CN104694751B - A kind of method of removing chloride ion in leachate from zinc hydrometallurgy - Google Patents
A kind of method of removing chloride ion in leachate from zinc hydrometallurgy Download PDFInfo
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Abstract
The invention provides a kind of method of removing chloride ion in leachate from zinc hydrometallurgy, comprise the following steps：First, the concentration and the concentration of copper ion of chlorion in zinc hydrometallurgy leachate are detected；2nd, the copper ion concentration measured by step one is analyzed；3rd, to copper ashes is added in zinc hydrometallurgy leachate, slurry is obtained；Four and then to reducibility gas are passed through in slurry, chlorion is formed precipitation；5th, the oxidation-reduction potential of slurry is detected, stops being passed through reducibility gas if requirement is met, filtered, obtain the zinc hydrometallurgy leachate of removing chloride ion；Otherwise return to step four.The present invention has that flow is short, low cost, chlorine removal efficiency is high, the features such as do not introduce other impurity, keep original zinc wet method smelting process, with extensive promotional value.
Description
Technical field
The invention belongs to chemical precipitation dechlorination technical field, and in particular to one kind from zinc hydrometallurgy leachate remove chlorine from
The method of son.
Background technology
Zinc hydrometallurgy refers to acid solution Leaching Zinc from zinc-oxide calcine or unclassified stores, then with being electrolysed deposition technique
The method that metallic zinc is produced from zinc lixiviating solution.Zinc hydrometallurgy mainly includes sulfuric acid, zinc calcine leaching process, purification of leaching liquor
Removal of impurities and zinc electrolysis deposit four master operations.In Zinc Hydrometallurgy Process, too high chlorion is to electricity in zinc electrolysis circulation fluid
The harm that zinc process and product quality are caused is larger, show as impurity lead content in heavy corrosion positive plate, product raise and
The problems such as energy consumption increases.
Problem is removed for wet zinc-making system chlorion, dechlorination method common at present mainly has：The silver sulfate precipitation method,
Ion-exchange, bismuth oxide dechlorination method, chlorine removal from copper residue method, zinc powder and copper ion dechlorination method.
The silver sulfate precipitation method are that silver sulfate is added to containing the silver nitride precipitation that indissoluble is formed in solutions of chlorine, with operation letter
The advantages of single, efficiency high, but it is high to there is silver salt price, the low problem of silver raising recovery rate, it is difficult to industrially realize.
Ion-exchange dechlorination is can be with the Cl in electrolyte using the exchangeable ion of ion exchange resin-Interact
Reaction, makes Cl in solution-On resin, chlorine removal effect is obvious, easily operated, technological process is short, but there is Cl for absorption-Absorption
Time is small compared with long, treating capacity, the low problem of efficiency, and commercial Application is less.
Bismuth oxide dechlorination is to be decomposed into bismuth ion in acid condition using bismuth oxide, and bismuth ion is generated with chloride binding
Bismuth trichloride, bismuth trichloride further generates the chlorine oxygen bismuth for being insoluble in water；Chlorine oxygen bismuth after dechlorination takes off under the conditions of low-temperature alkali
Go chlorion generate bismuth hydroxide, bismuth hydroxide be converted under the conditions of high temperature is high-alkali bismuth oxide can Reusability, with dechlorination
Time is short, and effect is good, but bismuth oxide is costly.
Chlorine removal from copper residue method is during copper ashes directly to be allocated into pickle liquor by a certain percentage, using elemental copper and copper ion and solution
In chlorion interact, formed indissoluble stannous chloride precipitation；The chlorine removal from copper residue time is more long, reaches the removing chlorine of chlorine
70%, at least need more than 5h；Temperature control is stricter, need to be between 50 DEG C~70 DEG C, and temperature is too high easily to cause stannous chloride
Redissolve, temperature is too low need to extend the reaction time.
