CN116116566A - Recycling method of complex zinc oxide ores in various zinc occurrence states - Google Patents
Recycling method of complex zinc oxide ores in various zinc occurrence states Download PDFInfo
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- CN116116566A CN116116566A CN202310049612.9A CN202310049612A CN116116566A CN 116116566 A CN116116566 A CN 116116566A CN 202310049612 A CN202310049612 A CN 202310049612A CN 116116566 A CN116116566 A CN 116116566A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
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- 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
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Abstract
The invention relates to a recycling method of complex zinc oxide ores in various zinc occurrence states, which comprises the following steps: (1) grinding; (2) Recovering and wrapping zinc oxide by using a pulsating high-gradient strong magnetic separator to obtain wrapped or combined zinc oxide concentrate I and magnetic separation tailings; and (3) floating and recovering free zinc oxide. Respectively adding sodium hexametaphosphate and a flotation reagent, and performing flotation in a flotation system to obtain zinc oxide concentrate II and tailings; (4) Roasting zinc oxide concentrate II obtained in the step (3) at a low temperature to obtain zinc oxide roasting slag; (5) And (3) carrying out acid leaching purification on the zinc oxide concentrate I obtained in the step (2) and the zinc oxide concentrate II roasting slag obtained in the step (4) to obtain zinc-containing pickling liquid and acid leaching slag, and treating the zinc-containing pickling liquid in an electrodeposition system to obtain high-quality zinc metal. The invention can effectively solve the difficult problems of complex difficult processing of zinc mine resources in various zinc occurrence states.
Description
Technical Field
The invention belongs to the technical field of mineral separation, and particularly relates to a method for recycling complex zinc oxide ores in various zinc occurrence states.
Background
Along with the continuous consumption of zinc sulfide ore resources, the development and utilization of zinc oxide ores are increasingly important, and particularly, the zinc oxide ores have the characteristics of low grade, high oxidation rate and binding rate, fine embedding granularity, complex mineral composition and the like aiming at a large number of complex zinc oxide ores; however, due to the complex nature of ores, reasonable and effective development and utilization are not always achieved, and meanwhile, serious threat is caused to environmental protection and safety, and a certain difficulty is also increased to some extent in environmental management. For a long time, the development and comprehensive recycling of slag resources have been highly focused by people in the industry, and a large amount of heart blood is poured. Through a great deal of research work, it was found that the treatment methods of this type of zinc ore are mainly divided into two types: flotation and chemical methods. The flotation method mainly treats the zinc ore which is easy to select, such as the calamine, but for the treatment of the complex zinc oxide ore, the zinc recovery rate is low, the consumption of the flotation reagent is large, and the like, because of the large physical and chemical property difference of each zinc-containing phase, the method cannot achieve the ideal effect. The chemical methods include an acid leaching-extraction method and an ammonia leaching-ammonia distillation crystallization method, wherein the acid leaching-extraction method adopts sulfuric acid to dissolve zinc oxide, then an extractant is added to enrich zinc in an organic phase, then the zinc is extracted back into an aqueous solution, and then the zinc is electrodeposited, but because the content of acid-soluble substances in low-grade zinc oxide ore is larger, a large amount of sulfuric acid is required to be consumed, the production cost is higher, a large amount of acid waste residues are generated, the environmental pollution problem exists, and the zinc is difficult to receive for society or enterprises; the ammonia leaching-ammonia distillation crystallization method is to use ammonia-carbon ammonia combined leaching to prepare zinc amine complex, then to purify, evaporate, dry and calcine to prepare zinc oxide product, but the method is not used for low-grade zinc oxide ore treatment all the time, because raw ore contains low zinc, leaching liquid contains low zinc concentration, leaching agent consumption is high, cost is high, and enterprises cannot accept the zinc. In summary, the processing of such ores has so far remained one of the most challenging subjects in the field of research. In order to effectively recycle complex zinc oxide ores in various zinc occurrence states, and overcome the defects of the existing traditional method, the method becomes a technical problem to be solved in the industry. Based on the above, the invention provides a method for recycling complex zinc oxide ores in various zinc occurrence states.
