CN113462887A - Method for treating sulfur-containing and multi-metal concentrate - Google Patents
Method for treating sulfur-containing and multi-metal concentrate Download PDFInfo
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- CN113462887A CN113462887A CN202110739556.2A CN202110739556A CN113462887A CN 113462887 A CN113462887 A CN 113462887A CN 202110739556 A CN202110739556 A CN 202110739556A CN 113462887 A CN113462887 A CN 113462887A
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000012141 concentrate Substances 0.000 title claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011593 sulfur Substances 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052737 gold Inorganic materials 0.000 claims abstract description 19
- 239000010931 gold Substances 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 230000001180 sulfating effect Effects 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 145
- 238000010521 absorption reaction Methods 0.000 claims description 134
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 133
- 239000002253 acid Substances 0.000 claims description 102
- 239000000428 dust Substances 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000746 purification Methods 0.000 claims description 17
- 239000002893 slag Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 14
- 238000005554 pickling Methods 0.000 claims description 12
- 239000003595 mist Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- 239000002918 waste heat Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000005864 Sulphur Substances 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 238000005507 spraying Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Classifications
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- 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
- C22B11/02—Obtaining noble metals by dry 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
- 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
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
-
- 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
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treating Waste Gases (AREA)
Abstract
The method can effectively recover microelements such as gold, silver, copper and the like while efficiently recovering sulfur elements by sulfating and roasting the sulfur-containing and multi-metal concentrate, so that the method has the characteristic of high multi-element recovery rate.
Description
Technical Field
The disclosure relates to the technical field of metallurgy, in particular to a method for treating sulfur-containing and multi-metal concentrate.
Background
Sulphur-containing and polymetallic concentrates contain a large amount of sulphur and a small amount of other metals such as copper, gold or silver, and in order to increase the resource utilization, these concentrates can be subjected to multi-element comprehensive recovery to produce sulphuric acid and metal products such as copper, gold and silver.
However, in the related art, when the sulfur-containing and multi-metal concentrate is subjected to multi-element comprehensive recovery, the recovery rate of each element is still low.
Disclosure of Invention
The purpose of this disclosure is to provide a method for the treatment of sulphur-containing and polymetallic concentrates, which allows simple and efficient recovery of sulphur, copper, gold or silver elements from the concentrate.
In order to achieve the above object, the present disclosure provides a method for treating a sulfur-containing and polymetallic concentrate, the method comprising:
s01, mixing sulfur-containing and multi-metal concentrate with water and then carrying out size mixing treatment to obtain ore concentrate pulp with the weight percentage concentration of the concentrate being 65% -70%, wherein in the sulfur-containing and multi-metal concentrate, the content of sulfur is not lower than 35 wt%, the content of copper is not lower than 1 wt%, the grade of gold is not lower than 2g/t, and the grade of silver is not lower than 80 g/t;
s02, feeding the concentrate ore pulp into a fluidized bed roaster to perform sulfating roasting to obtain roasting furnace gas and roasting furnace slag, wherein the temperature of sulfating roasting is 575-625 ℃;
s03, carrying out dust removal, purification and dry absorption treatment on the roasting furnace gas, and then carrying out five-stage conversion treatment of 3+2 twice to obtain a sulfuric acid product;
s04, carrying out acid washing treatment on the roasting furnace slag to obtain acid washing filtrate and acid washing filter residue;
and S05, extracting and electrodepositing the pickling filtrate to obtain solid copper, and carrying out cyaniding leaching and zinc powder replacement treatment on the pickling filter residue to obtain solid gold and solid silver.
Optionally, in step S03, after performing dust removal, purification, and dry absorption treatment on the roasting furnace gas, performing five stages of conversion treatment of "3 + 2" twice to obtain a sulfuric acid product, including:
s031, after the temperature of the roasting furnace gas is reduced to 375-425 ℃, sending the roasting furnace gas into a cyclone dust collector and/or an electric dust collector for dust removal treatment to obtain dust removal furnace gas, wherein the temperature of the dust removal furnace gas is 280-300 ℃, and the dust content is 290-310 mg/m3；
S032, sequentially feeding the dust removal furnace gas into an inner spray venturi tube and a filler cooling tower for closed acid cleaning purification treatment, and then feeding the dust removal furnace gas into an electric demister for demisting treatment to obtain the purified furnace gas, wherein the purified showering acid liquid is dilute sulfuric acid with the weight percentage concentration of 1-3%, the temperature of the purified furnace gas is not higher than 40 ℃, and the acid mist content is less than 0.03g/Nm3；
S033, mixing the purified furnace gas with air, feeding the mixture into a drying tower, and drying the mixture by using a drying and sprinkling acid liquor to obtain dry suction furnace gas, wherein the drying and sprinkling acid liquor is sulfuric acid with the weight percentage concentration of 93%, and SO is contained in the dry suction furnace gas2The volume percentage concentration of (A) is 7-10%, and the water content is 0.1g/Nm3The following;
s034, feeding the dry absorption furnace gas into a conversion tower to perform five-stage (3 + 2) twice conversion treatment and absorption treatment in an absorption tower to obtain a sulfuric acid product.
