High-efficiency beneficiation method for high-silicon gangue type low-grade zinc oxide ore

Abstract

High-silicon gangue type low-grade zinc oxide ore high-efficiency beneficiation method, using fatty acid collector preferentially desiliconized flotation carbonate + carbonate concentrate amine + xanthate zinc sulfidation combined process, obtain low SiO2 impurity content of zinc oxide concentrate, realize the efficient recovery of high-silicon gangue type low-grade zinc oxide ore, including the following steps and conditions: one stage grinding, grinding fineness -0.074mm accounts for 40~60%, using sulfuric acid to adjust the pulp, using fatty acid collector to rough select carbonate, adding inhibitor to rough selection foam to carry out 3 times of cleaning, obtain carbonate concentrate with preliminary enrichment of zinc spar, the dissociation degree of zinc spar in the ore reaches more than 85%; carbonate concentrate adding inhibitor, using amine + xanthate sulfidation process to rough select zinc oxide, adding inhibitor to rough selection foam to carry out 4 times of cleaning, obtain zinc oxide concentrate; adding amine + xanthate combined collector to the tailings of rough selection to carry out scavenging, the middlings of cleaning and the concentrate of scavenging are returned in sequence. It has the advantages of obtaining higher grade zinc oxide concentrate, reducing production cost and improving the utilization rate of silicon gangue type low-grade zinc oxide ore.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of zinc oxide ore dressing, and particularly relates to a high-efficiency dressing method for high-silica gangue type low-grade zinc oxide ore. BACKGROUND

[0002] According to the statistics of relevant departments in 2008, the zinc resource amount in China is 10393 million tons, ranking the second in the world, of which the zinc oxide ore resource is more than 4000 million tons. The zinc resource amount in Yunnan Province is 2028.9 million tons, accounting for 23% of the domestic zinc resource amount, ranking the first in China, of which the zinc oxide ore accounts for 41.8%, and most of them are low-grade ores. In addition, the northwest region of China also has a large amount of low-grade zinc oxide ore resources. Overall, the zinc oxide ore resource in China has low grade, the average grade is less than 5%, the resource amount is large, but is limited by the existing technical level, and is not efficiently developed and utilized. Especially in the development and utilization of the high-silica gangue type low-grade zinc oxide ore with the SiO2 content being greater than 70%, the zinc content being 2-6%, the lead content being less than 0.5%, and the zinc oxidation rate being greater than 80%, because of the low grade, the traditional acid leaching process is not applicable due to the high production cost. At the same time, because the acid leaching process has low selectivity, a large amount of soluble silicon in the ore is leached out, and the generated colloidal silicon is difficult to filter, resulting in that the production process is difficult to continue. The traditional amine sulfuration method flotation process is limited by the poor selectivity of amine collectors, and often has the problems of low concentrate grade and high SiO2 impurity content.

[0003] To solve the above or and similar problems, Chinese patent CN202111067879.8 discloses "Application in quartzite type zinc oxide ore sphalerite flotation collector and flotation method", obviously aiming at developing a new quartzite zinc oxide ore collector; Chinese patent CN201811195420.4 discloses "A dolomite and calcite type sulfide and oxidized lead-zinc ore flotation method", aiming at mixed lead-zinc ore, which has both sulfide lead-zinc ore flotation method and oxidized lead-zinc ore flotation method. In the flotation of oxidized zinc, dodecylamine and butyl xanthate collectors are used. The former is because the gangue mineral is dolomite and calcite, and the inhibitor used is different from that of quartz gangue type, and the addition ratio of dodecylamine and butyl xanthate is different; Chinese patent CN202210395531.X discloses "A high calcium and magnesium high argillaceous zinc carbonate flotation recovery method", aiming at another type of high calcium and magnesium high argillaceous zinc oxide ore, the gangue mineral is mainly dolomite and calcite, and the ore is easy to be slimed during grinding. Excessive slime will deteriorate the flotation. Therefore, there is a desliming process in the beneficiation process. The beneficiation process is different. Although dodecylamine and butyl xanthate are also used as collectors, the gangue mineral is dolomite and calcite, and the inhibitor used is different from that of quartz gangue type. In addition, this method has both sulfide lead-zinc ore flotation method and oxidized lead-zinc ore flotation method. In the flotation of oxidized zinc, dodecylamine and butyl xanthate are used as collectors. However, the gangue mineral is dolomite and calcite, and the inhibitor used is different from that of quartz gangue type, and the addition ratio of dodecylamine and butyl xanthate is different.