Disclosure of Invention
Aiming at the problems, the invention has wide raw material applicability, simple operation, low equipment requirement and environmental protection, and can effectively solve the difficult problems of complex zinc mine resource processing and utilization in various zinc occurrence states.
The specific technical scheme is as follows: a recycling method of complex zinc oxide ores with various zinc occurrence states comprises the following specific steps:
(1) Crushing and grinding complex zinc oxide ores until the granularity is-0.074 mm and 75% -80%;
(2) The method comprises the steps of (1) recycling coated zinc oxide through pulsed high-gradient strong magnetic separation, pulping ore pulp in the step (1), and then, recycling siderite and zinc ferrite through a pulsed high-gradient strong magnetic separator to obtain coated or combined zinc oxide concentrate I and magnetic separation tailings; in the process, the magnetic separation concentration is 20% -25%, the diameter of a magnetic medium is 1.5 mm-3 mm, and the background magnetic induction intensity is 1.3T-1.4T;
(3) Floating to recover free zinc oxide, adding sodium hexametaphosphate into the magnetic separation tailings obtained in the step (2) to carry out slurry mixing, adding a floating agent to carry out slurry mixing, and then conveying to a floating system to carry out free zinc oxide ore floating to obtain zinc oxide concentrate II and tailings;
(4) Roasting zinc oxide concentrate II by floatation, conveying the zinc oxide concentrate II obtained in the step (3) to a rotary kiln for low-temperature roasting to obtain zinc oxide roasting slag and flue gas, and removing the flue gas to a flue gas treatment tank;
and (3) acid leaching purification-electrodeposition, namely respectively treating the zinc oxide concentrate I of the coated or combined zinc obtained in the step (2) and the zinc oxide concentrate II roasting slag obtained in the step (4) in an acid leaching purification system to obtain zinc-containing pickling liquid and acid leaching slag, and treating the zinc-containing pickling liquid in an electrodeposition system to obtain high-quality zinc metal.
Further, in the step (3), the flotation system comprises two fine selection, one rough selection and two scavenging; the dosage of sodium sulfide is roughly 2500g/t, the first scavenging amount is 1000g/t, and the second scavenging amount is 500g/t; the dosage of octadecylamine acetate is roughly 150g/t, the first scavenging amount is 80g/t, and the second scavenging amount is 40g/t; the consumption of kerosene is roughly 100g/t, the first scavenging amount is 50g/t, and the second scavenging amount is 25g/t; the consumption of the No. 2 oil is roughly selected to be 50g/t, the first scavenging amount is 30g/t, and the second scavenging amount is 20g/t; the dosage of the coarse separation dispersant sodium hexametaphosphate is 150g/t; the concentration of rougher flotation is 20% -22%.
In the step (4), the zinc oxide concentrate II is subjected to flotation and roasting, and the zinc oxide concentrate II obtained in the step (3) is conveyed to a rotary kiln for low-temperature roasting at 400-600 ℃.
Further, in the step (5), sulfuric acid with the initial concentration of 2mol/l is adopted for acid leaching of the coated or combined zinc oxide concentrate I, the quantity ratio of sulfuric acid to iron and zinc substances is 1.2:1, the leaching temperature is 75-80 ℃, the leaching time is 3-4 hours, and basic zinc carbonate or roasting slag of the zinc oxide concentrate II is adopted for purification and is slowly adjusted to pH value=5.4; and (3) acid leaching and purifying the roasting slag of the flotation zinc oxide concentrate II, wherein the initial pH value is=2.0-2.5, the pH value is slowly adjusted to be=5.4, the leaching temperature is 75-80 ℃, and the leaching time is 2-3 hours.
The invention provides a method for recycling complex zinc oxide ores in various zinc occurrence states. The method is characterized by adopting a process for recovering wrapped zinc oxide minerals (siderite and gazeite) and floating recovered free zinc oxide minerals (siderite and calamine) from the ores by adopting a pulse high-gradient strong magnetic separation, roasting the obtained floating zinc oxide concentrate at a low temperature, and then carrying out an acid leaching purification-electrowinning zinc recovery process on the magnetic concentrate and roasting slag respectively, thereby improving the zinc oxide beneficiation effect, reducing the cost of flotation agents, improving the beneficiation economic benefit, and achieving the purposes of high-efficiency comprehensive utilization of resources and reduction of environmental pollution. The method has wide raw material applicability, simple operation, low equipment requirement and environmental protection, and effectively solves the technical problems of complex difficult-to-process zinc mine resource processing and utilization of various zinc occurrence states.
