Beneficiation method for enhancing carbon inhibition in stages and improving molybdenum grade

Abstract

The invention provides a beneficiation method for enhancing carbon inhibition and improving molybdenum grade by stages, which comprises the following steps: crushing ores to-3mm, grinding into ore pulp with the fineness of 60-75-0.074 mm and the ore pulp concentration of 25-40%, and enhancing molybdenum enrichment to obtain copper-molybdenum mixed rough concentrate; the concentration of the copper-molybdenum mixed rough concentrate is adjusted to be 15%-30%, carbonaceous gangue inhibitor water glass is added for first-order carbon inhibition, and then copper-molybdenum bulk concentrate is obtained through concentration; the concentration of the copper-molybdenum bulk concentrate is adjusted to be 15%-25%, and sodium sulfide is used for modifying and deactivating pretreatment; the concentration of the pretreated copper-molybdenum bulk concentrate is adjusted to be 5%-15%, a carbonaceous gangue inhibitor is added for second-order to fifth-order carbon inhibition, and then the grade of the molybdenum concentrate can be improved after molybdenum concentration. According to the method, the quality of the molybdenum concentrate is effectively improved by adopting enhanced molybdenum enrichment bulk flotation, modification and deactivation pretreatment, graded enhanced carbon inhibition and molybdenum concentrate decarburization and quality improvement, so that efficient resource comprehensive recycling of the refractory associated molybdenum copper ore is realized.

Description

Technical Field

[0001] The invention belongs to the field of metallurgy and chemical industry, and in particular relates to a ore dressing method for improving molybdenum grade by step-by-step enhanced carbon suppression. Background Art

[0002] Molybdenum has the advantages of heat resistance, small expansion coefficient, high strength, good thermal conductivity, and high electrical conductivity. It is widely used in steel smelting, chemical industry, electronic devices, superconducting materials, aerospace and other fields. The reserves of molybdenum on the earth are relatively small, accounting for only 0.001% of the weight of the earth's crust. The total reserves of molybdenum ore are about 15 million tons. On the global map, molybdenum is mainly distributed in the United States, Chile, Russia, Canada and other countries. With the continuous advancement of industry and technology, the demand for molybdenum is getting higher and higher. my country also has a very large demand for molybdenum resources, but the characteristics of my country's molybdenum resources are diverse deposit types, mostly co-existing with copper metals, and low molybdenum grades. Therefore, it is very important to develop and utilize copper-molybdenum polymetallic resources and increase the efficient separation and recovery of copper-molybdenum polymetallic resources to increase the amount of molybdenum resources. Summary of the invention

[0003] The object of the present invention is to provide a ore dressing method for improving molybdenum grade by step-by-step enhanced carbon suppression.

[0004] The object of the present invention is achieved in that the ore dressing method for improving molybdenum grade by step-by-step enhanced carbon suppression includes molybdenum enrichment, first-order carbon suppression, modification deactivation and multi-stage carbon suppression steps, specifically including: A. Molybdenum enrichment: (1) The raw ore to be processed is crushed and ground to a fineness of -0.074 mm accounting for 60-75%, and material a is obtained by slurry adjustment; (2) adjusting the pH value of material a to 8-9.5, adding a copper-molybdenum collector and a frother to enrich molybdenum to obtain a copper-molybdenum mixed coarse concentrate b; B. First-order carbon suppression: adjust the pulp concentration of the copper-molybdenum mixed rough concentrate b to 15-35%, add a carbonaceous gangue inhibitor for first-order carbon suppression, and then sequentially add a copper-molybdenum collector and a frother for 1-2 times of mixed concentration to obtain a copper-molybdenum mixed concentrate c; C. Modification and deactivation: The copper-molybdenum mixed concentrate c is adjusted to a pulp concentration of 15-25%, and sodium sulfide is used for modification and deactivation to obtain the copper-molybdenum mixed concentrate d; D. Multi-stage carbon suppression: (1) The copper-molybdenum mixed concentrate d is adjusted to a pulp concentration of 5-15%, a carbonaceous gangue inhibitor is added for secondary carbon inhibition, and then a copper inhibitor KMD135 and a molybdenum collector are sequentially added to separate copper and molybdenum to obtain a rough molybdenum concentrate e and a copper-molybdenum separation tailing f; (2) The molybdenum rough concentrate e is re-ground according to the monomer dissociation degree of molybdenum (the monomer dissociation degree of molybdenum mineral is determined by using a scanning electron microscope (SEM) or an optical microscope in conjunction with image analysis software to form an image of the mineral sample and find out the proportion of particles with 100% dissociation of molybdenum minerals in the measured sample to the total sample particles) to ensure that the 100% monomer dissociation degree of molybdenum is greater than 85%. After re-grinding, a carbonaceous gangue inhibitor is added to perform third to eighth stage carbon suppression, and copper inhibitor KMD135 and molybdenum collector are sequentially added to perform 1 to 6 rounds of concentration to obtain a molybdenum concentrate with improved molybdenum grade; (3) adding copper inhibitor KMD135 and molybdenum collector to the copper-molybdenum separation tailings and performing 2-3 molybdenum scavenging to obtain copper concentrate; The copper inhibitor KMD135 is composed of sodium sulfide, sodium thiosulfate and sodium hydrosulfide.