[0004] Therefore, it is of great significance to develop a low-cost, environmentally friendly and efficient high-silicon gangue type low-grade zinc oxide ore efficient beneficiation method. SUMMARY

[0005] The task of the present application is to overcome the shortcomings of the prior art and provide a high-silicon gangue type low-grade zinc oxide ore efficient beneficiation method, which can obtain high-grade zinc oxide concentrate and reduce production cost and improve the utilization rate of high-silicon gangue type low-grade zinc oxide ore.

[0006] The high-silicon gangue type low-grade zinc oxide ore efficient beneficiation method uses fatty acid collectors to preferentially remove silicon and float carbonates + carbonate concentrate amine + xanthate sulfide zinc combination process to obtain low-SiO2 impurity content zinc oxide concentrate, realizing efficient recovery of high-silicon gangue type low-grade zinc oxide ore, and specifically including the following steps and conditions:

[0007] (1) One-stage grinding, grinding fineness-0.074mm accounts for 40-60%, using sulfuric acid to adjust the pulp, using fatty acid collectors for carbonates roughing, adding inhibitors to the roughing foam for 3 times cleaning, obtaining carbonates concentrate with preliminary enrichment of sphalerite, and the sphalerite dissociation degree of the ore reaches more than 85%;

[0008] (2) Add inhibitors to carbonate concentrate and use amine + xanthate sulfidation process for zinc oxide roughing. Add inhibitors to the roughing foam for four cleaning processes to obtain zinc oxide concentrate. Add amine + xanthate combined collectors to the roughing tailings for scavenging. The middlings and scavenging concentrate are returned in sequence.

[0009] The innovation of this invention lies in the use of carbonate positive flotation to remove a large amount of SiO2, thereby initially enriching smithsonite in the carbonate concentrate. This effectively improves the SiO2 inhibition effect of subsequent zinc beneficiation using amine + xanthate sulfidation, resulting in a higher-grade zinc oxide concentrate. Reducing the SiO2 impurity content in the concentrate is beneficial for subsequent wet zinc extraction processes, significantly reducing the leaching of soluble silicon, improving the filterability of the leachate, and lowering costs, thus enabling the efficient development and utilization of low-grade zinc oxide ore.

[0010] In summary, compared with the prior art, the present invention has advantages or effects:

[0011] Because of the specific characteristics of the ore, carbonates are prioritized to remove a large amount of SiO2, which greatly improves the problem of SiO2 inhibition in the zinc beneficiation process of carbonate concentrate amine + xanthate sulfidation, resulting in a higher grade zinc oxide concentrate. At the same time, the zinc oxide concentrate with low SiO2 impurity content is beneficial to the subsequent wet zinc extraction process, thus greatly reducing the leaching of soluble silicon and improving the filterability of the leachate. In addition, due to the simplicity of the process, the production cost is low and the utilization rate of high-silica gangue type low-grade zinc oxide ore is significantly improved.

[0012] The percentages mentioned in the application documents refer to quality percentages. Attached Figure Description

[0013] Figure 1 This is a schematic diagram of the process flow for an efficient beneficiation method for high-silica gangue-type low-grade zinc oxide ore based on the present invention.

[0014] The present invention will now be described in further detail with reference to the accompanying drawings. Detailed Implementation

[0015] like Figure 1 As shown, to address the issues of high SiO2 content in the ore and zinc primarily occurring in smithsonite, a combined process of fatty acid collector-based desilication flotation of carbonates + carbonate concentrate amine + xanthate sulfidation zinc beneficiation is employed to obtain zinc oxide concentrate with low SiO2 impurity content. This achieves efficient recovery of high-silica gangue-type low-grade zinc oxide ore, specifically including the following steps and conditions:

[0016] (1) one stage grinding, grinding fineness -0.074mm accounts for 40-60%, using sulfuric acid to adjust the pulp, using fatty acid collector to roughen the carbonate, adding inhibitor to froth in roughing, and using 3 times of cleaning to obtain the carbonate concentrate of preliminary enrichment of smithsonite, and the dissociation degree of smithsonite in the ore reaches more than 85%;

[0017] (2) adding inhibitor to the carbonate concentrate, using amine + xanthate sulfuration process to roughen the zinc oxide, adding inhibitor to froth in roughing, and using 4 times of cleaning to obtain the zinc oxide concentrate; adding amine + xanthate combined collector to the tailings of roughing to conduct scavenging, and returning the middlings of cleaning and the concentrate of scavenging in sequence.

