CN107245572A - A kind of method for improving complicated nonferrous heavy metal comprehensive utilization of resources - Google Patents
A kind of method for improving complicated nonferrous heavy metal comprehensive utilization of resources Download PDFInfo
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- CN107245572A CN107245572A CN201710322050.5A CN201710322050A CN107245572A CN 107245572 A CN107245572 A CN 107245572A CN 201710322050 A CN201710322050 A CN 201710322050A CN 107245572 A CN107245572 A CN 107245572A
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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 invention belongs to non-ferrous metal metallurgy technical field, specifically related to a kind of method for improving complicated nonferrous heavy metal comprehensive utilization of resources, with hydrometallurgy, solution chemistry, organic solvent extraction chemistry and Physical Chemistry of Metallurgy multi-crossed disciplines integrated approach, to the copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite, analyze its leaching process, establish the technological parameter of smelting process and optimize, set up Recovering Copper, lead, zinc, silver process.The present invention is leached using conventional wet lay metallurgical technology and Strengthen education means to ore, metal recovery is carried out using existing ripe wet process smelting technique, whole technical process is Whote-wet method process, and the harmful components such as arsenic are not got into the air, and air ambient is not polluted；The present invention establishes the leaching process kinetic theory of copper-lead zinc-silver complex multi-metal ore deposit；Establish the integrated smelting recovery process of copper-lead zinc-silver complex multi-metal ore deposit；Copper, lead, zinc, leaching rate >=95% of silver, can provide foundation for actual production.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, and in particular to one kind improves complicated nonferrous heavy metal resource comprehensive
The method utilized.
Background technology
The copper-lead zinc-silver polymetallic ore that western mining industry possesses is that a resource is relatively enriched, grade is high, easily exploitation, difficult sorting,
The polymetallic deposits such as the more complicated silver of technological process, copper, lead, zinc, gold, current explored ore reserve is 7,810,000 tons, wherein
1867.53 tons of argentiferous, 8.09 ten thousand tons of copper, 40.09 ten thousand tons of lead, 65.19 ten thousand tons of zinc, 5.198 tons of gold, resource potential value is huge,
Mine prospective reserves is very considerable, is described as one of Chinese polymetallic ore " three big bright pearls ".But the copper-bearing mineral in ore is
2/3rds tetrahedrites, 1/3rd chalcopyrite, ore dressing difficulty are big, cause treatment scale smaller, while the copper obtained by ore dressing
The content of lead zinc-silver bulk concentrate arsenic impurities and antimony is high, is not suitable for using traditional fire metallurgy process, and it is leaded be more than 10%,
Also it is not suitable for using fluidized bed roasting -- extract technology.In wet processing, the bacterial oxidation leaching research for chalcopyrite is more,
Rarely has research to the copper mineral wet-leaching based on tetrahedrite.
The polymetal sulphide ore containing copper, lead and zinc that western mining industry possesses belongs to super-huge silver polymetallic deposits, aboundresources, copper,
Lead, zinc, silver-colored average grade are respectively 0.5%, 3%, 5%, 200g/t.Current selecting and purchasing system has been constructed and put into operation, using preferential
Floatation process output copper concentrate, zinc concentrate and lead concentrate are sold.But copper concentrate product quality is unqualified, main metal copper grade is inclined
It is low, also containing higher lead, zinc, silver, arsenic and antimony, higher zinc and copper are also contained in lead concentrate, causes recovery rate in ore-dressing relatively low.
Controling differential flotation process for copper is changed to the mixed floating mine tailing again of copper-lead and selects zinc technology, Copper-lead mixed concentrate is obtained and up-to-standard zinc concentrate, then
The economic benefit that metallurgy is remarkably improved mine is carried out to Copper-lead mixed concentrate.But complicated Copper-lead mixed concentrate is due to miscellaneous
The content height of matter arsenic, antimony, is to be most difficult to one of metallic ore of choosing at present, belongs to the polymetallic ore of complicated fine grain teeth cloth hardly possible separation,
The country only one, it is external also rare, it is difficult to be handled using traditional smelting process, up to the present not yet there is suitable such ore deposit
The high-efficiency comprehensive utilization smelting process planted.Therefore, so abundant metals resources mineral deposit is such as developed, smelting that need to be to this kind of ore
Sweetening process is studied, and develops the high-efficiency comprehensive utilization method of resource.