Optionally, in step S031, the roasting furnace gas is sent into a waste heat boiler to reduce the temperature of the roasting furnace gas to 375-425 ℃,
when the temperature of the roasting furnace gas is reduced, the method also comprises the operation of collecting saturated steam generated by the waste heat boiler.
Optionally, the internal spray venturi has a first circulation tank, the packed cooling tower has a second circulation tank, and in step S032, when performing the closed pickling purification process, the method further includes:
and filtering the purified waste acid liquor generated by the closed pickling purification treatment, and then sending the filtered waste acid liquor into the first circulation tank and/or the second circulation tank for recycling.
Optionally, in step S034, the feeding the dry absorber gas into a conversion tower to perform five stages of "3 + 2" twice conversion treatment and an absorption treatment in an absorption tower to obtain a sulfuric acid product, including:
s341, sending the dry absorption furnace gas into a heat exchanger for first heat exchange treatment to obtain first heat exchange furnace gas with the temperature of 400-450 ℃;
s342, sending the first heat exchange furnace gas into a first catalyst layer, a second catalyst layer and three catalyst layers of a converter for first conversion, and then sending the first heat exchange furnace gas into a heat exchanger for second heat exchange treatment to obtain second heat exchange furnace gas with the temperature of 150-200 ℃;
s343, feeding the second heat exchange furnace gas into a first absorption tower for absorption treatment to obtain a first absorption liquid and absorption furnace gas;
s344, feeding the absorption furnace gas into a heat exchanger for third heat exchange treatment to obtain third heat exchange furnace gas with the temperature of 370-420 ℃;
s345, sending the third heat exchange furnace gas into a fourth section catalyst layer and a fifth section catalyst layer of the converter for second conversion, and then sending the third heat exchange furnace gas into the converter for fourth heat exchange treatment to obtain fourth heat exchange furnace gas with the temperature of 130-170 ℃;
s346, sending the fourth heat exchange furnace gas into a second absorption tower for absorption treatment to obtain a second absorption liquid and tail gas;
s347, processing the first absorption liquid and/or the second absorption liquid to obtain a sulfuric acid product.
Optionally, the first absorption tower and the second absorption tower are communicated with a third circulation tank,
in step S343, the processing of the first absorption liquid and/or the second absorption liquid to obtain a sulfuric acid product includes:
and (3) feeding the first absorption liquid and/or the second absorption liquid into the third circulation tank, adding water for dilution to obtain diluted sulfuric acid with the weight percentage concentration of 93-98%, and taking part of the diluted sulfuric acid as the sulfuric acid product.
Optionally, the drying tower has a fourth circulation tank communicating with the third circulation tank, the first absorption tower, and the second absorption tower,
in step S033, when performing the drying process, the method further includes:
and (3) sending the dried waste acid liquor generated by the drying treatment into the fourth circulating tank, mixing the dried waste acid liquor with part of the diluted sulfuric acid from the third circulating tank to obtain sulfuric acid with the weight percentage concentration of 93%, and recycling the sulfuric acid as the dried showered acid liquor.
Optionally, when the absorption treatment is performed in step S343 and/or S346, the absorption showering acid solution used is sulfuric acid with a weight percentage concentration of 93% to 98%, and the method further includes:
and sending part of the diluted sulfuric acid in the third circulating tank and/or the redundant sulfuric acid with the weight percentage concentration of 93% in the fourth circulating tank into the first absorption tower and/or the second absorption tower to be used as the absorption showering acid liquid.
Optionally, in step S04, performing acid washing treatment on the baking slag by using a thickener and a horizontal tape filter to obtain the acid washing filtrate and the acid washing filter residue.
Optionally, in step S05, the extraction includes two stages of counter-current extraction, one stage of stripping, and organic phase recycle.
