Zinc collector GZ-1, and preparation method and application thereof

Abstract

The application provides a zinc collector GZ-1 and a preparation method and application thereof. The zinc collector GZ-1 is composed of isobutyl xanthate propylene ester, isobutyl xanthate ethyl formate, isobutyl methyl sulfide amine ester and 2-methyl-1-benzyl-2-propanol. The preparation method is mixing isobutyl xanthate propylene ester, isobutyl xanthate ethyl formate, isobutyl methyl sulfide amine ester and 2-methyl-1-benzyl-2-propanol in a proper ratio.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of metallurgical chemical industry, and particularly relates to a zinc collector GZ-1 and a preparation method and application thereof. BACKGROUND

[0002] Copper, lead and zinc minerals are usually symbiotic in nature, and due to the similar physical and chemical properties of copper, lead and zinc minerals and the dense symbiosis with quartz, feldspar and other gangue minerals, an efficient separation process needs to be developed in the beneficiation process to upgrade copper, lead and zinc minerals and reduce impurities. In recent years, with the development of economy, the demand for copper, lead and zinc in industry has greatly increased, resulting in a gradual decrease in easily selected ores and an increasing number of difficult-to-select polymetallic complex associated ores. In industry, ores with a grade lower than 3% are usually regarded as low-grade ores, and such ores usually contain valuable elements such as sulfur and iron that can be comprehensively recovered. The content and distribution of these elements have a huge impact on subsequent metal smelting processes, and therefore different methods of separation and recovery of associated metals are needed.

[0003] In order to comprehensively utilize copper, lead and zinc ores, a preferential flotation process, a bulk flotation process, an equal floatation process and an asynchronous flotation process can be used. Which process to use needs to consider the floatability difference of minerals, mineral properties, process test results and economic benefits and other factors, and the influence of different flotation sequences on beneficiation indexes is analyzed through test to determine the optimal flotation recovery process.

[0004] Due to the weathering of chalcopyrite in the ore, copper ions are easily oxidized and precipitated, resulting in the activation of pyrrhotite and pyrite. The use of xanthate collectors requires "strong pressure and strong pull", which greatly causes reagent waste, directly causing high treatment cost of beneficiation backwater and increased environmental protection pressure. For complex polymetallic ores, especially copper-iron polymetallic ores containing pyrrhotite, a zinc collector that can solve the above problems is urgently needed. SUMMARY

[0005] The first object of the present application is to provide a zinc collector GZ-1, the second object is to provide a preparation method of the zinc collector GZ-1, and the third object is to provide an application of the zinc collector GZ-1.

[0006] The first object of the present application is achieved by the zinc collector GZ-1 composed of isobutyl propylene xanthate, isobutyl ethyl xanthate formate, isobutyl methyl sulfonamide and 2-methyl-1-benzyl-2-propanol.

[0007] The second object of the present application is achieved by mixing the isobutyl propylene xanthate, isobutyl ethyl xanthate formate, isobutyl methyl sulfonamide and 2-methyl-1-benzyl-2-propanol in the formula.

[0008] The third object of the present application is achieved by the application of the zinc collector GZ-1 in a multi-metal comprehensive utilization and recovery process.

[0009] The zinc collector has high collecting capacity, can effectively separate zinc minerals and their associated minerals from ores, and has less usage amount of the reagent; has good selectivity, can collect specific minerals, reduces the inclusion of other minerals, and improves the concentrate quality; has strong alkali resistance or acid resistance, and wide use conditions; improves the flotation kinetics of fine-grained minerals, and improves the flotation speed; has good environmental performance, is easy to biodegrade, and has small environmental pollution. DETAILED DESCRIPTION

[0010] The present application is further described below in conjunction with examples, but does not limit the present application in any way, and any transformation or replacement based on the teaching of the present application belongs to the protection scope of the present application.

[0011] The zinc collector GZ-1 of the present application is composed of isobutyl propylene xanthate, isobutyl ethyl xanthate formate, isobutyl methyl sulfide amine and 2-methyl-1-benzyl-2-propanol.

[0012] The mass ratio of the isobutyl propylene xanthate, isobutyl ethyl xanthate formate, isobutyl methyl sulfide amine and 2-methyl-1-benzyl-2-propanol is (0.5-1.5):(0.5-1.5):(0.5-1.5):(0.4-0.6).