The content of the invention
Present invention aim to address opened at present for the smelting process of the copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite
Hair only rests on the laboratory research stage, and process conditions have the shortcomings that high temperature, high pressure or long period are difficult to industry
The problem of change.
Therefore, the invention provides a kind of method for improving complicated nonferrous heavy metal comprehensive utilization of resources, including following step
Suddenly：
Step one：Copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite is leached；
Step 2：Analyze the leaching process of the copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite；
Step 3：The technological parameter of smelting process is established according to the analysis result of step 2；
Step 4：The technological parameter of step 3 is optimized.
The leaching process of described step one is as follows：
（1）Constituent analysis is carried out to miberal powder, must there emerged a the content of metallic element；
（2）Weigh respectively and take miberal powder, sulfuric acid solution and salpeter solution so that solid-liquid mass ratio is 1:3, wherein sulphur in sulfuric acid solution
The amount of the material of acid and the amount of the material of nitric acid in salpeter solution be respectively in miberal powder respective metal element be completely dissolved aequum
2 times and 1.25 times；
（3）By step（2）Load weighted sulfuric acid solution is added in the miberal powder for having weighed up quality, is put into 85 DEG C of thermostat water baths
Heating, is stirred in heating with agitator；After temperature is constant, by step（2）Load weighted salpeter solution is with less than 10mlL/
Min rate of addition is added in sulfuric acid solution and mineral powder mixed material；After salpeter solution all adds 20min, ore pulp is entered
Row suction filtration, then carries out constituent analysis by the filter residue obtained after suction filtration, obtains the leaching rate of each metallic element.
Leaching process is analyzed in described step two to specifically include：
（1）The discriminating of complex multi-metal ore deposit metalliferous mineral is carried out first；
（2）Then using three-necked bottle carry out the copper of multi-metallic minerals, lead, zinc, silver metal leaching isothermal determine；Using tasting
Examination method carries out data processing, each factor of each leaching step of preliminary judgement Chemical Leaching process；
（3）Calculate and verify using apparent activation energy method again, finally drawing influences gold in complex multi-metal mineralising leaching process
Belong to the specific process parameter of leaching rate.
Described step（1）Chemical composition in middle use ICP dissolving analysis methods and XRF method of testings test raw ore.
Described step（2）The leaching step of middle Chemical Leaching process includes：
（2.1）The absorption of hydrogen ion in acid in mineral surfaces；
（2.2）Adsorbed hydrogen ion is to mineral diffusion inside；
（2.3）Oxide chemically reacts with hydrogen ion in mineral, generates respective metal ion；
（2.4）Metal ion to mineral surfaces from spreading inside mineral in mineral；
（2.5）The metal ion for being diffused into mineral surfaces spreads to leachate.
Described step three is established in the technological parameter of smelting process, and technological parameter includes extraction temperature, leaches stirring by force
Degree, leaching liquid-solid ratio, extraction time, leaching agent consumption.
Described step four carries out multifactor technological parameter orthogonal test using the method for orthogonal test, many to influenceing
The factor of metallic ore metal extraction rate optimizes choosing value, and the technological parameter after optimization is defined as into polymetallic ore smelting integrates back
Receive technological parameter.
Beneficial effects of the present invention：
1st, the present invention is leached using conventional wet lay metallurgical technology and Strengthen education means to ore, using existing ripe wet
Method smelting technique carries out metal recovery, and whole technical process is Whote-wet method process, and the harmful components such as arsenic do not get into the air, to sky
Compression ring border is not polluted.
2nd, the present invention establishes the leaching process kinetic theory of copper-lead zinc-silver complex multi-metal ore deposit；Establish copper-lead zinc-silver
The integrated smelting recovery process of complex multi-metal ore deposit；Copper, lead, zinc, leaching rate >=95% of silver；Propose process parameter optimizing side
Case, can provide foundation for actual production.