Aiming at zinc oxide ores with low grade, high oxidation rate and binding rate, fine embedded granularity and complex mineral composition, the method adopts the processes of recycling the wrapped zinc oxide minerals (siderite and hercynite) in the ores by pulsating high-gradient strong magnetic separation and recycling free zinc oxide minerals (siderite and calamine) by floatation, roasting the zinc oxide concentrate obtained by floatation, and then respectively carrying out acid leaching purification-electrowinning zinc recycling process on the magnetic concentrate and roasting slag, thereby improving the zinc oxide beneficiation effect, reducing the cost of flotation agents, improving the beneficiation economic benefit, and achieving the purposes of high-efficiency comprehensive utilization of resources and reduction of environmental pollution.
Compared with the prior method, has the advantages and positive effects
(1) According to zinc phase characteristics, zinc-containing minerals are classified and selected efficiently, so that the zinc beneficiation recovery rate is greatly improved;
(2) The pulsating high-gradient strong magnetic separator is skillfully adopted to pre-magnetically separate the magnetic zinc-bearing minerals, so that the beneficiation principle of 'early recovery' is realized, the fine-particle-grade limonite entering a flotation system is reduced, the flotation effect is improved, the consumption of flotation agents is reduced, the production cost is reduced, and the comprehensive economic benefit is increased;
(3) According to the zinc phase characteristics, the acid leaching purification and electrodeposition treatment are performed on the beneficiation products under different process conditions, so that the zinc recovery rate is greatly improved, the production cost is reduced, and the comprehensive economic benefit is increased.
(4) The zinc ore of the type is treated by adopting the process, so that the zinc recovery rate is greatly improved, the production cost is reduced, the comprehensive economic benefit is improved, the purpose of comprehensive and efficient utilization of resources is achieved, and meanwhile, the environmental pollution risk is also reduced;
(5) The method has wide raw material applicability, simple operation, low equipment requirement and environmental protection, and effectively solves the technical problems of complex difficult-to-process zinc mine resource processing and utilization of various zinc occurrence states. Has wide industrial and commercial application popularization value.
Drawings
Fig. 1: a method and equipment chart for recycling complex zinc oxide ores in various zinc occurrence states;
wherein, 1: jaw crusher, 2: ball mill, 3: pump sump, 4: hydrocyclone, 5: stirring barrel, 6: pulsating high gradient strong magnetic separator, 7: flotation system, 8: roasting rotary kiln, 9: acid leaching purification-electrodeposition system, 10: acid leaching tank, 11: filter, 12: an electrodeposition cell.
Description of the embodiments
The complex zinc oxide ore recovery system in various zinc occurrence states shown in fig. 1 comprises a jaw crusher 1, wherein a discharge port of the jaw crusher 1 is connected with a feed port of a ball mill 2, the discharge port of the ball mill 2 is connected with a feed port at the upper end of a hydrocyclone 4 through a pump pool and a pump, an overflow outlet of the hydrocyclone 4 is connected with a feed port of a stirring barrel A, the discharge port of the stirring barrel A is connected with a feed port of a pulsating high-gradient high-intensity magnetic separator 6 through a pump, a concentrate outlet of the pulsating high-gradient high-intensity magnetic separator 6 is iron-zinc-containing concentrate, and a concentrate outlet of the pulsating high-gradient high-intensity magnetic separator 6 is connected with a feed port of an acid leaching purification-electrodeposition system; the tailing outlet of the pulsating high-gradient strong magnetic separator 6 sequentially passes through a stirring barrel B and a stirring barrel C and then is connected with a flotation system, the flotation concentrate outlet of the flotation system is connected with the feeding port of the roasting rotary kiln 8, and the cinder outlet of the roasting rotary kiln 8 is connected with the feeding port of the acid leaching purification-electrodeposition system; the sedimentation outlet at the bottom of the hydrocyclone 4 is connected with the feed inlet of the ball mill 2.