[0005] The specific operations are as follows: A. Enhanced molybdenum enrichment mixed flotation (1) Grinding and slurry adjustment: crush the raw ore and grind it to a fineness of -0.074 mm accounting for 60% to 75%, adjust the slurry concentration to 25% to 40%, and obtain material a; (2) Enhanced molybdenum enrichment mixed flotation: Calcium oxide is added to material a to adjust the pulp pH value to 8-9.5, copper-molybdenum collectors thiocarbamate and dodecyl mercaptan, and frother polypropylene glycol are added. Dodecyl mercaptan can enhance molybdenum enrichment to obtain copper-molybdenum mixed rough concentrate b; dodecyl mercaptan molecular formula C 12 H 23 SH is a weak acid that can ionize to form RS - and H + , R.S. - It forms insoluble salt (RS)2Pb with molybdenum metal on the surface of molybdenum minerals, which improves the hydrophobicity of the surface of molybdenum minerals and plays a role in strengthening molybdenum enrichment; B. First-order carbon inhibition: (3) adjusting the slurry concentration of the copper-molybdenum mixed concentrate b in step (2) to 15% to 35%, adding water glass, a carbonaceous gangue inhibitor, for first-order carbon suppression, and then sequentially adding thiocarbamate and dodecyl mercaptan as collectors and polypropylene glycol as a frother, and performing 1 to 2 mixing and concentration operations to obtain a copper-molybdenum mixed concentrate c; C. Modification and deactivation pretreatment (4) adjusting the copper-molybdenum mixed concentrate c in step (3) to a pulp concentration of 15% to 25%, using sodium sulfide for modified deactivation pretreatment, deactivating the surface of the copper-molybdenum mixed concentrate adsorbing the collector, removing the pulp clarified liquid, and obtaining the copper-molybdenum mixed concentrate d; D. Multi-stage carbon suppression copper and molybdenum separation (5) The copper-molybdenum mixed concentrate d of step (4) is adjusted to a pulp concentration of 5% to 15%, and ferric chloride as a carbonaceous gangue inhibitor is added for secondary carbon inhibition. The copper inhibitor KMD135 and the molybdenum collector kerosene are sequentially added to separate the copper and molybdenum to obtain a rough molybdenum concentrate e and a copper-molybdenum separation "tailing" f.

[0006] (6) The molybdenum rough concentrate of step (5) can be re-grinded according to the monomer dissociation degree of molybdenum to ensure that the monomer dissociation degree of molybdenum 100% is greater than 85%. After re-grinding, ferric chloride, a carbonaceous gangue inhibitor, is added to perform third to eighth-order carbon suppression, and copper inhibitor KMD135 and molybdenum collector kerosene are sequentially added to perform 1 to 6 times of concentration to obtain a molybdenum concentrate with improved molybdenum grade; (7) Add copper inhibitor KMD135 and molybdenum collector kerosene to the copper-molybdenum separation "tailings" of step (5) and perform 2 to 3 molybdenum scavengings to obtain copper concentrate.