Embodiment
Embodiment 1：
The present embodiment provides a kind of method for improving complicated nonferrous heavy metal comprehensive utilization of resources, comprises the following steps：
Step one：Copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite is leached；
Step 2：Analyze the leaching process of the copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite；
Step 3：The technological parameter of smelting process is established according to the analysis result of step 2；
Step 4：The technological parameter of step 3 is optimized.
The method provided in an embodiment of the present invention for improving complicated nonferrous heavy metal comprehensive utilization of resources, with hydrometallurgy,
Solution chemistry, organic solvent extraction chemistry and Physical Chemistry of Metallurgy multi-crossed disciplines integrated approach, to the copper-lead zinc containing tetrahedrite
Silver-colored complex multi-metal ore deposit, analyzes its leaching process, establishes the technological parameter of smelting process and optimizes, sets up synthetical recovery
Copper, lead, zinc, silver process.
Embodiment 2：
The present embodiment is further illustrated on the basis of embodiment 1 to above-mentioned steps one, the leaching of described step one
Journey is as follows：
（1）Constituent analysis is carried out to miberal powder, must there emerged a the content of metallic element；
（2）Weigh respectively and take miberal powder, sulfuric acid solution and salpeter solution so that solid-liquid mass ratio is 1:3, wherein sulphur in sulfuric acid solution
The amount of the material of acid and the amount of the material of nitric acid in salpeter solution be respectively in miberal powder respective metal element be completely dissolved aequum
2 times and 1.25 times；The metallic element of some in miberal powder dissolves in sulfuric acid, and some metallic elements dissolve in nitric acid, according to step（1）
The miberal powder component content of analysis, sulfuric acid solution and salpeter solution required for calculating are weighed, the final gold caused in miberal powder
Category element can be completely dissolved；
（3）By step（2）Load weighted sulfuric acid solution is added in the miberal powder for having weighed up quality, is put into 85 DEG C of thermostat water baths
Heating, is stirred in heating with agitator；After temperature is constant, by step（2）Load weighted salpeter solution is with less than 10mlL/
Min rate of addition is added in sulfuric acid solution and mineral powder mixed material；After salpeter solution all adds 20min, ore pulp is entered
Row suction filtration, then carries out constituent analysis by the filter residue obtained after suction filtration, obtains the leaching rate of each metallic element.
The present embodiment is leached using conventional wet lay metallurgical technology and Strengthen education means to ore, utilizes existing maturation
Wet process smelting technique carry out metal recovery, whole technical process is Whote-wet method process, and the harmful components such as arsenic do not get into the air,
Air ambient is not polluted.After subsequent technique parameter optimization, industrial construction is being carried out using the method for this step, is improving multiple
The comprehensive utilization of miscellaneous nonferrous heavy metal resource.
Embodiment 3：
The present embodiment is further illustrated on the basis of embodiment 1 to above-mentioned steps two, and leaching is analyzed in described step two
Go out process to specifically include：
（1）The discriminating of complex multi-metal ore deposit metalliferous mineral is carried out first；Analysis method is dissolved using ICP and XRF method of testings are surveyed
The chemical composition in raw ore is tried, its purpose is to determine the content of the elements such as Cu, Fe, Zn, As, Pb, Sb, to calculate each member
The leaching rate of element.
（2）Then the isothermal measure of leaching of the copper of use three-necked bottle progress multi-metallic minerals, lead, zinc, silver metal, soaks
Stain isothermal curve refers to that solute carries out when process in leaching reaches balance them two on liquid-solid two-phase interface at a certain temperature
Relation curve in phase between content, typically dissolves analysis by ICP and is measured；Data processing is carried out using trial and error method, just
Step judges each factor of each leaching step of Chemical Leaching process；
The leaching step of Chemical Leaching process includes：
（2.1）The absorption of hydrogen ion in acid in mineral surfaces；
（2.2）Adsorbed hydrogen ion is to mineral diffusion inside；
（2.3）Oxide chemically reacts with hydrogen ion in mineral, generates respective metal ion；
（2.4）Metal ion to mineral surfaces from spreading inside mineral in mineral；
（2.5）The metal ion for being diffused into mineral surfaces spreads to leachate.
