CN107841626B - A kind of method of zinc hydrometallurgy kiln slag and waste acid Combined Treatment - Google Patents
A kind of method of zinc hydrometallurgy kiln slag and waste acid Combined Treatment Download PDFInfo
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- CN107841626B CN107841626B CN201710886398.7A CN201710886398A CN107841626B CN 107841626 B CN107841626 B CN 107841626B CN 201710886398 A CN201710886398 A CN 201710886398A CN 107841626 B CN107841626 B CN 107841626B
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- liquid
- slag
- leachate
- neutralization
- waste acid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- 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
- Y02P10/20—Recycling
Abstract
The present invention relates to the methods of a kind of zinc hydrometallurgy kiln slag and waste acid Combined Treatment, belong to chemical metallurgy technical field.Liquid after zinc kiln slag and heavy arsenic is neutralized first, liquid after the neutralization slag being obtained by filtration and neutralization, liquid is sent to sewage treatment plant processing after neutralization；It neutralizes slag once to be leached with secondary leachate, be obtained by filtration a leached mud and a leachate；Leached mud is mixed with waste acid and carries out secondary leaching, secondary leachate and copper silver slag is obtained by filtration, secondary leachate returns；Obtain leachate is passed through oxygen or air, sedimentation, arsenic oxidizing processing is carried out, liquid after heavy arsenic slag and heavy arsenic is obtained by filtration, liquid returns after heavy arsenic.This method has the characteristics that environmental protection, economy, resource utilization height, " waste recycling ".
Description
Technical field
The present invention relates to the methods of a kind of zinc hydrometallurgy kiln slag and waste acid Combined Treatment, belong to chemical metallurgy technical field.
Background technique
2016, China's metallic zinc yield was up to 6,300,000 tons, wherein 50% or more is produced using conventional wet lay process.In routine
In wet processing, waelz process processing zinc leaching residue is generallyd use.Under the conditions of 1100 ~ 1300 DEG C, zinc in zinc leaching residue,
The low boiling points such as lead, indium, volatile metal enter in Second-rate zinc oxide powder, and the higher boiling metal in zinc leaching residue then remains in kiln
In slag.Using conventional wet lay process, every 1 ton about 0.8 ton of metallic zinc output kiln slag of production.Annual China output kiln slag about 2,000,000
Ton.Although most Cu, Ag and Fe remain in zinc kiln slag in zinc leaching residue, Cu, Ag and Fe's contains in kiln slag
It measures lower.Currently, some smelting enterprises use the method for zinc kiln slag and pyrite mixture manufacturing copper matte regulus recycling kiln under the high temperature conditions
Copper and silver in slag.Since Cu, Ag content are lower in kiln slag, this method deficiency in economic performance.Some Domestic enterprise is using floating, magnetic separation
Equal physical methods handle above-mentioned kiln slag, respectively the substances such as output iron ore concentrate, copper mine and tailing.But Cu, Ag dispersion in kiln slag
Into iron ore concentrate and tailing, recovery rate of valuable metals is lower.In conclusion zinc hydrometallurgy kiln slag yield is big, valuable metal content
Height is a kind of higher mineral of value.But it can effectively be recycled in zinc kiln currently without efficient, clean processing method
Valuable metal.
Waste acid is washed caused by flue gas in metallurgical off-gas acid-making link.In flue gas washing purification process, in flue gas
The impurity such as As, F, Cl will enter in recycle acid.It is discharged when impurity enriched is to a certain concentration to outside system a certain amount of
Waste acid.The waste acid of non-ferrous smelt enterprise output has acidity height, heavy metal ion type more, and the spy that arsenic, fluorine, cl concn are high
Point.There are processing cost height, the dangerous waste slag scale of construction for the various processing methods such as the lime neutralisation, the chemical precipitation method that currently generally use
Big disadvantage, it is difficult to meet increasingly strict environmental requirement.How As, F, Cl in stable removal waste acid, and recycle in waste acid
Valuable metal and acid become researcher in face of a difficult problem.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of zinc hydrometallurgy kiln slag and combines with waste acid
The method of processing.This method has the characteristics that environmental protection, economy, resource utilization height, " waste recycling ".The present invention passes through following skill
Art scheme is realized.