[0007] Many molybdenum ores and copper-molybdenum ores coexist with carbonaceous gangues such as graphite and organic carbon, or the graphite and organic carbon in the ores are infiltrated into silicate gangue minerals. Because graphite crystallizes in flakes, has a low density and strong hydrophobicity, most small flake graphites have better floatability than molybdenite, which easily leads to similar flotation separation difficulties, resulting in a reduction in the grade of molybdenum concentrate. The present invention adopts a beneficiation process and method of enhanced molybdenum enrichment mixed flotation, modified deactivation pretreatment, staged enhanced carbon suppression, and molybdenum concentrate decarbonization and quality improvement to improve the grade of molybdenum concentrate, thereby realizing efficient and comprehensive recovery and utilization of carbonaceous gangue minerals and copper-molybdenum ore resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0009] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0010] The ore dressing method for improving molybdenum grade by step-by-step enhanced carbon suppression of the present invention comprises molybdenum enrichment, first-order carbon suppression, modification and deactivation, and multi-order carbon suppression steps, specifically comprising: A. Molybdenum enrichment: (1) The raw ore to be processed is crushed and ground to a fineness of -0.074 mm accounting for 60-75%, and material a is obtained by slurry adjustment; (2) adjusting the pH value of material a to 8-9.5, adding a copper-molybdenum collector and a frother to enrich molybdenum to obtain a copper-molybdenum mixed coarse concentrate b; B. First-order carbon suppression: adjust the pulp concentration of the copper-molybdenum mixed rough concentrate b to 15-35%, add a carbonaceous gangue inhibitor for first-order carbon suppression, and then sequentially add a copper-molybdenum collector and a frother for 1-2 times of mixed concentration to obtain a copper-molybdenum mixed concentrate c; C. Modification and deactivation: The copper-molybdenum mixed concentrate c is adjusted to a pulp concentration of 15-25%, and sodium sulfide is used for modification and deactivation to obtain the copper-molybdenum mixed concentrate d; D. Multi-stage carbon suppression: (1) The copper-molybdenum mixed concentrate d is adjusted to a pulp concentration of 5-15%, a carbonaceous gangue inhibitor is added for secondary carbon inhibition, and then a copper inhibitor KMD135 and a molybdenum collector are sequentially added to separate copper and molybdenum to obtain a rough molybdenum concentrate e and a copper-molybdenum separation tailing f; (2) The molybdenum rough concentrate e is re-ground according to the monomer dissociation degree of molybdenum (the monomer dissociation degree of molybdenum mineral is determined by using a scanning electron microscope (SEM) or an optical microscope in conjunction with image analysis software to form an image of the mineral sample and find out the proportion of particles with 100% dissociation of molybdenum minerals in the measured sample to the total sample particles) to ensure that the 100% monomer dissociation degree of molybdenum is greater than 85%. After re-grinding, a carbonaceous gangue inhibitor is added to perform third to eighth stage carbon suppression, and copper inhibitor KMD135 and molybdenum collector are sequentially added to perform 1 to 6 rounds of concentration to obtain a molybdenum concentrate with improved molybdenum grade; (3) adding copper inhibitor KMD135 and molybdenum collector to the copper-molybdenum separation tailings and performing 2-3 molybdenum scavenging to obtain copper concentrate; The copper inhibitor KMD135 is composed of sodium sulfide, sodium thiosulfate and sodium hydrosulfide.

[0011] The slurry concentration of material a in step A (1) is 25-40%.

[0012] The pH value is adjusted in step A (2) by using calcium oxide.

[0013] The copper-molybdenum collector is composed of thiocarbamate and dodecyl mercaptan.

[0014] The mass ratio of the thiocarbamate to dodecyl mercaptan is (0.5-1.5): (0.5-1.5).

[0015] The foaming agent is polypropylene glycol.

[0016] The carbonaceous gangue inhibitor described in step B is water glass.

[0017] The carbonaceous gangue inhibitor described in step D is ferric chloride.

[0018] The molybdenum collector is kerosene.

[0019] The present invention is further described below with specific implementation cases: Example 1

[0020] (1) Take the raw ore A, which contains 0.95% copper, 0.01% molybdenum, and 1.85% carbon. The carbonaceous gangue mainly includes graphite, ankerite, and calcite. Crush and grind the raw ore to a fineness of -0.074mm, accounting for 60% to 75%, and adjust the slurry concentration to 30% to obtain material a; (2) Calcium oxide was added to material a to adjust the pH value of the slurry to 8.5, 40 g / t of copper-molybdenum collector thiocarbamate and 10 g / t of dodecyl mercaptan, and 30 g / t of polypropylene glycol as a foaming agent were added. Dodecyl mercaptan can enhance molybdenum enrichment and increase the molybdenum recovery rate by 6 percentage points, thereby obtaining a copper-molybdenum mixed coarse concentrate b; (3) The copper-molybdenum mixed concentrate b was adjusted to a pulp concentration of 20%, 100 g / t of water glass as a carbonaceous gangue inhibitor was added for first-order carbon suppression, and then 10 g / t of thiocarbamate collector and 5 g / t of dodecyl mercaptan and 10 g / t of polypropylene glycol as a foaming agent were added to perform a first mixing and concentration to obtain a copper-molybdenum mixed concentrate c; (4) The copper-molybdenum mixed concentrate c was adjusted to a pulp concentration of 20%, and sodium sulfide 170 g / t was added and stirred for 5 min for modification and deactivation pretreatment. After the stirring was completed, the pulp was allowed to settle naturally, and the supernatant was removed to obtain the copper-molybdenum mixed concentrate d; (5) The copper-molybdenum mixed concentrate d was adjusted to a pulp concentration of 10%, and 200 g / t of ferric chloride, a carbonaceous gangue inhibitor, was added for secondary carbon suppression. 5000 g / t of copper inhibitor KMD135 and 50 g / t of molybdenum collector kerosene were added for copper-molybdenum separation to obtain a rough molybdenum concentrate e and a copper-molybdenum separation "tailing" f.

