CN113102094A - Method for comprehensively recovering iron, sulfur and titanium from complex multi-metal ores - Google Patents
Method for comprehensively recovering iron, sulfur and titanium from complex multi-metal ores Download PDFInfo
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Abstract
The invention discloses a method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores, which comprises the steps of grinding the complex polymetallic ores, then carrying out strong magnetic separation, weak magnetic separation and scavenging to obtain iron ore concentrates and final strong magnetic scavenging tailings, mixing the final strong magnetic scavenging tailings with oxalic acid, butyl xanthate and pine oil for sulfur flotation to obtain final sulfur ore concentrates and final sulfur flotation tailings; regrinding the final sulfur flotation tailings, mixing the obtained regrinding fine material with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium flotation, performing one-time roughing and more than one-time concentration to obtain titanium concentrate and concentrated flotation tailings of the corresponding-section concentrated flotation, and mixing the obtained titanium concentrate with hydrochloric acid and hydrofluoric acid to perform at least one-time acid leaching to obtain a titanium product. Therefore, high-quality titanium concentrate can be obtained, and meanwhile, effective recovery of valuable components of iron and sulfur is accompanied, so that resource utilization of the titanium-containing polymetallic ore is realized.
Description
Technical Field
The invention belongs to the field of mineral separation, and particularly relates to a method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores.
Background
Titanium is a very important element, metal titanium and titanium alloy have the excellent properties of high melting point, no magnetism, small thermal expansion coefficient, corrosion resistance, high temperature resistance, good plasticity and the like, and titanium dioxide products are widely applied to the fields of military aviation, aerospace, navigation, machinery, chemical industry and seawater desalination. Because titanium exists in nature and is dispersed, extraction is difficult.
Because titanium-containing ores often contain valuable components such as iron, sulfur and the like, the existing process mainly considers the recovery of titanium, and little attention is paid to the recovery of the associated valuable elements such as iron and sulfur, so that the waste of resources is caused. Therefore, a process and a method for comprehensively recovering iron, sulfur and titanium from complex multi-metal ores are needed to solve the problems.
Disclosure of Invention
The invention aims to: aiming at the problems, the method for comprehensively recovering iron, sulfur and titanium from the titanium-containing complex polymetallic ore can obtain high-quality titanium concentrate, and is accompanied with effective recovery of valuable components of iron and sulfur, so that resource utilization of the titanium-containing polymetallic ore is realized.
In order to achieve the above object, the present invention provides a method for comprehensively recovering metals from a polymetallic mineral, the method comprising the steps of:
(1) carrying out ore grinding treatment on the complex polymetallic ore to obtain ore grinding fine materials;
(2) performing strong magnetic separation, weak magnetic separation and scavenging on the fine grinding materials in the step (1) in sequence to obtain iron ore concentrate and final strong magnetic scavenging tailings, and performing magnetization roasting and first-stage weak magnetic separation on the iron ore concentrate to obtain an iron product;
(3) mixing the final strong magnetic scavenging tailings obtained in the step (2) with oxalic acid, butyl xanthate and pine oil for sulfur flotation to obtain final sulfur concentrate and final sulfur flotation tailings;
(4) regrinding the final sulfur flotation tailings obtained in the step (3) to obtain reground fine materials;
(5) mixing the reground fine material obtained in the step (4) with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium selecting flotation, performing one-time roughing and more than one-time concentration to obtain titanium concentrate and selected flotation tailings of the corresponding-section selected flotation, and mixing the obtained titanium concentrate with hydrochloric acid and hydrofluoric acid to perform at least one-time acid leaching to obtain a titanium product.
In order to improve the recovery rate of iron in the complex multi-metal ore, when the ore grinding fine materials are subjected to strong magnetic separation, weak magnetic separation and scavenging in sequence in the step (2), the method comprises the following steps:
(2.1) carrying out primary strong magnetic separation on the ground fine materials to obtain primary strong magnetic separation concentrate and primary strong magnetic separation tailings;
(2.2) carrying out primary low-intensity magnetic separation on the primary high-intensity magnetic separation concentrate obtained in the step (2.1) to obtain primary low-intensity magnetic separation concentrate and primary low-intensity magnetic separation tailings;
(2.3) carrying out secondary low-intensity magnetic separation concentration on the primary low-intensity magnetic separation concentrated ore concentrate to obtain the final iron ore concentrate and secondary low-intensity magnetic separation concentrated tailings;
(2.4) carrying out primary strong magnetic scavenging on the primary strong magnetic tailings obtained in the step (2.1) to obtain primary strong magnetic scavenging concentrate and primary strong magnetic scavenging tailings;
(2.5) carrying out second-stage strong magnetic scavenging on the first-stage strong magnetic scavenging tailings obtained in the step (2.4) to obtain second-stage strong magnetic scavenging concentrate and the final strong magnetic scavenging tailings.
