A beneficiation method for separating pyrrhotite from marmatite and a zinc-sulfur inhibitor

Abstract

The application discloses a beneficiation method for separating pyrrhotite from marmatite and a zinc-sulfur inhibitor, the raw ore is marmatite containing pyrrhotite and pyrrhotite, the zinc-sulfur inhibitor T28 is added into the raw ore for grinding to obtain a slurry, CuSO4 is added into the slurry for sufficient stirring, zinc collector ZY402 is added into the stirred slurry for zinc roughing to obtain roughing zinc concentrate and roughing zinc tailings, the roughing zinc concentrate is subjected to three times of cleaning operation, the roughing zinc tailings are added with the zinc collector for three times of scavenging, finally, zinc scavenging tailings and zinc concentrate are obtained, the zinc scavenging tailings are subjected to one time of sulfur roughing, two times of sulfur scavenging and one time of sulfur cleaning to obtain sulfur concentrate and tailings. The application has the advantages of simple technological process, low equipment investment, low reagent cost, high separation efficiency, strong adaptability to ore property fluctuation, stable process, great theoretical value and economic value for the development of lead-zinc ore beneficiation which meets the increasingly strict environmental protection requirements.

Description

Technical Field

[0001] This invention relates to the field of sulfide ore beneficiation and separation technology, specifically to a beneficiation method for separating pyrrhotite and sphalerite, and a zinc-sulfur inhibitor. Background Technology

[0002] Both pyrrhotite and sphalerite possess a degree of magnetism, and pyrrhotite exhibits variable floatability, easily entering the concentrate during flotation, thus posing a significant challenge to separating them. Currently, in ores where pyrrhotite and sphalerite coexist, magnetic separation is commonly used to remove pyrrhotite and high-alkali flotation of sphalerite. However, the beneficiation method of removing pyrrhotite and high-alkali sphalerite by magnetic separation mainly uses lime to suppress pyrrhotite and pyrrhotite. The large-scale use of magnetic separation and lime has the following problems: (1) Magnetic separation easily causes some sphalerite to be lost in the magnetic concentrate; (2) Before zinc beneficiation, the tailings of magnetic separation need to be concentrated, which requires the addition of corresponding equipment and increases the cost of equipment use and maintenance; (3) Magnetic separation and concentration operations increase the exposure time of the slurry in the air, which changes the ore properties and increases the difficulty of flotation of sphalerite; (4) The use of lime causes equipment scaling and corrosion, which increases the cost of equipment maintenance; (5) High-alkali return water causes serious environmental pollution; (6) After the pyrrhotite that has not been recovered by magnetic separation is severely suppressed by lime, it is difficult to activate. A large amount of strong acid needs to be added for activation. The use of strong acid and strong alkali is not conducive to environmental protection requirements. In summary, magnetic separation complicates mineral processing operations and reduces the recovery rate of iron sphalerite. At the same time, under strict environmental protection requirements, sulfur flotation using lime-based depressants requires strong acid activation, and the application of strong acids and alkalis does not meet environmental protection requirements. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a beneficiation method for separating pyrrhotite and sphalerite, along with a zinc-sulfur inhibitor. This method eliminates the need for magnetic separation and avoids environmental pollution and pipeline calcium buildup caused by lime-based inhibitors. Furthermore, it avoids the difficulties in subsequent activation processes caused by excessive inhibition during flotation, thus facilitating further improvement in zinc metal recovery. The development of novel composite non-toxic zinc-sulfur inhibitors and zinc flotation collectors has significant practical implications for the beneficiation of pyrrhotite and sphalerite.

[0004] The specific technical solution is as follows:

[0005] This invention protects a mineral processing method for separating pyrrhotite and sphalerite, specifically comprising the following steps:

[0006] Step 1, Grinding: Grind the raw ore to a fineness of -0.074mm, accounting for 55% to 85%, to obtain raw ore slurry. During grinding, zinc-sulfur inhibitor T28 is added.

[0007] Step 2, stirring: After adding CuSO4 to the raw ore slurry obtained in Step 1, it is then added to a mixing tank and stirred thoroughly to obtain slurry A. The stirring time of the raw ore slurry is ≥9 minutes.

[0008] Step 3, Zinc flotation: Add the slurry A obtained in step 2 to the flotation machine for one zinc roughing, three zinc scavenging and three zinc cleaning to obtain zinc concentrate and zinc scavenging tailings. During the zinc roughing process, zinc collector ZY402 is added. During each zinc cleaning process, zinc sulfur inhibitor T28 is added. During each zinc scavenging process, zinc collector ZY402 is added.

[0009] The zinc-sulfur inhibitor T28 is a composite inhibitor composed of sodium sulfite and humate, wherein the mass ratio of each component in the composite inhibitor is 60-70:10-30.

[0010] The zinc collector ZY402 is composed of the following raw materials in parts by weight: 40-80 parts of N,N-dialkyldithioaminoethylene ester, 40-60 parts of hydrocarbon dithiophosphate thioether ester, 20-30 parts of carbon disulfide, and 10-20 parts of sodium hydroxide.