Zinc powder and copper ion dechlorination method are to utilize zinc powder by Cu2+Reduction forms Cu+, Cu powder and Cl-Phase separation generates chlorination
Cuprous precipitation, because that need to add zinc powder, causes production cost to raise.
The content of the invention
The technical problems to be solved by the invention are for above-mentioned the deficiencies in the prior art, there is provided a kind of from zinc hydrometallurgy
The method of removing chloride ion in leachate.The method has that short flow, low cost, chlorine removal efficiency are high, other impurity are not introduced,
The features such as keeping original zinc wet method smelting process, with extensive promotional value.
In order to solve the above technical problems, the technical solution adopted by the present invention is：One kind is removed from zinc hydrometallurgy leachate
The method of chlorion, it is characterised in that the method is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Step 3, to adding copper ashes in zinc hydrometallurgy leachate, it is well mixed after obtain slurry；The addition of the copper ashes
It is 40~70 times of chlorine ions in zinc hydrometallurgy leachate；Copper of the copper ashes produced by the cleaning procedure of zinc hydrometallurgy
Slag；
Step 4, be 40 DEG C~70 DEG C in temperature under conditions of, to being passed through reducibility gas in slurry described in step 3,
Make the copper ion in zinc hydrometallurgy leachate be reduced into cuprous ion and be formed with chlorion to precipitate；The reducibility gas are roasting
Burn zinc concentrate produced by containing SO2Gas, the intake of the reducibility gas is：The reducibility gas being passed through per hour
Volume be 150~300 times of zinc hydrometallurgy leachate volume；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4.
The method of removing chloride ion in a kind of above-mentioned leachate from zinc hydrometallurgy, it is characterised in that described in step one
The concentration C 1 of chlorion meets：300mg/L≤C1≤1500mg/L.
The method of removing chloride ion in a kind of above-mentioned leachate from zinc hydrometallurgy, it is characterised in that described in step 3
The weight/mass percentage composition of copper is 70%~80% in copper ashes.
The method of removing chloride ion in a kind of above-mentioned leachate from zinc hydrometallurgy, it is characterised in that described in step 4
SO in reducibility gas2Volumn concentration be not less than 30%.
The present invention has advantages below compared with prior art：
1st, the present invention using wet zinc-making system roasting the zinc concentrate stage collected by containing SO2Gas is reducing agent, will
It is passed through in zinc hydrometallurgy leachate, can quickly strengthen reducing atmosphere, while by adjusting solution copper ion concentration, and match somebody with somebody
Enter the copper ashes of the cleaning procedure institute output of zinc hydrometallurgy, under conditions of certain proportion, be reduced to the copper ion in solution
Cuprous ion, and combine to form precipitation in the form of stannous chloride with chlorion and be filtered to remove, you can realize after dechlorination chlorine in liquid
Purpose of the ion concentration less than 100mg/L.Reaction equation of the invention is：
2Cu2++2Cl-+SO2+2H2O=2CuCl ↓+SO4 2-+4H+。
2nd, the present invention has short flow, low cost, chlorine removal efficiency is high, do not introduce other impurity, keep original zinc wet method
The features such as smelting process, with extensive promotional value.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Brief description of the drawings
Fig. 1 is the process chart of present invention removing chloride ion from zinc hydrometallurgy leachate.
Specific embodiment
Embodiment 1
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=1346mg/L, C2=820mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=2334mg/L in zinc lixiviating solution；
Step 3, to adding 82.5g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 70% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 45 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 70%, the reducibility gas
Intake is：270L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 1h, Q=86mV is measured, then stops being passed through reducibility gas, mistake
Filter, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measure chlorine after being processed through the present embodiment in leachate from
Sub- concentration is down to 83mg/L.It is confirmed that the method stabilization of the present embodiment removing chloride ion from zinc hydrometallurgy leachate, it is quick,
Effectively.