Preferably, the present invention further comprises the steps of:
(2.6) mixing the primary low-intensity magnetic separation fine tailings obtained in the step (2.2) with the grinding fine materials for primary high-intensity magnetic separation;
(2.7) mixing the second-stage low-intensity magnetic separation concentration tailings obtained in the step (2.3) with the first-stage high-intensity magnetic separation concentrate obtained in the step (2.1) to perform first-stage low-intensity magnetic separation concentration;
(2.8) mixing the primary strong magnetic separation scavenging concentrate obtained in the step (2.4) with the grinding fine material for primary strong magnetic separation;
(2.9) mixing the second-stage strong magnetic separation scavenging concentrate obtained in the step (2.5) with the first-stage strong magnetic separation tailings obtained in the step (2.1) to perform first-stage strong magnetic separation scavenging.
In order to improve the recovery rate of sulfur in the complex polymetallic ore, when the final strong magnetic scavenging tailings are mixed with oxalic acid, butyl xanthate and pine oil to perform sulfur-selecting flotation in the step (3), the method comprises the following steps:
(3.1) mixing the final strong magnetic scavenging tailings with oxalic acid, butyl xanthate and pine oil to perform first-stage sulfur flotation to obtain final sulfur concentrate and first-stage sulfur flotation tailings;
(3.2) mixing the first-stage sulfur-dressing flotation tailings obtained in the step (3.1) with oxalic acid, butyl xanthate and pine oil to perform first-stage sulfur-dressing scavenging to obtain first-stage sulfur-dressing scavenging concentrates and first-stage sulfur-dressing scavenging tailings;
and (3.3) mixing the first-stage sulfur scavenging tailings obtained in the step (3.2) with oxalic acid, butyl xanthate and pine oil to perform second-stage sulfur scavenging to obtain second-stage sulfur scavenging concentrates and the final sulfur flotation tailings.
Preferably, in the step (5), 5-stage concentration is adopted, the concentrated flotation tailings obtained in each stage are returned to the last stage for titanium flotation, and the titanium concentrates subjected to five-stage concentration flotation are subjected to primary acid leaching to obtain primary acid leaching residues and primary acid leaching leachate; and mixing the primary acid leaching residue with hydrochloric acid and hydrofluoric acid for secondary acid leaching to obtain a titanium product.
Preferably, in the step (1), the proportion of the grain diameter of the ore grinding fine material is not higher than 0.074mm is 60-65%; in the step (4), the proportion of the reground fine material with the grain diameter not higher than 0.074mm is 90-95%.
In the step (2), the intensity of the strong magnetic field of the section is 900-1000 kA/m; in the step (3), the intensity of the magnetic field selected by the first-stage low-intensity magnetic separation is 300-400 kA/m; in the step (4), the magnetic field intensity of the two-stage low-intensity magnetic separation and concentration is 300-400 kA/m; in the step (6), the intensity of the magnetic field swept by the strong magnetic separation section is 900-1000 kA/m; in the step (7), the magnetic field intensity of the two-stage strong magnetic separation scavenging is 900-1000 kA/m. In the step (2), the magnetizing roasting conditions are as follows: the roasting temperature is 900-1100 ℃, the roasting time is 30min, the carbon powder proportion is 20%, and the magnetic field intensity of the low-intensity magnetic separation is 300-400 kA/m.
Preferably, in the step (3.1), based on 1t of the complex polymetallic ore, the dosage of oxalic acid for the first-stage sulfur flotation is 700-800 g, the dosage of butyl xanthate is 400-600 g, and the dosage of terpineol is 500-600 g; in the step (3.2), the dosage of oxalic acid is 350-400 g, the dosage of butyl xanthate is 200-300 g, and the dosage of terpineol is 250-300 g; in the step (3.3), the dosage of oxalic acid is 150-200 g, the dosage of butyl xanthate is 100-150 g, and the dosage of terpineol is 100-150 g.
In order to improve the recovery rate of titanium in the complex multi-metal ore, the titanium separation flotation in the step (5) adopts one coarse, five fine and three sweeps, and based on 1t of the complex multi-metal ore, the dosage of a roughing medicament is as follows: 700-800 g of sodium fluosilicate, 400-600 g of water glass, 500-600 g of citric acid, 500-600 g of sodium hexametaphosphate, 800-1000 g of lead nitrate, 500-600 g of benzohydroxamic acid and 500-600 g of salicylhydroxamic acid; the agent dosage of the first four times of concentration of the fifth concentration is gradually reduced by two thirds relative to the agent dosage of the last flotation, and the fifth concentration is blank concentration without adding agent; the dosage of the chemicals for the third scavenging is gradually reduced by one half compared with the dosage of the chemicals for the previous stage of flotation; the acid leaching conditions are as follows: the hydrochloric acid concentration is 10-15%, the hydrofluoric acid concentration is 4-10%, and the liquid-solid ratio is 5:1, the acid leaching time is 4 hours.