A kind of method of zinc hydrometallurgy kiln slag and waste acid Combined Treatment, the specific steps of which are as follows:
Liquid after heavy arsenic that zinc kiln slag and step 4 obtain is neutralized by step 1 first, control reaction temperature when neutralization
Degree is 25 DEG C ~ 75 DEG C, the reaction time is 30 ~ 120min, liquid-solid ratio is 5:1 ~ 20:1ml/g, reaction end pH=3.5 ~ 6.0, mistake
Liquid after filtering obtained neutralization slag and neutralizing, liquid is sent to sewage treatment plant processing after neutralization；
The secondary leachate that the neutralization slag that step 2, step 1 obtain is obtained with step 3 is once leached, when once leaching
Control reaction temperature be 40 DEG C ~ 95 DEG C, the reaction time is 30 ~ 180min, liquid-solid ratio is 5:1 ~ 20:1ml/g, reaction end pH=
1.0 ~ 2.0, the leached mud and a leachate being obtained by filtration；
A leached mud that step 2 obtains is mixed with waste acid and carries out secondary leaching by step 3, and control is anti-when secondary leaching
Answering temperature is 60 DEG C ~ 95 DEG C, the reaction time is 60 ~ 180min, liquid-solid ratio is 5:1 ~ 20:1ml/g, and secondary leachate is obtained by filtration
With copper silver slag, secondary leachate is returned in step 2；
Step 4, a leachate for obtaining step 2 are passed through oxygen or air, at 80 ~ 95 DEG C, reaction 180 ~
420min carries out sedimentation, arsenic oxidizing processing, and liquid after heavy arsenic slag and heavy arsenic is obtained by filtration, and liquid returns in step 1 after heavy arsenic.
Zinc kiln slag is the kiln slag for leached mud output after pyrogenic attack that Zinc hydrometallurgy process obtains in the step 1.Zinc
The main component of kiln slag is as shown in table 1.
Table 1
Step 3 waste acid is the waste acid of non-ferrous smelt enterprise roasting technique output, the main component of waste acid such as 2 institute of table
Show.
Table 2
When using this method for the first time, secondary leachate needed for liquid and step 2 can be used and sink after heavy arsenic needed for step 1
Liquid and the identical dilution heat of sulfuric acid of secondary leachate sulfuric acid concentration are leached for the first time after arsenic.
The beneficial effects of the present invention are:
(1) present invention uses the combination treatment method of zinc hydrometallurgy kiln slag and waste acid, breaches zinc kiln slag in conventional method
The limitation individually handled with waste acid opens the Combined Treatment of zinc kiln slag and waste acid, the new way of " waste recycling ".With tradition
Independent processing method is compared, and this method uses combination treatment method, take full advantage of that acidity in waste acid is high and zinc kiln slag in iron contain
Measured feature makes the iron in zinc kiln slag enter solution by two sections of leachings, by zinc kiln slag copper and silver be enriched in leached mud
In；In leaching process, most acid is consumed in waste acid, and there are a large amount of ferrous ions in solution, are subsequent with arsenic
Arsenic removing in waste acid is created advantageous condition by the form of sour iron or scorodite.
(2) this method realizes the separation and recovery of valuable metal in zinc kiln slag, and synchronizes and realize the efficient, clear of waste acid
Clean processing is a kind of resource-effective, environmental-friendly method.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
As shown in Figure 1, the method for the zinc hydrometallurgy kiln slag and waste acid Combined Treatment, the specific steps of which are as follows:
Step 1, first by 100g zinc kiln slag (main component of zinc kiln slag are as follows: Fe39.54wt%, Cu1.16wt%,
Ag214.3g/t, Zn2.28wt%, As0.65wt%, S3.95wt%) and the obtained 2.0L of step 4 sink liquid after arsenic and carry out at neutralization
Reason, when neutralization control reaction temperature be 25 DEG C, reaction time 120min, liquid-solid ratio 20:1ml/g, reaction end pH=3.5,
Liquid after the neutralization slag being obtained by filtration and neutralization, liquid is sent to sewage treatment plant processing after neutralization；
The secondary leachate that the neutralization slag that step 2, step 1 obtain is obtained with step 3 is once leached, when once leaching
Control reaction temperature be 40 DEG C, reaction time 180min, liquid-solid ratio 5:1ml/g, reaction end pH=1.0, be obtained by filtration
Leached mud and a leachate；
Step 3, the leached mud that step 2 is obtained and the waste acid (main component of waste acid are as follows: H2SO489.70g/L,
F2.36g/L, Cl3.51g/L, Cu0.28g/L, As8.54g/L) mixing carries out secondary leaching, control reaction temperature when secondary leaching
Degree is 60 DEG C, reaction time 180min, liquid-solid ratio 5:1ml/g, and secondary leachate and copper silver slag is obtained by filtration, and (copper silver slag contains
Cu2.84%, Ag387.1g/t), secondary leachate returns in step 2；
Step 4, a leachate for obtaining step 2 are passed through 1800mL/h oxygen, at 80 DEG C, reaction 420min progress
Sedimentation, arsenic oxidizing processing, is obtained by filtration liquid after heavy arsenic slag and heavy arsenic, and liquid returns in step 1 after heavy arsenic.
