Treatment method for improving carbon recovery and separation in stone coal vanadium ore

Abstract

The present invention discloses a treatment method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore, comprising the following steps: 1) heating and activating the stone coal vanadium ore, cold quenching and pulping fine grinding to obtain a pulp; 2) flotation of the pulp to enrich and recover the carbonaceous materials. The present invention pre-treats the stone coal vanadium ore by using an additive heating activation method combined with cold quenching and pulping fine grinding, effectively improving the degree of dissociation of carbonaceous materials from gangue and improving the flotation effect, recovering the carbonaceous resources in stone coal, and making comprehensive use of stone coal resources; then enriching and recovering the carbonaceous materials in the stone coal vanadium ore by froth flotation, reducing the impact of carbonaceous materials on leaching and vanadium extraction, avoiding the pollution caused by roasting and decarbonization, and having great environmental and economic advantages; at the same time, the carbonaceous concentrate is separated from the stone coal vanadium ore by froth flotation technology, which can be used as fuel or combustion ingredients for power generation and heat supply, thereby achieving clean, environmentally friendly, and energy-saving emission reduction of stone coal vanadium extraction.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing engineering, and in particular relates to a processing method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore. Background Art

[0002] Stone coal is a low-quality anthracite primarily found in ancient strata such as the Cambrian, Sinian, and Silurian systems. Hundreds of millions of years ago, it was formed through the sapropelization and coalification of the remains of lower organisms, such as fungi and algae, in shallow seas and bays. During diagenesis, due to factors such as hydrothermal impregnation, stone coal became enriched with associated elements such as vanadium, copper, molybdenum, nickel, selenium, uranium, gallium, silver, and other precious metals. Vanadium is the primary element that can be industrially recovered.

[0003] Stone coal vanadium ore is a unique and strategic vanadium resource in my country, with proven reserves of 61.88 billion tons. Currently, domestic stone coal is primarily used for vanadium extraction, smelting, combustion for power generation, construction materials, and fertilizer production. Although stone coal has a low carbon content and poor grade, it has a significant calorific value and a large total reserve. Therefore, it is important to fully utilize this carbonaceous material to obtain low-calorific energy and improve resource utilization. The separation and enrichment of carbon in stone coal is crucial to the comprehensive utilization and economic efficiency of stone coal resources. Currently, the main processes include flotation decarbonization, roasting decarbonization, and gravity decarbonization. Decarbonization of stone coal by flotation can improve vanadium grade and comprehensively recover carbon resources. Furthermore, incorporating a decarbonization process into the wet process of stone coal vanadium extraction not only achieves decarbonization through flotation but also enriches vanadium-containing minerals, reducing the content of acid-consuming gangue minerals. This improves the vanadium grade of the wet process feed, reduces ore processing volume, and reduces acid consumption, ultimately lowering the production cost of stone coal vanadium extraction. On the other hand, roasting the vanadium-containing concentrate after flotation can greatly reduce oxygen consumption, increase the oxidation conversion rate of vanadium, and thus improve the vanadium leaching efficiency.

[0004] The carbon particles in stone coal-vanadium ore are extremely fine, highly dispersed, and possess strong adsorption capacity. Some carbonaceous materials are closely intertwined with gangue minerals or vanadium ore. The vast majority of this carbonaceous material is organic carbon or poorly crystallized amorphous carbon, with some existing as cryptocrystalline graphite. The intertwined particles are relatively small and primarily exhibit vein-like, disseminated, flake-like, and irregular shapes, intertwined with or intercalated with quartz and feldspar. Fine-grained slimes hinder flotation, increasing the amount of flotation reagents used, reducing selectivity, and lowering flotation grade. Some carbonaceous materials are closely intertwined with other minerals or intercalated with them, making them difficult to fully dissociate through direct grinding and ineffectively captured by flotation reagents. Due to the complex ore structure and diverse properties, as well as the influence of stone coal smelting and vanadium extraction processes, most stone coal vanadium extraction processes rely on roasting without carbon recovery. This ineffectively utilizes the stone coal's inherent carbon resources and results in the loss of carbonaceous energy during roasting. Therefore, it is necessary to develop new technical methods or mineral processing equipment to enrich and recover the carbon in stone coal so that carbon resources can be comprehensively utilized. Summary of the Invention

[0005] The present invention aims to solve, at least to a certain extent, one of the technical problems in the related art. To this end, the main purpose of the present invention is to provide a treatment method for improving the recovery and separation of carbonaceous materials from stone coal vanadium ore. The method aims to pretreat the stone coal vanadium ore by using additive heating activation and cold quenching pulping and fine grinding to synergistically destroy the ore structure of the stone coal vanadium ore, improve the degree of dissociation of carbonaceous materials from gangue, reduce the consumption of chemical reagents in flotation, improve the flotation separation effect of carbonaceous materials, and thus realize the resource utilization of stone coal vanadium ore.