According to the method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores, the grade of an iron product obtained after roasting and magnetic separation is 64.82-65.17%, the recovery rate is 74.35-74.82%, the grade of a sulfur product is 44.93-45.53%, the recovery rate is 62.95-64.11%, the grade of a selected flotation titanium concentrate is 42.56-43.22%, the recovery rate is 66.80-67.32%, the grade of titanium of a two-stage acid leaching slag is 92.84-93.67%, and the recovery rate is 58.21-59.22%. Therefore, the method can obtain the high-quality titanium concentrate, and is accompanied with the effective recovery of valuable components of iron and sulfur, so that the resource utilization of the complex multi-metal ore is realized, and the economic benefit of enterprises is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of the main flow of the process for recovering iron, sulfur and titanium from complex polymetallic ores according to the present invention;
FIG. 2 shows a flow chart for obtaining iron, sulfur and titanium respectively according to the flow chart shown in FIG. 1;
fig. 3 is a detailed flow chart of the present invention.
Detailed Description
The invention will be described in detail with reference to fig. 1, 2, 3 and the embodiments.
As can be seen from FIG. 1, the process of the method mainly comprises five steps, namely, the complex multi-metal ore is ground; secondly, carrying out strong and weak magnetic separation on the ground material to obtain iron ore concentrate; thirdly, performing mixed flotation on the magnetic separation tailings, oxalic acid, butyl xanthate and terpineol to obtain sulfur concentrate; fourthly, regrinding the sulfur-selecting tailings to obtain a superfine grinding material; and fifthly, mixing and floating the superfine grinding material, sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to obtain titanium concentrate. The second major step is to further magnetize and roast the iron ore concentrate, obtain an iron product through low-intensity magnetic separation, obtain a sulfur product through the third major step, and obtain a titanium product through acid leaching through the fifth major step, as shown in fig. 2. FIG. 3 is a detailed flow chart of the present invention, according to which the inventors have conducted the following experiments:
example 1
In the complex multi-metal ore used in the invention, the average iron grade is 13.20%, the sulfur grade is 5.49%, and the titanium grade is 2.96%.
First step of
And performing primary grinding operation, wherein the grain diameter of the ground fine material is not higher than 65% of the grain diameter of 0.074 mm.
Second step of
And (3) carrying out primary strong magnetic separation on the ground fine materials, wherein the magnetic field intensity is 960kA/m, and obtaining primary strong magnetic separation concentrate and primary strong magnetic separation tailings.
And (3) carrying out primary low-intensity magnetic separation concentration on the primary high-intensity magnetic separation concentrate, wherein the magnetic field intensity is 400kA/m, and thus primary low-intensity magnetic separation concentrate and primary low-intensity magnetic separation tailings are obtained. And (3) carrying out second-stage low-intensity magnetic separation concentration on the first-stage low-intensity magnetic separation concentrate, wherein the magnetic field intensity is 300kA/m, so as to obtain second-stage low-intensity magnetic separation concentrate and second-stage low-intensity magnetic separation tailings.
And (3) carrying out primary strong magnetic scavenging on the primary strong magnetic tailings with the magnetic field intensity of 900kA/m to obtain primary strong magnetic scavenging concentrate and primary strong magnetic scavenging tailings. And (3) carrying out second-stage strong magnetic scavenging on the first-stage strong magnetic scavenging tailings with the magnetic field intensity of 900kA/m to obtain second-stage strong magnetic scavenging concentrate and second-stage strong magnetic scavenging tailings.
The first-stage low-intensity magnetic separation tailings, the second-stage low-intensity magnetic separation tailings, the first-stage high-intensity magnetic separation scavenging concentrates and the second-stage high-intensity magnetic separation scavenging concentrates are returned to be subjected to magnetic separation step by step.
Roasting the second-stage low-intensity magnetic separation concentrate for 30 minutes at 1100 ℃ under the condition that the carbon powder content is 20%, and carrying out low-intensity magnetic separation on the roasted product with the magnetic field intensity of 300kA/m to obtain an iron product with the grade of 65.17% and the recovery rate of 74.35%.
