CN110846511B - Method for co-processing zinc leaching residues and gypsum residues - Google Patents
Method for co-processing zinc leaching residues and gypsum residues Download PDFInfo
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- CN110846511B CN110846511B CN201911125818.5A CN201911125818A CN110846511B CN 110846511 B CN110846511 B CN 110846511B CN 201911125818 A CN201911125818 A CN 201911125818A CN 110846511 B CN110846511 B CN 110846511B
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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
- C22B7/04—Working-up slag
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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
- C22B7/001—Dry processes
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- 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 discloses a method for co-processing zinc leaching residues and gypsum residues. Firstly, uniformly mixing zinc leaching residues and gypsum residues to form a mixed material; adding quartz sand into the mixed material, uniformly mixing, adding water, and granulating to obtain mixed granules; introducing the obtained mixed granules into a smelting furnace, adding a reducing agent, then adding natural gas and oxygen, and controlling the furnace temperature to react; copper matte is continuously siphoned and discharged in the furnace, and slag is continuously overflowed and discharged; the copper matte is transferred out of the system for further recovery; a slag discharge system; the smoke dust is treated by the subsequent procedures and then is emptied. The treatment method has the advantages of short process route and low production cost, effectively solves the problems of inventory occupation and environmental pollution of the heavy metal gypsum slag, and can improve the reasonable recovery of valuable metals. The invention has remarkable economic benefit and social benefit.
Description
The technical field is as follows:
the invention relates to the field of hazardous waste cooperative treatment in the field of non-ferrous metallurgy, in particular to a method for cooperatively treating hazardous waste zinc leaching slag produced in the zinc hydrometallurgy process and hazardous waste gypsum slag produced in an industrial waste acid treatment system, which is a novel harmless and quantitative reduction process.
Secondly, background art:
the zinc leaching slag belongs to dangerous waste residues in the national records of dangerous wastes, and the collection, storage, transportation, utilization, treatment and disposal of the zinc leaching slag must meet the national treatment regulations of solid wastes. Therefore, realizing the clean production and the harmless treatment of the zinc leaching residues is an important problem to be solved by zinc smelting enterprises. Meanwhile, the zinc leaching residue contains various valuable metals such as Zn, Pb, Ga, Ge, Cd, In, Au, Ag and the like, and the production benefit of a smelting enterprise can be improved by effectively treating the valuable metals.
In addition, when the tail gas, waste acid and waste water containing S acid are treated in the non-ferrous smelting process, a large amount of gypsum slag is generated by adopting a calcium carbonate neutralization process, wherein the gypsum slag is industrial waste slag taking calcium sulfate as a main component and contains a certain amount of heavy metals such as Pb, Zn, Cu and the like. The output discharge amount of the gypsum residues containing heavy metals is large, a large amount of gypsum residues are taken as industrial wastes to be stockpiled for a long time, large land is occupied, and water-soluble heavy metal ions and the like in the gypsum residues pollute water and soil, harm agricultural production and human health and threaten the growth and reproduction of livestock.
In view of the above, it is necessary to develop an effective method for combined treatment of zinc-leached residues and gypsum residues.
Thirdly, the invention content:
the technical problem to be solved by the invention is as follows: according to the treatment problem of two dangerous waste residues, namely zinc leaching residues and gypsum residues, in the technical field of smelting, the invention provides a method for cooperatively treating the zinc leaching residues and the gypsum residues. The invention adopts the fire process to cooperatively treat the industrial hazardous waste zinc leaching residue and the gypsum slag containing heavy metals, not only effectively treats the zinc leaching residue, but also harmlessly and quantitatively treats the gypsum slag containing heavy metals, and reasonably and effectively recovers the valuable metals.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a method for co-processing zinc leaching residues and gypsum residues, which comprises the following steps:
a. firstly, weighing two main raw materials, namely zinc leaching slag and gypsum slag containing heavy metals, wherein the addition amount of the gypsum slag accounts for 7-10% of the weight of the zinc leaching slag, fully mixing the weighed two main raw materials, and uniformly mixing to form a mixed material for later use;
b. b, adding quartz sand serving as an auxiliary material into the mixed material obtained in the step a, wherein the adding proportion of the quartz sand is according to the content of Fe element in the mixed material and SiO in the quartz sand2The proportion of the total content is Fe: SiO 22Blending 0.8-1.6, fully mixing, uniformly mixing, adding water, and granulating to obtain mixed granules;
c. b, feeding the mixed granules obtained in the step b into a furnace through a feeding port of a pyrometallurgical furnace, and simultaneously adding a reducing agent into the pyrometallurgical furnace, wherein the adding amount of the reducing agent is 6-10% of the weight of the mixed granules;
d. and then continuously adding fuel natural gas and combustion-supporting gas oxygen into the pyrometallurgical furnace, wherein the volume ratio of the natural gas to the oxygen in the amount of the gas fed into the furnace is 1: 1.5-2.5;
e. heating a pyrometallurgical furnace, controlling the furnace temperature to be 950-1150 ℃, continuously adding the mixed granules and a reducing agent into the pyrometallurgical furnace for reaction, continuously siphoning and discharging copper matte in the furnace, and continuously overflowing and discharging slag;
f. the copper matte produced by the metallurgical furnace is transferred out of the system, and valuable metals in the copper matte are further separated and recovered by adopting subsequent processes; the soot collected by the dust collection system is transferred out of the system, and further separated by adopting subsequent procedures, and valuable metals in the soot are recovered; the obtained smelting slag is taken as waste slag to be discharged out of the system; and (3) carrying out sulfur recovery or tail gas treatment on the S-containing flue gas after dust collection in the smelting furnace by adopting subsequent procedures, and then emptying.