Through the technical scheme, in the method, sulfur-containing and multi-metal concentrate is sulfated and roasted, so that the trace elements such as gold, silver, copper and the like can be effectively recovered while the sulfur element is efficiently recovered, and therefore, the method has the characteristic of high multi-element recovery rate.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a method for treating sulfur-containing and multi-metal concentrates, the method comprising: s01, mixing sulfur-containing and multi-metal concentrate with water and then carrying out size mixing treatment to obtain ore concentrate pulp with the weight percentage concentration of the concentrate being 65% -70%, wherein in the sulfur-containing and multi-metal concentrate, the content of sulfur is not lower than 35 wt%, the content of copper is not lower than 1 wt%, the grade of gold is not lower than 2g/t, and the grade of silver is not lower than 80 g/t; s02, feeding the concentrate ore pulp into a fluidized bed roaster to perform sulfating roasting to obtain roasting furnace gas and roasting furnace slag, wherein the temperature of sulfating roasting is 575-625 ℃; s03, carrying out dust removal, purification and dry absorption treatment on the roasting furnace gas, and then carrying out five-stage conversion treatment of 3+2 twice to obtain a sulfuric acid product; s04, carrying out acid washing treatment on the roasting furnace slag to obtain acid washing filtrate and acid washing filter residue; and S05, extracting and electrodepositing the pickling filtrate to obtain solid copper, and carrying out cyaniding leaching and zinc powder replacement treatment on the pickling filter residue to obtain solid gold and solid silver.
In particular, the sulphur-containing and polymetallic concentrate may be, for example, a sulphur concentrate or a copper concentrate. Through the technical scheme, in the method, sulfur-containing and multi-metal concentrate is sulfated and roasted, so that the trace elements such as gold, silver, copper and the like can be effectively recovered while the sulfur element is efficiently recovered, and therefore, the method has the characteristic of high multi-element recovery rate.
According to the disclosure, in step S03, the roasting furnace gas is subjected to dust removal, purification and dry absorption treatmentAnd carrying out five stages of '3 + 2' and twice conversion treatment to obtain a sulfuric acid product, wherein the five stages of '3 + 2' and twice conversion treatment can comprise: s031, after the temperature of the roasting furnace gas is reduced to 375-425 ℃, sending the roasting furnace gas into a cyclone dust collector and/or an electric dust collector for dust removal treatment to obtain dust removal furnace gas, wherein the temperature of the dust removal furnace gas is 280-300 ℃, and the dust content is 290-310 mg/m3(ii) a S032, sequentially feeding the dust removal furnace gas into an inner spray venturi tube and a filler cooling tower for closed acid cleaning purification treatment, and then feeding the dust removal furnace gas into an electric demister for demisting treatment to obtain the purified furnace gas, wherein the purified showering acid liquid is dilute sulfuric acid with the weight percentage concentration of 1-3%, the temperature of the purified furnace gas is not higher than 40 ℃, and the acid mist content is less than 0.03g/Nm3(ii) a S033, mixing the purified furnace gas with air, feeding the mixture into a drying tower, and drying the mixture by using a drying and sprinkling acid liquor to obtain dry suction furnace gas, wherein the drying and sprinkling acid liquor is sulfuric acid with the weight percentage concentration of 93%, and SO is contained in the dry suction furnace gas2The volume percentage concentration of (A) is 7-10%, and the water content is 0.1g/Nm3The following; s034, feeding the dry absorption furnace gas into a conversion tower to perform five-stage (3 + 2) twice conversion treatment and absorption treatment in an absorption tower to obtain a sulfuric acid product.
According to the present disclosure, in order to further increase the resource utilization rate, increase the product diversity, and improve the economic benefit, in step S031, the roasting furnace gas may be sent into a waste heat boiler, so as to implement the operation of reducing the temperature of the roasting furnace gas to 375-425 ℃, and meanwhile, when the roasting furnace gas is subjected to cooling treatment, the saturated steam generated by the waste heat boiler is collected. In the present disclosure, by introducing the exhaust-heat boiler, not only can the effective cooling be carried out to the roasting furnace gas, but also saturated steam can be generated for sale or use.
According to the present disclosure, the internal spray venturi may have a first circulation tank, the packed cooling tower may have a second circulation tank, and in the step S032, when the closed pickling purification process is performed, the method may further include: and filtering the purified waste acid liquor generated by the closed pickling purification treatment, and then sending the filtered waste acid liquor into the first circulation tank and/or the second circulation tank for recycling.
In the disclosure, in step S032, the dust removing furnace gas from the electric dust remover may be sent to the internal spraying venturi tube, a part of the mineral dust is removed by the purifying and showering acid solution, and then sent to the packed cooling tower to further remove harmful substances such as mineral dust, arsenic and fluorine, and the gas temperature is reduced to below 40 ℃, and then sent to the electric mist eliminator to remove the acid mist, so as to obtain the product with the acid mist content not greater than 0.03g/Nm3The dust removal furnace gas.
The internal spraying venturi tube can adopt adiabatic evaporation, a circulating acid system is not provided with a cooler, and heat is taken away by a dilute acid cooler of a rear filler cooling tower. The purified waste acid liquid in the inner spraying venturi tube flows out and is filtered by a Sieen filter, clear liquid returns to a first circulating groove of the venturi tube and enters a circulating system for recycling, a part of circulating liquid is pumped into a degassing tower through a circulating pump, and the clear liquid after desorption is sent into a dilute acid storage tank through the circulating pump of the degassing tower and is sent into a phosphate fertilizer factory for self-use as a dilute acid byproduct. And discharging the sludge filtered by the Sien filter into an acid ditch, and neutralizing the sludge by using lime and then sending the neutralized sludge into a slag yard.