[0013] The mass ratio of the isobutyl propylene xanthate, isobutyl ethyl xanthate formate, isobutyl methyl sulfide amine and 2-methyl-1-benzyl-2-propanol is 1:1:1:0.5.

[0014] The preparation method of the zinc collector GZ-1 of the present application is to mix the isobutyl propylene xanthate, isobutyl ethyl xanthate formate, isobutyl methyl sulfide amine and 2-methyl-1-benzyl-2-propanol with the formula ratio.

[0015] The application of the zinc collector GZ-1 of the present application is the application of the zinc collector GZ-1 in a multi-metal comprehensive utilization and recovery process.

[0016] The present application is further described below in conjunction with specific implementation cases:

[0017] Example 1

[0018] Isobutyl propylene xanthate 5Kg, isobutyl ethyl xanthate formate 5Kg, isobutyl methyl sulfide amine 5Kg and 2-methyl-1-benzyl-2-propanol 4Kg are weighed, and the target zinc collector GZ-1 is obtained by stirring and mixing uniformly.

[0019] Example 2

[0020] The isobutyl xanthate propylene ester 15 Kg, isobutyl xanthate methyl formate ethyl ester 15 Kg, isobutyl methyl sulfide ester 15 Kg and 2-methyl-1-benzyl-2-propanol 6 Kg were weighed and stirred to obtain the target zinc collector GZ-1.

[0021] Example 3

[0022] The isobutyl xanthate propylene ester 12 Kg, isobutyl xanthate methyl formate ethyl ester 15 Kg, isobutyl methyl sulfide ester 10 Kg and 2-methyl-1-benzyl-2-propanol 5 Kg were weighed and stirred to obtain the target zinc collector GZ-1.

[0023] Example 4

[0024] The isobutyl xanthate propylene ester 8 Kg, isobutyl xanthate methyl formate ethyl ester 12 Kg, isobutyl methyl sulfide ester 10 Kg and 2-methyl-1-benzyl-2-propanol 5 Kg were weighed and stirred to obtain the target zinc collector GZ-1.

[0025] Example 5

[0026] The isobutyl xanthate propylene ester 12 Kg, isobutyl xanthate methyl formate ethyl ester 11 Kg, isobutyl methyl sulfide ester 12 Kg and 2-methyl-1-benzyl-2-propanol 6 Kg were weighed and stirred to obtain the target zinc collector GZ-1.

[0027] Example 6

[0028] The GZ-1 zinc collector prepared in Example 3 was tested, as follows:

[0029] 1 Sample properties

[0030] 1.1 Chemical composition and mineral composition

[0031] The ore was dark brown and gray green in color under naked eye observation, and the mineral aggregate was distributed without orientation, forming a sparse disseminated structure of the ore. The chemical multi-element analysis results of the ore sample are shown in Table 1, and the chemical phase analysis results of lead, zinc, copper and iron are shown in Tables 2, 3, 4 and 5.

[0032] Table 1 Main element chemical analysis results of the ore sample / %

[0033]

[0034] Table 2 Lead phase analysis results of the raw ore / %

[0035]

[0036] Table 3 Zinc phase analysis results of the raw ore / %

[0037]

[0038] Table 4 Ore phase analysis results of copper / %

[0039]

[0040] Table 5 Ore phase analysis results of iron / %

[0041]

[0042] The ore sample is a lead-zinc polymetallic sulfide ore, and the main valuable elements are lead, zinc and iron, with contents of 2.64%, 1.45% and 26.81%, respectively. Other associated valuable elements include Au 0.10 g / t, Ag 10.8 g / t, Cu 0.045%, In 55.3 g / t and sulfur 3.94%. Through polarizing microscope observation, X-ray diffraction analysis and MLA analysis, it is found that there are five types of 23 minerals in the ore, including sulfides, oxides, silicates, sulfates and phosphates. The main minerals in the ore include galena, marmatite, magnetite, pyrite / pyrite, pyrrhotite, zinnwaldite, ferrohortblende, quartz, calcite, etc.

[0043] 1.2 Analysis of the dissemination state of main minerals

[0044] Under the condition of grinding fineness of 64.39% passing 0.075 mm, MLA is used to measure and count the dissemination size of the main target minerals in the ore, including galena, marmatite, pyrrhotite, pyrite / pyrite, magnetite, hematite / brown iron ore, zinnwaldite, ferrohortblende, calcium iron garnet, epidote and iron talc. The dissemination size of marmatite, zinnwaldite and ferrohortblende is the coarsest, with +75 μm particle size accounting for 33.29%, 38.54% and 31.23%, respectively, which is similar to the size of the ore. The dissemination size of galena, pyrrhotite, pyrite / pyrite, magnetite, calcium iron garnet and iron talc is slightly finer than the former, with +75 μm particle size accounting for 28.17%, 26.98%, 25.16%, 29.55%, 27.37% and 26.39%, respectively.