According to the method for the synergistic treatment of the zinc leaching residues and the gypsum residues, when the zinc leaching residues and the gypsum residues are uniformly mixed and water is added for granulation in the step b, the water content of the obtained mixed granules is controlled to be 6-12%.
According to the method for the synergistic treatment of the zinc leaching residues and the gypsum residues, the reducing agent in the step c is lump coal or coke.
According to the method for the synergistic treatment of the zinc leaching residues and the gypsum residues, the pyrometallurgical furnace is a bottom-blowing furnace, a top-blowing furnace, a side-blowing furnace, a reverberatory furnace, a blast furnace, a fuming furnace or an electric furnace.
In the treatment process of the invention, the main physical and chemical changes and element flow directions in the pyrometallurgical furnace are as follows: converting Cu, part of Fe and part of S in the mixed material into a metal sulfide mixture, carrying out siphonage on the mixture in a copper matte mode through the bottom of a smelting furnace to produce, and dissolving noble metal Ag and the like in the mixed material in the copper matte mode by taking the copper matte as a trapping agent; metals Zn and Pb In the mixed material are converted into ZnO and PbO soot which is collected and recovered from a dust collecting system of the pyrometallurgical furnace, other valuable metals Ga, Ge, Cd, In and the like are enriched In the soot and are simultaneously output, and the effective recovery of various valuable metals can be realized by further processing the soot.
The pyrometallurgical furnace used in the treatment method of the present invention is not limited to bottom-blown furnaces, top-blown furnaces, side-blown furnaces, reverberatory furnaces, blast furnaces, fuming furnaces, electric furnaces and other various pyrometallurgical furnace types.
The oxygen in the furnace used in the treatment method can be provided by pure oxygen or compressed air and the like. The gas pressure suitable for the furnace type can be selected according to the different furnace inlet gas pressures of the furnace types.
The invention has the following positive beneficial effects:
1. the method carries out pyrogenic treatment on the nonferrous industrial hazardous waste zinc leaching residues, prolongs the process route, and thus effectively recovers valuable metals in the nonferrous industrial hazardous waste zinc leaching residues.
2. The invention realizes the synergistic treatment of the gypsum slag containing heavy metals by adding the zinc leaching slag, thereby effectively recovering the valuable metals in the gypsum slag, effectively utilizing the calcium component in the gypsum slag as a slagging agent and reducing the production and operation cost.
3. The treatment method realizes the harmless treatment of the industrial hazardous waste zinc leaching residues and the gypsum residues, and solves the environmental protection pressure.
4. The treatment method has the advantages of short process route and low production cost, effectively solves the problems of inventory occupation and environmental pollution of the heavy metal gypsum slag, and can improve the reasonable recovery of valuable metals.
In conclusion, the invention has obvious economic benefit and social benefit.
Fourthly, explanation of the attached drawings:
FIG. 1 is a schematic flow chart of a method for co-processing zinc leaching residues and gypsum residues.