[0006] The carbonaceous particles in stone coal vanadium ore are fine and highly dispersed, closely coexisting with other minerals, and have strong adsorption capacity, which greatly reduces the flotation performance of the carbonaceous particles. To address this problem, the purpose of the present invention is achieved through the following technical solutions:

[0007] A method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore comprises the following steps:

[0008] 1) The stone coal vanadium ore is subjected to heating activation, cold quenching, pulping and fine grinding treatment to obtain ore pulp;

[0009] 2) The pulp is subjected to flotation to enrich and recover carbon.

[0010] In certain specific embodiments, the heating activation in step 1) is as follows: adding additives to the stone coal vanadium ore, mixing thoroughly, and activating at a heating activation temperature of 100° C. to 350° C. for 30 min to 480 min.

[0011] Furthermore, the heating activation temperature is 200° C. to 300° C.; and the heating activation time is 60 min to 180 min.

[0012] In certain specific embodiments, the cold quenching pulping and fine grinding treatment in step 1) is specifically: cold quenching the stone coal vanadium ore after the heat activation treatment to prepare a slurry, and then ball milling to obtain a ball-milled slurry.

[0013] Furthermore, the cold quenching pulping in step 1) is: quickly placing the heated and activated stone coal vanadium ore in tap water for cold quenching pulping, and the mass ratio of the stone coal vanadium ore to tap water is 1:1.

[0014] Furthermore, the ball milling in step 1) is as follows: the prepared slurry is put into a ball mill for fine grinding, and the fineness is -200 mesh, which accounts for more than 80%;

[0015] More preferably, the proportion of fineness -200 mesh is greater than 85%.

[0016] In some specific embodiments, in step 2), the flotation is as follows: a depressant, a collector and a frother are sequentially added to the ore pulp prepared in step 1), and flotation is performed through a "one roughing - two sweeping - two fine" closed-circuit flotation process.

[0017] In some specific embodiments, the additive is at least one of an acid compound, a base compound, and a salt compound; the amount of the additive is 500 g / t to 3000 g / t;

[0018] Furthermore, the additive is an acid compound, which can enhance the destruction and dissociation of stone coal ore, thereby obtaining a better flotation quality improvement effect.

[0019] More preferably, it is 1500 g / t to 2000 g / t.

[0020] In certain specific embodiments, the total usage of the inhibitor, collector, and foaming agent is 1000 g / t to 1200 g / t, 300 g / t to 500 g / t, and 80 g / t to 150 g / t, respectively.

[0021] In some specific embodiments, the inhibitor is at least one of water glass, sodium hexametaphosphate, ferrous sulfate, and sodium carbonate; the flotation collector is at least one of kerosene and diesel; the flotation frother is 2 # At least one of oil and pine oil.

[0022] Compared with the prior art, the present invention has at least the following advantages:

[0023] 1) The present invention provides a treatment method for improving the recovery and separation of carbonaceous materials in stone coal-vanadium ore. The stone coal-vanadium ore is pretreated by using an additive for heating and activation and then quickly placed in tap water for quenching and slurrying to grind. This method can effectively improve the degree of dissociation of carbonaceous materials from gangue and improve the flotation effect, effectively recover the carbonaceous resources in stone coal, and make comprehensive utilization of stone coal resources. The carbonaceous materials in the stone coal-vanadium ore are then enriched and recovered by froth flotation, thereby improving the resource utilization of the stone coal-vanadium ore, reducing the influence of carbonaceous materials on leaching and vanadium extraction, avoiding the pollution caused by roasting and decarbonization, and having great environmental and economic advantages. At the same time, the carbonaceous concentrate is separated from the stone coal-vanadium ore by froth flotation technology, which can be used as fuel or combustion ingredient for power generation and heat supply, thereby achieving clean, environmentally friendly and energy-saving emission reduction of vanadium extraction from stone coal, and improving the comprehensive utilization rate of stone coal-vanadium ore resources.