The filler cooling tower can be a tower-groove integrated structure, and the purified waste acid liquid flows out from a second circulating groove at the bottom of the cooling tower and is pumped into the cooling tower through a circulating pump of the cooling tower for recycling. The increased circulating acid is connected in series with the first circulating groove of the venturi tube, and the heat of the whole purification system is taken away by the dilute acid plate cooler. Meanwhile, in the disclosure, considering that high-temperature furnace gas influences purification equipment due to sudden power failure, a high-level water tank can be arranged above the venturi, and downstream equipment and pipelines are protected by interlocking the air temperature at the outlet of the venturi and the water outlet valve of the high-level water tank of the venturi.
According to the disclosure, in step S034, the feeding the dry absorber gas into a conversion tower for "3 + 2" five-stage twice conversion treatment and an absorption treatment in an absorption tower to obtain a sulfuric acid product may include: s341, sending the dry absorption furnace gas into a heat exchanger for first heat exchange treatment to obtain first heat exchange furnace gas with the temperature of 400-450 ℃; s342, sending the first heat exchange furnace gas into a first catalyst layer, a second catalyst layer and three catalyst layers of a converter for first conversion, and then sending the first heat exchange furnace gas into a heat exchanger for second heat exchange treatment to obtain second heat exchange furnace gas with the temperature of 150-200 ℃; s343, feeding the second heat exchange furnace gas into a first absorption tower for absorption treatment to obtain a first absorption liquid and absorption furnace gas; s344, feeding the absorption furnace gas into a heat exchanger for third heat exchange treatment to obtain third heat exchange furnace gas with the temperature of 370-420 ℃; s345, sending the third heat exchange furnace gas into a fourth section catalyst layer and a fifth section catalyst layer of the converter for second conversion, and then sending the third heat exchange furnace gas into the converter for fourth heat exchange treatment to obtain fourth heat exchange furnace gas with the temperature of 130-170 ℃; s346, sending the fourth heat exchange furnace gas into a second absorption tower for absorption treatment to obtain a second absorption liquid and tail gas; s347, processing the first absorption liquid and/or the second absorption liquid to obtain a sulfuric acid product.
According to the disclosure, the first absorption tower and the second absorption tower may be in communication with a third circulation tank, and the processing of the first absorption liquid and/or the second absorption liquid to obtain a sulfuric acid product in step S343 may include: and (3) feeding the first absorption liquid and/or the second absorption liquid into the third circulation tank, adding water for dilution to obtain diluted sulfuric acid with the weight percentage concentration of 93-98%, and taking part of the diluted sulfuric acid as the sulfuric acid product.
According to the present disclosure, the drying tower may have a fourth circulation tank, and the fourth circulation tank may be in communication with the third circulation tank, the first absorption tower, and the second absorption tower, and in step S033, the method may further include, when performing the drying process: and (3) sending the dried waste acid liquor generated by the drying treatment into the fourth circulating tank, mixing the dried waste acid liquor with part of the diluted sulfuric acid from the third circulating tank to obtain sulfuric acid with the weight percentage concentration of 93%, and recycling the sulfuric acid as the dried showered acid liquor.
According to the disclosure, when the absorption treatment is performed in step S343 and/or S346, the absorption showering acid solution used may be sulfuric acid with a weight percentage concentration of 93% to 98%, and the method may further include: and sending part of the diluted sulfuric acid in the third circulating tank and/or the redundant sulfuric acid with the weight percentage concentration of 93% in the fourth circulating tank into the first absorption tower and/or the second absorption tower to be used as the absorption showering acid liquid.
Specifically, the drying tower may be a packed tower with a wire mesh demister on top. The tower is internally showered with sulfuric acid with the weight percentage concentration of 93 percent, the sulfuric acid absorbs water during the drying process and flows into a fourth circulating tank of the drying tower from the tower bottom after being diluted, and the diluted sulfuric acid which is connected in series from an outlet of an acid cooler of the absorption tower is distributed into the fourth circulating tank so as to maintain the concentration of the circulating acid in the fourth circulating tank. And pumping the circulating acid in the fourth circulating tank into a drying tower acid cooler through a drying tower circulating pump for cooling, and then entering the drying tower for recycling. And the increased 93 percent of acid is totally connected into the first absorption tower in series through a drying tower circulating pump to be used as absorption showering acid liquid.