Embodiment 2
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=1152mg/L, C2=774mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=1913mg/L in zinc lixiviating solution；
Step 3, to adding 71.3g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 78% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 55 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 60%, the reducibility gas
Intake is：220L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 1.5h, Q=92mV is measured, then stops being passed through reducibility gas,
Filtering, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measures the chlorine in leachate after being processed through the present embodiment
Ion concentration is down to 76mg/L.It is confirmed that the method for the present embodiment removing chloride ion from zinc hydrometallurgy leachate is stable, fast
It is fast, effective.
Embodiment 3
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=906mg/L, C2=861mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=1812mg/L in zinc lixiviating solution；
Step 3, to adding 52.1g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 76% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 65 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 65%, the reducibility gas
Intake is：180L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 2h, Q=84mV is measured, then stops being passed through reducibility gas, mistake
Filter, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measure chlorine after being processed through the present embodiment in leachate from
Sub- concentration is down to 91mg/L.It is confirmed that the method stabilization of the present embodiment removing chloride ion from zinc hydrometallurgy leachate, it is quick,
Effectively.
Embodiment 4
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=810mg/L, C2=681mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=1534mg/L in zinc lixiviating solution；
Step 3, to adding 45.5g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 75% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 40 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 50%, the reducibility gas
Intake is：240L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 2.5h, Q=86mV is measured, then stops being passed through reducibility gas,
Filtering, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measures the chlorine in leachate after being processed through the present embodiment
Ion concentration is down to 80mg/L.It is confirmed that the method for the present embodiment removing chloride ion from zinc hydrometallurgy leachate is stable, fast
It is fast, effective.
Embodiment 5
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=713mg/L, C2=871mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=1732mg/L in zinc lixiviating solution；
Step 3, to adding 36.1g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 78% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 50 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 45%, the reducibility gas
Intake is：250L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 3h, Q=93mV is measured, then stops being passed through reducibility gas, mistake
Filter, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measure chlorine after being processed through the present embodiment in leachate from
Sub- concentration is down to 88mg/L.It is confirmed that the method stabilization of the present embodiment removing chloride ion from zinc hydrometallurgy leachate, it is quick,
Effectively.
Embodiment 6
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=603mg/L, C2=910mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=1688mg/L in zinc lixiviating solution；
Step 3, to adding 30.3g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 80% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 60 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 51%, the reducibility gas
Intake is：230L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 2.5h, Q=84mV is measured, then stops being passed through reducibility gas,
Filtering, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measures the chlorine in leachate after being processed through the present embodiment
Ion concentration is down to 90mg/L.It is confirmed that the method for the present embodiment removing chloride ion from zinc hydrometallurgy leachate is stable, fast
It is fast, effective.
Embodiment 7
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=510mg/L, C2=886mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=1530mg/L in zinc lixiviating solution；
Step 3, to adding 26.3g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 75% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 40 DEG C~70 DEG C, then to being passed through reducibility gas in slurry,
Make the copper ion in zinc hydrometallurgy leachate be reduced into cuprous ion and be formed with chlorion to precipitate；The reducibility gas are roasting
Burn zinc concentrate collected by containing SO2Gas, SO in the reducibility gas2Volumn concentration be 48%, the reproducibility
The intake of gas is：190L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 2h, Q=82mV is measured, then stops being passed through reducibility gas, mistake
Filter, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measure chlorine after being processed through the present embodiment in leachate from
Sub- concentration is down to 86mg/L.It is confirmed that the method stabilization of the present embodiment removing chloride ion from zinc hydrometallurgy leachate, it is quick,
Effectively.
Embodiment 8
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=300mg/L, C2=498mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 meets C2 >=1.7C1 in the present embodiment, therefore, it is directly entered step 3；
Step 3, to adding 21.0g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 78% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 70 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 30%, the reducibility gas
Intake is：150L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, the present embodiment measures Q=230mV after being passed through reducibility gas 1h, is unsatisfactory for 80mV≤Q≤100mV, then
Return to step three proceeds precipitation reaction, then measures Q=80mV after being passed through reducibility gas 2h, meet 80mV≤Q≤
100mV, then stop be passed through reducibility gas, filter, the chlorine ion concentration in zinc hydrometallurgy leachate is detected, measure through
Chlorine ion concentration after the present embodiment treatment in leachate is down to 81mg/L.It is confirmed that the present embodiment is from zinc hydrometallurgy leachate
The method of middle removing chloride ion is stable, quick, effective.