The third step
Mixing the second-stage strong magnetic separation scavenging tailings with oxalic acid, butyl xanthate and terpineol for first-stage flotation, wherein the using amount of the oxalic acid is 700g, the using amount of the butyl xanthate is 500g, the using amount of the terpineol is 500g, the flotation time is 3 minutes, first-stage sulfur separation flotation concentrate (sulfur product) and first-stage sulfur separation flotation tailings are obtained, the grade of the sulfur product is 45.53%, and the recovery rate is 62.95%.
Mixing the first-stage sulfur-selecting flotation tailings with oxalic acid, butyl xanthate and terpineol to perform first-stage flotation scavenging, wherein the using amount of the oxalic acid is 350g, the using amount of the butyl xanthate is 250g, the using amount of the terpineol is 250g, and the flotation time is 3 minutes to obtain first-stage sulfur-selecting scavenging concentrate and first-stage sulfur-selecting scavenging tailings. Mixing the first-stage sulfur-dressing scavenging tailings with oxalic acid, butyl xanthate and terpineol to perform second-stage sulfur-dressing scavenging, wherein the using amount of the oxalic acid is 150g, the using amount of the butyl xanthate is 100g, the using amount of the terpineol is 100g, and the flotation time is 3 minutes to obtain second-stage sulfur-dressing scavenging concentrate and second-stage sulfur-dressing scavenging tailings. And returning the first-stage sulfur-selecting scavenging concentrate and the second-stage sulfur-selecting scavenging concentrate to flotation step by step.
The fourth step
Regrinding the second-stage sulfur-dressing scavenging tailings to obtain micro-fine particles, wherein the proportion of the particle size in the micro-fine particles is not higher than 95% of 0.074 mm.
The fifth step
Mixing the reground micro-fine particles with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform first-stage titanium flotation, wherein the use amount of the sodium fluosilicate is 800g, the use amount of the water glass is 600g, the use amount of the citric acid is 600g, the use amount of the sodium hexametaphosphate is 600g, the lead nitrate is 800g, the use amount of the benzohydroxamic acid is 550g, the use amount of the salicylhydroxamic acid is 550g, and the flotation time is 3 minutes, so that first-stage titanium flotation concentrate and first-stage titanium flotation tailings are obtained.
Mixing the first-stage titanium flotation concentrate with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium flotation concentration, wherein the concentration is performed for 5 times, the dosage of each agent in the first 4 times of concentration is one third of that in the first-stage flotation, the 5 th time of concentration is blank concentration without adding any agent, and tailings obtained in each stage of concentration are returned to flotation step by step for 3 minutes each time of flotation. The 5 th concentration obtains titanium concentrate with the grade of 43.22 percent and the recovery rate of 66.80 percent.
Mixing the first-stage titanium flotation tailings with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium flotation scavenging for 3 times, wherein the dosage of scavenging for each time is one half of that of the previous-stage flotation, and the concentrate obtained by scavenging at each stage is returned to flotation step by step for 3 minutes each time.
Mixing the five-section titanium-separation selected concentrate with hydrochloric acid and hydrofluoric acid for acid leaching, wherein the concentration of the hydrochloric acid is 15%, the concentration of the hydrofluoric acid is 8%, and the liquid-solid ratio is 5:1, acid leaching for 4 hours to obtain primary acid leaching residue, mixing the primary acid leaching residue with hydrochloric acid and hydrofluoric acid for acid leaching, wherein the concentration of the hydrochloric acid is 10%, the concentration of the hydrofluoric acid is 4%, and the liquid-solid ratio is 5:1, acid leaching for 4 hours to obtain secondary acid leaching residue, namely a titanium product with the grade of 93.67 percent and the recovery rate of 58.21 percent.
Example 2
The ore samples used were the ore samples of example 1.
First step of
And performing primary grinding operation, wherein the grain size of the ground fine material is not higher than 62% of the grain size of 0.074 mm.
Second step of
And (3) carrying out primary strong magnetic separation on the ground fine materials, wherein the magnetic field intensity is 1000kA/m, and obtaining primary strong magnetic separation concentrate and primary strong magnetic separation tailings.
And (3) carrying out primary low-intensity magnetic separation concentration on the primary high-intensity magnetic separation concentrate, wherein the magnetic field intensity is 350kA/m, so as to obtain primary low-intensity magnetic separation concentrate and primary low-intensity magnetic separation tailings. And performing second-stage low-intensity magnetic separation concentration on the first-stage low-intensity magnetic separation concentrate, wherein the magnetic field intensity is 400kA/m, and thus obtaining second-stage low-intensity magnetic separation concentrate and second-stage low-intensity magnetic separation tailings.