The first absorption tower and the second absorption tower are both packed towers, share a third circulation tank, absorb the sprayed acid solution with the weight percentage concentration of 93-98%, and absorb SO3And the first absorption liquid and/or the second absorption liquid flow into a third circulation tank to be mixed, then water is added for adjustment to obtain diluted sulfuric acid with the weight percentage concentration of 93-98%, and the diluted sulfuric acid is pumped into an absorption tower acid cooler through an absorption tower circulation pump for cooling and then enters an absorption tower for recycling. And one part of the increased diluted sulfuric acid is connected in series with a fourth circulating tank of the drying tower, and the other part of the diluted sulfuric acid is used as finished acid and is directly input into a finished acid storage after passing through an underground tank.
According to the disclosure, in step S04, a thickener and a horizontal tape filter may be used to perform acid washing treatment on the roasting slag, so as to obtain the acid washing filtrate and the acid washing residue. Particularly, the washing rate of copper can be improved by utilizing the repeated cleaning action of the horizontal adhesive tape type filter, and the continuous stable convenient operation of production can be ensured by selecting the horizontal adhesive tape type filter.
According to the present disclosure, in step S05, the extraction may include two stages of counter-current extraction, one stage of stripping, and organic phase recycle. Specifically, LX-948N is adopted to extract and enrich the copper-containing acid washing filtrate, and the enriched copper-containing feed liquid is directly electrodeposited to produce cathode copper.
Aiming at the characteristics of more fine particles, high viscosity and the like of the roasted furnace slag, the traditional cyaniding leaching-solid-liquid separation-zinc powder replacement process can be adopted when the gold and silver extraction is carried out on the acid washing filter residue, and the process has the characteristics of high maturity, simple operation and the like.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The raw materials, reagents, instruments and equipment involved in the examples of the present disclosure may be purchased without specific reference.
Examples
The sulfur concentrate is subjected to multi-element comprehensive recovery treatment according to the following method.
(1) Sending sulfur concentrate (the sulfur content is 37.20 wt%, the copper content is 1.46 wt%, the gold grade is 2.47g/t, and the silver grade is 84.65g/t) to a pulp adjusting tank by using a bridge grab bucket, adding water to prepare concentrate pulp with the concentrate weight percentage concentration of 65-70%, vibrating, screening, removing impurities, sending into an intermediate storage tank, and sending into a pulp storage tank of a roasting section by using a hose pump;
(2) sending the concentrate ore pulp in the pulp storage tank into an ore pulp distribution tank by using a hose pump, spraying the concentrate ore pulp into a fluidized bed furnace by using compressed air through a spray gun, and carrying out sulfating roasting at the temperature of 600 ℃ to obtain roasting furnace gas and roasting furnace slag;
(3) reducing the temperature of the roasting furnace gas to 400 ℃ by utilizing a waste heat boiler, then sending the roasting furnace gas into a cyclone dust collector and an electric dust collector for further cooling and dedusting to obtain dedusting furnace gas, wherein the temperature of the dedusting furnace gas is about 300 ℃, and the dust content is about 300mg/m3；
(4) Feeding the dust-removing furnace gas flowing out of electric dust remover into internal spray venturi tube, removing a part of mine dust by using dilute sulfuric acid whose weight percentage concentration is about 2%, then feeding the ore dust into filler cooling tower to further remove harmful substances of mine dust, arsenic and fluorine, etc. so as to make furnace gas temp. be reduced to below 40 deg.C, then removing acid mist by using electric demister to obtain acid mist content<0.03g/Nm3The purified furnace gas of (1);
(5) mixing the purified furnace gas with a certain amount of air, and controlling SO2The volume percentage concentration of the gas is about 8.5 percent, and then the gas is sent into a drying tower for dry absorption treatment to obtain dry absorption furnace gas, wherein,the water content in the dry absorption furnace gas is about 0.1g/Nm3；
(6) The dry absorption furnace gas is defoamed by a metal wire mesh demister of a drying tower, enters a sulfur dioxide blower for boosting pressure, then is subjected to heat exchange to about 430 ℃ by a heat exchanger III and a heat exchanger I, and is sent to a converter for first conversion, wherein the first conversion is subjected to heat exchange by a catalyst layer I, a catalyst layer II and a catalyst layer III respectively, the conversion rate reaches 92.4%, the furnace gas after the reaction heat exchange is cooled to about 180 ℃, and enters a first absorption tower for absorbing SO3Then, after heat exchange by a V-th heat exchanger, a IV-th heat exchanger and a II-th heat exchanger respectively, the gas enters a fourth section and a fifth section of the converter for secondary conversion, the total conversion rate reaches 99.85 percent, the temperature of secondary conversion gas is reduced to about 156 ℃ after heat exchange by a V-th heat exchanger, and the gas enters a second absorption tower for absorbing SO3；
The first absorption tower and the second absorption tower are both packed towers, the first absorption tower and the second absorption tower share one acid circulation tank, and the showering acid is sulfuric acid with the weight percentage concentration of 98 percent and absorbs SO3The acid flows into an absorption tower circulating groove from the bottom of the tower to be mixed, water is added to adjust the acid concentration to 98%, then the acid is pumped into an absorption tower acid cooler through an absorption tower circulating pump to be cooled and then enters an absorption tower to be recycled, 98% of the increased sulfuric acid is partially connected in series with a drying tower circulating groove, and the acid serving as a finished product is directly input into a finished product acid warehouse after passing through an underground groove; the second absorption tower absorbs SO3Demisting the tail gas obtained by the tail gas treatment by a fiber demister at the top of the tower, and discharging the tail gas through a chimney with the size of 60m after reaching the standard;
(7) respectively feeding the roasting slag obtained in the step (2) and high-temperature mine dust from a waste heat boiler and a cyclone dust collector into a cooling roller through an ash discharge valve for cooling, and then carrying out acid washing treatment to obtain acid washing filtrate and acid washing filter residue;
(8) LX-948N is adopted to extract and enrich the acid washing filtrate, and the enriched copper-containing feed liquid is directly electrodeposited to produce cathode copper; and extracting gold and silver from the acid-washed filter residue by adopting the traditional cyaniding leaching-solid-liquid separation-zinc powder replacement process.
