentration cyanide-containing wastewater - Has a content of 800-2500 mg/L, Cu 2+ The content is 800-3000 mg/L.
Further, in step S2, the pH value of the electrolysis is 4-5, and the electrolysis time is 1 h.
The beneficial effect of adopting the further scheme is that: electrolysis under this acidic condition is beneficial to the removal of heavy metals in cyanide-containing wastewater.
Further, in the step S3 and the step S5, the pH value of the natural precipitation is 9-10, and the natural precipitation is carried out in a thickener.
The beneficial effect of adopting the further scheme is that: under alkaline conditions, heavy metals are more easily precipitated and separated.
Further, in step S4, the primary cyanide breaking agent is sodium sulfite in an amount of CN in the cyanide-containing wastewater in step 1 - 6-10 times of the content; the first cyanogen breaking catalyst is copper sulfate, and the dosage is 10kg/m 3 (ii) a The pH value of the primary cyanogen breaking reaction is 8-9.5, the time of the primary cyanogen breaking reaction is 3 hours, and the primary cyanogen breaking reaction is carried out in a cyanogen breaking groove.
The beneficial effect of adopting the further scheme is that: breaking cyanogen under alkaline condition can reduce the generation of hydrocyanic acid, can reduce the harm of hydrocyanic acid to environment, and is favorable for maintaining the stability of wastewater treatment.
Further, in step S6, the iron removal is performed in an iron removal filter, and an iron removal catalyst is filled in the iron removal filter, wherein the iron removal catalyst is manganese sand with a particle size of 0.4-1.2 mm.
The beneficial effect of adopting the above further scheme is: the manganese sand can react with iron ions in the wastewater to produce iron-containing precipitates, and the iron-containing precipitates can effectively remove the medium iron element in the wastewater after being filtered.
Further, MnO is contained in the manganese sand 2 The mass percentage content of (A) is more than 20 percent.
Adopt the above-mentioned advance oneThe beneficial effects of the step scheme are as follows: using a material containing MnO 2 The manganese sand can effectively remove iron elements in the wastewater.
In step S7, the secondary cyanogen breaker is sodium sulfite, and the dosage of the secondary cyanogen breaker is CN in the cyanogen-containing wastewater in step 1 - 6-10 times of the content; the secondary cyanogen breaking catalyst is copper sulfate, and the dosage is 5kg/m 3 (ii) a The pH value of the secondary cyanogen breaking reaction is 8-9.5, the time of the secondary cyanogen breaking reaction is 1.5h, and the secondary cyanogen breaking reaction is carried out in a cyanogen breaking groove.
The beneficial effect of adopting the further scheme is that: the sodium sulfite is adopted as the cyanogen breaking agent, which is beneficial to removing CN in the cyanogen-containing wastewater by oxidation - Copper sulfate as a catalyst can promote the cyanogen breaking reaction.
Further, in step S8, the precipitation filtration is any one of advection precipitation, electric flocculation precipitation and inclined plate precipitation or a plurality of step-by-step series connection.
Further, in the step S8, the precipitation and filtration are one of advection precipitation, electric flocculation precipitation and inclined plate precipitation or multiple types of step-by-step series connection.
The beneficial effect of adopting the further scheme is that: by adopting advection precipitation, electric flocculation precipitation or inclined plate precipitation, solid matters in the wastewater after secondary cyanogen breaking can be effectively removed, and the removal of the solid matters generated by heavy metal reaction in the wastewater is facilitated.
Further, the heavy metal Cu is removed 2+ In solution, CN - Is less than 2mg/L, Cu 2+ The content is less than 10 mg/L.