[0045] 1.3 Symbiotic relationship of main minerals

[0046] Under the current grinding conditions, the free surface area of marmatite, pyrite and pyrrhotite is good, all greater than 91%, and the free surface area of galena, magnetite and hematite / brown iron ore is slightly lower than the former, between 83% and 86%.

[0047] Galena mainly intergrows with marmatite, magnetite, zinnwaldite, and ferrohedenbergite, and the proportion of the common surface area is 3.60%, 1.18%, 2.10%, and 1.99%, respectively. The proportion of the free surface area of galena is 86.50%.

[0048] Marmatite mainly intergrows with zinnwaldite and ferrohedenbergite, and the proportion of the common surface area is 1.24% and 1.30%, respectively. The proportion of the free surface area of marmatite is 93.89%.

[0049] Pyrite / marcasite mainly intergrows with marmatite, pyrrhotite, and zinnwaldite, and the proportion of the common surface area is 1.24%, 1.64%, and 1.69%, respectively. The proportion of the free surface area of pyrite / marcasite is 91.18%.

[0050] Pyrrhotite mainly intergrows with pyrite / marcasite, magnetite, and zinnwaldite, and the proportion of the common surface area is 1.05%, 1.45%, and 1.24%, respectively. The proportion of the free surface area of pyrrhotite is 92.54%.

[0051] Magnetite mainly intergrows with zinnwaldite, ferrohedenbergite, calcite, and smithsonite, and the proportion of the common surface area is 4.20%, 2.12%, 1.30%, and 1.96%, respectively. The proportion of the free surface area of magnetite is 85.34%.

[0052] 1.4 Dissemination characteristics of main minerals

[0053] The dissemination size of galena is between 0.001 and 1.37 mm, and the aggregate is granular and compact massive. Galena is closely associated with marmatite, magnetite, and pyrite, and is mostly intergrown or wrapped. In particular, part of the galena is wrapped in magnetite in a fine-grained form and is difficult to separate.

[0054] The dissemination size of marmatite is between 0.005 and 4.75 mm, and is irregular granular. Marmatite is mostly distributed between transparent minerals such as zinnwaldite and ferrohedenbergite, and is partially wrapped in zinnwaldite and ferrohedenbergite. Marmatite is partially intergrown or wrapped with galena, magnetite, pyrite, and pyrrhotite. In particular, part of the galena, magnetite, and pyrite is wrapped in marmatite in a fine-grained or milky form, and may partially enter the zinc concentrate, affecting the grade of the zinc concentrate.

[0055] The dissemination size of chalcopyrite is between 0.001 and 1.00 mm, and is irregular granular. Chalcopyrite is mostly intergrown with marmatite, galena, pyrite, and pyrrhotite, and is partially wrapped in marmatite in a fine-grained or milky form. A small number of chalcopyrite is distributed between transparent minerals in a star-like form.

[0056] The dissemination size of pyrrhotite is between 0.005-0.55mm, and the pyrrhotite is itomorphic granular. It is often associated with pyrite, marcasite, magnetite, marmatite and galena. Some of the pyrrhotite is metasomatized by marcasite and magnetite, and is distributed separately or mixedly.

[0057] The dissemination size of pyrite / marcasite is between 0.005-6.00mm, and the pyrite / marcasite is often self-similar-hemihedral-itomorphic granular. It is often distributed between the transparent minerals such as melanocerite and calcium iron pyroxene in disseminated form, and is often associated with marmatite, pyrrhotite and galena. Some of the pyrite is metasomatized by marcasite and magnetite, and is mixedly distributed separately.

[0058] The dissemination size of magnetite is between 0.005-1.25mm, and the magnetite is itomorphic granular. It is often closely associated with hematite, galena, marmatite and pyrite, and is partially filled between the acicular and platy hematite grains, partially inlaid and associated with galena, and partially simply associated with marmatite and pyrite. Some of the magnetite is metasomatized by hematite, and some of the pyrite is metasomatized by magnetite.

