Combined grinding and flotation method of acid leaching residue-coke powder of stone coal vanadium ore

Abstract

The present invention discloses a combined grinding method for stone coal vanadium ore acid leaching residue and coke fines, wherein a slurry consisting of stone coal vanadium ore acid leaching residue, coke fines, and water is subjected to combined grinding treatment to obtain a combined grinding slurry. The present invention also discloses a carrier flotation method for the combined grinding slurry. The present invention combines stone coal vanadium ore acid leaching residue and coke fines for grinding, and through the combined control of process parameters, can achieve a physical-chemical synergistic effect, facilitate the highly selective distribution of components and the reconstruction of the physical structure, improve the separation selectivity of carbon and ash in the combined treatment, and efficiently achieve the recovery of fine carbonaceous particles in the stone coal vanadium ore acid leaching residue through carrier flotation; the carrier flotation method provided by the present invention can effectively save flotation reagents, especially collectors, and can obtain higher flotation separation selectivity of coal and ash. The low-ash refined carbon product obtained by flotation can be used for boiler heating, and the obtained micro-carbon tailings can be used to prepare unburned bricks and other building materials after dehydration; thereby achieving high-value utilization of stone coal vanadium ore acid leaching residue and comprehensive resource utilization.

Description

Technical Field

[0001] The invention belongs to the technical field of comprehensive utilization of mineral processing waste resources, and particularly relates to a stone coal vanadium ore acid leaching residue-coke powder combined grinding and flotation method. Background Art

[0002] As a key strategic metal, vanadium is widely used in the steel and alloy industries due to its excellent tensile strength, hardness, and fatigue resistance. China, a major vanadium producer, leads the world in both production and consumption of vanadium products. my country's vanadium resources are primarily found in vanadium-titanium magnetite and stone coal. Stone coal, a unique vanadium-containing resource in my country, boasts total V2O5 reserves of 118 million tons, accounting for over 47% of China's total vanadium reserves and serving as the primary raw material for my country's vanadium industry. The orderly development and efficient utilization of stone coal-vanadium ore have become crucial resources for supporting the sustainable development of my country's vanadium industry. With the growing demand for vanadium, an increasing amount of stone coal-vanadium ore is being mined as a key vanadium resource. Currently, the main processes for extracting vanadium from stone coal include roasting, leaching, precipitation, and calcination.

[0003] Depending on the leaching process, vanadium tailings from stone coal extraction can be divided into acid leaching, alkaline leaching, and water leaching. Currently, acid leaching is the predominant vanadium leaching process in my country, resulting in the largest amount of acid leaching residue to be processed. Due to the low vanadium grade in stone coal (0.13% to 1.2%), the acid leaching process requires large ore tonnage and consumes a lot of acid. Consequently, the vanadium leaching residue produced by this process is characterized by large tonnage, high acid residue, and significant environmental hazards. The acid leaching residue contains highly corrosive acidic substances and various heavy metals, posing a potential environmental risk to water resources and soil pollution. With the rapid development of the stone coal vanadium extraction industry, the amount of stone coal vanadium tailings produced continues to increase year by year. Traditional methods for disposing of vanadium tailings, such as stockpiling and landfilling, not only occupy a large amount of land resources and pose significant environmental safety risks, but also result in resource waste, severely hindering the development of the stone coal vanadium extraction industry. Therefore, it is urgent to develop effective resource utilization methods for stone coal vanadium tailings, especially acid leaching residues. Summary of the Invention