And (3) carrying out primary strong magnetic scavenging on the primary strong magnetic tailings with the magnetic field intensity of 1000kA/m to obtain primary strong magnetic scavenging concentrate and primary strong magnetic scavenging tailings. And (3) carrying out second-stage strong magnetic scavenging on the first-stage strong magnetic scavenging tailings with the magnetic field intensity of 1000kA/m to obtain second-stage strong magnetic scavenging concentrate and second-stage strong magnetic scavenging tailings.
The first-stage low-intensity magnetic separation tailings, the second-stage low-intensity magnetic separation tailings, the first-stage high-intensity magnetic separation scavenging concentrates and the second-stage high-intensity magnetic separation scavenging concentrates are returned to be subjected to magnetic separation step by step.
Roasting the second-stage low-intensity magnetic separation concentrate for 30 minutes at 900 ℃ under the condition that the carbon powder content is 20%, and carrying out low-intensity magnetic separation on the roasted product with the magnetic field intensity of 400kA/m to obtain an iron product with the grade of 64.82% and the recovery rate of 75.38%.
The third step
Mixing the second-stage strong magnetic separation scavenging tailings with oxalic acid, butyl xanthate and terpineol for first-stage flotation, wherein the using amount of oxalic acid is 750g, the using amount of butyl xanthate is 550g, the using amount of terpineol is 550g, the flotation time is 3 minutes, first-stage sulfur separation flotation concentrate (sulfur product) and first-stage sulfur separation flotation tailings are obtained, the grade of the sulfur product is 45.12%, and the recovery rate is 63.29%.
Mixing the first-stage sulfur-selecting flotation tailings with oxalic acid, butyl xanthate and terpineol to perform first-stage flotation scavenging, wherein the using amount of the oxalic acid is 370g, the using amount of the butyl xanthate is 270g, the using amount of the terpineol is 270g, and the flotation time is 3 minutes to obtain first-stage sulfur-selecting scavenging concentrate and first-stage sulfur-selecting scavenging tailings. Mixing the first-stage sulfur-dressing scavenging tailings with oxalic acid, butyl xanthate and terpineol to perform second-stage sulfur-dressing scavenging, wherein the dosage of the oxalic acid is 170g, the dosage of the butyl xanthate is 120g, the dosage of the terpineol is 120g, and the flotation time is 3 minutes to obtain second-stage sulfur-dressing scavenging concentrate and second-stage sulfur-dressing scavenging tailings. And returning the first-stage sulfur-selecting scavenging concentrate and the second-stage sulfur-selecting scavenging concentrate to flotation step by step.
The fourth step
Regrinding the second-stage sulfur-dressing scavenging tailings to obtain micro-fine particles, wherein the particle size of the micro-fine particles is not higher than 90% of the particle size of 0.074 mm.
The fifth step
Mixing the reground micro-fine particles with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform first-stage titanium flotation, wherein the use amount of the sodium fluosilicate is 750g, the use amount of the water glass is 400g, the use amount of the citric acid is 500g, the use amount of the sodium hexametaphosphate is 500g, the use amount of the lead nitrate is 900g, the use amount of the benzohydroxamic acid is 500g, and the use amount of the salicylhydroxamic acid is 500g, wherein the flotation time is 3 minutes, so that first-stage titanium flotation concentrate and first-stage titanium flotation tailings are obtained.
Mixing the first-stage titanium flotation concentrate with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium flotation concentration, wherein the concentration is performed for 5 times, the dosage of each agent in the first 4 times of concentration is one third of that in the previous stage, the concentration in the 5 th time is blank concentration without adding any agent, and tailings obtained in each stage of concentration are returned to flotation step by step for 3 minutes each time of flotation. The 5 th concentration obtains titanium concentrate with the grade of 42.56 percent and the recovery rate of 66.95 percent.
Mixing the first-stage titanium flotation tailings with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium flotation scavenging for 3 times, wherein the dosage of scavenging for each time is one half of that of the previous stage, and concentrate obtained by scavenging at each stage is returned to flotation step by step for 3 minutes each time.
Mixing the five-section titanium-separation selected concentrate with hydrochloric acid and hydrofluoric acid for acid leaching, wherein the concentration of the hydrochloric acid is 10%, the concentration of the hydrofluoric acid is 6%, and the liquid-solid ratio is 5:1, acid leaching for 4 hours to obtain primary acid leaching residue, mixing the primary acid leaching residue with hydrochloric acid and hydrofluoric acid for acid leaching, wherein the concentration of the hydrochloric acid is 8 percent, the concentration of the hydrofluoric acid is 6 percent, and the liquid-solid ratio is 5:1, acid leaching for 4 hours to obtain secondary acid leaching slag, namely a titanium product with the grade of 92.84 percent and the recovery rate of 58.73 percent.