Above-mentioned heavy arsenic slag contains As21.13wt%, Fe24.82wt%.The rate of deposition of arsenic is 74.76% during heavy arsenic.
Embodiment 2
As shown in Figure 1, the method for the zinc hydrometallurgy kiln slag and waste acid Combined Treatment, the specific steps of which are as follows:
Step 1, first by 100g zinc kiln slag (main component of zinc kiln slag are as follows: Fe33.24wt%, Cu1.26wt%,
Ag205.0g/t, Zn2.71wt%, As0.79wt%, S2.74wt%) and the obtained heavy arsenic of step 4 after liquid be neutralized, in
With when control reaction temperature be 75 DEG C, reaction time 30min, liquid-solid ratio 10:1ml/g, reaction end pH=4.2, filter
Liquid after the neutralization slag arrived and neutralization, liquid is sent to sewage treatment plant processing after neutralization；
The secondary leachate that the neutralization slag that step 2, step 1 obtain is obtained with step 3 is once leached, when once leaching
Control reaction temperature be 95 DEG C, reaction time 30min, liquid-solid ratio 20:1ml/g, reaction end pH=2.0, be obtained by filtration
Leached mud and a leachate；
Step 3, the leached mud that step 2 is obtained and the waste acid (main component of waste acid are as follows: H2SO489.70g/L,
F2.36g/L, Cl3.51g/L, Cu0.28g/L, As8.54g/L) mixing carries out secondary leaching, control reaction temperature when secondary leaching
Degree is 95 DEG C, reaction time 60min, liquid-solid ratio 20:1ml/g, and secondary leachate and copper silver slag, secondary leaching is obtained by filtration
Liquid returns in step 2；
Step 4, a leachate for obtaining step 2 are passed through 4500mL/h air, at 95 DEG C, reaction 180min progress
Sedimentation, arsenic oxidizing processing, is obtained by filtration liquid after heavy arsenic slag and heavy arsenic, and liquid returns in step 1 after heavy arsenic.
Above-mentioned heavy arsenic slag contains As20.79wt%, Fe22.74wt%.The rate of deposition of arsenic is 84.62% during heavy arsenic.
Embodiment 3
As shown in Figure 1, the method for the zinc hydrometallurgy kiln slag and waste acid Combined Treatment, the specific steps of which are as follows:
Step 1, first by 100g zinc kiln slag (main component of zinc kiln slag are as follows: Fe33.24wt%, Cu1.26wt%,
Ag205.0g/t, Zn2.71wt%, As0.79wt%, S2.74wt%) and the obtained heavy arsenic of step 4 after liquid be neutralized, in
With when control reaction temperature be 55 DEG C, reaction time 90min, liquid-solid ratio 5:1ml/g, reaction end pH=6.0, filter
Liquid after the neutralization slag arrived and neutralization, liquid is sent to sewage treatment plant processing after neutralization；
The secondary leachate that the neutralization slag that step 2, step 1 obtain is obtained with step 3 is once leached, when once leaching
Control reaction temperature be 75 DEG C, reaction time 120min, liquid-solid ratio 15:1ml/g, reaction end pH=1.5, be obtained by filtration
A leached mud and a leachate；
Step 3, the leached mud that step 2 is obtained and the waste acid (main component of waste acid are as follows: H2SO489.70g/L,
F2.36g/L, Cl3.51g/L, Cu0.28g/L, As8.54g/L) mixing carries out secondary leaching, control reaction temperature when secondary leaching
Degree is 85 DEG C, reaction time 120min, liquid-solid ratio 15:1ml/g, and secondary leachate and copper silver slag, secondary leaching is obtained by filtration
Liquid returns in step 2 out；
Step 4, a leachate for obtaining step 2 are passed through 3000mL/h air, at 85 DEG C, reaction 300min progress
Sedimentation, arsenic oxidizing processing, is obtained by filtration liquid after heavy arsenic slag and heavy arsenic, and liquid returns in step 1 after heavy arsenic.