[0004] The present invention aims to at least partially address one of the technical problems in the related art. To this end, the main purpose of the present invention is to provide a combined grinding and flotation method for stone coal vanadium ore acid leaching residue and coke fines. This method aims to achieve synergistic activation of the stone coal vanadium ore acid leaching residue and coke fines, improve the floatability of the carbon in the subsequent stone coal vanadium ore acid leaching residue and its selectivity for separation from ash, and achieve efficient separation of the carbon and ash through carrier flotation.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] This invention is the first in the industry to combine grinding and flotation of the acid-leached residue and coke from stone coal vanadium ore. Stone coal, formed in ancient strata, is composed of the remains of bacteria and algae, which undergo sapropelization and coalification in shallow seas, lagoons, and bays. Its carbon is evenly and sporadically distributed, making flotation separation difficult. Acid-leaching of stone coal for vanadium extraction leaves behind numerous pores that adsorb flotation reagents, increasing the amount of reagent required. In order to solve the technical problems of poor floatability of carbon in acid leaching residue of stone coal vanadium ore, low flotation selectivity and large consumption of flotation reagents, the present invention innovatively adopts stone coal vanadium ore acid leaching residue-coke powder for joint grinding. Through the chemical and physical effects in the grinding stage, the fine particles of carbon in the stone coal vanadium ore acid leaching residue adhere to the surface of the coke powder, which not only improves the carbon separation selectivity in the stone coal vanadium ore acid leaching residue through carrier flotation, but also can use the adsorption effect of the coke powder to block the pores to reduce the consumption of flotation reagents, which helps to solve the problems faced by the recovery and treatment of carbon in the stone coal vanadium ore acid leaching residue.

[0007] In a first aspect, a stone coal vanadium ore acid leaching residue-coke powder combined grinding method is provided, wherein a slurry consisting of stone coal vanadium ore acid leaching residue, coke powder and water is subjected to combined grinding treatment to obtain a combined grinding slurry.

[0008] In certain specific embodiments, coke dust and water in a mass ratio of 1:(1-10) are premixed to prepare a premixed slurry; and the premixed slurry is co-ground with stone coal vanadium ore acid leaching residue to obtain a co-ground slurry.

[0009] In the present invention, premixing is performed in advance and then combined grinding is performed, which can further improve the physical and chemical synergy in the stone coal vanadium ore acid leaching residue-coke combined grinding stage, help to further solve the problems faced by the combined treatment, and can unexpectedly improve the separation selectivity of carbon and ash in the stone coal vanadium ore acid leaching residue in the combined treatment.

[0010] Furthermore, the mass ratio of the coke dust to water is 1:(2-5);

[0011] In certain specific embodiments, in the composition of stone coal vanadium ore acid leaching residue and coke fines, the coke fines account for 20 to 85 wt %, preferably 20 to 35 wt %.

[0012] In certain specific embodiments, the stone coal vanadium ore acid leaching residue has an ash content of 40-90% and a calorific value of 2-10 MJ / Kg, preferably 2-5 MJ / Kg.

[0013] In certain specific embodiments, the mass proportion of the coke particles with a diameter between 0.1 and 0.3 mm is greater than 70%; the ash content is 5 to 15%, preferably 8 to 12%; and the calorific value is 25 to 31 MJ / kg, preferably 28 to 30 MJ / kg.

[0014] In certain specific embodiments, the concentration of the combined grinding slurry is 20-70%, preferably 40-55%, wherein the mass concentration of the combined grinding slurry is calculated by [(stone coal vanadium ore acid leaching residue + coke fines) / (stone coal vanadium ore acid leaching residue + coke fines + water)];

[0015] In a second aspect, a combined grinding slurry is prepared by the aforementioned stone coal vanadium ore acid leaching residue-coke powder combined grinding method, wherein the combined grinding slurry contains 60% to 98% of particles smaller than 0.075 mm, preferably 88% to 98%.

[0016] In the third aspect, a carrier flotation method for combined grinding slurry is provided, wherein the combined grinding slurry is added to a flotation machine, an inhibitor, a frother and a collector are sequentially added for stirring and mineralization, and then multi-stage flotation is performed to obtain clean coal products and micro-carbon tailings.

[0017] In the present invention, the combined grinding method based on acid leaching residue and coke powder of stone coal vanadium ore can realize the physical and chemical synergistic preparation to obtain the combined grinding slurry, which is beneficial to the separation of carbon and ash in the subsequent flotation stage, and is beneficial to obtaining high-grade carbon with high recovery rate, as well as obtaining high-ash micro-carbonaceous tailings.

[0018] In some specific embodiments, the inhibitor is water glass, and the amount of the inhibitor is 100g / t to 5000g / t; the foaming agent is 2-octanol, and the amount of the foaming agent is 50g / t to 5000g / t; the collector is wash oil, and the amount of the collector is 100g / t to 3000g / t.