[0011] Step 4, sulfur flotation: The zinc scavenging tailings obtained in step 3 are subjected to one sulfur roughing, two sulfur scavenging and one sulfur cleaning to obtain sulfur concentrate and tailings. Sulfur collector and frother are added during the sulfur roughing process and sulfur collector is added during each sulfur scavenging process.

[0012] Furthermore, in step 1, the grinding fineness has different requirements depending on the different raw ores.

[0013] Furthermore, in step 2, the stirring time of the raw ore slurry is ≥9 minutes.

[0014] Furthermore, in step 3, the humate is one or both of sodium humate and potassium humate.

[0015] Furthermore, in step 3, the amount of zinc collector ZY402 added is related to the content of iron sphalerite in the raw ore, and the amount is 10-200 g / t, and the amount of zinc-sulfur inhibitor T28 added is 10-200 g / t.

[0016] Furthermore, in step 3, the preparation method of zinc collector ZY402 specifically includes the following steps:

[0017] 1) Prepare a 10% aqueous solution of sodium hydroxide in the above proportions;

[0018] 2) After N,N-dialkyldithioaminoethylene ester and hydrocarbon dithiophosphate thioether ester are mixed evenly, the temperature is raised to 60°C, sodium hydroxide solution is slowly added dropwise, and the mixture is refluxed for 0.5 hours.

[0019] 3) Cool down to 25°C, add carbon disulfide in the above proportion, adjust the speed to 300 rpm and stir for 0.5 hours. After the reaction is complete, the mixture will separate into layers. The upper layer of brown transparent organic matter is the zinc collector ZY402.

[0020] Furthermore, in step 4, the amount of sulfur collector and frother added is related to the content and properties of pyrrhotite in the raw ore. The amount of sulfur collector is 50-800 g / t, and the amount of frother is 10-50 g / t. The sulfur collector is any one or two of ethyl xanthate, butyl ammonium black powder, and Z200. The frother is any one of No. 2 oil, pine oil, camphor oil, and cresol.

[0021] Furthermore, the middlings produced during the zinc flotation and sulfur flotation processes are sequentially returned to the previous stage.

[0022] This invention also protects the zinc-sulfur inhibitor T28 used in the above-mentioned beneficiation method for separating pyrrhotite and sphalerite. The zinc-sulfur inhibitor T28 is a composite inhibitor composed of sodium sulfite and humate, wherein the mass ratio of each component in the composite inhibitor is 60-70:10-30; and the humate is one or both of sodium humate and potassium humate.

[0023] Compared with existing technologies, the present invention has the following beneficial effects:

[0024] The raw ore of this invention is iron sphalerite containing pyrite and pyrrhotite. Under natural pH conditions, zinc-sulfur inhibitor T28 is added to the raw ore for grinding to obtain a slurry. CuSO4 is added to the slurry and the mixture is thoroughly stirred. Zinc collector ZY402 is added to the stirred slurry for zinc roughing to obtain rough zinc concentrate and rough zinc tailings. The rough zinc concentrate undergoes three cleaning operations. Zinc collector is added to the rough zinc tailings for three scavenging operations, ultimately yielding zinc scavenged tailings and zinc concentrate. The zinc scavenged tailings undergo one sulfur roughing, two sulfur scavenging, and one sulfur cleaning to obtain sulfur concentrate and tailings. This invention features a simple process flow, low equipment investment, low reagent costs, high separation efficiency, strong adaptability to ore property fluctuations, and stable process. It has significant theoretical and economic value for the development of lead-zinc ore beneficiation with increasingly stringent environmental protection requirements. Specifically:

[0025] 1. The present invention provides a mineral processing method for separating pyrrhotite and sphalerite, which achieves efficient recovery of sphalerite and has significant theoretical and economic value for improving the flotation level of sphalerite in my country.

[0026] 2. The flotation process used in this invention is carried out under natural pH conditions, which is more efficient and environmentally friendly than the traditional high-alkali process represented by lime. It can separate pyrrhotite and sphalerite without magnetic separation, avoiding environmental pollution and pipeline calcium buildup caused by lime-based inhibitors. At the same time, it avoids the strong acid activation in subsequent operations caused by excessive inhibition during the flotation process, which is conducive to further improving the metal recovery rate of sulfur and is more environmentally friendly.

[0027] 3. The zinc-sulfur inhibitor T28 of this invention is a composite inhibitor composed of sodium sulfite and humate. It selectively inhibits pyrrhotite, has low reagent cost, and enhances the inhibitory effect on pyrrhotite through synergistic action, making it widely applicable. The raw material sodium humate of this composite zinc-sulfur inhibitor has excellent characteristics such as low cost, high separation efficiency, and strong adaptability to fluctuations in ore properties.

[0028] 4. The process of this invention does not require magnetic separation to achieve efficient recovery of sphalerite and pyrrhotite. It has the advantages of simple process flow, high flotation efficiency and strong adaptability to fluctuations in ore properties. Attached Figure Description

[0029] Figure 1 This is a process flow diagram of the method of the present invention;

[0030] Figure 2 This is a process flow diagram of the comparative method of the present invention. Detailed Implementation

[0031] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] A beneficiation method for separating pyrrhotite and sphalerite according to the present invention includes grinding, stirring, zinc flotation, and sulfur flotation steps. The beneficiation method is specifically illustrated through examples and comparative examples. The comparative examples employ a conventional high-alkali process for zinc and sulfur recovery.