[0059] 1.5 Analysis of the mineralogical factors affecting the beneficiation indexes

[0060] The carrier minerals of lead in the ore are only galena, and the carrier minerals of zinc are only marmatite, which are independent sulfide minerals and are beneficial to the independent recovery by flotation. The Fe content in the marmatite is 12.69%, and this part of iron cannot be removed by physical beneficiation method, so the upper limit of the grade of zinc concentrate is grade VI. Most of the marmatite in the ore is wrapped with fine-grained and milky chalcopyrite, which is difficult to dissociate by grinding and may enter the zinc concentrate, affecting the grade of the zinc concentrate. Some of the galena is closely associated with marmatite, which may cause the marmatite to enter the lead concentrate with the galena, affecting the grade of the lead concentrate. There are many carrier minerals of iron in the ore, and only magnetite is the useful mineral of iron, and the distribution rate of iron in it is only 12.91%.

[0061] 2 Beneficiation test research

[0062] The valuable minerals in the ore are mainly galena, marmatite, chalcopyrite, pyrrhotite, magnetite and pyrite. Based on the surface characteristics and magnetism of the above minerals, the process flow of mineral recovery mainly includes the combined process of magnetic separation followed by flotation and the combined process of flotation followed by magnetic separation. Due to the small amount of magnetic separation, the magnetic separation is placed before lead flotation, and the thickening and dewatering before flotation is needed, which increases the complexity of the process. Therefore, the combined process of flotation followed by magnetic separation is adopted. The particles of galena with a size of less than 5 μm account for 3.72%, and most of the fine particles of galena are wrapped in magnetite. The selective collector can be used to pre-enrich the coarse concentrate, which can prevent the cost of fine grinding from being too high and reduce the degree of overgrinding of the target mineral. Due to the variety of recoverable minerals in the ore, the difficulty of the test lies in how to fully and efficiently recover various minerals and obtain high-quality concentrates. Since the copper content in the raw ore is very low, the direct preferential flotation is not economical, and therefore the principle process flow of copper-lead bulk flotation-zinc flotation-sulfur flotation-iron magnetic separation is initially determined.

[0063] 2.1 Grinding fineness test

[0064] The full dissociation of useful minerals and gangue minerals is a prerequisite for efficient separation and recovery of minerals. Different grinding fineness not only relates to the dissociation of minerals, but also ensures the high activity of mineral fresh surface, strengthens the full action of mineral surface and collector, and thus enhances the recovery and separation of minerals. In order to ensure high indicators of flotation, it is of great significance to determine the grinding fineness in combination with the properties of the ore. Since the ore contains calcite, iron asparagus and other easily-mud gangues, the appropriate grinding fineness should not only consider the dissociation degree of useful minerals, but also reduce the overgrinding of gangues to deteriorate the flotation slurry environment. Through the test, the grinding fineness of-74 μm accounting for 60% is more appropriate. Under the grinding fineness, when the flotation slurry concentration is 30%, the flotation machine stirring speed is 2000 r / min, the flotation machine air charge is 0.4 m 3 / h, and the natural pH value is adopted, the copper-lead collector type test is carried out with the process flow of one roughing and one scavenging by using different collectors, and the test results are shown in Table 6. As shown in Table 6, the five kinds of collectors are the copper-lead collectors with good selectivity screened out in the early stage, which basically do not capture pyrite at the natural pH value, effectively reducing the test of pyrite depressant. When Pa is used as the copper-lead collector alone, the lead grade of the rough concentrate is the highest, and the lead and copper recovery rate is the lowest; when Pb-1 and F5B are combined, the loss rate of lead in the tailings is the lowest, but the loss rate of copper is as high as 52.54%; when 25# black drug and GTB1 are combined, the loss rate of copper in the tailings is the lowest, and the lead recovery rate of the rough concentrate obtained by roughing is the highest. In order to comprehensively recover copper and lead minerals, the combination of 25# black drug and GTB1 is more appropriate.