[0018] The process of the application can be further:

[0019] The tailings of roughing in step (1) are added with fatty acid collector to conduct scavenging.

[0020] The middlings of cleaning and the concentrate of scavenging in step (1) are returned in sequence for re-concentration.

[0021] The tailings of roughing in step (2) are added with amine + xanthate combined collector to conduct scavenging.

[0022] The middlings of cleaning and the concentrate of scavenging in step (2) are returned in sequence for re-concentration.

[0023] The pH value of the pulp is adjusted to 5.5-6.5 using sulfuric acid in step (1).

[0024] The collector for roughing and scavenging of the carbonate in step (1) is fatty acid collector PA67, which has good selectivity and collecting capacity for carbonate minerals under weak acid condition.

[0025] The dosage of fatty acid collector PA67 for roughing of the carbonate in step (1) is 400-800g / t.

[0026] The dosage of fatty acid collector PA67 for scavenging of the carbonate in step (1) is 100-150g / t.

[0027] The inhibitor for cleaning of the carbonate in step (1) is sodium silicate with modulus of 2.5-3.0, and the dosage is 100-150g / t, which can inhibit quartz.

[0028] The inhibitor for re-concentration of the carbonate in step (2) is combined reagent of carboxymethyl cellulose CMC + sodium silicate with modulus of 2.5-3.0, which can further strengthen the inhibition of quartz, and the dosage of CMC for roughing is 40-60g / t, the dosage of sodium silicate for roughing is 80-120g / t, the dosage of CMC for cleaning is 4-25g / t, and the dosage of sodium silicate for cleaning is 8-50g / t.

[0029] The zinc sulfidation agent for the step (2) re-concentration of the carbonate concentrate is sodium sulfide, and the dosage is 500-800 g / t.

[0030] The step (2) re-concentration of the carbonate concentrate is rough concentration and scavenging concentration of zinc, and the collecting agent is a combination of fatty acid collecting agent dodecylamine and butyl xanthate, which has strong collecting capacity for smithsonite.

[0031] The dosage of the collecting agent dodecylamine for the step (2) rough concentration of the carbonate concentrate is 5-15 g / t, and the dosage of butyl xanthate is 10-30 g / t.

[0032] The dosage of the collecting agent dodecylamine for the step (2) scavenging concentration of the carbonate concentrate is 2-5 g / t, and the dosage of butyl xanthate is 4-8 g / t.

[0033] The flotation process for the step (1) preferential flotation of carbonate is a closed-circuit process of “one rough concentration-three concentration-one scavenging”, and the middlings of concentration and the concentrate of scavenging are sequentially returned to re-concentration.

[0034] The flotation process for the step (2) re-concentration of the carbonate concentrate is a closed-circuit process of “one rough concentration-four concentration-one scavenging”, and the middlings of concentration and the concentrate of scavenging are sequentially returned to re-concentration.

[0035] Example 1

[0036] The beneficiation test research is conducted on the high-silicon and low-grade zinc oxide ore of a zinc oxide ore site 1 in Xinjiang by using the method of the present application, and the element analysis of the raw ore is shown in Table 1.

[0037] Table 1 Element analysis results of the raw ore of the site 1 (%)

[0038]

[0039] *g / t

[0040] From the data in Table 1, it can be known that the main metal element that can be recovered from the ore is Zn, and according to the properties of the raw ore, the process of the present application is adopted, and the specific process flow is as follows:

[0041] (1) One-stage grinding, the pulp is adjusted by sulfuric acid, the rough concentration of carbonate is conducted by using fatty acid collecting agent, the foam of rough concentration is added with an inhibitor to conduct three times of concentration, and the carbonate concentrate is obtained; the tailings of rough concentration are added with fatty acid collecting agent to conduct scavenging concentration, and the middlings of concentration and the concentrate of scavenging are sequentially returned.

[0042] (2) The carbonate concentrate is added with an inhibitor, and the zinc oxide rough concentration is conducted by using amine+ xanthate sulfidation process. The foam of rough concentration is added with an inhibitor to conduct four times of concentration, and the zinc oxide concentrate is obtained; the tailings of rough concentration are added with a combination of (amine+ xanthate) collecting agent to conduct scavenging concentration, and the middlings of concentration and the concentrate of scavenging are sequentially returned.