Example 3
The sample was used as in example 1.
First step of
And performing primary grinding operation, wherein the percentage of the grain diameter in the ground fine material is not higher than 60% of that in the ground fine material of 0.074 mm.
Second step of
And (3) carrying out primary strong magnetic separation on the ground fine materials, wherein the magnetic field intensity is 900kA/m, and obtaining primary strong magnetic separation concentrate and primary strong magnetic separation tailings.
And (3) carrying out primary low-intensity magnetic separation concentration on the primary high-intensity magnetic separation concentrate, wherein the magnetic field intensity is 300kA/m, and thus primary low-intensity magnetic separation concentrate and primary low-intensity magnetic separation tailings are obtained. And performing second-stage low-intensity magnetic separation concentration on the first-stage low-intensity magnetic separation concentrate, wherein the magnetic field intensity is 350kA/m, so as to obtain second-stage low-intensity magnetic separation concentrate and second-stage low-intensity magnetic separation tailings.
And (3) carrying out primary strong magnetic scavenging on the primary strong magnetic tailings with the magnetic field intensity of 960kA/m to obtain primary strong magnetic scavenging concentrate and primary strong magnetic scavenging tailings. And (4) carrying out second-stage strong magnetic scavenging on the first-stage strong magnetic scavenging tailings with the magnetic field intensity of 960kA/m to obtain second-stage strong magnetic scavenging concentrate and second-stage strong magnetic scavenging tailings.
The first-stage low-intensity magnetic separation tailings, the second-stage low-intensity magnetic separation tailings, the first-stage high-intensity magnetic separation scavenging concentrates and the second-stage high-intensity magnetic separation scavenging concentrates are returned to be subjected to magnetic separation step by step.
Roasting the second-stage low-intensity magnetic separation concentrate for 30 minutes at the temperature of 1000 ℃ and under the condition that the carbon powder content is 20%, and carrying out low-intensity magnetic separation on the roasted product with the magnetic field intensity of 350kA/m to obtain an iron product with the grade of 64.91% and the recovery rate of 74.82%.
The third step
Mixing the second-stage strong magnetic separation scavenging tailings with oxalic acid, butyl xanthate and terpineol for first-stage flotation, wherein the using amount of the oxalic acid is 800g, the using amount of the butyl xanthate is 600g, the using amount of the terpineol is 600g, the flotation time is 3 minutes, first-stage sulfur separation flotation concentrate (sulfur product) and first-stage sulfur separation flotation tailings are obtained, the grade of the sulfur product is 44.93%, and the recovery rate is 64.11%.
Mixing the first-stage sulfur-selecting flotation tailings with oxalic acid, butyl xanthate and terpineol to perform first-stage flotation scavenging, wherein the using amount of the oxalic acid is 400g, the using amount of the butyl xanthate is 300g, the using amount of the terpineol is 300g, and the flotation time is 3 minutes to obtain first-stage sulfur-selecting scavenging concentrate and first-stage sulfur-selecting scavenging tailings. Mixing oxalic acid, butyl xanthate and terpineol in the first-stage sulfur-dressing scavenging tailings to perform second-stage sulfur-dressing scavenging, wherein the using amount of the oxalic acid is 200g, the using amount of the butyl xanthate is 150g, the using amount of the terpineol is 150g, and the flotation time is 3 minutes, so that second-stage sulfur-dressing scavenging concentrate and second-stage sulfur-dressing scavenging tailings are obtained.
And returning the first-stage sulfur-selecting scavenging concentrate and the second-stage sulfur-selecting scavenging concentrate to flotation step by step.
The fourth step
Regrinding the second-stage sulfur-dressing scavenging tailings to obtain micro-fine particles, wherein the particle size of the micro-fine particles is not higher than 92% of the particle size of 0.074 mm.
The fifth step
Mixing the reground micro-fine particles with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform first-stage titanium flotation, wherein the use amount of the sodium fluosilicate is 700g, the use amount of the water glass is 550g, the use amount of the citric acid is 550g, the use amount of the sodium hexametaphosphate is 550g, the use amount of the lead nitrate is 1000g, the use amount of the benzohydroxamic acid is 600g, and the use amount of the salicylhydroxamic acid is 600g, and the flotation time is 3 minutes, so that first-stage titanium flotation concentrate and first-stage titanium flotation tailings are obtained.
Mixing the first-stage titanium flotation concentrate with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium flotation concentration, wherein the concentration is performed for 5 times, the dosage of each agent in the first 4 times of concentration is one third of that in the previous stage, the concentration in the 5 th time is blank concentration without adding any agent, and tailings obtained in each stage of concentration are returned to flotation step by step for 3 minutes each time of flotation. The 5 th concentration obtains titanium concentrate with the grade of 42.88 percent and the recovery rate of 67.32 percent.