Preferably, the flotation system 7 comprises a rougher, a scavenger first, a scavenger second and a cleaner first and a cleaner second systems; the roughing system is formed by sequentially connecting 5 flotation machines from left to right, and a feed inlet of a first flotation machine in the roughing system is connected with a discharge outlet of a stirring barrel C; the scavenging system is formed by sequentially connecting 4 flotation machines from left to right, and a tailing outlet of the last flotation machine in the roughing system is connected with a feed inlet of the first flotation machine in the scavenging system; the foam tank of the scavenging system is connected with the feed inlet of the first flotation machine in the roughing system; the scavenging two systems are formed by sequentially connecting 4 flotation machines from left to right, a tailing outlet of the last flotation machine in the scavenging two systems is connected with a feeding hole of the first flotation machine in the scavenging two systems, a foam tank of the scavenging two systems is connected with a feeding hole of the first flotation machine in the scavenging two systems, and tailings of the last flotation machine in the scavenging two systems are flotation tailings; the flotation system is composed of 4 flotation machines which are connected in reverse order (from right to left), the outlet of a flotation machine foam tank of the roughing system is connected with the feed inlet of the last flotation machine in the flotation system, and the outlet of the first flotation machine tail ore of the flotation system is connected with the feed inlet of the first flotation machine of the roughing system; the second system of carefully choosing is composed of 3 flotation machines which are connected in reverse order (from right to left), the outlet of the flotation machine foam tank of the first system of carefully choosing is connected with the feed inlet of the last flotation machine of the second system of carefully choosing, the tailing outlet of the first flotation machine of the second system of carefully choosing is connected with the feed inlet of the last flotation machine of the first system of carefully choosing, and the outlet of the flotation machine foam tank of the second system of carefully choosing is the flotation zinc concentrate. The first flotation machine is the sequence number from left to right, and the last flotation machine is the sequence number from left to right.
Examples
Raw material 1#: some zinc oxide ore comprises the following chemical components: 14.97% of Zn, 17.11% of Fe and SiO 2 7.82、AL 2 O 3 7.91% 、 CaO14.34%, and its zinc phase composition is that of wurtzite 7.85%, zinc silicate 2.01%, zinc sulfide 0.68% and zinc ferrite 4.53%.
The complex difficult-to-treat zinc ores in various zinc occurrence states are implemented by adopting the process, and the technical steps comprise:
(1) Crushing and grinding complex zinc oxide ores until the granularity is-0.074 mm and 75% -80%;
(2) And (3) recovering and wrapping zinc oxide (hydrozincite and zincite) by pulsating high-gradient strong magnetic separation. And (3) conveying the ore pulp subjected to the step (1) to a stirring tank A for size mixing, and then, feeding the ore pulp into a pulsating high-gradient strong magnetic separator for recycling the siderite and the zinc spinel to obtain the coated or combined zinc oxide concentrate I and the magnetic separation tailings. In the process, the magnetic separation concentration is 20%, the diameter of the magnetic medium is 1.5mm, and the background magnetic induction intensity is 1.3T.
(3) And (3) floating to recover free zinc oxide (siderite and heterolite). And (3) conveying the magnetic separation tailings obtained in the step (2) to a stirring tank B, adding sodium hexametaphosphate for size mixing, then to a stirring tank C, adding a flotation reagent for size mixing, and then conveying to a flotation system for free zinc oxide ore flotation to obtain zinc oxide concentrate II and tailings. In the process, two carefully selecting, one rough selecting and two scavenging are carried out; the dosage of sodium sulfide is roughly 2500g/t, the first scavenging amount is 1000g/t, and the second scavenging amount is 500g/t; the dosage of octadecylamine acetate is roughly 150g/t, the first scavenging amount is 80g/t, and the second scavenging amount is 40g/t; the consumption of kerosene is roughly 100g/t, the first scavenging amount is 50g/t, and the second scavenging amount is 25g/t; the consumption of the No. 2 oil is roughly selected to be 50g/t, the first scavenging amount is 30g/t, and the second scavenging amount is 20g/t; the dosage of the coarse separation dispersant sodium hexametaphosphate is 150g/t; the rougher flotation concentration was 20%.