[0033] The properties of the raw ore used in the selected examples and comparative examples are shown in Table 1, and the test results are shown in Table 2.

[0034] Table 1 Properties of Raw Ore

[0035]

[0036] Example 1

[0037] A mineral processing method for separating pyrrhotite from sphalerite specifically includes the following steps:

[0038] Step 1, Grinding: Grind the raw ore to a fineness of -0.074mm, accounting for 58.26%, to obtain raw ore slurry. During grinding, add 800g / t of zinc-sulfur inhibitor T28.

[0039] Step 2, stirring: After adding 500g / t CuSO4 to the raw ore slurry obtained in Step 1, it is then added to a mixing tank and stirred thoroughly to obtain slurry A. The stirring time of the raw ore slurry is 9 minutes.

[0040] Step 3, Zinc Flotation: The slurry A obtained in Step 2 is added to a flotation machine for primary zinc roughing, tertiary zinc scavenging, and tertiary zinc cleaning. During the zinc roughing process, 60 g / t of zinc collector ZY402 is added and stirred for 2 minutes to obtain zinc rough concentrate and zinc roughing tailings. 100 g / t of zinc sulfur inhibitor T28 is added to the zinc rough concentrate and stirred for 1 minute for primary zinc cleaning, obtaining primary zinc cleaning concentrate and primary zinc cleaning tailings. 50 g / t of zinc sulfur inhibitor T28 is added to the primary zinc cleaning concentrate and stirred for 1 minute for secondary zinc cleaning, obtaining secondary zinc cleaning concentrate and secondary zinc cleaning tailings. 25 g / t of zinc sulfur inhibitor is added to the secondary zinc cleaning concentrate. T28 is stirred for 1 minute to perform a three-stage zinc beneficiation process, yielding lead concentrate and zinc tailings from the three-stage zinc beneficiation process. 30 g / t of zinc collector ZY402 is added to the zinc roughing tailings and stirred for 1 minute to perform a one-stage zinc scavenging process, yielding zinc concentrate and zinc tailings from the one-stage zinc scavenging process. 15 g / t of zinc collector ZY402 is added to the zinc tailings from the one-stage zinc scavenging process and stirred for 1 minute to perform a two-stage zinc scavenging process, yielding zinc concentrate and zinc tailings from the two-stage zinc scavenging process. 10 g / t of zinc collector ZY402 is added to the zinc tailings from the two-stage zinc scavenging process and stirred for 1 minute to perform a three-stage zinc scavenging process, yielding zinc concentrate and zinc tailings from the three-stage zinc scavenging process. The zinc beneficiation tailings and zinc scavenging concentrate are then returned to the previous stage in this order.

[0041] The zinc-sulfur inhibitor T28 is a composite inhibitor composed of sodium sulfite and humate, wherein the mass ratio of each component in the composite inhibitor is 60-70:10-30; the humate is one or both of sodium humate and potassium humate.

[0042] The zinc collector ZY402 is composed of the following raw materials in parts by weight: 40-80 parts of N,N-dialkyldithioaminoethylene ester, 40-60 parts of hydrocarbon dithiophosphate thioether ester, 20-30 parts of carbon disulfide, and 10-20 parts of sodium hydroxide.

[0043] The preparation method of zinc collector ZY402 specifically includes the following steps:

[0044] 1) Prepare a 10% aqueous solution of sodium hydroxide in the above proportions;

[0045] 2) After N,N-dialkyldithioaminoethylene ester and hydrocarbon dithiophosphate thioether ester are mixed evenly, the temperature is raised to 60°C, sodium hydroxide solution is slowly added dropwise, and the mixture is refluxed for 0.5 hours.

[0046] 3) Cool down to 25°C, add carbon disulfide in the above proportion, adjust the speed to 300 rpm and stir for 0.5 hours. After the reaction is complete, the mixture will separate into layers. The upper layer of brown transparent organic matter is the zinc collector ZY402.

[0047] Step 4, Sulfur Flotation: The zinc scavenging tailings obtained in Step 3 are subjected to one sulfur roughing, two sulfur scavenging, and one sulfur cleaning. During the sulfur roughing process, 300 g / t of sulfur collector ethyl xanthate and 30 g / t of frother No. 2 oil are added and stirred for 2 minutes to obtain sulfur rough concentrate and sulfur roughing tailings. Sulfur cleaning is performed on the sulfur rough concentrate without adding reagents to obtain sulfur concentrate and sulfur cleaning tailings. 100 g / t of sulfur collector ethyl xanthate is added to the sulfur roughing tailings and stirred for 1 minute to obtain sulfur first scavenging concentrate and sulfur first scavenging tailings. 50 g / t of sulfur collector ethyl xanthate is added to the sulfur first scavenging tailings and stirred for 1 minute to obtain sulfur second scavenging concentrate and sulfur tailings. The sulfur cleaning tailings and sulfur scavenging concentrate are returned to the previous stage in the above order.