[0024] 2) The present invention enriches the carbon in stone coal vanadium ore, which can not only reduce the processing volume of smelting and vanadium extraction, lower smelting costs, and increase vanadium production, but also improve the comprehensive utilization rate of my country's low-grade stone coal vanadium ore resources; it achieves dual recovery of vanadium and carbon in stone coal vanadium ore, improves the comprehensive utilization of its resources, and can not only expand the production source of strategic metal vanadium in my country, but also broaden the energy source and save high-quality coal. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the specific embodiments of the present invention, the following briefly introduces the drawings required for the specific embodiments or the description of the prior art.

[0026] Figure 1 A schematic flow chart of a treatment method for improving the recovery and separation of carbonaceous materials in stone coal alum ore provided by the present invention; DETAILED DESCRIPTION

[0027] The present invention will be further described in detail below with reference to the accompanying drawings and examples. The following examples are merely illustrative and non-restrictive, and should not be used to limit the scope of protection of the present invention.

[0028] When expressing a certain amount, concentration or other value or parameter in the form of a range, preferred range, or preferred upper and lower numerical limits, it should be understood that it is equivalent to specifically disclosing any range by combining any pair of upper range limits or preferred numerical values ​​with any lower range limit or preferred numerical value, without considering whether the range is specifically disclosed. Unless otherwise indicated, the numerical range values ​​listed herein include the endpoints of the range and all integers and fractions within the range.

[0029] Unless otherwise indicated, all percentages, parts, ratios, etc. herein are by weight.

[0030] The materials, methods, and examples herein are illustrative and, unless otherwise indicated, are not to be construed as limiting.

[0031] The test methods used in the following examples include:

[0032] By testing the main properties of each test sample respectively, the sorting effect of the prepared concentrate product and low-carbon tailings can be reflected; the main properties tested for the prepared concentrate product and low-carbon tailings in this application include yield, ash content, etc.

[0033] The prepared concentrate products and low carbon tailings were dried in an oven and then tested for yield and ash content.

[0034] 1) Yield test;

[0035] The yield is the percentage of the dry weight of the flotation product to the mass (dry weight) of the flotation feed, and the calculation formula is as follows:

[0036] α=M i / M×100%

[0037] Where α is the yield of flotation product, %; M i is the mass of flotation product, g; M is the mass of flotation feed (dry weight), g;

[0038] 2) Ash content test

[0039] Ash analysis was performed using a box-type resistance furnace (muffle furnace) according to the slow ashing method mentioned in the Industrial Analysis Methods of Coal (GB / T212-2008).

[0040] Example 1

[0041] The present invention provides a method for improving the recovery and separation of carbonaceous materials in anthracite ore, the flow chart of which is as follows: Figure 1 As shown, specifically, a stone coal vanadium ore (Aad = 88.58%) from a factory in Fenghuang County, Hunan Province was used as raw material, 500g of ore sample was weighed, and concentrated sulfuric acid with a mass concentration of 98% was used as an additive at an addition amount of 2000g / t (1g was added to 500g of ore sample in the experiment). 98% concentrated sulfuric acid), fully mixed and placed in a ceramic dish, sealed, placed in a muffle furnace and heated at 280 ° C for 120 minutes, the heated activated stone coal vanadium ore was taken out and immediately placed in 500g of tap water (room temperature tap water) for quenching, and the prepared slurry was then placed in a conical ball mill for fine grinding. The slurry fineness obtained after grinding and dissociation was -200 mesh, accounting for 90%; the slurry was added to a 1.5L flotation tank, sodium hexametaphosphate was selected as the inhibitor, the total amount was 1200g / t, kerosene was selected as the collector, the total amount was 500g / t, pine oil was selected as the foaming agent, the total amount was 100g / t, and a closed-circuit flotation process of one roughing, two scavenging and two concentrating was adopted (see Appendix). Figure 1 As shown), a carbonaceous concentrate product and low-carbon tailings are obtained.