The beneficial effect of adopting the further scheme is that: CN in the solution obtained by adopting the process - Is less than 2mg/L, Cu 2+ The content is less than 10mg/L, the difficulty of subsequent wastewater treatment can be reduced, the heavy metal Cu can be recovered, and the resource waste is reduced.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
The method for removing heavy metals by cyanide-breaking of high-concentration cyanide-containing wastewater in gold production comprises the following steps:
s1, flocculating and settling: pumping 2L of high-concentration cyanide-containing wastewater into a thickener at the temperature of 20 ℃, and adding polyaluminium chloride (PAC) for flocculation and precipitation to obtain a first supernatant;
s2, electrolysis: overflowing the first supernatant into an electrolytic bath, and electrolyzing under the condition that the pH value is 4 to remove heavy metal Cu 2+ The time of electrolytic reaction is 1h, and electrolyte is obtained;
s3, primary natural precipitation: adjusting the electrolyte to be alkaline with the pH value of 10, pumping the electrolyte into a thickener for natural precipitation, and obtaining a second supernatant with the pH value of 10 of the natural precipitation;
s4, primary cyanogen breaking: overflowing the second supernatant to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to perform a cyanogen breaking reaction for 3 hours under the condition that the pH value is 9 to obtain a first cyanogen breaking solution;
s5, secondary natural precipitation: pumping the primary cyanogen breaking solution into a thickener again for natural precipitation to obtain a third supernatant;
s6, iron removal: overflowing the third supernatant to an iron removal filter taking manganese sand of 0.4-1.2 mm as a filler for catalytic filtration for 1 hour, and removing iron elements in the third supernatant to obtain filtrate;
s7, secondary cyanogen breaking: overflowing the filtrate to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to carry out a secondary cyanogen breaking reaction under the alkaline condition of pH 9, wherein the dosage of the copper sulfate is 5kg/m 3 The time of the cyanogen breaking reaction is 1.5h, and secondary cyanogen breaking liquid is obtained;
s8, precipitation treatment: after the secondary cyanogen breaking liquid is subjected to advection precipitation filtration treatment, heavy metal Cu is removed 2+ And (3) solution.
The performance of the raw materials is as follows: the total cyanogen concentration of the high-concentration cyanogen-containing wastewater generated in the gold production is 1876mg/L, the copper ion concentration is 1547mg/L, and the pH value is as follows: 7-8.
Respectively measuring electrolyte, primary cyanide breaking solution, secondary cyanide breaking solution and removing heavy metal Cu 2+ Solutions ofCN in (1) - Concentration and heavy metal Cu 2+ The test results are as follows:
CN - concentration: 813mg/L of electrolyte, 178mg/L of primary cyanogen breaking solution and 0.39mg/L of secondary cyanogen breaking solution, and removing heavy metal Cu 2+ The solution is 0.39 mg/L; CN - The treatment rate of (2) was 99.979%;
heavy metal Cu 2+ The concentration of (a): 656mg/L of electrolyte, 89mg/L of primary cyanogen breaking solution and 0.89mg/L of secondary cyanogen breaking solution, and removing heavy metal Cu 2+ The solution is 0.89 mg/L; heavy metal Cu 2+ The treatment rate of (3) was 99.94%.
Measurement of removal of heavy Metal Cu 2+ The pH result of the solution is 8-9.
Example 2
The method for removing heavy metals by breaking cyanogen in the high-concentration cyanogen-containing wastewater in the gold production comprises the following steps:
flocculation and precipitation: pumping 50L of high-concentration cyanide-containing wastewater into a thickener at the temperature of 20 ℃, and adding polyaluminium chloride (PAC) for flocculation and precipitation to obtain a first supernatant;
electrolysis: overflowing the first supernatant into an electrolytic tank, and electrolyzing at pH 4 to remove heavy metal Cu 2+ The time of the electrolytic reaction is 1h, and electrolyte is obtained;
primary natural precipitation: adjusting the electrolyte to be alkaline with the pH value of 10, pumping the electrolyte into a thickener for natural precipitation, and obtaining a second supernatant with the pH value of 10 of the natural precipitation;
primary cyanogen breaking: overflowing the second supernatant to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to perform a cyanogen breaking reaction for 3 hours under the condition that the pH value is 9 to obtain a first cyanogen breaking solution;
secondary natural precipitation: pumping the primary cyanogen breaking solution into a thickener again for natural precipitation to obtain a third supernatant;
iron removal: overflowing the third supernatant to an iron removal filter taking manganese sand of 0.4-1.2 mm as a filler for catalytic filtration for 1 hour, and removing iron elements in the third supernatant to obtain a filtrate;
secondary cyanogen breaking: filtering the aboveOverflowing the solution to a cyanogen breaking tank, adding sodium sulfite and copper sulfate to carry out secondary cyanogen breaking reaction under the alkaline condition of pH 9, wherein the dosage of the copper sulfate is 5kg/m 3 The time of the cyanogen breaking reaction is 1.5h, and secondary cyanogen breaking liquid is obtained;
and (3) precipitation treatment: after the secondary cyanogen breaking liquid is subjected to advection precipitation filtration treatment, heavy metal Cu is removed 2+ And (3) solution.
The performance of the raw materials is as follows: high-concentration cyanide-containing wastewater CN generated in gold production - The concentration was 1849mg/L, the copper ion concentration was 1534mg/L, pH: 7 to 8.