（3）Step is leached using apparent activation energy method to above-mentioned 5 to be calculated and verified, finally draw complicated more golden again
Belong to the dynamic control principle of mineralising leaching process, obtain influenceing metal leaching rate in complex multi-metal mineralising leaching process
Specific process parameter, including acidity, temperature, oxidizer and mixing speed etc..
Embodiment 4：
The present embodiment is further illustrated on the basis of embodiment 1 to above-mentioned steps three and four, and described step three is established
In the technological parameter of smelting process, technological parameter includes extraction temperature, leaches stirring intensity, leaches liquid-solid ratio, extraction time, leaching
Go out agent consumption.
Described step four carries out multifactor technological parameter orthogonal test using the method for orthogonal test, many to influenceing
The factor of metallic ore metal extraction rate optimizes choosing value, and the technological parameter after optimization is defined as into polymetallic ore smelting integrates back
Receive technological parameter.
The optimization of technological parameter is carried out by the present embodiment, obtains being more suitable for the technique that polymetallic ore smelts synthetical recovery
Parameter, is carrying out hydrometallurgy, improves the comprehensive utilization of complicated nonferrous heavy metal resource.
The present invention establishes the leaching process kinetic theory of copper-lead zinc-silver complex multi-metal ore deposit；Copper-lead zinc-silver is established to answer
The integrated smelting recovery process of miscellaneous polymetallic ore；Copper, lead, zinc, leaching rate >=95% of silver；Propose process parameter optimizing side
Case, can provide foundation for actual production.
（1）The synthetical recovery of the ore resources of multi-metal complex containing tetrahedrite can be achieved.
At present, being saved in Yunnan, Sichuan, Guizhou, Jiangxi, Tibet etc. has many refractory copper ores and Copper ore containing arsenic, and copper reserves exist
It is more than millions of tons, these difficult ore dressings and low grade copper ores using it is conventional adopt, select, metallurgical method can not be returned effectively
Receive.This project achievement in research can fill up the domestic deficiency to the mining and metallurgy sweetening process of multi-metal complex containing tetrahedrite, mitigate traditional
To the pollution of air ambient etc. in fire metallurgy process, the need for meeting the developments of resources such as copper-lead zinc-silver.
（2）Huge economic benefit can be produced, promotes western minorities development.
The polymetal sulphide ore containing copper, lead and zinc that western mining industry possesses is located at western minorities, current explored ore deposit
Stone reserves be 7,810,000 tons, wherein 1867.53 tons of argentiferous, 8.0 9 ten thousand tons of copper, 4 0.0 9 ten thousand tons of lead, 6 5.1 9 ten thousand tons of zinc,
5.1 98 tons of gold, resource potential value is up to more than 280 hundred million yuan of people.This good mineral deposit of exploitation will be with will greatly promoting western less-developed area
Area's economy, benefits the local common people, and the harmony for promoting area is stable.
It is exemplified as above be only to the present invention for example, do not constitute the limitation to protection scope of the present invention, it is all
It is to be belonged to the same or analogous design of the present invention within protection scope of the present invention.
Claims (7)
1. a kind of method for improving complicated nonferrous heavy metal comprehensive utilization of resources, it is characterised in that：Comprise the following steps：
Step one：Copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite is leached；
Step 2：Analyze the leaching process of the copper-lead zinc-silver complex multi-metal ore deposit containing tetrahedrite；
Step 3：The technological parameter of smelting process is established according to the analysis result of step 2；
Step 4：The technological parameter of step 3 is optimized.