[0043] As shown in the accompanying drawings, Figure 1As shown, the ore is first ground, the grinding fineness is controlled to be 54.38% of -0.074 mm, then flotation is carried out, sulfuric acid is added to adjust the pH value of the ore pulp to 6, fatty acid collector PA67 is added at 550 g / t for roughing; the rough concentrate is subjected to three times of cleaning, the inhibitors water glass (modulus 2.7) are added at 140 g / t and 120 g / t for cleaning I and cleaning II respectively, and no inhibitor is added for cleaning III; the roughing tailings are subjected to one time of scavenging, and the collector PA67 is added at 130 g / t.

[0044] The re-selection step of the carbonate concentrate is carried out, the combined inhibitor CMC + water glass is added at 50 + 100 g / t, sodium sulfide is used as a sulfidizing agent at 600 g / t, and the combined collector dodecylamine + butyl xanthate is used at 10 + 20 g / t; the rough concentrate is subjected to four times of cleaning, the combined agents CMC + water glass (modulus 2.7) are added at 20 + 40 g / t, 10 + 20 g / t and 5 + 10 g / t for cleaning I, cleaning II and cleaning III respectively; no inhibitor is added for cleaning IV; the roughing tailings are subjected to one time of scavenging, and the collector dodecylamine + butyl xanthate is added at 3 + 5 g / t.

[0045] The test results are shown in Table 2. As can be seen from the test results in Table 2, by using the combined process flow of preferential selection of carbonate (one roughing-three cleaning-one scavenging)-sulfidation of carbonate concentrate (amine + xanthate) selection of zinc (one roughing-four cleaning-one scavenging), a zinc concentrate with a zinc grade of 29.79%, a lead content of 1.66% and a SiO2 content of 8.88% can be obtained, and the zinc recovery rate is 74.28%.

[0046] Table 2 Test results of Example 1 (%)

[0047]

[0048] Example 2

[0049] The beneficiation test research is carried out on the high-silicon low-grade zinc oxide ore of a zinc oxide ore site 2 in Xinjiang by using the method of the present application, and the element analysis of the raw ore is shown in Table 3.

[0050] Table 3 Element analysis results of raw ore of site 2 (%)

[0051]

[0052] *g / t

[0053] As can be seen from the data in Table 1, the main metal element that can be recovered from the ore is Zn, and according to the properties of the raw ore, the process of the present application is adopted, and the specific process flow is as follows:

[0054] (1) One stage grinding, using sulfuric acid to adjust pulp, using fatty acid as collector to rough concentrate carbonate, adding inhibitor to froth to concentrate carbonate by three times cleaning, using fatty acid as collector to clean tailings, middlings of cleaning and cleaned concentrate return in order.

[0055] (2) Adding inhibitor to carbonate concentrate, using amine + xanthate to rough concentrate zinc oxide, adding inhibitor to froth to concentrate zinc oxide by four times cleaning, using (amine + xanthate) as combined collector to clean tailings, middlings of cleaning and cleaned concentrate return in order.

[0056] The ore is first ground to a fineness of -0.074 mm 49.93%, then floated, using sulfuric acid to adjust pH of the pulp to 6, using fatty acid as collector to rough concentrate carbonate, using sodium silicate as inhibitor to concentrate carbonate by three times cleaning, using fatty acid as collector to clean tailings.

[0057] The carbonate concentrate is re-concentrated, using combined inhibitor CMC + sodium silicate to rough concentrate carbonate, using sodium sulfide as sulfidizing agent, using dodecylamine + butyl xanthate as combined collector, using sodium silicate as inhibitor to concentrate carbonate by four times cleaning, using dodecylamine + butyl xanthate as combined collector to clean tailings.

[0058] The test results are shown in Table 4. From the test results in Table 4, using the combined process of preferentially concentrating carbonate (one rough - three clean - one clean) and sulfidizing carbonate concentrate (amine + xanthate) to concentrate zinc (one rough - four clean - one clean), zinc concentrate with zinc grade 27.71%, lead content 2.41%, SiO2 content 9.83% is obtained, with zinc recovery 69.92%.

[0059] Table 4 Test results of Example 2 (%)

[0060]

[0061] *g / t

[0062] The application can be realized as above. The above embodiment is only the best mode of the application, but the embodiment of the application is not limited by the above embodiment, and other changes, modifications, replacements, combinations, simplifications, which are not deviated from the spirit and principles of the application, should be equivalent replacement modes, and all are included in the protection scope of the application.