(4) Roasting the flotation zinc oxide concentrate II. And (3) conveying the zinc oxide concentrate II obtained in the step (3) to a rotary kiln for low-temperature roasting to obtain zinc oxide roasting slag and flue gas (a flue gas removal treatment tank). In this process, the firing temperature was 400 ℃.
(5) Acid leaching purification-electrodeposition. And (3) respectively feeding the zinc oxide concentrate I of the coated or combined zinc obtained in the step (2) and the zinc oxide concentrate II roasting slag obtained in the step (4) into an acid leaching-purifying system for treatment to obtain zinc-containing pickling liquid and acid leaching slag (comprising ferrate leaching slag and ferrate leaching slag), and feeding the zinc-containing pickling liquid into an electrodeposition system for treatment to obtain high-quality zinc metal. In the process, the acid leaching of the coated or combined zinc oxide concentrate I adopts sulfuric acid with the initial concentration of 2mol/l, the quantity ratio of sulfuric acid to iron and zinc substances is 1.2:1, the leaching temperature is 75 ℃, the leaching time is 3 hours, and the pH value is slowly regulated to be=5.4 by adopting basic zinc carbonate or roasting slag of the zinc oxide concentrate II; and (3) acid leaching and purifying the roasting slag of the flotation zinc oxide concentrate II, wherein the initial pH value is=2.0, the pH value is slowly adjusted to be=5.4, the leaching temperature is 75 ℃, and the leaching time is 2 hours.
By the above steps, a zinc recovery rate of 80.56% was obtained.
Examples
The raw material No. 2 is a certain zinc oxide ore, and the chemical components are as follows: 12.68% of Zn, 17.69% of Fe and SiO 2 19.31、AL 2 O 3 9.47% 、 CaO9.54%, and its zinc phase composition is 7.00% of siderite, 1.38% of zinc silicate, 0.63% of zinc sulfide and 3.67% of zinc ferrite.
The zinc oxide ore is implemented by adopting the process, and the technical steps comprise:
(1) Crushing and grinding complex zinc oxide ores until the granularity is-0.074 mm and 75% -80%;
(2) And (3) recovering and wrapping zinc oxide (hydrozincite and zincite) by pulsating high-gradient strong magnetic separation. And (3) conveying the ore pulp subjected to the step (1) to a stirring tank A for size mixing, and then, feeding the ore pulp into a pulsating high-gradient strong magnetic separator for recycling the siderite and the zinc spinel to obtain the coated or combined zinc oxide concentrate I and the magnetic separation tailings. In this process, the magnetic concentration was 25%, the magnetic medium diameter was 2mm, and the background magnetic induction was 1.4T.
(3) And (3) floating to recover free zinc oxide (siderite and heterolite). And (3) conveying the magnetic separation tailings obtained in the step (2) to a stirring tank B, adding sodium hexametaphosphate for size mixing, then to a stirring tank C, adding a flotation reagent for size mixing, and then conveying to a flotation system for free zinc oxide ore flotation to obtain zinc oxide concentrate II and tailings. In the process, two carefully selecting, one rough selecting and two scavenging are carried out; the dosage of sodium sulfide is roughly 2500g/t, the first scavenging amount is 1000g/t, and the second scavenging amount is 500g/t; the dosage of octadecylamine acetate is roughly 150g/t, the first scavenging amount is 80g/t, and the second scavenging amount is 40g/t; the consumption of kerosene is roughly 100g/t, the first scavenging amount is 50g/t, and the second scavenging amount is 25g/t; the consumption of the No. 2 oil is roughly selected to be 50g/t, the first scavenging amount is 30g/t, and the second scavenging amount is 20g/t; the dosage of the coarse separation dispersant sodium hexametaphosphate is 150g/t; the rougher flotation concentration was 22%.
(4) Roasting the flotation zinc oxide concentrate II. And (3) conveying the zinc oxide concentrate II obtained in the step (3) to a rotary kiln for low-temperature roasting to obtain zinc oxide roasting slag and flue gas (a flue gas removal treatment tank). In this process, the firing temperature was 500 ℃.