[0021] (6) The molybdenum coarse concentrate is re-grinded, and the molybdenum 100% monomer dissociation degree is 85%. The carbon gangue inhibitor ferric chloride 100+50+30+20g / t is added for fourth-order carbon suppression. After four times of concentration, a molybdenum concentrate with a molybdenum grade of 35% is obtained, and the molybdenum grade is increased by 10 percentage points. Concentration I adds copper inhibitor KMD135 3000g / t and molybdenum collector kerosene 30g / t; Concentration II adds copper inhibitor KMD135 2000g / t and molybdenum collector kerosene 20g / t; Concentration III adds copper inhibitor KMD135 1000g / t and molybdenum collector kerosene 10g / t; Concentration IV adds copper inhibitor KMD135 500g / t and molybdenum collector kerosene 5g / t.

[0022] (7) The copper-molybdenum separation "tailings" were subjected to two molybdenum scavengings to obtain copper concentrate. In scavenging I, 2000 g / t of copper inhibitor KMD135 and 20 g / t of molybdenum collector kerosene were added; in scavenging II, 1000 g / t of copper inhibitor KMD135 and 10 g / t of molybdenum collector kerosene were added.

[0023] Example 2

[0024] (1) Take the raw ore A, which contains 0.83% copper, 0.012% molybdenum, and 2.45% carbon. The carbonaceous gangue mainly includes organic carbon, siderite, and calcite. The raw ore is crushed and ground to a fineness of -0.074mm, accounting for 70%, and the pulp concentration is adjusted to 36% to obtain material a; (2) Calcium oxide was added to material a to adjust the pH value of the slurry to 9, 30 g / t of copper-molybdenum collector thiocarbamate and 10 g / t of dodecyl mercaptan, and 40 g / t of polypropylene glycol as a foaming agent were added. Dodecyl mercaptan can enhance molybdenum enrichment and increase the molybdenum recovery rate by 8 percentage points, thereby obtaining a copper-molybdenum mixed coarse concentrate b; (3) The copper-molybdenum mixed concentrate b was adjusted to a pulp concentration of 30%, 80 g / t of water glass as a carbonaceous gangue inhibitor was added for first-order carbon suppression, and then 10 g / t of thiocarbamate collector and 5 g / t of dodecyl mercaptan and 10 g / t of polypropylene glycol as a foaming agent were added to perform secondary mixing and concentration to obtain the copper-molybdenum mixed concentrate c; (4) The copper-molybdenum mixed concentrate c was adjusted to a pulp concentration of 18%, and sodium sulfide 140 g / t was added and stirred for 5 min for modification and deactivation pretreatment. After the stirring was completed, the pulp was allowed to settle naturally, and the supernatant was removed to obtain the copper-molybdenum mixed concentrate d; (5) The copper-molybdenum mixed concentrate d was adjusted to a pulp concentration of 15%, and 1000 g / t of ferric chloride, a carbonaceous gangue inhibitor, was added for secondary carbon suppression. 6000 g / t of copper inhibitor KMD135 and 60 g / t of molybdenum collector kerosene were added for copper-molybdenum separation to obtain a rough molybdenum concentrate e and a copper-molybdenum separation "tailing" f.

[0025] (6) The molybdenum coarse concentrate is re-grinded, the molybdenum 100% monomer dissociation degree is 90%, and the carbon gangue inhibitor ferric chloride 150+80+50+30+10g / t is added for five-stage carbon suppression. After five times of concentration, a molybdenum concentrate with a molybdenum grade of 40% is obtained, and the molybdenum grade is increased by 8 percentage points. Concentration I adds copper inhibitor KMD135 3000g / t and molybdenum collector kerosene 40g / t; Concentration II adds copper inhibitor KMD135 2000g / t and molybdenum collector kerosene 20g / t; Concentration III adds copper inhibitor KMD135 1000g / t and molybdenum collector kerosene 10g / t; Concentration IV adds copper inhibitor KMD135 1000g / t and molybdenum collector kerosene 5g / t; Concentration V adds copper inhibitor KMD135 500g / t and molybdenum collector kerosene 0g / t.