Claims

1. A high-efficiency beneficiation method for high-silica gangue type low-grade zinc oxide ore, characterized in that... A combined process of preferential desilication flotation of carbonates using fatty acid collectors, followed by carbonate concentrate amine and xanthate sulfidation zinc beneficiation, yields zinc oxide concentrate with low SiO2 impurity content. This achieves efficient recovery of high-silica gangue-type low-grade zinc oxide ore. The specific steps and conditions include: (1) First-stage grinding, with a grinding fineness of -0.074mm accounting for 40-60%, sulfuric acid is used to adjust the slurry, and fatty acid collectors are used for carbonate roughing. The roughing foam is treated with inhibitors and three cleaning processes are carried out to obtain carbonate concentrate with preliminary enrichment of smithsonite. The degree of liberation of smithsonite in the ore reaches more than 85%. (2) Add inhibitors to carbonate concentrate and use amine + xanthate sulfidation process for zinc oxide roughing. Add inhibitors to roughing foam and perform 4 cleaning processes to obtain zinc oxide concentrate. Add amine + xanthate combined collectors to roughing tailings for scavenging. The middlings and scavenging concentrate are returned in sequence.

2. The method according to claim 1, characterized in that: In step (1), fatty acid collectors are added to the roughing tailings for scavenging.

3. The method according to claim 1 or 2, characterized in that: In step (1), the selected middlings and scavenged concentrate are returned to the selection process in sequence.

4. The method according to claim 1, characterized in that: In step (2), the rough tailings are scavenged by adding an amine + xanthate combined collector.

5. The method according to claim 1 or 4, characterized in that: In step (2), the selected middlings and scavenged concentrate are returned to the selection process in sequence.

6. The method according to claim 1, characterized in that: In step (1), sulfuric acid is used to adjust the pH value of the slurry, and the pH value of the slurry is controlled between 5.5 and 6.

5.

7. The method according to claim 1, characterized in that: The carbonate roughing and scavenging collector in step (1) is fatty acid collector PA67.

8. The method according to claim 1, characterized in that: The amount of carbonate crude fatty acid collector PA67 used in step (1) is 400-800 g / t.

9. The method according to claim 1, characterized in that: The amount of carbonate scavenging fatty acid collector PA67 used in step (1) is 100-150 g / t.

10. The method according to claim 1, 6, 8 or 9, characterized in that... The carbonate inhibitor selected in step (1) is water glass with a modulus of 2.5 to 3.0, and the dosage is 100 to 150 g / t, which can inhibit quartz.

11. The method according to claim 1, characterized in that: The carbonate reselection zinc inhibitor in step (2) is a combination of carboxymethyl cellulose (CMC) and water glass with a modulus of 2.5 to 3.0, which can further enhance the inhibition of quartz.

12. The method according to claim 1, characterized in that: In step (2), the amount of CMC used for rough selection is 40-60 g / t, and the amount of water glass used is 80-120 g / t.

13. The method according to claim 1, characterized in that: In step (2), the amount of CMC used is 4-25 g / t and the amount of water glass is 8-50 g / t.

14. The method according to claim 1, characterized in that: In step (2), the zinc sulfiding agent for the re-selection of carbonate concentrate is sodium sulfide, and the dosage is 500-800 g / t.

15. The method according to claim 1, characterized in that: In step (2), the zinc roughing and scavenging collector for the re-selection of carbonate concentrate is a combination of fatty acid collector dodecylamine and butyl xanthate.

16. The method according to claim 1, characterized in that: In step (2), the amount of dodecylamine collector used in the zinc roughing process of carbonate concentrate is 5-15 g / t, and the amount of butyl xanthate is 10-30 g / t.

17. The method according to claim 1, 11, 12, 13, 14, 15 or 16, characterized in that: In step (2), the amount of dodecylamine, the zinc scavenging collector used in the re-selection of carbonate concentrate, is 2-5 g / t, and the amount of butyl xanthate is 4-8 g / t.

18. The method according to claim 1, characterized in that... Step (1) The flotation process for priority carbonate flotation is a closed-loop process of "one rougher - three cleaners - one scavenger". The middlings from the cleaner flotation and the scavenger concentrate are returned sequentially for further flotation.

19. The method according to claim 1 or 18, characterized in that: The zinc flotation process for carbonate concentrate in step (2) is a closed-loop process of "one roughing-four cleaning-one scavenging", in which the middlings from the cleaned concentrate and the scavenged concentrate are returned sequentially for further selection.

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