Respectively measuring electrolyte, primary cyanide breaking solution, secondary cyanide breaking solution and removing heavy metal Cu 2+ CN in solution - Concentration and heavy metal Cu 2+ The test results are as follows:
CN - concentration: 791mg/L of electrolyte, 164mg/L of primary cyanide breaking solution and 0.45mg/L of secondary cyanide breaking solution, and removing heavy metal Cu 2+ The solution is 0.45 mg/L; CN - The treatment rate of (A) is 99.976%
Heavy metal Cu 2+ The concentration of (a): 598mg/L of electrolyte, 92mg/L of primary cyanogen breaking solution and 0.56mg/L of secondary cyanogen breaking solution, and removing heavy metal Cu 2+ The solution is 0.56 mg/L; heavy metal Cu 2+ The treatment rate of (2) was 99.96%.
Measurement of removal of heavy Metal Cu 2+ The pH result of the solution is 8-9.
Example 3
The method for removing heavy metals by cyanide-breaking of high-concentration cyanide-containing wastewater in gold production comprises the following steps:
flocculation and precipitation: pumping 1000L of high-concentration cyanide-containing wastewater into a thickener at the temperature of 20 ℃, and adding polyaluminium chloride (PAC) for flocculation and precipitation to obtain a first supernatant;
electrolysis: overflowing the first supernatant into an electrolytic bath, and electrolyzing under the condition that the pH value is 4 to remove heavy metal Cu 2+ The time of electrolytic reaction is 1h, and electrolyte is obtained;
primary natural precipitation: adjusting the electrolyte to be alkaline with the pH value of 10, pumping the electrolyte into a thickener for natural precipitation, and obtaining a second supernatant with the pH value of 10 of the natural precipitation;
primary cyanogen breaking: overflowing the second supernatant to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to perform a cyanogen breaking reaction for 3 hours under the condition that the pH value is 9 to obtain a first cyanogen breaking solution;
secondary natural precipitation: pumping the primary cyanogen breaking solution into a thickener again for natural precipitation to obtain a third supernatant;
iron removal: overflowing the third supernatant to an iron removal filter taking manganese sand of 0.4-1.2 mm as a filler for catalytic filtration for 1 hour, and removing iron elements in the third supernatant to obtain a filtrate;
secondary cyanogen breaking: overflowing the filtrate to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to carry out a secondary cyanogen breaking reaction under the alkaline condition of pH 9, wherein the dosage of the copper sulfate is 5kg/m 3 The time of the cyanogen breaking reaction is 1.5h, and secondary cyanogen breaking liquid is obtained;
and (3) precipitation treatment: after the secondary cyanogen breaking liquid is subjected to advection precipitation filtration treatment, heavy metal Cu is removed 2+ And (3) solution.
The performance of the raw materials is as follows: high-concentration cyanide-containing wastewater CN generated in gold production - The concentration is 1861mg/L, the copper ion concentration is 1579mg/L, the pH: 7 to 8.
Respectively measuring electrolyte, primary cyanide breaking solution, secondary cyanide breaking solution and removing heavy metal Cu 2+ CN in solution - Concentration and heavy metal Cu 2+ The test results are as follows:
CN - concentration: 821mg/L of electrolyte, 203mg/L of primary cyanide breaking solution and 0.42mg/L of secondary cyanide breaking solution, and heavy metal Cu is removed 2+ The solution is 0.42 mg/L; CN - The treatment rate of (A) is 99.977%
Heavy metal Cu 2+ The concentration of (a): 673mg/L electrolyte, 87mg/L primary cyanide breaking solution and 0.72mg/L secondary cyanide breaking solution, and removing heavy metal Cu 2+ The solution is 0.72 mg/L; heavy metal Cu 2+ The treatment rate of (3) was 99.95%.
Measurement of removal of heavy Metal Cu 2+ The pH result of the solution is 8-9.
Comparative example 1
The method for removing heavy metals by cyanide-breaking of high-concentration cyanide-containing wastewater in gold production comprises the following steps:
flocculation and precipitation: pumping 2L of high-concentration cyanide-containing wastewater into a thickener at the temperature of 20 ℃, and adding polyaluminum chloride (PAC) for flocculation and precipitation to obtain a first supernatant;
primary cyanogen breaking: overflowing the first supernatant to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to perform a cyanogen breaking reaction for 6 hours under the condition that the pH value is 9 to obtain a first cyanogen breaking solution;
secondary natural precipitation: pumping the primary cyanogen breaking solution into a thickener again for natural precipitation to obtain a second supernatant;
secondary cyanogen breaking: overflowing the second supernatant to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to perform a secondary cyanogen breaking reaction under the alkaline condition of pH 9, wherein the dosage of the copper sulfate is 5kg/m 3 The time of the cyanogen breaking reaction is 3 hours, and secondary cyanogen breaking liquid is obtained;
and (3) precipitation treatment: carrying out advection precipitation filtration treatment on the secondary cyanogen breaking solution to obtain the heavy metal Cu removed 2+ And (3) solution.