[0042] The prepared concentrate product and low carbon tailings were dried in an oven and then tested for yield and ash content. The results were as follows:

[0043]

[0044] As can be seen from the table, the ash content of the concentrate product is 58.73%, which is 29.85% lower than the ash content of the raw material. The ash content of the tailings is 97.60%, indicating that the carbon is mainly concentrated in the concentrate product and the carbon content of the tailings is extremely low, achieving a good recovery and sorting effect.

[0045] Example 2

[0046] Compared with Example 1, the only difference is that the dosage of the additives is: Group (1): 1000g / t; Group (2): 1500g / t; Group (3): 2500g / t. The test results are:

[0047]

[0048]

[0049] It can be seen from the table that increasing the dosage of additives can reduce the ash content of concentrate and increase the ash content of tailings, which can improve the carbon recovery and sorting effect. When the dosage of additives exceeds 2000g / t, the change is small.

[0050] Example 3

[0051] Compared with Example 1, the only difference is that the additives are: Group (1): citric acid; Group (2): oxalic acid; Group (3): sodium hydroxide; (4) calcium oxide; (5) sodium carbonate; (6) calcium peroxide; (7) calcium chloride. The test results are:

[0052]

[0053] As can be seen from the table, additives such as acid compounds, alkaline compounds, and salt compounds have a certain improvement effect on the carbon recovery and separation effect, but the addition of acid compounds is relatively better.

[0054] Example 4

[0055] Compared with Example 1, the only difference is that the heating temperature is: Group (1): 160°C; Group (2): 200°C; Group (3): 240°C; Group (4): 320°C. The test results are:

[0056]

[0057] As can be seen from the table, increasing the heating activation temperature can better improve the carbon recovery and separation effect. When the temperature is 320°C, the ash content of the concentrate is 58.86% and the ash content of the tailings is 97.22%, which is not much different from that of Example 1. Therefore, the temperature is not further increased.

[0058] Example 5

[0059] Compared with Example 1, the only difference is that the heating time is: Group (1): 60 minutes; Group (2): 80 minutes; Group (3): 160 minutes. The test results are:

[0060]

[0061] As can be seen from the table, by increasing the heating activation time, the ash content of the concentrate of group (III) decreased by 7.19% compared with group (I), but the ash content of the tailings did not change much. However, the heating activation time had a certain impact on the yield of the two products, which in turn affected the sorting effect.

[0062] Example 6

[0063] Compared with Example 1, the only difference is that the grinding fineness is: Group (1): -200 mesh accounts for 80%; Group (2): -200 mesh accounts for 85%; Group (3): -200 mesh accounts for 95%. The test results are:

[0064]

[0065] It can be seen from the table that increasing the grinding fineness has a certain effect on the yield and ash content of the two products. When the -200 mesh accounts for 95%, the ash content of the concentrate is 59.69% and the ash content of the tailings is 96.40%. Compared with Example 1, the sorting effect is reduced. The reason may be that excessive refinement causes flotation to carry fine mud, which reduces the stability of the flotation foam.

[0066] Comparative Example 1

[0067] Compared to Example 1, the only difference is that no additives were added and no heat activation was performed. A 500 g sample was mixed with 500 g of tap water (room temperature) to form a slurry, which was then directly ground in a ball mill. Other operating methods and conditions were the same as in Example 1, including, for example, the grinding fineness and flotation mechanism.

[0068] The test results are:

[0069]

[0070] As can be seen from the table, under the experimental conditions of no additives and no heating activation, the ash content of the concentrate only decreased by 4.17%, the ash content of the tailings did not change much compared with the feed ore, and the carbon recovery and separation effect was poor.

[0071] Comparative Example 2

[0072] The only difference from Example 1 is that no additives are used during the heating and activation. Other operating methods and conditions are the same as those in Example 1, for example, the heating and activation temperature, grinding fineness, and flotation mechanism are the same as those in Example 1.

[0073] The test results are:

[0074]

[0075] As can be seen from the table, under the experimental conditions of heating activation but without using additives, the ash content of the concentrate decreased by 8.02% compared with the original ore, but compared with Example 1, the carbon recovery and separation effect was poor.

[0076] Comparative Example 3

[0077] Compared with Example 1, the only difference is that the pulping is carried out directly after the additive is applied without heating and activation. Other operating methods and conditions are the same as those in Example 1, for example, the amount of additive, grinding fineness, and flotation mechanism are the same as those in Example 1. The test results are as follows:

[0078]

[0079] It can be seen from the table that under the experimental conditions of using additives but not heating activation, the ash content of concentrates and tailings changes little, and the carbon recovery and separation effect is poor.