[0048] Comparative Example 1

[0049] Lead preferential flotation was performed using a conventional combination of zinc sulfate and lime as depressants. The specific procedures are as follows:

[0050] Step 1: Grind the raw ore to obtain a slurry with a grinding fineness of 0.074 mm, accounting for 58.26%;

[0051] Step 2: The ore obtained in Step 1 is subjected to magnetic roughing with a magnetic field strength of 450mT to obtain magnetic roughing concentrate and magnetic roughing tailings. The magnetic roughing concentrate is then ground to obtain magnetic roughing concentrate with a grinding fineness of 0.038mm accounting for 88.69%. The ground magnetic roughing concentrate is then subjected to magnetic cleaning with a magnetic field strength of 350mT to obtain magnetic concentrate and magnetic cleaning tailings. The magnetic roughing tailings and magnetic cleaning tailings are combined and fed into a thickening tank for thickening to obtain thickened slurry.

[0052] Step 3: Add 2500 g / t lime to the thickened slurry obtained in Step 2 and stir for 3 minutes. Then add 500 g / t CuSO4 and stir for 3 minutes. Next, add 120 g / t zinc collector pentoxamate and 30 g / t frother No. 2 oil and stir for 2 minutes. Perform zinc roughing to obtain zinc rough concentrate and zinc roughing tailings. Add 500 g / t lime to the zinc rough concentrate and stir for 1 minute to perform zinc primary cleaning to obtain zinc primary cleaning concentrate and zinc primary cleaning tailings. Add 300 g / t lime to the zinc primary cleaning concentrate and stir for 1 minute to perform zinc secondary cleaning to obtain zinc secondary cleaning concentrate and zinc secondary cleaning tailings. Add 150 g / t lime to the zinc secondary cleaning concentrate and stir for 1 minute to perform zinc tertiary cleaning. The process yields lead concentrate and zinc tailings from the third zinc beneficiation. 50 g / t of zinc collector pentoxanol is added to the zinc roughing tailings and stirred for 1 minute for a first zinc scavenging operation, yielding a first zinc scavenging concentrate and tailings. 25 g / t of zinc collector pentoxanol is added to the first zinc scavenging tailings and stirred for 1 minute for a second zinc scavenging operation, yielding a second zinc scavenging concentrate and tailings. 15 g / t of zinc collector pentoxanol is added to the second zinc scavenging tailings and stirred for 1 minute for a third zinc scavenging operation, yielding a third zinc scavenging concentrate and tailings. The process is repeated, returning to the previous stage in the order of zinc beneficiation tailings and zinc scavenging concentrate.

[0053] Step 4: Add 1000g / t sulfuric acid (sulfur activator), 250g / t xanthate (sulfur collector), and 30g / t oil (foaming agent) to the zinc tailings obtained in Step 3 and stir for 2 minutes for sulfur roughing to obtain sulfur rough concentrate and sulfur roughing tailings. Add 300g / t sulfuric acid (sulfur activator) to the sulfur rough concentrate for sulfur cleaning to obtain sulfur concentrate and sulfur cleaning tailings. Add 70g / t xanthate (sulfur collector) to the sulfur roughing tailings and stir for 1 minute for sulfur primary scavenging to obtain sulfur primary scavenging concentrate and sulfur primary scavenging tailings. Add 40g / t xanthate (sulfur collector) to the sulfur primary scavenging tailings and stir for 1 minute for sulfur secondary scavenging to obtain sulfur secondary scavenging concentrate and sulfur tailings. Return the sulfur cleaning tailings and sulfur scavenging concentrate to the previous step in the above order.

[0054] Example 2

[0055] A mineral processing method for separating pyrrhotite from sphalerite specifically includes the following steps:

[0056] Step 1, Grinding: Grind the raw ore to a fineness of -0.074mm, accounting for 73.26%, to obtain raw ore slurry. During grinding, 1000g / t of zinc-sulfur inhibitor T28 is added.

[0057] Step 2, stirring: Add 400g / t CuSO4 to the raw ore slurry obtained in Step 1, and then add it to the mixing tank and stir thoroughly to obtain slurry A. The stirring time of the raw ore slurry is 10 minutes.