The fifth embodiment is as follows:
the invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1:
the invention relates to a method for the cooperative treatment of zinc leaching residues and gypsum residues, which comprises the following detailed steps:
a. firstly, weighing two main raw materials of zinc leaching residues and gypsum residues containing heavy metals, wherein the zinc leaching residues are proportioned according to the amount of 2t per hour, the gypsum residues are proportioned according to the amount of 200kg per hour, the two main raw materials are fully mixed, and a mixed material is formed after uniform mixing for later use;
b. b, adding an auxiliary material quartz sand into the mixed material obtained in the step a, mixing the quartz sand according to the amount of 420kg per hour, fully mixing after mixing, adding water after uniformly mixing for granulating to obtain mixed granules, wherein the water content in the mixed granules is 8%;
c. passing the mixed granules obtained in step b through a filter
Feeding a charging port of the small bottom blowing furnace into the furnace (two sets of bottom blowing oxygen lances are configured), and simultaneously adding reducing agent lump coal into the furnace, wherein the addition amount of the lump coal is 250kg per hour;
d. then continuously adding fuel natural gas and combustion-supporting gas oxygen into the furnace, wherein the total amount of the natural gas fed into the furnace is 120Nm3Per, 300Nm total of oxygen charged into the furnace3/h；
e. Heating, controlling the furnace temperature to 1050 ℃, continuously adding various materials into the furnace for reaction, continuously siphoning and discharging copper matte in the furnace, and continuously overflowing a slag tap to continuously discharge smelting slag;
f. the produced copper matte is transferred out of the system, and a copper production system in the subsequent process is adopted to further separate and recover the metal copper; the dust collected by the dust collecting system is transferred out of the system, and further separated by adopting subsequent procedures, and valuable metals (such as Zn, Pb, Ga, Ge, Cd, In and the like) In the system are recovered; the obtained smelting slag is taken as waste slag to be discharged out of the system; and (3) carrying out sulfur recovery or tail gas treatment on the S-containing flue gas after dust collection in the smelting furnace by adopting subsequent procedures, and then emptying.
The main chemical components of the zinc leaching residue and the gypsum residue processed by the embodiment are detailed in tables 1 and 2.
TABLE 1 main chemical composition of zinc leaching residue
TABLE 2 main chemical composition of heavy metal gypsum residue
Example 2:
the invention relates to a method for the cooperative treatment of zinc leaching residues and gypsum residues, which comprises the following detailed steps:
a. firstly, weighing two main raw materials of zinc leaching residues and gypsum residues containing heavy metals, wherein the zinc leaching residues are proportioned according to the amount of 6t per hour, the gypsum residues are proportioned according to the amount of 600kg per hour, the two main raw materials are fully mixed, and a mixed material is formed after uniform mixing for later use;
b. b, adding an auxiliary material quartz sand into the mixed material obtained in the step a, mixing the quartz sand according to the amount of 1.5t per hour, fully mixing after mixing, adding water after uniformly mixing for granulating to obtain mixed granules, wherein the water content in the mixed granules is 10%;
c. passing the mixed pellets obtained in step b through a 4m stand2Feeding a charging port of a side-blown converter into the converter (provided with 6 sets of side-blown gas spray guns), and simultaneously adding reducing agent coke into the converter, wherein the adding amount of the coke is 800kg per hour;
d. then continuously adding fuel natural gas and combustion-supporting gas oxygen into the furnace, wherein the total amount of the natural gas fed into the furnace is 360Nm3Per hour, total oxygen in furnace 800Nm3/h；
e. Heating, controlling the furnace temperature to be 1100 ℃, continuously adding various materials into the furnace for reaction, continuously siphoning and discharging copper matte in the furnace, and continuously overflowing a slag tap to continuously discharge smelting slag;
f. the produced copper matte is transferred out of the system, and a copper production system in the subsequent process is adopted to further separate and recover the metal copper; the dust collected by the dust collecting system is transferred out of the system, and further separated by adopting subsequent procedures, and valuable metals (such as Zn, Pb, Ga, Ge, Cd, In and the like) In the system are recovered; the obtained smelting slag is taken as waste slag to be discharged out of the system; and (3) carrying out sulfur recovery or tail gas treatment on the S-containing flue gas after dust collection in the smelting furnace by adopting subsequent procedures, and then emptying.
The main chemical components of the zinc leaching residue and the gypsum residue processed by the embodiment are detailed in tables 3 and 4.