(5) Acid leaching purification-electrodeposition. And (3) respectively feeding the zinc oxide concentrate I of the coated or combined zinc obtained in the step (2) and the zinc oxide concentrate II roasting slag obtained in the step (4) into an acid leaching-purifying system for treatment to obtain zinc-containing pickling liquid and acid leaching slag (comprising ferrate leaching slag and ferrate leaching slag), and feeding the zinc-containing pickling liquid into an electrodeposition system for treatment to obtain high-quality zinc metal. In the process, the acid leaching of the coated or combined zinc oxide concentrate I adopts sulfuric acid with the initial concentration of 2mol/l, the quantity ratio of sulfuric acid to iron and zinc substances is 1.2:1, the leaching temperature is 80 ℃, the leaching time is 4 hours, and the purification adopts basic zinc carbonate or zinc oxide concentrate II roasting slag to be slowly regulated to pH value=5.4; and (3) acid leaching and purifying the roasting slag of the flotation zinc oxide concentrate II, wherein the initial pH value is=2.5, the pH value is slowly adjusted to be=5.4, the leaching temperature is 80 ℃, and the leaching time is 3 hours.
By the above steps, a zinc recovery rate of 80.06% was obtained.
Examples
Raw material 3#: some zinc oxide ore comprises the following chemical components: 12.27% of Zn, 18.16% of Fe and 16% of SiO 2 21.67%、AL 2 O 3 9.36% 、 CaO11.55%, its zinc phase composition is 6.67% of siderite, 1.21% of zinc silicate, 0.76% of zinc sulfide and 3.67% of zinc ferrite.
The zinc oxide ore is implemented by adopting the process, and the technical steps comprise:
(1) Crushing and grinding complex zinc oxide ores until the granularity is-0.074 mm and 75% -80%;
(2) And (3) recovering and wrapping zinc oxide (hydrozincite and zincite) by pulsating high-gradient strong magnetic separation. And (3) conveying the ore pulp subjected to the step (1) to a stirring tank A for size mixing, and then, feeding the ore pulp into a pulsating high-gradient strong magnetic separator for recycling the siderite and the zinc spinel to obtain the coated or combined zinc oxide concentrate I and the magnetic separation tailings. In this process, the magnetic concentration was 25%, the magnetic medium diameter was 3mm, and the background magnetic induction was 1.4T.
(3) And (3) floating to recover free zinc oxide (siderite and heterolite). And (3) conveying the magnetic separation tailings obtained in the step (2) to a stirring tank B, adding sodium hexametaphosphate for size mixing, then to a stirring tank C, adding a flotation reagent for size mixing, and then conveying to a flotation system for free zinc oxide ore flotation to obtain zinc oxide concentrate II and tailings. In the process, two carefully selecting, one rough selecting and two scavenging are carried out; the dosage of sodium sulfide is roughly 2500g/t, the first scavenging amount is 1000g/t, and the second scavenging amount is 500g/t; the dosage of octadecylamine acetate is roughly 150g/t, the first scavenging amount is 80g/t, and the second scavenging amount is 40g/t; the consumption of kerosene is roughly 100g/t, the first scavenging amount is 50g/t, and the second scavenging amount is 25g/t; the consumption of the No. 2 oil is roughly selected to be 50g/t, the first scavenging amount is 30g/t, and the second scavenging amount is 20g/t; the dosage of the coarse separation dispersant sodium hexametaphosphate is 150g/t; the rougher flotation concentration was 22%.
(4) Roasting the flotation zinc oxide concentrate II. And (3) conveying the zinc oxide concentrate II obtained in the step (3) to a rotary kiln for low-temperature roasting to obtain zinc oxide roasting slag and flue gas (a flue gas removal treatment tank). In this process, the firing temperature was 600 ℃.