The performance of the raw materials is as follows: high-concentration cyanide-containing wastewater CN generated in gold production - The concentration is 1876mg/L, the copper ion concentration is 1547mg/L, the pH: 7-8.
Respectively measuring primary cyanogen breaking liquid and secondary cyanogen breaking liquid and removing heavy metal Cu 2+ CN in solution - Concentration and heavy Metal Cu 2+ The test results are as follows:
CN - concentration: the primary cyanogen breaking solution is 653mg/L, the secondary cyanogen breaking solution is 27.6mg/L, and the heavy metal Cu is removed 2+ The solution is 27.6 mg/L; CN - The treatment rate of (2) was 98.53%
Heavy metal Cu 2+ The concentration of (a): the first cyanogen breaking solution is 421mg/L, the second cyanogen breaking solution is 232mg/L, and the heavy metal Cu is removed 2 + The solution is 232 mg/L; heavy metal Cu 2+ The treatment rate of (2) was 85.00%.
Measurement of removal of heavy Metal Cu 2+ The pH result of the solution is 8 to E9。
Comparative example 2
The method for removing heavy metals by cyanide-breaking of high-concentration cyanide-containing wastewater in gold production comprises the following steps:
flocculation and precipitation: pumping 2L of high-concentration cyanide-containing wastewater into a thickener at the temperature of 20 ℃, and adding polyaluminium chloride (PAC) for flocculation and precipitation to obtain a first supernatant;
electrolysis: overflowing the first supernatant into an electrolytic bath, and electrolyzing under the condition that the pH value is 4 to remove heavy metal Cu 2+ The time of electrolytic reaction is 1h, and electrolyte is obtained;
primary natural precipitation: adjusting the electrolyte to be alkaline with the pH value of 10, pumping the electrolyte into a thickener for natural precipitation, and obtaining a second supernatant with the pH value of 10 of the natural precipitation;
primary cyanogen breaking: overflowing the second supernatant to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to perform a cyanogen breaking reaction for 3 hours under the condition that the pH value is 9 to obtain a first cyanogen breaking solution;
secondary natural precipitation: pumping the primary cyanogen breaking solution into a thickener again for natural precipitation to obtain a third supernatant;
secondary cyanogen breaking: overflowing the third supernatant to a cyanogen breaking tank, and adding sodium sulfite and copper sulfate to perform a secondary cyanogen breaking reaction under the alkaline condition of pH 9, wherein the dosage of the copper sulfate is 5kg/m 3 The time of the cyanogen breaking reaction is 1.5h, and secondary cyanogen breaking liquid is obtained;
and (3) precipitation treatment: after the secondary cyanogen breaking liquid is subjected to advection precipitation and filtration treatment, heavy metal Cu is removed 2+ And (3) solution.
The performance of the raw materials is as follows: high-concentration cyanide-containing wastewater CN generated in gold production - The concentration is 1876mg/L, the copper ion concentration is 1547mg/L, the pH: 7 to 8.
Respectively measuring electrolyte, primary cyanide breaking solution, secondary cyanide breaking solution and removing heavy metal Cu 2+ CN in solution - Concentration and heavy metal Cu 2+ The test results are as follows:
CN - concentration: 809mg/L of electrolyte and 173 mg/L of primary cyanide breaking solutionmg/L, secondary cyanogen breaking liquid is 9.12mg/L, and heavy metal Cu is removed 2+ The solution is 9.12 mg/L; CN - The treatment rate of (A) is 99.51%
Heavy metal Cu 2+ The concentration of (a): 661mg/L of electrolyte, 91mg/L of primary cyanogen breaking solution and 24.28mg/L of secondary cyanogen breaking solution, and removing heavy metal Cu 2+ The solution is 24.28 mg/L; heavy metal Cu 2+ The treatment rate of (2) was 98.43%.
Measurement of removal of heavy Metal Cu 2+ The pH result of the solution is 8-9.