Embodiment 9
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=484mg/L, C2=915mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 meets C2 >=1.7C1 in the present embodiment, therefore is directly entered step 3；
Step 3, to adding 19.38g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed
After obtain slurry；The weight/mass percentage composition of copper is 76% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 40 DEG C~70 DEG C, then to being passed through reducibility gas in slurry,
Make the copper ion in zinc hydrometallurgy leachate be reduced into cuprous ion and be formed with chlorion to precipitate；The reducibility gas are roasting
Burn zinc concentrate collected by containing SO2Gas, SO in the reducibility gas2Volumn concentration be 65%, the reproducibility
The intake of gas is：150L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 3h, Q=100mV is measured, meets 80mV≤Q≤100mV, then
Stopping is passed through reducibility gas, filters, and the chlorine ion concentration in zinc hydrometallurgy leachate is detected, measures through the present embodiment
Chlorine ion concentration after treatment in leachate is down to 98mg/L.It is confirmed that the present embodiment removes chlorine from zinc hydrometallurgy leachate
The method of ion is stable, quick, effective.
Embodiment 10
With reference to Fig. 1, the present embodiment method of removing chloride ion from zinc hydrometallurgy leachate is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure chlorion in step one, respectively detection zinc hydrometallurgy leachate
Concentration be C1, the concentration of copper ion is mg/L for the unit of C2, C1 and C2；
In the present embodiment, 1L zinc hydrometallurgy leachates are taken, measure C1=1500mg/L, C2=751mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter
Enter step 3；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, makes C3
Meet C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Through analysis, C2 is unsatisfactory for C2 >=1.7C1 in the present embodiment, therefore, wet method is refined using the method for addition copper sulphate
The concentration of copper ion is adjusted to C3=7500mg/L in zinc lixiviating solution；
Step 3, to adding 68.9g zinc hydrometallurgy cleaning procedures to produce copper ashes in zinc hydrometallurgy leachate, it is well mixed after
Obtain slurry；The weight/mass percentage composition of copper is 75% in the copper ashes；
Step 4, slurry described in step 3 is warming up to 40 DEG C, then to reducibility gas are passed through in slurry, makes wet method
Copper ion in zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc essence
Collected by ore deposit containing SO2Gas, SO in the reducibility gas2Volumn concentration be 41%, the reducibility gas
Intake is：300L/h；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV
≤ Q≤100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, return
Return step 4；
After testing, after the present embodiment is passed through reducibility gas 3h, Q=95mV is measured, then stops being passed through reducibility gas, mistake
Filter, detects to the chlorine ion concentration in zinc hydrometallurgy leachate, measure chlorine after being processed through the present embodiment in leachate from
Sub- concentration is down to 92mg/L.It is confirmed that the method stabilization of the present embodiment removing chloride ion from zinc hydrometallurgy leachate, it is quick,
Effectively.