(5) Acid leaching purification-electrodeposition. And (3) respectively feeding the zinc oxide concentrate I of the coated or combined zinc obtained in the step (2) and the zinc oxide concentrate II roasting slag obtained in the step (4) into an acid leaching-purifying system for treatment to obtain zinc-containing pickling liquid and acid leaching slag (comprising ferrate leaching slag and ferrate leaching slag), and feeding the zinc-containing pickling liquid into an electrodeposition system for treatment to obtain high-quality zinc metal. In the process, the acid leaching of the coated or combined zinc oxide concentrate I adopts sulfuric acid with the initial concentration of 2mol/l, the quantity ratio of sulfuric acid to iron and zinc substances is 1.2:1, the leaching temperature is 80 ℃, the leaching time is 3-4 hours, and the pH value is slowly regulated to be 5.4 by adopting basic zinc carbonate or roasting slag of the zinc oxide concentrate II; and (3) acid leaching and purifying the roasting slag of the flotation zinc oxide concentrate II, wherein the initial pH value is=2.5, the pH value is slowly adjusted to be=5.4, the leaching temperature is 80 ℃, and the leaching time is 3 hours.
By the above steps, a zinc recovery rate of 78.88% was obtained.
Examples
The zinc oxide ore is implemented by adopting the process, and the technical steps comprise:
(1) Crushing and grinding complex zinc oxide ores until the granularity is-0.074 mm and 75% -80%;
(2) And (3) recovering and wrapping zinc oxide (hydrozincite and zincite) by pulsating high-gradient strong magnetic separation. And (3) conveying the ore pulp subjected to the step (1) to a stirring tank A for size mixing, and then, feeding the ore pulp into a pulsating high-gradient strong magnetic separator for recycling the siderite and the zinc spinel to obtain the coated or combined zinc oxide concentrate I and the magnetic separation tailings. In the process, the magnetic separation concentration is 20%, the diameter of the magnetic medium is 1.5mm, and the background magnetic induction intensity is 1.4T.
(3) And (3) floating to recover free zinc oxide (siderite and heterolite). And (3) conveying the magnetic separation tailings obtained in the step (2) to a stirring tank B, adding sodium hexametaphosphate for size mixing, then to a stirring tank C, adding a flotation reagent for size mixing, and then conveying to a flotation system for free zinc oxide ore flotation to obtain zinc oxide concentrate II and tailings. In the process, two carefully selecting, one rough selecting and two scavenging are carried out; the dosage of sodium sulfide is roughly 2500g/t, the first scavenging amount is 1000g/t, and the second scavenging amount is 500g/t; the dosage of octadecylamine acetate is roughly 150g/t, the first scavenging amount is 80g/t, and the second scavenging amount is 40g/t; the consumption of kerosene is roughly 100g/t, the first scavenging amount is 50g/t, and the second scavenging amount is 25g/t; the consumption of the No. 2 oil is roughly selected to be 50g/t, the first scavenging amount is 30g/t, and the second scavenging amount is 20g/t; the dosage of the coarse separation dispersant sodium hexametaphosphate is 150g/t; the rougher flotation concentration was 20%.
(4) Roasting the flotation zinc oxide concentrate II. And (3) conveying the zinc oxide concentrate II obtained in the step (3) to a rotary kiln for low-temperature roasting to obtain zinc oxide roasting slag and flue gas (a flue gas removal treatment tank). In this process, the firing temperature was 400 ℃.
(5) Acid leaching purification-electrodeposition. And (3) respectively feeding the zinc oxide concentrate I of the coated or combined zinc obtained in the step (2) and the zinc oxide concentrate II roasting slag obtained in the step (4) into an acid leaching-purifying system for treatment to obtain zinc-containing pickling liquid and acid leaching slag (comprising ferrate leaching slag and ferrate leaching slag), and feeding the zinc-containing pickling liquid into an electrodeposition system for treatment to obtain high-quality zinc metal. In the process, the acid leaching of the coated or combined zinc oxide concentrate I adopts sulfuric acid with the initial concentration of 2mol/l, the quantity ratio of sulfuric acid to iron and zinc substances is 1.2:1, the leaching temperature is 80 ℃, the leaching time is 4 hours, and the purification adopts basic zinc carbonate or zinc oxide concentrate II roasting slag to be slowly regulated to pH value=5.4; and (3) acid leaching and purifying the roasting slag of the flotation zinc oxide concentrate II, wherein the initial pH value is=2.0, the pH value is slowly adjusted to be=5.4, the leaching temperature is 75 ℃, and the leaching time is 2 hours.
By the above steps, a zinc recovery of 77.13% was obtained.