Mixing the first-stage titanium flotation tailings with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium flotation scavenging for 3 times, wherein the dosage of scavenging for each time is one half of that of the previous stage, and concentrate obtained by scavenging at each stage is returned to flotation step by step for 3 minutes each time.
Mixing the five-section titanium-selecting concentrated concentrate with hydrochloric acid and hydrofluoric acid for acid leaching, wherein the concentration of the hydrochloric acid is 12%, the concentration of the hydrofluoric acid is 10%, the liquid-solid ratio is 5:1, and the acid leaching is carried out for 4 hours to obtain primary acid leaching residue, mixing the primary acid leaching residue with the hydrochloric acid and the hydrofluoric acid for acid leaching, wherein the concentration of the hydrochloric acid is 12%, the concentration of the hydrofluoric acid is 8%, the liquid-solid ratio is 5:1, and the acid leaching is carried out for 4 hours to obtain secondary acid leaching residue, namely a titanium product with the grade of 93.05% and the.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for comprehensively recovering iron, sulfur and titanium from complex multi-metal ores is characterized by comprising the following steps:
(1) carrying out ore grinding treatment on the complex polymetallic ore to obtain ore grinding fine materials;
(2) performing strong magnetic separation, weak magnetic separation and scavenging on the fine grinding materials in the step (1) in sequence to obtain iron ore concentrate and final strong magnetic scavenging tailings, and performing magnetization roasting and first-stage weak magnetic separation on the iron ore concentrate to obtain an iron product;
(3) mixing the final strong magnetic scavenging tailings obtained in the step (2) with oxalic acid, butyl xanthate and pine oil for sulfur flotation to obtain sulfur products and final sulfur flotation tailings;
(4) regrinding the final sulfur flotation tailings obtained in the step (3) to obtain reground fine materials;
(5) mixing the reground fine material obtained in the step (4) with sodium fluosilicate, water glass, citric acid, sodium hexametaphosphate, lead nitrate, benzohydroxamic acid and salicylhydroxamic acid to perform titanium selecting flotation, performing one-time roughing and more than one-time concentration to obtain titanium concentrate and selected flotation tailings of the corresponding-section selected flotation, and mixing the obtained titanium concentrate with hydrochloric acid and hydrofluoric acid to perform at least one-time acid leaching to obtain a titanium product.
2. The method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores according to claim 1, characterized in that when the ore grinding fine materials are subjected to strong magnetic separation, weak magnetic separation and scavenging in sequence in the step (2), the method comprises the following steps:
(2.1) carrying out primary strong magnetic separation on the ground fine materials to obtain primary strong magnetic separation concentrate and primary strong magnetic separation tailings;
(2.2) carrying out primary low-intensity magnetic separation on the primary high-intensity magnetic separation concentrate obtained in the step (2.1) to obtain primary low-intensity magnetic separation concentrate and primary low-intensity magnetic separation tailings;
(2.3) carrying out secondary low-intensity magnetic separation concentration on the primary low-intensity magnetic separation concentrated ore concentrate to obtain the final iron ore concentrate and secondary low-intensity magnetic separation concentrated tailings;
(2.4) carrying out primary strong magnetic scavenging on the primary strong magnetic tailings obtained in the step (2.1) to obtain primary strong magnetic scavenging concentrate and primary strong magnetic scavenging tailings;
(2.5) carrying out second-stage strong magnetic scavenging on the first-stage strong magnetic scavenging tailings obtained in the step (2.4) to obtain second-stage strong magnetic scavenging concentrate and the final strong magnetic scavenging tailings.
3. The method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores according to claim 2, which is characterized by further comprising the following steps:
(2.6) mixing the primary low-intensity magnetic separation fine tailings obtained in the step (2.2) with the grinding fine materials for primary high-intensity magnetic separation;
(2.7) mixing the second-stage low-intensity magnetic separation concentration tailings obtained in the step (2.3) with the first-stage high-intensity magnetic separation concentrate obtained in the step (2.1) to perform first-stage low-intensity magnetic separation concentration;
(2.8) mixing the primary strong magnetic separation scavenging concentrate obtained in the step (2.4) with the grinding fine material for primary strong magnetic separation;
(2.9) mixing the second-stage strong magnetic separation scavenging concentrate obtained in the step (2.5) with the first-stage strong magnetic separation tailings obtained in the step (2.1) to perform first-stage strong magnetic separation scavenging.