The above, is only presently preferred embodiments of the present invention, and not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (3)
1. in a kind of leachate from zinc hydrometallurgy removing chloride ion method, it is characterised in that the method is comprised the following steps：
The concentration and the concentration of copper ion of chlorion, measure the dense of chlorion in step one, respectively detection zinc hydrometallurgy leachate
It is C1 to spend, and the concentration of copper ion is mg/L for the unit of C2, C1 and C2；The concentration C 1 of the chlorion meets：300mg/L≤
C1≤1500mg/L；
Step 2, the concentration C 2 to the copper ion measured by step one are analyzed, if C2 meets C2 >=1.7C1, enter step
Rapid three；Otherwise, the concentration of copper ion in zinc hydrometallurgy leachate is adjusted to by C3 using the method for addition copper sulphate, meets C3
C3: C1=(1.7~5.0): 1, subsequently into step 3；The unit of the C3 is mg/L；
Step 3, to adding copper ashes in zinc hydrometallurgy leachate, it is well mixed after obtain slurry；The addition of the copper ashes is wet
40~70 times of chlorine ions in method zinc metallurgy leachate；Copper ashes of the copper ashes produced by the cleaning procedure of zinc hydrometallurgy；
Step 4, temperature be 40 DEG C~70 DEG C under conditions of, to reducibility gas are passed through in slurry described in step 3, make wet
Copper ion in method zinc metallurgy leachate is reduced into cuprous ion and is formed with chlorion and precipitates；The reducibility gas are roasting zinc
Produced by concentrate containing SO2Gas, the intake of the reducibility gas is：The body of the reducibility gas being passed through per hour
Product is 150~300 times of zinc hydrometallurgy leachate volume；
After step 5, property gas to be restored are passed through 1h~3h, the oxidation-reduction potential Q of slurry is detected, if Q meets：80mV≤Q≤
100mV, then stop being passed through reducibility gas, filters, and obtains the zinc hydrometallurgy leachate of removing chloride ion；Otherwise, step is returned
Rapid four.
2. in a kind of leachate from zinc hydrometallurgy according to claim 1 removing chloride ion method, it is characterised in that step
The weight/mass percentage composition of copper is 70%~80% in copper ashes described in rapid three.
3. in a kind of leachate from zinc hydrometallurgy according to claim 1 removing chloride ion method, it is characterised in that step
SO in reducibility gas described in rapid four2Volumn concentration be not less than 30%.
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| CN107354484A (en) * | 2017-05-23 | 2017-11-17 | 西北矿冶研究院 | Method for removing chlorine in zinc electrolysis waste liquid |
| CN107475530A (en) * | 2017-08-16 | 2017-12-15 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Dechlorination process in zinc hydrometallurgy |
| CN108220599A (en) * | 2018-01-18 | 2018-06-29 | 河南豫光锌业有限公司 | A kind of method of solution of zinc sulfate auto purification dechlorination |
| CN109680142A (en) * | 2019-02-21 | 2019-04-26 | 张伟晓 | The method to dechlorinate from roasting method gold hydrometallurgy acid waste water |
| CN112540162A (en) * | 2020-11-25 | 2021-03-23 | 江苏雅信昆成检测科技有限公司 | Water quality biotoxicity detection method |
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| FR2323766A1 (en) * | 1975-04-21 | 1977-04-08 | Penarroya Miniere Metallurg | HYDROMETALLURGIC PROCESS FOR TREATING SULPHIDE ORES |
| CN1030139C (en) * | 1993-07-19 | 1995-10-25 | 董才华 | Quick method of producting cuprous chloride using waste acid and waste cupron |
| CN1041405C (en) * | 1994-05-17 | 1998-12-30 | 西安建筑科技大学 | Process for producing cuprous chloride by combined method |
| CN1032703C (en) * | 1994-06-29 | 1996-09-04 | 北京有色冶金设计研究总院 | Method for removal of copper from electrolytic nickel anodic liquid |
| CN101457295A (en) * | 2007-12-10 | 2009-06-17 | 巴彦淖尔紫金有色金属有限公司 | Dechlorination method in zinc hydrometallurgy circulation solution system |
| CN100572570C (en) * | 2008-05-23 | 2009-12-23 | 祥云县飞龙实业有限责任公司 | The method that dechlorinates in a kind of zinc electrolytic solution |
| CN101633982A (en) * | 2009-08-15 | 2010-01-27 | 蒙自矿冶有限责任公司 | Method for circularly removing chlorine in zinc sulphate solution by copper slag |
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