[0026] (7) The copper-molybdenum separation "tailings" were subjected to three molybdenum scavengings to obtain copper concentrate. In scavenging I, 1000 g / t of copper inhibitor KMD135 and 20 g / t of molybdenum collector kerosene were added; in scavenging II, 500 g / t of copper inhibitor KMD135 and 10 g / t of molybdenum collector kerosene were added; in scavenging III, 200 g / t of copper inhibitor KMD135 and 5 g / t of molybdenum collector kerosene were added.

Claims

1. A method for beneficiation by step-by-step strengthening of carbon suppression to improve molybdenum grade, characterized in that: The ore dressing method for improving molybdenum grade by step-by-step enhanced carbon suppression includes molybdenum enrichment, first-order carbon suppression, modification and deactivation, and multi-order carbon suppression steps, specifically including: A. Molybdenum enrichment: (1) The raw ore to be processed is crushed and ground to a fineness of -0.074 mm accounting for 60-75%, and material a is obtained by slurry adjustment; (2) adjusting the pH value of material a to 8-9.5, adding a copper-molybdenum collector and a frother to enrich molybdenum to obtain a copper-molybdenum mixed coarse concentrate b; B. First-order carbon suppression: adjust the pulp concentration of the copper-molybdenum mixed rough concentrate b to 15-35%, add a carbonaceous gangue inhibitor for first-order carbon suppression, and then sequentially add a copper-molybdenum collector and a frother for 1-2 times of mixed concentration to obtain a copper-molybdenum mixed concentrate c; C. Modification and deactivation: The copper-molybdenum mixed concentrate c is adjusted to a pulp concentration of 15-25%, and sodium sulfide is used for modification and deactivation to obtain the copper-molybdenum mixed concentrate d; D. Multi-stage carbon suppression: (1) The copper-molybdenum mixed concentrate d is adjusted to a pulp concentration of 5-15%, a carbonaceous gangue inhibitor is added for secondary carbon inhibition, and then a copper inhibitor KMD135 and a molybdenum collector are sequentially added to separate copper and molybdenum to obtain a rough molybdenum concentrate e and a copper-molybdenum separation tailing f; (2) The molybdenum rough concentrate e is re-grinded according to the monomer dissociation degree of molybdenum to ensure that the monomer dissociation degree of molybdenum 100% is greater than 85%. After re-grinding, a carbonaceous gangue inhibitor is added to perform three to eight-stage carbon suppression, and a copper inhibitor KMD135 and a molybdenum collector are sequentially added to perform 1 to 6 rounds of concentration to obtain a molybdenum concentrate with an improved molybdenum grade; (3) adding copper inhibitor KMD135 and molybdenum collector to the copper-molybdenum separation tailings and performing 2-3 molybdenum scavenging to obtain copper concentrate; The copper inhibitor KMD135 is composed of sodium sulfide, sodium thiosulfate and sodium hydrosulfide.

2. The method for beneficiation of improving molybdenum grade by step-by-step strengthening of carbon suppression according to claim 1 is characterized in that: The slurry concentration of material a in step A (1) is 25-40%.

3. The method for ore dressing for improving molybdenum grade by step-by-step strengthening of carbon suppression according to claim 1 is characterized in that: The pH value is adjusted in step A (2) by using calcium oxide.

4. The method for beneficiation of step-by-step strengthening of carbon suppression and improving molybdenum grade according to claim 1 is characterized in that: The copper-molybdenum collector is composed of thiocarbamate and dodecyl mercaptan.

5. The method for beneficiation of improving molybdenum grade by step-by-step strengthening of carbon suppression according to claim 4 is characterized in that: The mass ratio of the thiocarbamate to dodecyl mercaptan is (0.5-1.5): (0.5-1.5).

6. The method for ore dressing for improving molybdenum grade by step-by-step strengthening of carbon suppression according to claim 1 is characterized in that: The foaming agent is polypropylene glycol.

7. The method for ore dressing for improving molybdenum grade by step-by-step strengthening of carbon suppression according to claim 1 is characterized in that: The carbonaceous gangue inhibitor described in step B is water glass.

8. The method for beneficiation of step-by-step enhanced carbon suppression and improved molybdenum grade according to claim 1, characterized in that: The carbonaceous gangue inhibitor described in step D is ferric chloride.

9. The method for beneficiation of improving molybdenum grade by step-by-step strengthening of carbon suppression according to claim 1 is characterized in that: The molybdenum collector is kerosene.

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