[0065] Table 6 Grinding fineness test results

[0066]

[0067] 2.2 Copper-lead bulk concentrate regrinding site test

[0068] The copper-lead rough concentrate obtained by copper-lead roughing is subjected to three-stage cleaning to improve the copper-lead quality of the final concentrate. In order to investigate the influence of regrinding site on copper-lead recovery, comparative tests of no regrinding of rough concentrate, regrinding of rough concentrate to-0.049 mm accounting for 90%, regrinding of cleaning 1 concentrate to-0.049 mm accounting for 90%, and regrinding of cleaning 2 concentrate to-0.049 mm accounting for 90% are carried out to investigate the feasibility of reducing the copper-lead grade of middlings, improving the copper-lead bulk concentrate quality, and compared with no regrinding of rough concentrate, the lead grade of cleaning 1 concentrate can be greatly improved after regrinding of rough concentrate. Overall, the lead grade of copper-lead bulk concentrate obtained by cleaning 3 operation after regrinding of cleaning 2 is the highest, and the lead grade of copper-lead bulk concentrate is: regrinding of cleaning 2 > regrinding of cleaning 1 > regrinding of rough concentrate > no regrinding. Since cleaning 3 operation is carried out after regrinding of cleaning 2, the copper-lead recovery rate of copper-lead bulk concentrate is the largest, and comprehensive consideration shows that regrinding of cleaning 1 is more appropriate. The lead grade of copper-lead bulk concentrate obtained under the regrinding condition of cleaning 1 is 64.85%, and the copper grade is 0.91%. Since the copper grade is low, no subsequent copper-lead separation is carried out.

[0069] 2.3 Zinc sulfide ore depressant type test

[0070] According to X-ray energy spectrum analysis, the wurtzite contains Zn 53.54% and Fe 12.69%. With the increase of iron content in wurtzite, the iron ions change the surface properties, affect the adsorption of the collector on the surface, and cause the floatability to gradually decrease. The ore contains 1.44% of white pyrite / pyrite and 2.54% of pyrrhotite. According to X-ray energy spectrum analysis and MLA analysis, the pyrrhotite in the ore is monoclinic system, and the pyrrhotite contains Fe 60.56%. The floatability of white pyrite / pyrite, pyrrhotite and wurtzite gradually decreases. In order to obtain high-quality zinc concentrate, it is necessary to use sulfide ore depressant to inhibit white pyrite / pyrite and pyrrhotite. Different types of sulfide ore depressants, such as lime (3000 g / t), inorganic depressant LY1 (2000 g / t) and organic depressant LY2 (600 g / t), are used to investigate the effect of different depressants on zinc-sulfur separation. The effect of using lime as the depressant for white pyrite / pyrite and pyrrhotite is the best. Through one-stage zinc roughing and one-stage zinc scavenging, the foam product (combined zinc rough concentrate and zinc middlings) has the highest zinc grade of 29.64% and the highest zinc recovery rate of 85.39%.

[0071] 2.4 Zinc collector type test

[0072] The valuable minerals in the ore, such as pyrite and iron tourmaline, are easy to react with the collector, which interferes with the flotation process. A suitable zinc collector can not only significantly improve the flotation efficiency of zinc minerals, but also reduce the consumption of reagents, so a suitable zinc collector is an important prerequisite for achieving efficient and low-consumption flotation process. In this paper, the zinc collector species test was carried out by comparing the widely adaptable and strong collecting ability of butyl xanthate and ethylthiuram with the selective thioamino acid ester collector A2 and GZ-1. The most suitable collector for high-iron sphalerite was screened. The loss rate of tailings zinc was about 2% when GZ-1 and butyl xanthate were used as collectors, but the sulfur recovery rate of tailings obtained by GZ-1 was higher than that of butyl xanthate, indicating that butyl xanthate had strong collecting ability and more pyrite was collected into zinc rough concentrate and zinc concentrate; the collecting performance of A2 and ethylthiuram was basically similar, and the loss rate of zinc and the recovery rate of sulfur in the tailings were similar. In order to obtain the highest zinc recovery rate and minimize the pyrite entering the zinc rough concentrate and zinc concentrate, GZ-1 is more suitable.