Through measurement and calculation, in the embodiment, the recovery rate of the sulfur element is 99.1%, the recovery rate of the copper is 80.3%, the recovery rate of the gold is 65.9%, and the recovery rate of the silver is 90.7%.
Comparative example
The sulfur concentrate is subjected to multi-element comprehensive recovery treatment according to the following method.
(1) Continuously and uniformly feeding sulfur concentrate (the sulfur content is 37.20 wt%, the copper content is 1.46 wt%, the gold grade is 2.47g/t, and the silver grade is 84.65g/t) from a feeding hopper of a roasting furnace to a fluidized bed roaster through a belt feeder for oxidizing roasting to obtain roasting furnace gas and roasting furnace slag;
(2) reducing the temperature of the roasting furnace gas to 400 ℃ by utilizing a waste heat boiler, then sending the roasting furnace gas into a cyclone dust collector and an electric dust collector for further cooling and dedusting to obtain dedusting furnace gas, wherein the temperature of the dedusting furnace gas is about 300 ℃, and the dust content is about 300mg/m3；
(3) Feeding the dust-removing furnace gas flowing out of electric dust remover into internal spray venturi tube, removing a part of mine dust by using dilute sulfuric acid whose weight percentage concentration is about 2%, then feeding the ore dust into filler cooling tower to further remove harmful substances of mine dust, arsenic and fluorine, etc. so as to make furnace gas temp. be reduced to below 40 deg.C, then removing acid mist by using electric demister to obtain acid mist content<0.03g/Nm3The purified furnace gas of (1);
(4) mixing the purified furnace gas with a certain amount of air, and controlling SO2Is about 8.5 percent, and then is sent into a drying tower for dry absorption treatment to obtain dry absorption furnace gas, wherein the water content in the dry absorption furnace gas is about 0.1g/Nm3；
(5) The dry absorption furnace gas is defoamed by a metal wire mesh demister of a drying tower, enters a sulfur dioxide blower for boosting pressure, then is subjected to heat exchange to about 430 ℃ by a heat exchanger III and a heat exchanger I, and is sent to a converter for first conversion, wherein the first conversion is subjected to heat exchange by a catalyst layer I, a catalyst layer II and a catalyst layer III respectively, the conversion rate reaches 92.1%, the furnace gas after the reaction heat exchange is cooled to about 180 ℃, and enters a first absorption tower for absorbing SO3Then, after heat exchange by a V-th heat exchanger, a IV-th heat exchanger and a II-th heat exchanger respectively, the gas enters a fourth section and a fifth section of the converter for secondary conversion, the total conversion rate reaches 99.65 percent, the temperature of secondary conversion gas is reduced to about 156 ℃ after heat exchange by a V-th heat exchanger, and the gas enters a second absorption tower for absorbing SO3；
The first absorption tower and the second absorption tower are both packed towers, the first absorption tower and the second absorption tower share one acid circulating tank, and the showering acid is 98% sulfuric acid and absorbs SO3The acid flows into an absorption tower circulating groove from the bottom of the tower to be mixed, water is added to adjust the acid concentration to 98%, then the acid is pumped into an absorption tower acid cooler through an absorption tower circulating pump to be cooled and then enters an absorption tower to be recycled, 98% of the increased sulfuric acid is partially connected in series with a drying tower circulating groove, and the acid serving as a finished product is directly input into a finished product acid warehouse after passing through an underground groove; the second absorption tower absorbs SO3Demisting the tail gas obtained by the tail gas treatment by a fiber demister at the top of the tower, and discharging the tail gas through a chimney with the size of 60m after reaching the standard;
(6) respectively feeding the roasting slag obtained in the step (2) and high-temperature mine dust from a waste heat boiler and a cyclone dust collector into a cooling roller through an ash discharge valve for cooling, and then carrying out acid washing treatment to obtain acid washing filtrate and acid washing filter residue;
(7) LX-948N is adopted to extract and enrich the acid washing filtrate, and the enriched copper-containing feed liquid is directly electrodeposited to produce cathode copper; and extracting gold and silver from the acid-washed filter residue by adopting the traditional cyaniding leaching-solid-liquid separation-zinc powder replacement process.