In conclusion, the complex zinc oxide ores in various zinc occurrence states are implemented by the process, the recovery rate of the obtained zinc is stable between 77% and 81%, and in general, the method has wide raw material applicability, is simple to operate, has low equipment requirements and is environment-friendly, the technical problem of processing and utilizing complex difficult-to-handle zinc ore resources in various zinc occurrence states is effectively solved, the production cost is relatively low, better economic benefit can be obtained, mineral resources are effectively and comprehensively utilized, and the method has better industrial and commercial popularization and application values.
Claims (4)
1. A recycling method of complex zinc oxide ores in various zinc occurrence states is characterized by comprising the following specific steps:
(1) Crushing and grinding complex zinc oxide ores until the granularity is-0.074 mm and 75% -80%;
(2) The method comprises the steps of (1) recycling coated zinc oxide through pulsed high-gradient strong magnetic separation, pulping ore pulp in the step (1), and then, recycling siderite and zinc ferrite through a pulsed high-gradient strong magnetic separator to obtain coated or combined zinc oxide concentrate I and magnetic separation tailings; in the process, the magnetic separation concentration is 20% -25%, the diameter of a magnetic medium is 1.5 mm-3 mm, and the background magnetic induction intensity is 1.3T-1.4T;
(3) Floating to recover free zinc oxide, adding sodium hexametaphosphate into the magnetic separation tailings obtained in the step (2) to carry out slurry mixing, adding a floating agent to carry out slurry mixing, and then conveying to a floating system to carry out free zinc oxide ore floating to obtain zinc oxide concentrate II and tailings;
(4) Roasting zinc oxide concentrate II by floatation, conveying the zinc oxide concentrate II obtained in the step (3) to a rotary kiln for low-temperature roasting to obtain zinc oxide roasting slag and flue gas, and removing the flue gas to a flue gas treatment tank;
and (3) acid leaching purification-electrodeposition, namely respectively treating the zinc oxide concentrate I of the coated or combined zinc obtained in the step (2) and the zinc oxide concentrate II roasting slag obtained in the step (4) in an acid leaching purification system to obtain zinc-containing pickling liquid and acid leaching slag, and treating the zinc-containing pickling liquid in an electrodeposition system to obtain high-quality zinc metal.
2. The method for recycling complex zinc oxide ores in various zinc occurrence states according to claim 1, wherein,
in the step (3), the flotation system comprises two fine selection, one rough selection and two scavenging; the dosage of sodium sulfide is roughly 2500g/t, the first scavenging amount is 1000g/t, and the second scavenging amount is 500g/t; the dosage of octadecylamine acetate is roughly 150g/t, the first scavenging amount is 80g/t, and the second scavenging amount is 40g/t; the consumption of kerosene is roughly 100g/t, the first scavenging amount is 50g/t, and the second scavenging amount is 25g/t; the consumption of the No. 2 oil is roughly selected to be 50g/t, the first scavenging amount is 30g/t, and the second scavenging amount is 20g/t; the dosage of the coarse separation dispersant sodium hexametaphosphate is 150g/t; the concentration of rougher flotation is 20% -22%.
3. The method for recycling complex zinc oxide ores in various zinc occurrence states according to claim 1, wherein,
in the step (4), roasting the zinc oxide concentrate II, and conveying the zinc oxide concentrate II obtained in the step (3) to a rotary kiln for low-temperature roasting at 400-600 ℃.
4. The method for recycling complex zinc oxide ores in various zinc occurrence states according to claim 1, wherein,
in the step (5), the acid leaching of the coated or combined zinc oxide concentrate I adopts sulfuric acid with the initial concentration of 2mol/l, the quantity ratio of sulfuric acid to iron and zinc substances is 1.2:1, the leaching temperature is 75-80 ℃, the leaching time is 3-4 hours, and the purification adopts basic zinc carbonate or zinc oxide concentrate II roasting slag to slowly adjust the pH value to be=5.4; and (3) acid leaching and purifying the roasting slag of the flotation zinc oxide concentrate II, wherein the initial pH value is=2.0-2.5, the pH value is slowly adjusted to be=5.4, the leaching temperature is 75-80 ℃, and the leaching time is 2-3 hours.
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