[0073] 2.4 Zinc concentrate upgrading and impurity reduction test

[0074] The zinc rough concentrate is subjected to cleaning test, and it is found that, by adding lime and through three cleaning, the zinc grade of cleaning 1 concentrate is increased from 29.76% to 36.26%, increased by 6.50 percentage points; by cleaning 2, the zinc grade of cleaning 2 concentrate is increased from 36.26% to 39.12%, increased by 2.86 percentage points, and the increase is relatively small; by cleaning 3, the zinc grade of cleaning 3 concentrate (i.e. zinc secondary concentrate) is increased from 39.12% to 41.36%, increased by 2.24 percentage points, and the increase is relatively small. If the fourth cleaning is continued, the zinc increase of zinc concentrate is only 1.5 percentage points, but the loss rate of zinc is greatly increased, and the zinc grade of zinc concentrate is difficult to increase to more than 45%. The cleaning 3 concentrate is subjected to microscopic examination, and it is found that, the iron wurtzite is in irregular granular shape, most of which is single dissociated particle, part of the wurtzite is wrapped with fine chalcopyrite, and part of the wurtzite is intergrown with transparent mineral, pyrrhotite and pyrite; the pyrrhotite is in irregular granular shape, most of which is single dissociated particle, and part of which is intergrown with wurtzite; the pyrite is in irregular granular shape, and is mostly intergrown with wurtzite; the chalcopyrite is in irregular granular shape, and is mostly wrapped in wurtzite. The results show that the main factors affecting the zinc grade of zinc concentrate are pyrrhotite and pyrite. The floatability of the part of pyrrhotite and pyrite is good, and it is difficult to be inhibited by adding lime, and excessive addition of lime will cause significant inhibition of iron wurtzite. On the one hand, the zinc secondary concentrate is subjected to flotation test of adding dispersant and auxiliary lime for improving quality and reducing impurities, and on the other hand, the zinc secondary concentrate is subjected to magnetic separation test for removing impurities. Considering that the pyrrhotite is easy to be magnetically agglomerated and wrapped with iron wurtzite, sodium hexametaphosphate and widely used sodium silicate are used as dispersants. The results show that, by using magnetic separation for improving quality and reducing impurities of zinc concentrate, the recovery rate of zinc is relatively high, and is basically more than 99%. By comparing the results of four groups of tests, it is found that, by using 0.25T magnetic field for magnetic separation of zinc secondary concentrate, the zinc grade of zinc concentrate is 45.77%, and the recovery rate of zinc is 99.04%. The use of dispersant for flotation to improve the zinc grade of zinc concentrate results in a large loss rate of zinc. In view of the above, it is appropriate to use 0.25T for magnetic separation of zinc secondary concentrate for removing impurities.

[0075] 2.5 Whole-process closed-circuit test

[0076] The optimal regrinding fineness, the optimal magnetic field strength and the optimal reagent system were determined by conditional tests. The closed-circuit test was conducted to investigate the separation and recovery of each target mineral in copper-lead concentrate, zinc concentrate, sulfur concentrate, iron concentrate and tailings. The copper-lead mixed concentrate was obtained by one roughing, two scavenging and three cleaning in the copper-lead bulk flotation. The zinc secondary concentrate was obtained by two roughing, three cleaning and one scavenging in the zinc flotation. The zinc concentrate was obtained by 0.25T magnetic separation of the zinc secondary concentrate. The sulfur concentrate 1 was obtained by one roughing, one cleaning and one scavenging of the zinc tailings. The iron rough concentrate and tailings 1 were obtained by magnetic separation of the sulfur tailings. The sulfur concentrate 2 and the desulfurized iron concentrate were obtained by one regrinding, one desulfurizing roughing, one desulfurizing cleaning and one desulfurizing scavenging of the iron rough concentrate. The final iron concentrate was obtained by 0.15T magnetic cleaning of the desulfurized iron concentrate. The test results are shown in Table 7.

[0077] Table 7 Closed-circuit test results

[0078]

[0079] (1) The copper-lead mixed concentrate obtained by the test has a lead grade of 60.12%, a copper grade of 0.73%, a copper recovery rate of 33.36% and a lead recovery rate of 94.72%. The main factors affecting the quality of the copper-lead mixed concentrate are pyrite and marmatite. Since the associated copper grade is very low (copper content is 0.045%) and chalcopyrite is often intergrown with marmatite, galena, pyrite and pyrrhotite, the copper recovery rate of the copper-lead mixed concentrate is relatively low, and the copper content of the copper-lead mixed concentrate is only 0.73%, so the copper-lead separation is not economical, and thus the copper-lead separation is not performed. Part of the galena is mainly intergrown with marmatite, resulting in a zinc grade of 6.89% in the copper-lead mixed concentrate, which can be further studied to improve the separation efficiency of lead and zinc.

[0080] (2) The zinc concentrate has a zinc grade of 46.99% and a zinc recovery rate of 88.26%. Since part of the chalcopyrite is in the form of fine particles and milky white inclusions in the marmatite, 30.34% of the copper metal is lost in the zinc concentrate.