[0058] Step 3, Zinc Flotation: The slurry A obtained in Step 2 is added to a flotation machine for primary zinc roughing, tertiary zinc scavenging, and tertiary zinc cleaning. During the zinc roughing process, 50 g / t of zinc collector ZY402 is added and stirred for 2 minutes to obtain zinc rough concentrate and zinc roughing tailings. 200 g / t of zinc sulfur inhibitor T28 is added to the zinc rough concentrate and stirred for 1 minute for primary zinc cleaning, obtaining primary zinc cleaning concentrate and primary zinc cleaning tailings. 100 g / t of zinc sulfur inhibitor T28 is added to the primary zinc cleaning concentrate and stirred for 1 minute for secondary zinc cleaning, obtaining secondary zinc cleaning concentrate and secondary zinc cleaning tailings. 50 g / t of zinc sulfur inhibitor is added to the secondary zinc cleaning concentrate. Zinc is subjected to a three-stage zinc beneficiation process by stirring with agent T28 for 1 minute to obtain lead concentrate and zinc tailings from the three-stage zinc beneficiation process. 20 g / t of zinc collector ZY402 is added to the zinc roughing tailings and stirred for 1 minute to conduct a one-stage zinc scavenging process to obtain zinc concentrate and zinc tailings from the one-stage zinc scavenging process. 10 g / t of zinc collector ZY402 is added to the zinc tailings from the one-stage zinc scavenging process and stirred for 1 minute to conduct a two-stage zinc scavenging process to obtain zinc concentrate and zinc tailings from the two-stage zinc scavenging process. 5 g / t of zinc collector ZY402 is added to the zinc tailings from the two-stage zinc scavenging process and stirred for 1 minute to conduct a three-stage zinc scavenging process to obtain zinc concentrate and zinc tailings from the three-stage zinc scavenging process. The zinc beneficiation tailings and zinc scavenging concentrate are then returned to the previous stage in this order.

[0059] The zinc-sulfur inhibitor T28 is a composite inhibitor composed of sodium sulfite and humate, wherein the mass ratio of each component in the composite inhibitor is 60-70:10-30; the humate is one or both of sodium humate and potassium humate.

[0060] The zinc collector ZY402 is composed of the following raw materials in parts by weight: 40-80 parts of N,N-dialkyldithioaminoethylene ester, 40-60 parts of hydrocarbon dithiophosphate thioether ester, 20-30 parts of carbon disulfide, and 10-20 parts of sodium hydroxide.

[0061] The preparation method of zinc collector ZY402 specifically includes the following steps:

[0062] 1) Prepare a 10% aqueous solution of sodium hydroxide in the above proportions;

[0063] 2) After N,N-dialkyldithioaminoethylene ester and hydrocarbon dithiophosphate thioether ester are mixed evenly, the temperature is raised to 60°C, sodium hydroxide solution is slowly added dropwise, and the mixture is refluxed for 0.5 hours.

[0064] 3) Cool down to 25°C, add carbon disulfide in the above proportion, adjust the speed to 300 rpm and stir for 0.5 hours. After the reaction is complete, the mixture will separate into layers. The upper layer of brown transparent organic matter is the zinc collector ZY402.

[0065] Step 4, Sulfur Flotation: The zinc scavenging tailings obtained in Step 3 are subjected to a first sulfur roughing, two sulfur scavenging, and a first sulfur cleaning. During the sulfur roughing process, 150 g / t of sulfur collector butylammonium black powder, 50 g / t of sulfur collector pentachlorophenate, and 20 g / t of frother pine oil are added and stirred for 2 minutes to obtain sulfur rough concentrate and sulfur roughing tailings. Sulfur cleaning is performed on the sulfur rough concentrate without the addition of reagents to obtain sulfur concentrate and sulfur cleaning tailings. 80 g / t of sulfur collector butylammonium black powder is added to the sulfur roughing tailings and stirred for 1 minute to obtain sulfur first scavenging concentrate and sulfur first scavenging tailings. 40 g / t of sulfur collector butylammonium black powder is added to the sulfur first scavenging tailings and stirred for 1 minute to obtain sulfur second scavenging concentrate and sulfur tailings. The sulfur cleaning tailings and sulfur scavenging concentrate are returned to the previous stage in the above order.

[0066] Comparative Example 2

[0067] Lead preferential flotation was performed using a conventional combination of zinc sulfate and lime as depressants. The specific procedures are as follows:

[0068] Step 1: Grind the raw ore to obtain a slurry with a grinding fineness of 0.074 mm, accounting for 73.26%;

[0069] Step 2: The ore obtained in Step 1 is subjected to magnetic roughing with a magnetic field strength of 450mT to obtain magnetic roughing concentrate and magnetic roughing tailings. The magnetic roughing concentrate is then ground to obtain magnetic roughing concentrate with a grinding fineness of 0.038mm accounting for 95.26%. The ground magnetic roughing concentrate is then subjected to magnetic cleaning with a magnetic field strength of 350mT to obtain magnetic concentrate and magnetic cleaning tailings. The magnetic roughing tailings and magnetic cleaning tailings are combined and fed into a thickening tank for thickening to obtain thickened slurry.