4. The method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores according to claim 1 or 2, characterized in that when the final strong magnetic scavenging tailings are mixed with oxalic acid, butyl xanthate and pine oil for sulfur flotation in the step (3), the method comprises the following steps:
(3.1) mixing the final strong magnetic scavenging tailings with oxalic acid, butyl xanthate and pine oil to perform first-stage sulfur flotation to obtain sulfur products and first-stage sulfur flotation tailings;
(3.2) mixing the first-stage sulfur-dressing flotation tailings obtained in the step (3.1) with oxalic acid, butyl xanthate and pine oil to perform first-stage sulfur-dressing scavenging to obtain first-stage sulfur-dressing scavenging concentrates and first-stage sulfur-dressing scavenging tailings;
(3.3) mixing the first-stage sulfur-dressing scavenging tailings obtained in the step (3.2) with oxalic acid, butyl xanthate and pine oil to perform second-stage sulfur-dressing scavenging to obtain second-stage sulfur-dressing scavenging concentrates and the final sulfur flotation tailings;
and (3.4) returning the first-stage sulfur-concentration scavenging concentrate obtained in the step (3.2) and the second-stage sulfur-concentration scavenging concentrate obtained in the step (3.3) to flotation step by step.
5. The method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores according to claim 1, characterized in that the step (5) adopts five-section concentration and three-section scavenging by one-section roughing, wherein 5-section concentration is adopted, the concentration flotation tailings obtained in each section are returned to the previous section for titanium flotation, the concentrates obtained in each stage of scavenging are returned to flotation step by step, and the titanium concentrates subjected to five-section concentration flotation are subjected to primary acid leaching to obtain primary acid leaching slag and primary acid leaching liquid; and mixing the primary acid leaching residue with hydrochloric acid and hydrofluoric acid for secondary acid leaching to obtain a titanium product.
6. The method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores according to one of claims 1 to 5, characterized in that in the step (1), the percentage of the ore grinding fine materials with the particle size not higher than 0.074mm accounts for 60-65%; in the step (4), the proportion of the reground fine material with the grain diameter not higher than 0.074mm is 90-95%.
7. The method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores according to claim 2, characterized in that in step (2), the magnetic field intensity of the first-stage strong magnetic separation is 900-1000 kA/m, in step (3), the magnetic field intensity of the first-stage weak magnetic separation is 300-400 kA/m, in step (4), the magnetic field intensity of the second-stage weak magnetic separation is 300-400 kA/m, in step (6), the magnetic field intensity of the first-stage strong magnetic separation is 900-1000 kA/m, and in step (7), the magnetic field intensity of the second-stage strong magnetic separation is 900-1000 kA/m.
8. The method for comprehensively recovering iron, sulfur and titanium from complex polymetallic ores according to claim 1, characterized in that in the step (2), the magnetizing roasting conditions are as follows: the roasting temperature is 900-1100 ℃, the roasting time is 30min, the carbon powder proportion is 20%, and the magnetic field intensity of the low-intensity magnetic separation is 300-400 kA/m.
9. The method for comprehensively recovering iron, sulfur and titanium from complex multi-metal ores according to claim 4, wherein in the step (3.1), based on 1t of the complex multi-metal ores, the dosage of oxalic acid for the first-stage sulfur flotation is 700-800 g, the dosage of butyl xanthate is 400-600 g, and the dosage of terpineol is 500-600 g; in the step (3.2), the dosage of oxalic acid is 350-400 g, the dosage of butyl xanthate is 200-300 g, and the dosage of terpineol is 250-300 g; in the step (3.3), the dosage of oxalic acid is 150-200 g, the dosage of butyl xanthate is 100-150 g, and the dosage of terpineol is 100-150 g.
10. The method for comprehensively recovering iron, sulfur and titanium from complex multi-metal ores according to claim 1, wherein the titanium flotation adopts one coarse, five fine and three sweeps, and based on 1t of the complex multi-metal ores, the dosage of a roughing medicament is as follows: 700-800 g of sodium fluosilicate, 400-600 g of water glass, 500-600 g of citric acid, 500-600 g of sodium hexametaphosphate, 800-1000 g of lead nitrate, 500-600 g of benzohydroxamic acid and 500-600 g of salicylhydroxamic acid; the agent dosage of the first four times of concentration of the fifth concentration is gradually reduced by two thirds relative to the agent dosage of the last flotation, and the fifth concentration is blank concentration without adding agent; the dosage of the chemicals for the third scavenging is gradually reduced by one half compared with the dosage of the chemicals for the previous stage of flotation; the acid leaching conditions are as follows: the hydrochloric acid concentration is 10-15%, the hydrofluoric acid concentration is 4-10%, and the liquid-solid ratio is 5:1, the acid leaching time is 4 hours.
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