TABLE 3 main chemical composition of zinc leaching residue
TABLE 4 main chemical composition of heavy metal gypsum residue
Example 3:
the invention relates to a method for the cooperative treatment of zinc leaching residues and gypsum residues, which comprises the following detailed steps:
a. firstly, weighing two main raw materials of zinc leaching residues and gypsum residues containing heavy metals, wherein the zinc leaching residues are proportioned according to the amount of 2t per hour, the gypsum residues are proportioned according to the amount of 200kg per hour, the two main raw materials are fully mixed, and a mixed material is formed after uniform mixing for later use;
b. b, adding an auxiliary material quartz sand into the mixed material obtained in the step a, mixing the quartz sand according to the amount of 420kg per hour, fully mixing after mixing, adding water after uniformly mixing for granulating to obtain mixed granules, wherein the water content in the obtained mixed granules is 8%;
c. b, treating the mixed granules obtained in the step b by using a reverberatory furnace, feeding the mixed granules into the reverberatory furnace through a furnace top feeding port of the reverberatory furnace, and simultaneously adding reducing agent lump coal into the reverberatory furnace, wherein the adding amount of the lump coal is 250kg per hour;
d. continuously injecting fuel natural gas and combustion-supporting gas oxygen into the furnace through a gas burner arranged on the end wall of the reverberatory furnace, wherein the total amount of the natural gas entering the furnace is 120Nm3Per, 300Nm total of oxygen charged into the furnace3H, heating the furnace by burning natural gas;
e. controlling the furnace temperature to 1050 ℃ during normal production, adding the mixed materials into the furnace in batches or continuously for reaction, taking a smelting slag sample at the upper part of a molten pool from an observation hole arranged on a furnace wall after reacting for a period of time, judging that the reaction is finished when the zinc content of the slag is less than or equal to 2 percent, and respectively producing copper matte and smelting slag through a matte discharging port and a slag discharging port of a reverberatory furnace;
f. the produced copper matte is transferred out of the system, and a copper production system in the subsequent process is adopted to further separate and recover the metal copper; the dust collected by the dust collecting system is transferred out of the system, and further separated by adopting subsequent procedures, and valuable metals (such as Zn, Pb, Ga, Ge, Cd, In and the like) In the system are recovered; the obtained smelting slag is taken as waste slag to be discharged out of the system; and (3) carrying out sulfur recovery or tail gas treatment on the S-containing flue gas after dust collection in the smelting furnace by adopting subsequent procedures, and then emptying.
The main chemical components of the zinc leaching residue and the gypsum residue processed by the embodiment are detailed in tables 5 and 6.
TABLE 5 main chemical composition of zinc leaching residue
TABLE 6 main chemical composition of heavy metal gypsum residue
Example 4:
the invention relates to a method for the cooperative treatment of zinc leaching residues and gypsum residues, which comprises the following detailed steps:
a. firstly, weighing two main raw materials of zinc leaching residues and gypsum residues containing heavy metals, wherein the zinc leaching residues are proportioned according to the amount of 2t per hour, the gypsum residues are proportioned according to the amount of 200kg per hour, the two main raw materials are fully mixed, and a mixed material is formed after uniform mixing for later use;
b. b, adding an auxiliary material quartz sand into the mixed material obtained in the step a, mixing the quartz sand according to the amount of 420kg per hour, fully mixing after mixing, adding water after uniformly mixing for granulating to obtain mixed granules, wherein the water content in the obtained mixed granules is 6%;
c. passing the mixed pellets obtained in step b through a 4m stand2Treating by a small fuming furnace, feeding the mixture into the furnace in batches through a cold material feeding port of the fuming furnace, and simultaneously adding reducing agent lump coal into the furnace, wherein the adding amount of the lump coal is 250kg per hour;
d. the natural gas and the combustion-supporting gas oxygen are fed into the furnace through a tuyere arranged at the bottom of the fuming furnace, and the total feed natural gas is 120Nm3Per, 300Nm total of oxygen charged into the furnace3/h；
e. Natural gas and oxygen are combusted in the furnace for heat supply, the temperature of the furnace is controlled to be 1000 ℃, after single furnace materials completely react in the furnace, hot liquid in the furnace is discharged to a steamed stuffed bun or a groove through a discharge hole of the fuming furnace at the same time for sedimentation and slow cooling, and copper matte and smelting slag are manually separated after cooling and demoulding; controlling the time point when the materials completely react in the furnace according to the corresponding relation between the blowing time of each furnace material and the zinc content of the smelting slag by exploration, wherein the zinc content of the smelting slag is controlled to be less than or equal to 2 percent;
f. the produced copper matte is transferred out of the system, and a copper production system in the subsequent process is adopted to further separate and recover the metal copper; the dust collected by the dust collecting system is transferred out of the system, and further separated by adopting subsequent procedures, and valuable metals (such as Zn, Pb, Ga, Ge, Cd, In and the like) In the system are recovered; the obtained smelting slag is taken as waste slag to be discharged out of the system; and (3) carrying out sulfur recovery or tail gas treatment on the S-containing flue gas after dust collection in the smelting furnace by adopting subsequent procedures, and then emptying.