[0070] Step 3: Add 4000 g / t lime to the thickened slurry obtained in Step 2 and stir for 3 minutes. Then add 400 g / t CuSO4 and stir for 3 minutes. Next, add 100 g / t zinc collector pentoxanone, 50 g / t zinc collector butyl xanthate, and 30 g / t frother #2 oil and stir for 2 minutes. Perform zinc roughing to obtain zinc rough concentrate and zinc roughing tailings. Add 1500 g / t lime to the zinc rough concentrate and stir for 1 minute to perform primary zinc cleaning to obtain primary zinc cleaning concentrate and zinc primary cleaning tailings. Add 800 g / t lime to the primary zinc cleaning concentrate and stir for 1 minute to perform secondary zinc cleaning to obtain secondary zinc cleaning concentrate and zinc secondary cleaning tailings. Add 350 g / t lime to the secondary zinc cleaning concentrate and stir for 1 minute to... A three-stage zinc beneficiation process is performed to obtain lead concentrate and zinc tailings. 40 g / t of zinc collector pentoxanol is added to the zinc roughing tailings and stirred for 1 minute for a first-stage zinc scavenging process, yielding a first-stage zinc scavenging concentrate and tailings. 20 g / t of zinc collector pentoxanol is added to the first-stage zinc scavenging tailings and stirred for 1 minute for a second-stage zinc scavenging process, yielding a second-stage zinc scavenging concentrate and tailings. 10 g / t of zinc collector pentoxanol is added to the second-stage zinc scavenging tailings and stirred for 1 minute for a third-stage zinc scavenging process, yielding a third-stage zinc scavenging concentrate and tailings. The process is repeated, returning to the previous stage in the order of zinc beneficiation tailings and zinc scavenging concentrate.

[0071] Step 4: Add 2000g / t sulfuric acid (sulfur activator), 250g / t xanthate (sulfur collector), and 30g / t oil (foaming agent) to the zinc tailings obtained in Step 3 and stir for 2 minutes for sulfur roughing to obtain sulfur rough concentrate and sulfur roughing tailings. Add 600g / t sulfuric acid (sulfur activator) to the sulfur rough concentrate for sulfur cleaning to obtain sulfur concentrate and sulfur cleaning tailings. Add 50g / t xanthate (sulfur collector) to the sulfur roughing tailings and stir for 1 minute for sulfur primary scavenging to obtain sulfur primary scavenging concentrate and sulfur primary scavenging tailings. Add 25g / t xanthate (sulfur collector) to the sulfur primary scavenging tailings and stir for 1 minute for sulfur secondary scavenging to obtain sulfur secondary scavenging concentrate and sulfur tailings. The sulfur cleaning tailings and sulfur scavenging concentrate are returned to the previous step in the above order.

[0072] Example 3

[0073] A mineral processing method for separating pyrrhotite from sphalerite specifically includes the following steps:

[0074] Step 1, Grinding: Grind the raw ore to a fineness of -0.074mm, accounting for 68.15%, to obtain raw ore slurry. During grinding, 700g / t of zinc-sulfur inhibitor T28 is added.

[0075] Step 2, stirring: After adding 800g / t CuSO4 to the raw ore slurry obtained in Step 1, it is then added to a mixing tank and stirred thoroughly to obtain slurry A. The stirring time of the raw ore slurry is 9 minutes.

[0076] Step 3, Zinc Flotation: The slurry A obtained in Step 2 is added to a flotation machine for primary zinc roughing, tertiary zinc scavenging, and tertiary zinc cleaning. During the zinc roughing process, 100 g / t of zinc collector ZY402 is added and stirred for 2 minutes to obtain zinc rough concentrate and zinc roughing tailings. 180 g / t of zinc sulfur inhibitor T28 is added to the zinc rough concentrate and stirred for 1 minute for primary zinc cleaning, obtaining primary zinc cleaning concentrate and primary zinc cleaning tailings. 90 g / t of zinc sulfur inhibitor T28 is added to the primary zinc cleaning concentrate and stirred for 1 minute for secondary zinc cleaning, obtaining secondary zinc cleaning concentrate and secondary zinc cleaning tailings. 40 g / t of zinc sulfur inhibitor is added to the secondary zinc cleaning concentrate. Zinc is subjected to a three-stage zinc beneficiation process by stirring with agent T28 for 1 minute to obtain lead concentrate and zinc tailings from the three-stage zinc beneficiation process. Then, 50 g / t of zinc collector ZY402 is added to the zinc roughing tailings and stirred for 1 minute to conduct a one-stage zinc scavenging process, yielding zinc concentrate and zinc tailings from the one-stage zinc scavenging process. Next, 25 g / t of zinc collector ZY402 is added to the zinc tailings from the one-stage zinc scavenging process and stirred for 1 minute to conduct a two-stage zinc scavenging process, yielding zinc concentrate and zinc tailings from the two-stage zinc scavenging process. Finally, 15 g / t of zinc collector ZY402 is added to the zinc tailings from the two-stage zinc scavenging process and stirred for 1 minute to conduct a three-stage zinc scavenging process, yielding zinc concentrate and zinc tailings from the three-stage zinc scavenging process. The zinc beneficiation tailings and zinc scavenging concentrate are then returned to the previous stage in this order.

[0077] The zinc-sulfur inhibitor T28 is a composite inhibitor composed of sodium sulfite and humate, wherein the mass ratio of each component in the composite inhibitor is 60-70:10-30; the humate is one or both of sodium humate and potassium humate.

[0078] The zinc collector ZY402 is composed of the following raw materials in parts by weight: 40-80 parts of N,N-dialkyldithioaminoethylene ester, 40-60 parts of hydrocarbon dithiophosphate thioether ester, 20-30 parts of carbon disulfide, and 10-20 parts of sodium hydroxide.