[0019] In some specific embodiments, the multi-stage flotation in step 2) includes one roughing operation, one to three cleaning operations, and one to two scavenging operations.

[0020] Compared with the prior art, the present invention has at least the following advantages:

[0021] The present invention innovatively combines the acid leaching residue and coke of stone coal vanadium ore for grinding, and further cooperates with the joint control of the parameters, which can achieve chemical-physical synergy, facilitate the highly selective distribution of components and the reconstruction of physical structure, improve the separation selectivity of carbon and ash in the combined treatment, and efficiently realize the recovery of fine carbon in the acid leaching residue of stone coal vanadium ore through carrier flotation. The carrier flotation method provided by the present invention can effectively save flotation agents, especially collectors, and can obtain higher flotation separation selectivity of coal and ash. The obtained low-ash refined carbon product can be used for boiler heating, and the obtained micro-carbon tailings can be used to prepare unburned bricks and other building materials after dehydration; thus realizing the high-value utilization of stone coal vanadium ore acid leaching residue and comprehensive resource utilization. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 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.

[0023] Figure 1 In the present invention, the combined grinding pulp obtained by the combined grinding of stone coal vanadium ore acid leaching residue and coke powder is subjected to a closed-circuit flotation test process of "one coarse, two fine and one sweep". DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments, but it should not be understood as limiting the scope of protection of the present invention. Any formal equivalent transformation based on the concept of the present invention should be considered as the scope of the present invention.

[0025] This document provides general and / or specific descriptions of the materials and experimental methods used in the experiments. Unless otherwise specified, all experimental or testing methods are conventional methods. All reagents and instruments used, unless the manufacturer is specified, are commercially available, conventional products and were prepared or used using conventional methods.

[0026] In the following examples, the weight of coke fines is calculated on a dry basis. The coke fines blend ratio is calculated as coke fines / (coke fines + stone coal vanadium ore acid leaching residue) x 100%. During flotation, the amount of inhibitor and frother used is based on the total weight of the coke fines and stone coal vanadium ore acid leaching residue.

[0027] Example 1

[0028] In this example, the raw materials are stone coal vanadium ore acid leaching residue (88% by mass of particles less than 0.10 mm) with an ash content of 87.36% and a calorific value of 2.80 MJ / kg from Sinosteel Phoenix Mining Co., Ltd. and coke dust (76% by mass of particles with a particle size of 0.1-0.3 mm) with an ash content of 10.97% and a calorific value of 25.94 MJ / kg from a metallurgical company in Anyang, Henan Province. The coke dust accounts for 20% of the blending ratio. The specific steps are as follows:

[0029] (1) Coke dust and water were mixed in a mass ratio of 1:3 and stirred for 30 minutes to obtain a premixed slurry;

[0030] (2) The acid leaching residue of stone coal vanadium ore is mixed with the premixed slurry of step (1) and then added to the mill, water is added to control the slurry concentration to 25-30%, the grinding time is 12 minutes, and the fineness of the combined grinding slurry obtained after grinding and dissociation is less than 0.075 mm, accounting for 98%;

[0031] (3) The obtained pulp is subjected to closed-circuit flotation according to the "one coarse, two fine, one sweep" process (such as Figure 1 As shown), coal concentrate products and tailings products enriched with high ash content are separated;

[0032] Specifically, the inhibitor is water glass, and the dosage is 1000 g / t; the foaming agent is octanol, and the dosage is 600 g / t; and the collecting agent is wash oil, and the dosage is 500 g / t.

[0033] The test results are:

[0034]

[0035] Example 2

[0036] Compared with Example 1, the only difference between this embodiment and Example 1 is that the proportion of coke dust blended is 2%, 5%, 10%, 15%, 25%, 30%, and 35% respectively;

[0037]

[0038] Example 3

[0039] Compared with Example 1, the only difference between this embodiment and Example 1 is that this embodiment uses stone coal vanadium ore acid leaching slag with an ash content of 55.63% and a calorific value of 12.08 MJ / kg from a factory in southern Shaanxi and coke powder (particle size 0.1-0.3 mm, mass proportion 75%) with an ash content of 14.69% and a calorific value of 20.46 MJ / kg from a metallurgical plant in Pingdingshan, Henan as raw materials.