According to measurement, in the comparative example, the recovery rate of the sulfur element is 98.8%, the recovery rate of the copper is 50.7%, the recovery rate of the gold is 55.7%, and the recovery rate of the silver is 72.9%.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. A method for treating a sulfur-containing and multi-metal concentrate, the method comprising:
s01, mixing sulfur-containing and multi-metal concentrate with water and then carrying out size mixing treatment to obtain ore concentrate pulp with the weight percentage concentration of the concentrate being 65% -70%, wherein in the sulfur-containing and multi-metal concentrate, the content of sulfur is not lower than 35 wt%, the content of copper is not lower than 1 wt%, the grade of gold is not lower than 2g/t, and the grade of silver is not lower than 80 g/t;
s02, feeding the concentrate ore pulp into a fluidized bed roaster to perform sulfating roasting to obtain roasting furnace gas and roasting furnace slag, wherein the temperature of sulfating roasting is 575-625 ℃;
s03, carrying out dust removal, purification and dry absorption treatment on the roasting furnace gas, and then carrying out five-stage conversion treatment of 3+2 twice to obtain a sulfuric acid product;
s04, carrying out acid washing treatment on the roasting furnace slag to obtain acid washing filtrate and acid washing filter residue;
and S05, extracting and electrodepositing the pickling filtrate to obtain solid copper, and carrying out cyaniding leaching and zinc powder replacement treatment on the pickling filter residue to obtain solid gold and solid silver.
2. The method of claim 1,
in step S03, after performing dust removal, purification, and dry absorption treatment on the roasting furnace gas, performing five stages of conversion treatment of "3 + 2" twice to obtain a sulfuric acid product, including:
s031, after the temperature of the roasting furnace gas is reduced to 375-425 ℃, sending the roasting furnace gas into a cyclone dust collector and/or an electric dust collector for dust removal treatment to obtain dust removal furnace gas, wherein the temperature of the dust removal furnace gas is 280-300 ℃, and the dust content is 290-310 mg/m3；
S032, sequentially feeding the dust removal furnace gas into an internal spray venturi tube and a filler cooling tower for closed acid cleaning and purification treatment, and then feeding the dust removal furnace gas into an electric demister for demisting treatment to obtain purified furnace gas, wherein the purified furnace gas is usedThe acid solution is diluted sulfuric acid with the weight percentage concentration of 1-3%, the temperature of the purified furnace gas is not higher than 40 ℃, and the acid mist content is less than 0.03g/Nm3；
S033, mixing the purified furnace gas with air, feeding the mixture into a drying tower, and drying the mixture by using a drying and sprinkling acid liquor to obtain dry suction furnace gas, wherein the drying and sprinkling acid liquor is sulfuric acid with the weight percentage concentration of 93%, and SO is contained in the dry suction furnace gas2The volume percentage concentration of (A) is 7-10%, and the water content is 0.1g/Nm3The following;
s034, feeding the dry absorption furnace gas into a conversion tower to perform five-stage (3 + 2) twice conversion treatment and absorption treatment in an absorption tower to obtain a sulfuric acid product.
3. The method of claim 2,
in step S031, the roasting furnace gas is sent into a waste heat boiler to reduce the temperature of the roasting furnace gas to 375-425 ℃,
when the temperature of the roasting furnace gas is reduced, the method also comprises the operation of collecting saturated steam generated by the waste heat boiler.
4. The method of claim 2,
the inner spray venturi has a first circulation tank, the packed cooling tower has a second circulation tank,
in step S032, when the closed pickling purification treatment is performed, the method further includes:
and filtering the purified waste acid liquor generated by the closed pickling purification treatment, and then sending the filtered waste acid liquor into the first circulation tank and/or the second circulation tank for recycling.