Above-mentioned heavy arsenic slag contains As22.35wt%, Fe24.27wt%.The rate of deposition of arsenic is 85.37% during heavy arsenic.
In conjunction with attached drawing, the embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned
Embodiment within the knowledge of a person skilled in the art can also be before not departing from present inventive concept
Put that various changes can be made.
Claims (3)
1. a kind of method of zinc hydrometallurgy kiln slag and waste acid Combined Treatment, it is characterised in that specific step is as follows:
Liquid after heavy arsenic that zinc kiln slag and step 4 obtain is neutralized by step 1 first, and control reaction temperature is when neutralization
25 DEG C ~ 75 DEG C, the reaction time be 30 ~ 120min, liquid-solid ratio is 5:1 ~ 20:1ml/g, reaction end pH=3.5 ~ 6.0, filter
Liquid after the neutralization slag arrived and neutralization, liquid is sent to sewage treatment plant processing after neutralization；
The secondary leachate that the neutralization slag that step 2, step 1 obtain is obtained with step 3 is once leached, and is controlled when once leaching
Reaction temperature is 40 DEG C ~ 95 DEG C, the reaction time is 30 ~ 180min, liquid-solid ratio is 5:1 ~ 20:1ml/g, reaction end pH=1.0 ~
2.0, the leached mud and a leachate being obtained by filtration；
A leached mud that step 2 obtains is mixed with waste acid and carries out secondary leaching by step 3, control reaction temperature when secondary leaching
Degree is 60 DEG C ~ 95 DEG C, the reaction time is 60 ~ 180min, liquid-solid ratio is 5:1 ~ 20:1ml/g, and secondary leachate and copper is obtained by filtration
Silver-colored slag, secondary leachate return in step 2；
Step 4, a leachate for obtaining step 2 are passed through oxygen or air, at 80 ~ 95 DEG C, 180 ~ 420min of reaction
Sedimentation, arsenic oxidizing processing is carried out, liquid after heavy arsenic slag and heavy arsenic is obtained by filtration, liquid returns in step 1 after heavy arsenic；
When using this method for the first time, secondary leachate needed for liquid and step 2 is used and liquid after heavy arsenic after heavy arsenic needed for step 1
And the identical dilution heat of sulfuric acid of secondary leachate sulfuric acid concentration is leached for the first time.
2. the method for zinc hydrometallurgy kiln slag and waste acid Combined Treatment according to claim 1, it is characterised in that: the step
Zinc kiln slag is the kiln slag for leached mud output after pyrogenic attack that Zinc hydrometallurgy process obtains in 1.
3. the method for zinc hydrometallurgy kiln slag and waste acid Combined Treatment according to claim 1, it is characterised in that: the step
3 waste acids are the waste acid of non-ferrous smelt enterprise roasting technique output.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652264A (en) * | 1968-11-20 | 1972-03-28 | Mines Fond Zinc Vieille | Recovery of zinc values from zinc plant residue |
| US4452706A (en) * | 1982-11-11 | 1984-06-05 | Interox Chemicals Limited | Metals recovery |
| CN103695662A (en) * | 2013-12-13 | 2014-04-02 | 中南大学 | Comprehensive utilization method of slag iron concentrates of wet-type zinc smelting furnace |
| CN104745810A (en) * | 2015-04-01 | 2015-07-01 | 昆明理工大学科技产业经营管理有限公司 | Treatment technique of copper-containing high-indium high-iron zinc sulfide concentrate |
| CN105950874A (en) * | 2016-06-30 | 2016-09-21 | 中南大学 | Combined treatment method for copper smelting soot and polluted acid |
-
2017
- 2017-09-27 CN CN201710886398.7A patent/CN107841626B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652264A (en) * | 1968-11-20 | 1972-03-28 | Mines Fond Zinc Vieille | Recovery of zinc values from zinc plant residue |
| US4452706A (en) * | 1982-11-11 | 1984-06-05 | Interox Chemicals Limited | Metals recovery |
| CN103695662A (en) * | 2013-12-13 | 2014-04-02 | 中南大学 | Comprehensive utilization method of slag iron concentrates of wet-type zinc smelting furnace |
| CN104745810A (en) * | 2015-04-01 | 2015-07-01 | 昆明理工大学科技产业经营管理有限公司 | Treatment technique of copper-containing high-indium high-iron zinc sulfide concentrate |
| CN105950874A (en) * | 2016-06-30 | 2016-09-21 | 中南大学 | Combined treatment method for copper smelting soot and polluted acid |
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