[0080] Comparative Example 4

[0081] Compared with Example 1, the only difference is that cold quenching pulping is not performed. That is, after heating and activation, the ore sample is cooled to room temperature before pulping. Other operating methods and conditions are the same as those in Example 1, for example, the heating and activation temperature, grinding fineness, and flotation process mechanism are the same as in Example 1. The test results are as follows:

[0082]

[0083] As can be seen from the table, under the experimental conditions of Comparative Example 4, the ash content of the concentrate decreased by 7.65% compared with the original ore, and the ash content of the tailings increased slightly, but the carbon recovery and separation effect was still poor.

[0084] Comparative Example 5

[0085] Compared with Example 1, the only difference is that the grinding fineness is: Group (1): -80 mesh accounts for 85%; Group (2): -150 mesh accounts for 85%; Group (3): -200 mesh accounts for 70%. The test results are:

[0086]

[0087] It can be seen from the table that, based on the experimental conditions of heating activation and cold quenching pulping, the grinding fineness affects the carbon recovery and sorting effect. Within a certain range, the smaller the grinding fineness, the better the recovery and sorting effect. When the grinding fineness of -200 mesh accounts for 70%, the ash content of the concentrate is reduced by 12.69% compared with the original ore. However, compared with Example 1, it still does not achieve a better recovery and sorting effect.

[0088] In summary, the present invention pre-treats stone coal vanadium ore using a method involving heating and activating additives and cold quenching, pulping, and fine grinding. This method fully dissociates the carbonaceous material from the gangue, allowing for the flotation enrichment and recovery of the carbonaceous material using appropriate flotation agents and processes. This not only enriches and recovers the carbon resources in the stone coal, avoiding energy loss during carbonaceous roasting, but also eliminates the harmful effects of carbonaceous material on subsequent vanadium extraction through smelting. The flotation concentrate obtained by the present invention can be used for co-firing for heating and power generation, and the flotation tailings can be directly acid-leached for vanadium extraction, thereby improving the comprehensive utilization rate of my country's low-grade stone coal vanadium ore resources.

[0089] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and description of the present invention.

Claims

1. A method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore, characterized in that: The steps include: 1) The stone coal vanadium ore is subjected to heating activation, cold quenching and pulping fine grinding to obtain ore pulp; 2) Flotation of the slurry to enrich and recover carbon; The heating activation in step 1) is as follows: adding the additive to the stone coal vanadium ore, mixing thoroughly, and then activating at a heating activation temperature of 100°C to 350°C for 30 min to 480 min; The cold quenching pulping and fine grinding treatment is specifically as follows: the stone coal vanadium ore after the heat activation treatment is quickly placed in tap water for cold quenching, configured into ore pulp, and then ball milling is performed to obtain ball-milled ore pulp; wherein the additive is at least one of an acid compound, an alkaline compound, and a salt compound.

2. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 1, characterized in that: The heating activation temperature is 200°C to 300°C; and the heating activation time is 60 min to 180 min.

3. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 2, characterized in that: The mass ratio of the stone coal vanadium ore to tap water is 1:

1.

4. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 3, characterized in that: The ball milling in step 1) is as follows: the prepared slurry is placed in a ball mill and finely ground until the proportion of -200 mesh is greater than 80%.

5. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 1, characterized in that: In step 2), the flotation is as follows: a depressant, a collector and a frother are sequentially added to the ore pulp obtained in step 1), and flotation is performed through a "one roughing - two sweeping - two refining" closed-circuit flotation process.

6. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 5, characterized in that: The dosage of the additive is 500 g / t to 3000 g / t.

7. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 6, characterized in that: The dosage of the additive is 1500 g / t to 2000 g / t.

8. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 7, characterized in that: The total usage of the inhibitor, collector and foaming agent is 1000 g / t-1200 g / t, 300 g / t-500 g / t and 80 g / t-150 g / t respectively.

9. The method for improving the recovery and separation of carbonaceous materials in stone coal vanadium ore according to claim 8, characterized in that: The inhibitor is at least one of water glass, sodium hexametaphosphate, ferrous sulfate, and sodium carbonate; the flotation collector is at least one of kerosene and diesel; the flotation frother is 2 # At least one of oil and pine oil.

Images