CN obtained according to examples 1 to 3 - And heavy metal Cu 2+ Compared with comparative example 1 and comparative example 2, the method for removing heavy metals by cyanogen-containing wastewater with high concentration in gold production can effectively remove CN in the cyanogen-containing wastewater - And heavy metal Cu 2+ In which CN - The treatment rate of the copper alloy can reach 99.97 percent or more, and the heavy metal Cu 2+ The treatment rate of (2) can reach 99.94% or above, the heavy metal Cu in the cyanide-containing wastewater can be effectively treated and recovered, and the CN in the cyanide-containing wastewater can be effectively removed - The difficulty of subsequent wastewater treatment can be reduced, the heavy metal Cu can be recovered, and the resource waste is reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. The method for removing heavy metals by cyanide-breaking of high-concentration cyanide-containing wastewater in gold production is characterized by comprising the following steps:
s1, flocculating and settling: adding polyaluminium chloride into high-concentration cyanogen-containing wastewater to be treated, and flocculating and precipitating to obtain a first supernatant;
s2, electrolysis: electrolyzing the first supernatant obtained in the step S1 to remove heavy metal Cu 2+ Obtaining electrolyte; the pH value of the electrolysis is 4-5, and the electrolysis time is 1 h;
s3, primary natural precipitation: adjusting the electrolyte obtained in the step S2 to be alkaline, and performing natural precipitation to obtain a second supernatant;
s4, primary cyanogen breaking: respectively adding a primary cyanogen breaking agent and a primary cyanogen breaking catalyst into the second supernatant obtained in the step S3, and performing a primary cyanogen breaking reaction to obtain a primary cyanogen breaking solution;
s5, secondary natural precipitation: naturally precipitating the primary cyanogen breaking solution obtained in the step S4 to obtain a third supernatant;
s6, iron removal: removing iron element from the third supernatant obtained in the step S5 to obtain filtrate; the iron removal is carried out in an iron removal filter, wherein an iron removal catalyst is filled in the iron removal filter, and the iron removal catalyst is manganese sand with the particle size of 0.4-1.2 mm; MnO in the manganese sand 2 The mass percentage content of the compound is more than 20 percent;
s7, secondary cyanogen breaking: respectively adding a secondary cyanogen breaking agent and a secondary cyanogen breaking catalyst into the filtrate obtained in the step S6 under an alkaline condition, and performing a secondary cyanogen breaking reaction to obtain a secondary cyanogen breaking solution;
s8, precipitation treatment: precipitating and filtering the secondary cyanogen breaking solution obtained in the step S7 to obtain the heavy metal Cu removed solution 2+ And (3) solution.
2. The method for removing heavy metals by cyanide-breaking of high-concentration cyanide-containing wastewater in gold production according to claim 1, wherein in step 1, CN in the high-concentration cyanide-containing wastewater is - Has a content of 800-2500 mg/L, Cu 2+ The content is 800-3000 mg/L.
3. The method for removing heavy metals by cyanide-containing wastewater with high concentration in gold production according to claim 1, wherein in step S3 and step S5, the pH value of the natural precipitation is 9-10, and the natural precipitation is carried out in a thickener.
4. The method for removing heavy metals by cyanide-containing wastewater with high concentration in gold production according to claim 1, wherein in step S4, the primary cyanide-removing agent is sodium sulfite in an amount of CN in the cyanide-containing wastewater in step 1 - 6-10 times of the content; the first cyanogen breaking catalyst is copper sulfate, and the dosage is 10kg/m 3 (ii) a The pH value of the primary cyanogen breaking reaction is 8-9.5, the time of the primary cyanogen breaking reaction is 3 hours, and the primary cyanogen breaking reaction is carried out in a cyanogen breaking groove.
5. The method for removing heavy metals by cyanide-containing wastewater with high concentration in gold production according to claim 1, wherein in step S7, the secondary cyanide breaking agent is sodium sulfite in an amount of CN in the cyanide-containing wastewater in step 1 - 6-10 times of the content; the secondary cyanogen breaking catalyst is copper sulfate, and the dosage is 5kg/m 3 (ii) a The pH value of the secondary cyanogen breaking reaction is 8-9.5, the time of the secondary cyanogen breaking reaction is 1.5h, and the secondary cyanogen breaking reaction is carried out in a cyanogen breaking groove.
6. The method for removing heavy metals by cyanide-containing wastewater with high concentration in gold production according to claim 1, wherein in step S8, the precipitation filtration is any one of advection precipitation, electroflocculation precipitation and inclined plate precipitation or a plurality of step-by-step series connection.
7. The method for removing heavy metals by cyanide breaking of high-concentration cyanide-containing wastewater in gold production according to any one of claims 1 to 6, wherein the heavy metals Cu are removed 2+ In solution, CN - Is less than 2mg/L, Cu 2+ The content is less than 10 mg/L.
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