5. The method of claim 2,
in step S034, the dry absorption furnace gas is sent to a conversion tower to perform a conversion treatment twice in five stages of "3 + 2" and an absorption treatment in an absorption tower, so as to obtain a sulfuric acid product, including:
s341, sending the dry absorption furnace gas into a heat exchanger for first heat exchange treatment to obtain first heat exchange furnace gas with the temperature of 400-450 ℃;
s342, sending the first heat exchange furnace gas into a first catalyst layer, a second catalyst layer and three catalyst layers of a converter for first conversion, and then sending the first heat exchange furnace gas into a heat exchanger for second heat exchange treatment to obtain second heat exchange furnace gas with the temperature of 150-200 ℃;
s343, feeding the second heat exchange furnace gas into a first absorption tower for absorption treatment to obtain a first absorption liquid and absorption furnace gas;
s344, feeding the absorption furnace gas into a heat exchanger for third heat exchange treatment to obtain third heat exchange furnace gas with the temperature of 370-420 ℃;
s345, sending the third heat exchange furnace gas into a fourth section catalyst layer and a fifth section catalyst layer of the converter for second conversion, and then sending the third heat exchange furnace gas into the converter for fourth heat exchange treatment to obtain fourth heat exchange furnace gas with the temperature of 130-170 ℃;
s346, sending the fourth heat exchange furnace gas into a second absorption tower for absorption treatment to obtain a second absorption liquid and tail gas;
s347, processing the first absorption liquid and/or the second absorption liquid to obtain a sulfuric acid product.
6. The method of claim 5,
the first absorption tower and the second absorption tower are communicated with a third circulation tank,
in step S343, the processing of the first absorption liquid and/or the second absorption liquid to obtain a sulfuric acid product includes:
and (3) feeding the first absorption liquid and/or the second absorption liquid into the third circulation tank, adding water for dilution to obtain diluted sulfuric acid with the weight percentage concentration of 93-98%, and taking part of the diluted sulfuric acid as the sulfuric acid product.
7. The method of claim 6,
the drying tower has a fourth circulation tank communicating with the third circulation tank, the first absorption tower, and the second absorption tower,
in step S033, when performing the drying process, the method further includes:
and (3) sending the dried waste acid liquor generated by the drying treatment into the fourth circulating tank, mixing the dried waste acid liquor with part of the diluted sulfuric acid from the third circulating tank to obtain sulfuric acid with the weight percentage concentration of 93%, and recycling the sulfuric acid as the dried showered acid liquor.
8. The method of claim 7,
when the absorption treatment is performed in step S343 and/or S346, the absorption showering acid solution used is sulfuric acid with a weight percentage concentration of 93% -98%, and the method further includes:
and sending part of the diluted sulfuric acid in the third circulating tank and/or the redundant sulfuric acid with the weight percentage concentration of 93% in the fourth circulating tank into the first absorption tower and/or the second absorption tower to be used as the absorption showering acid liquid.
9. The method according to any one of claims 1 to 8,
in step S04, the roasting slag is subjected to acid washing by using a thickener and a horizontal tape filter to obtain the acid washing filtrate and the acid washing residue.
10. The method according to any one of claims 1 to 8,
in step S05, the extraction includes two stages of counter-current extraction, one stage of back extraction, and organic phase recycle.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101768661A (en) * | 2008-12-29 | 2010-07-07 | 厦门紫金矿冶技术有限公司 | Method for comprehensive utilization of iron and sulfur in tailing containing iron and sulfur |
| CN103131849A (en) * | 2013-03-22 | 2013-06-05 | 陈斌 | Sulfur concentrate sand roasting method favorable for comprehensive resource utilization |
| CN103303878A (en) * | 2013-05-30 | 2013-09-18 | 福建省邵武市永飞化工有限公司 | Method for preparing sulfuric acid by iron pyrite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768661A (en) * | 2008-12-29 | 2010-07-07 | 厦门紫金矿冶技术有限公司 | Method for comprehensive utilization of iron and sulfur in tailing containing iron and sulfur |
| CN103131849A (en) * | 2013-03-22 | 2013-06-05 | 陈斌 | Sulfur concentrate sand roasting method favorable for comprehensive resource utilization |
| CN103303878A (en) * | 2013-05-30 | 2013-09-18 | 福建省邵武市永飞化工有限公司 | Method for preparing sulfuric acid by iron pyrite |
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Inventor after: Wang Tianming Inventor after: Chen Xiaohui Inventor after: Song Hongwang Inventor after: Li Zhiwei Inventor after: Liu Chunyu Inventor after: Zhang Changzheng Inventor after: Li Da Inventor after: Zhang Xiao Inventor after: Zhang Bangqiong Inventor after: Zhu Baojun Inventor after: Gai Baowen Inventor before: Wang Tianming Inventor before: Chen Xiaohui Inventor before: Song Hongwang Inventor before: Li Zhiwei Inventor before: Liu Chunyu Inventor before: Zhang Changzheng Inventor before: Li Da Inventor before: Zhang Xiao Inventor before: Zhang Bangqiong Inventor before: Zhu Baojun Inventor before: Gai Baowen |
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