2. the method as claimed in claim 1 for improving complicated nonferrous heavy metal comprehensive utilization of resources, it is characterised in that：Described
The leaching process of step one is as follows：
（1）Constituent analysis is carried out to miberal powder, must there emerged a the content of metallic element；
（2）Weigh respectively and take miberal powder, sulfuric acid solution and salpeter solution so that solid-liquid mass ratio is 1:3, wherein sulphur in sulfuric acid solution
The amount of the material of acid and the amount of the material of nitric acid in salpeter solution be respectively in miberal powder respective metal element be completely dissolved aequum
2 times and 1.25 times；
（3）By step（2）Load weighted sulfuric acid solution is added in the miberal powder for having weighed up quality, is put into 85 DEG C of thermostat water baths
Heating, is stirred in heating with agitator；After temperature is constant, by step（2）Load weighted salpeter solution is with less than 10mlL/
Min rate of addition is added in sulfuric acid solution and mineral powder mixed material；After salpeter solution all adds 20min, ore pulp is entered
Row suction filtration, then carries out constituent analysis by the filter residue obtained after suction filtration, obtains the leaching rate of each metallic element.
3. the method as claimed in claim 1 for improving complicated nonferrous heavy metal comprehensive utilization of resources, it is characterised in that：Described
Leaching process is analyzed in step 2 to specifically include：
（1）The discriminating of complex multi-metal ore deposit metalliferous mineral is carried out first；
（2）Then using three-necked bottle carry out the copper of multi-metallic minerals, lead, zinc, silver metal leaching isothermal determine；Using tasting
Examination method carries out data processing, each factor of each leaching step of preliminary judgement Chemical Leaching process；
（3）Calculate and verify using apparent activation energy method again, finally drawing influences gold in complex multi-metal mineralising leaching process
Belong to the specific process parameter of leaching rate.
4. the method as claimed in claim 3 for improving complicated nonferrous heavy metal comprehensive utilization of resources, it is characterised in that：Described
Step（1）Chemical composition in middle use ICP dissolving analysis methods and XRF method of testings test raw ore.
5. the method as claimed in claim 3 for improving complicated nonferrous heavy metal comprehensive utilization of resources, it is characterised in that：Described
Step（2）The leaching step of middle Chemical Leaching process includes：
（2.1）The absorption of hydrogen ion in acid in mineral surfaces；
（2.2）Adsorbed hydrogen ion is to mineral diffusion inside；
（2.3）Oxide chemically reacts with hydrogen ion in mineral, generates respective metal ion；
（2.4）Metal ion to mineral surfaces from spreading inside mineral in mineral；
（2.5）The metal ion for being diffused into mineral surfaces spreads to leachate.
6. the method as claimed in claim 1 for improving complicated nonferrous heavy metal comprehensive utilization of resources, it is characterised in that：Described
Step 3 establish smelting process technological parameter in, technological parameter include extraction temperature, leach stirring intensity, leach liquid-solid ratio,
Extraction time, leaching agent consumption.
7. the method as claimed in claim 1 for improving complicated nonferrous heavy metal comprehensive utilization of resources, it is characterised in that：Described
The method that step 4 uses orthogonal test, carries out multifactor technological parameter orthogonal test, to influence polymetallic ore metal leaching
The factor of rate optimizes choosing value, and the technological parameter after optimization is defined as into polymetallic ore smelts comprehensive recycling process parameter.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4084961A (en) * | 1976-09-10 | 1978-04-18 | Sunshine Mining Company | Treatment of metal bearing mineral material |
| CN1120355A (en) * | 1993-01-27 | 1996-04-10 | R及O采矿加工有限公司 | Hydrometallurgical recovery of metals from complex ores |
-
2017
- 2017-05-09 CN CN201710322050.5A patent/CN107245572A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4084961A (en) * | 1976-09-10 | 1978-04-18 | Sunshine Mining Company | Treatment of metal bearing mineral material |
| CN1120355A (en) * | 1993-01-27 | 1996-04-10 | R及O采矿加工有限公司 | Hydrometallurgical recovery of metals from complex ores |
Non-Patent Citations (2)
| Title |
|---|
| 田君等: "西南稀土矿黑色风化矿泥还原浸锰的动力学", 《化工冶金》 * |
| 邱廷省等: "离子型稀土矿浸出过程优化与分析", 《有色金属科学与工程》 * |
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Application publication date: 20171013 |