[0081] (3) The sulfur concentrate 1 and the sulfur concentrate 2 are combined into a sulfur concentrate, which has a sulfur grade of 37.41%, an iron grade of 47.69%, a sulfur recovery rate of 34.57% and an iron recovery rate of 6.23%. The ratio of pyrite / white pyrite:pyrrhotite in the ore is 1:1.76, and the maximum theoretical sulfur grade of the sulfur concentrate that can be obtained from the ore is 48.38%, and the iron grade is 51.62%. The results show that part of the pyrite / white pyrite is lost in the copper-lead mixed concentrate and the zinc concentrate, resulting in a low sulfur grade of the sulfur concentrate.

[0082] (4) The iron rough concentrate with iron grade of 61.00% and sulfur grade of 0.97% is obtained after sulfur scavenging and magnetic separation of the tailings. In order to obtain high-quality iron concentrate with iron grade of more than 65% and sulfur grade of less than 0.5%, the iron rough concentrate needs to be re-ground and then subjected to flotation desulfurization and magnetic separation.

[0083] (5) The iron recovery rate of the iron concentrate obtained by magnetic separation is 9.33%. According to the combination phase analysis and MLA analysis, the iron in the magnetite accounts for 13.15% of the total iron, indicating that the phase recovery rate of the magnetite in the iron concentrate is 70.95%. According to the analysis of the iron monomer dissociation degree of the tailings, most of the magnetite lost in the tailings is not dissociated, and this part of the magnetite is difficult to be economically recovered.

[0084] 3 Conclusion

[0085] (1) The main valuable elements of the polymetallic ore in Qinghai are lead, zinc and iron, with contents of 2.64%, 1.45% and 26.81%, respectively. Other associated valuable elements are Au 0.10 g / t, Ag 10.8 g / t, Cu 0.045%, In 55.3 g / t and sulfur 3.94%.

[0086] (2) The ore is composed of five types of 23 minerals. The independent minerals of copper, lead and zinc are chalcopyrite, galena and marmatite. There are 12 independent minerals of iron, and iron mainly exists in the form of independent minerals in melanocerite, hedenbergite and magnetite. The distribution rates of iron in them are 46.83%, 16.71% and 13.15%, respectively. Only the iron in the magnetite has recovery value.

[0087] (3) The ore is treated by the combined process of copper-lead bulk flotation-zinc flotation-sulfur flotation-iron magnetic separation-iron flotation, and the mixed copper-lead concentrate with lead grade of 60.12% and copper grade of 0.73% is obtained, with copper recovery rate of 33.36% and lead recovery rate of 94.72%. The zinc concentrate with zinc grade of 46.99% is obtained, with zinc recovery rate of 88.26%. The iron concentrate with iron grade of 67.22% is obtained, with iron recovery rate of 9.33%.

[0088] Example 7

[0089] The zinc collecting agent GZ-1 prepared by example 1, example 2, example 4 and example 5 is respectively subjected to experiments, and the method is the same as that in example 6. The results all show that the zinc collecting agent GZ-1 is more suitable in the process of comprehensive recovery of copper and lead minerals.

Claims

1. A zinc collector GZ-1, characterized in that, The zinc collector GZ-1 is composed of isobutyl xanthate propylene ester, isobutyl xanthate ethyl formate, isobutyl methyl sulfide and 2-methyl-1-benzyl-2-propanol; the mass ratio of isobutyl xanthate propylene ester, isobutyl xanthate ethyl formate, isobutyl methyl sulfide and 2-methyl-1-benzyl-2-propanol is (0.5-1.5):(0.5-1.5):(0.5-1.5):(0.4-0.6).

2. The zinc collector GZ-1 according to claim 1, characterized in that, The mass ratio of the isobutyl xanthate propylene ester, isobutyl xanthate ethyl formate, isobutyl methyl sulfide and 2-methyl-1-benzyl-2-propanol is 1:1:1:0.

5.

3. A process for the preparation of the zinc collector GZ-1 according to claim 1 or 2, characterized in that, The isobutyl xanthate propylene ester, isobutyl xanthate ethyl formate, isobutyl methyl sulfide and 2-methyl-1-benzyl-2-propanol are mixed uniformly.

4. Use of the zinc collector GZ-1 according to claim 1 or 2, characterized in that The application of the zinc collector GZ-1 in a multi-metal comprehensive utilization and recovery process.

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