The main chemical components of the zinc leaching residue and the gypsum residue processed by the embodiment are shown in tables 7 and 8.
TABLE 7 main chemical composition of zinc leaching residue
TABLE 8 main chemical composition of heavy metal gypsum residue
Claims (2)
1. A method for the cooperative treatment of zinc leaching residues and gypsum residues is characterized by comprising the following steps:
a. firstly, weighing two main raw materials, namely zinc leaching slag and gypsum slag containing heavy metals, wherein the addition amount of the gypsum slag accounts for 7-10% of the weight of the zinc leaching slag, fully mixing the weighed two main raw materials, and uniformly mixing to form a mixed material for later use;
b. b, adding quartz sand serving as an auxiliary material into the mixed material obtained in the step a, wherein the adding proportion of the quartz sand is according to the content of Fe element in the mixed material and SiO in the quartz sand2The proportion of the total content is Fe: SiO 22Mixing materials according to the ratio of 0.8 to 1.6, fully mixing the materials, uniformly mixing the materials, adding water, and granulating to obtain mixed granules;
when water is added for granulation after uniform mixing, controlling the water content of the obtained mixed granules to be 6-12%;
c. b, feeding the mixed granules obtained in the step b into a furnace through a feeding port of a pyrometallurgical furnace, and simultaneously adding a reducing agent into the pyrometallurgical furnace, wherein the adding amount of the reducing agent is 6-10% of the weight of the mixed granules;
the reducing agent is lump coal or coke;
d. and then continuously adding fuel natural gas and combustion-supporting gas oxygen into the pyrometallurgical furnace, wherein the volume ratio of the natural gas to the oxygen in the amount of the gas fed into the furnace is 1: 1.5-2.5;
e. heating a pyrometallurgical furnace, controlling the furnace temperature to be 950-1150 ℃, continuously adding the mixed granules and a reducing agent into the pyrometallurgical furnace for reaction, continuously siphoning and discharging copper matte in the furnace, and continuously overflowing and discharging slag;
f. the copper matte produced by the metallurgical furnace is transferred out of the system, and valuable metals in the copper matte are further separated and recovered by adopting subsequent processes; the soot collected by the dust collection system is transferred out of the system, and further separated by adopting subsequent procedures, and valuable metals in the soot are recovered; the obtained smelting slag is taken as waste slag to be discharged out of the system; and (3) carrying out sulfur recovery or tail gas treatment on the S-containing flue gas after dust collection in the smelting furnace by adopting subsequent procedures, and then emptying.
2. The method for the co-processing of zinc leaching slag and gypsum slag according to claim 1, wherein: the pyrometallurgical furnace is a bottom-blown furnace, a top-blown furnace, a side-blown furnace, a reverberatory furnace, a blast furnace, a fuming furnace or an electric furnace.
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| CN111826522A (en) * | 2020-06-24 | 2020-10-27 | 济源豫光有色冶金设计研究院有限公司 | Method for treating electroplating sludge by adopting gypsum residues |
| CN114540628B (en) * | 2022-01-20 | 2023-11-14 | 云南云铜锌业股份有限公司 | Method for treating zinc-impregnated slag, zinc smelting gypsum slag and blast furnace gas ash |
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| JP5049311B2 (en) * | 2009-03-31 | 2012-10-17 | パンパシフィック・カッパー株式会社 | Method and system for dry treatment of converter slag in copper smelting |
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| CN104404259B (en) * | 2014-11-16 | 2017-01-04 | 中南大学 | The method that Cu, Ni and Co metallurgical slag reclaims valuable metal with gypsum tailings cooperative disposal |
| CN104911365B (en) * | 2015-04-14 | 2018-01-09 | 中南大学 | A kind of method that cadmia reduction melting prepares low phosphor iron |
| CN109811143A (en) * | 2019-01-08 | 2019-05-28 | 河套学院 | A kind of method of nickel sludge, rich scum, cullet and gypsum tailings cooperative disposal |
| CN110055412A (en) * | 2019-04-28 | 2019-07-26 | 广东飞南资源利用股份有限公司 | A kind of method of cupric tin electroplating sludge and desulfurized gesso of flue gas slag cooperative disposal and synthetical recovery copper and tin |
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