[0079] The preparation method of zinc collector ZY402 specifically includes the following steps:

[0080] 1) Prepare a 10% aqueous solution of sodium hydroxide in the above proportions;

[0081] 2) After N,N-dialkyldithioaminoethylene ester and hydrocarbon dithiophosphate thioether ester are mixed evenly, the temperature is raised to 60°C, sodium hydroxide solution is slowly added dropwise, and the mixture is refluxed for 0.5 hours.

[0082] 3) Cool down to 25°C, add carbon disulfide in the above proportion, adjust the speed to 300 rpm and stir for 0.5 hours. After the reaction is complete, the mixture will separate into layers. The upper layer of brown transparent organic matter is the zinc collector ZY402.

[0083] Step 4, Sulfur Flotation: The zinc scavenging tailings obtained in Step 3 are subjected to one sulfur roughing, two sulfur scavenging, and one sulfur cleaning. During the sulfur roughing process, 250 g / t of sulfur collector butyl xanthate and 40 g / t of frother pine oil are added and stirred for 2 minutes to obtain sulfur rough concentrate and sulfur roughing tailings. Sulfur cleaning is performed on the sulfur rough concentrate without adding reagents to obtain sulfur concentrate and sulfur cleaning tailings. 100 g / t of sulfur collector butyl xanthate is added to the sulfur roughing tailings and stirred for 1 minute to obtain sulfur first scavenging concentrate and sulfur first scavenging tailings. 50 g / t of sulfur collector butyl xanthate is added to the sulfur first scavenging tailings and stirred for 1 minute to obtain sulfur second scavenging concentrate and sulfur tailings. The sulfur cleaning tailings and sulfur scavenging concentrate are returned to the previous stage in the above order.

[0084] Comparative Example 3

[0085] Lead preferential flotation was performed using a conventional combination of zinc sulfate and lime as depressants. The specific procedures are as follows:

[0086] Step 1: Grind the raw ore to obtain a slurry with a grinding fineness of 0.074 mm, accounting for 68.15%;

[0087] Step 2: The ore obtained in Step 1 is subjected to magnetic roughing with a magnetic field strength of 450mT to obtain magnetic roughing concentrate and magnetic roughing tailings. The magnetic roughing concentrate is then ground to obtain magnetic roughing concentrate with a grinding fineness of 0.038mm accounting for 92.26%. The ground magnetic roughing concentrate is then subjected to magnetic cleaning with a magnetic field strength of 350mT to obtain magnetic concentrate and magnetic cleaning tailings. The magnetic roughing tailings and magnetic cleaning tailings are combined and fed into a thickening tank for thickening to obtain thickened slurry.

[0088] Step 3: Add 5000 g / t lime to the thickened slurry obtained in Step 2 and stir for 3 minutes. Then add 700 g / t CuSO4 and stir for 3 minutes. Next, add 130 g / t zinc collector pentoxanone, 65 g / t zinc collector butyl xanthate, and 30 g / t frother #2 oil and stir for 2 minutes. Perform zinc roughing to obtain zinc rough concentrate and zinc roughing tailings. Add 2000 g / t lime to the zinc rough concentrate and stir for 1 minute to perform zinc primary cleaning to obtain zinc primary cleaning concentrate and zinc primary cleaning tailings. Add 1000 g / t lime to the zinc primary cleaning concentrate and stir for 1 minute to perform zinc secondary cleaning to obtain zinc secondary cleaning concentrate and zinc secondary cleaning tailings. Add 500 g / t lime to the zinc secondary cleaning concentrate and stir for 1 minute to perform zinc tertiary cleaning to obtain lead concentrate and zinc tertiary concentrate. For the tailings, add 50g / t of zinc collector pentoxanol and 25g / t of zinc collector butyl xanol to the zinc roughing tailings and stir for 1 minute to perform a first zinc scavenging operation, obtaining a first zinc scavenging concentrate and a first zinc scavenging tailings. Add 20g / t of zinc collector pentoxanol and 10g / t of zinc collector butyl xanol to the zinc first scavenging tailings and stir for 1 minute to perform a second zinc scavenging operation, obtaining a second zinc scavenging concentrate and a second zinc scavenging tailings. Add 10g / t of zinc collector pentoxanol and 5g / t of zinc collector butyl xanol to the zinc second scavenging tailings and stir for 1 minute to perform a third zinc scavenging operation, obtaining a third zinc scavenging concentrate and zinc tailings. The process is repeated from zinc beneficiation tailings to zinc scavenging concentrate, returning to the previous stage.

[0089] Step 4: Add 3000g / t sulfuric acid (sulfur activator), 400g / t xanthate (sulfur collector), and 50g / t No. 2 oil (foaming agent) to the zinc tailings obtained in Step 3 and stir for 2 minutes for sulfur roughing to obtain sulfur rough concentrate and sulfur roughing tailings. Add 1200g / t sulfuric acid (sulfur activator) to the sulfur rough concentrate for sulfur cleaning to obtain sulfur concentrate and sulfur cleaning tailings. Add 150g / t xanthate (sulfur collector) to the sulfur roughing tailings and stir for 1 minute for primary sulfur scavenging to obtain primary sulfur scavenging concentrate and sulfur primary scavenging tailings. Add 75g / t xanthate (sulfur collector) to the primary sulfur scavenging tailings and stir for 1 minute for secondary sulfur scavenging to obtain secondary sulfur scavenging concentrate and sulfur tailings. Return the sulfur cleaning tailings and sulfur scavenging concentrate to the previous step in the above order.

[0090] Table 2 Experimental Results

[0091]

[0092] The experimental results show that this invention can effectively achieve the flotation separation of pyrrhotite and sphalerite, and the combined inhibitor has a good inhibitory effect on pyrrhotite. The comparative example uses conventional magnetic separation to desulfurize pyrrhotite using a high-alkali process with lime as the inhibitor. The example uses the composite zinc-sulfur inhibitor T28 and zinc collector ZY402 of this invention, and the obtained zinc concentrate Zn grade and Zn recovery rate, as well as the sulfur concentrate S grade and S recovery rate are all higher. This indicates that the flotation separation process of pyrrhotite and sphalerite using the combined inhibitor and zinc collector ZY402 of this invention can effectively achieve the separation of pyrrhotite and sphalerite, achieving the goal of environmentally friendly and efficient recovery of pyrrhotite and sphalerite.

[0093] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A mineral processing method for separating pyrrhotite from sphalerite, characterized in that, Specifically, the steps include the following: Step 1, Grinding: Grind the raw ore to a fineness of -0.074mm, accounting for 55%~85%, to obtain raw ore slurry. During grinding, zinc-sulfur inhibitor T28 is added. Step 2, stirring: After adding CuSO4 to the raw ore slurry obtained in Step 1, add it to a mixing tank and stir thoroughly to obtain slurry A; Step 3, Zinc flotation: Add the slurry A obtained in step 2 to the flotation machine for one zinc roughing, three zinc scavenging and three zinc cleaning to obtain zinc concentrate and zinc scavenging tailings. During the zinc roughing process, zinc collector ZY402 is added. During each zinc cleaning process, zinc sulfur inhibitor T28 is added. During each zinc scavenging process, zinc collector ZY402 is added. The zinc-sulfur inhibitor T28 is a composite inhibitor composed of sodium sulfite and humate, wherein the mass ratio of each component in the composite inhibitor is 60-70:10-30. The zinc collector ZY402 is composed of the following raw materials in parts by weight: 40-80 parts of N,N-dialkyldithioaminoethylene ester, 40-60 parts of hydrocarbon dithiophosphate thioether ester, 20-30 parts of carbon disulfide, and 10-20 parts of sodium hydroxide. Step 4, sulfur flotation: The zinc scavenging tailings obtained in step 3 are subjected to one sulfur roughing, two sulfur scavenging and one sulfur cleaning to obtain sulfur concentrate and tailings. Sulfur collector and frother are added during the sulfur roughing process and sulfur collector is added during each sulfur scavenging process.

2. The mineral processing method for separating pyrrhotite and sphalerite according to claim 1, characterized in that, In step 1, the grinding fineness has different requirements depending on the different raw ores.

3. The beneficiation method for separating pyrrhotite and sphalerite according to claim 1, characterized in that, In step 2, the stirring time of the raw ore slurry is ≥9 minutes.

4. The mineral processing method for separating pyrrhotite and sphalerite according to claim 1, characterized in that, In step 3, the humate is one or both of sodium humate and potassium humate.

5. The beneficiation method for separating pyrrhotite and sphalerite according to claim 1, characterized in that, In step 3, the amount of zinc collector ZY402 added is related to the content of iron sphalerite in the raw ore, and the amount is 10~200g / t; the amount of zinc sulfur inhibitor T28 added is 10~200g / t.

6. The mineral processing method for separating pyrrhotite and sphalerite according to claim 1, characterized in that, In step 3, the preparation method of zinc collector ZY402 specifically includes the following steps: 1) Prepare a 10% aqueous solution of sodium hydroxide in the above proportions; 2) After N,N-dialkyldithioaminoethylene ester and hydrocarbon dithiophosphate thioether ester are mixed evenly, the temperature is raised to 60°C, sodium hydroxide solution is slowly added dropwise, and the mixture is refluxed for 0.5 hours. 3) Cool down to 25°C, add carbon disulfide in the above proportion, adjust the speed to 300 rpm and stir for 0.5 hours. After the reaction is complete, the mixture will separate into layers. The upper layer of brown transparent organic matter is the zinc collector ZY402.

7. The beneficiation method for separating pyrrhotite and sphalerite according to claim 1, characterized in that, In step 4, the amount of sulfur collector and frother added is related to the content and properties of pyrrhotite in the raw ore. The amount of sulfur collector is 50-800 g / t, and the amount of frother is 10-50 g / t. The sulfur collector is any one or two of ethyl xanthate, butyl ammonium black powder, and Z200. The frother is any one of No. 2 oil, pine oil, camphor oil, and cresol.

8. The beneficiation method for separating pyrrhotite and sphalerite according to claim 1, characterized in that, The middlings produced during the zinc flotation and sulfur flotation processes are sequentially returned to the previous stage.

Images