[0040] The test results are:

[0041]

[0042] Example 4

[0043] The only difference between this embodiment and Example 1 is that this embodiment uses acid leaching residue of stone coal vanadium mine with an ash content of 70.63% and a calorific value of 6.26 MJ / kg in western Zhejiang and coke powder (particle size 0.1-0.3 mm, mass proportion 78%) in Hebei with an ash content of 10.08% and a calorific value of 25.78 MJ / kg as raw materials.

[0044] The test results are:

[0045]

[0046] Example 5

[0047] Compared with Example 1, the only difference is that the dosage of flotation depressant is: Group (1): 500 g / t; Group (2): 1200 g / t; Group (3): 1500 g / t;

[0048] The test results are:

[0049]

[0050] Example 6

[0051] The only difference between this embodiment and embodiment 1 is that the dosage of the flotation frother is: group (1): 300 g / t; group (2): 800 g / t; group (3): 1200 g / t.

[0052] The test results are:

[0053]

[0054] Example 7

[0055] The only difference between this embodiment and Example 1 is that the dosage of the flotation collector is: Group (1): 300 g / t; Group (2): 800 g / t; Group (3): 1000 g / t.

[0056] The test results are:

[0057]

[0058] Comparative Example 1

[0059] Compared with Example 1, the only difference between this comparative example and Example 1 is that the experimental groups are: (1) the coke powder blending ratio is: 0%; Group (2): 100%;

[0060] The test results are:

[0061]

[0062] Comparative Example 2

[0063] Compared with Example 1, the stone coal vanadium ore acid leaching residue and coke fines were not ground together. Instead, they were ground separately and then mixed for flotation. The specific steps are as follows:

[0064] (1) Grinding the coke dust and water separately to control the pulp fineness to be less than 0.075 mm, accounting for 98%, to obtain coke dust pulp;

[0065] (2) grinding the stone coal vanadium ore acid leaching residue and water separately to control the slurry fineness to be less than 0.075 mm, accounting for 98%; obtaining the stone coal vanadium ore acid leaching residue slurry;

[0066] (3) The ore pulps of step (1) and step (2) are mixed, and the ratio of acid leaching residue of stone coal vanadium ore to coke and the solid content of the mixed slurry are the same as those in Example 1; and flotation is carried out using the method of Example 1.

[0067]

[0068] The results of Examples 1 and 2 show that when the coke blending ratio reaches 20% or more, the rate of grade improvement of the flotation concentrate slows significantly, and the ash content of the tailings drops sharply, which not only causes the loss of combustible materials in the tailings but also directly affects the strength and ignition loss performance of its building materials. Therefore, a coke blending ratio of 20% is more appropriate; the results of Examples 3 and 4 show that the technical solution of the present invention is also applicable to the flotation decarbonization of stone coal vanadium ore acid leaching residues with different calorific values ​​in other regions, and has certain promotion significance; and according to Comparative Example 1, it can be seen that the effect of grinding and flotation decarbonization of stone coal vanadium ore acid leaching residue alone is poor. According to Comparative Example 2, if the pulps after the two are ground separately are simply blended, no effective gain effect can be achieved. Combining Comparative Examples 1 and 2, it can be seen that the key to the technology of the present invention is that the physical and chemical synergistic effect of the combined grinding of stone coal vanadium ore acid leaching residue and coke promotes the sorting effect of subsequent carrier flotation.

[0069] In summary, the present invention combines the acid leaching residue and coke powder of stone coal vanadium ore for grinding, and further cooperates with the joint control of the above parameters to achieve chemical-physical synergy, which is beneficial to the highly selective distribution of components and the reconstruction of the physical structure, improves the sorting selectivity of carbon and ash in the combined treatment, and efficiently realizes the recovery of fine-grained carbon in the acid leaching residue of stone coal vanadium ore through carrier flotation, effectively saving the cost of reagents.

[0070] 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 carrier flotation method for combined grinding slurry, characterized in that: The steps include: 1) Combined grinding is performed on a slurry consisting of acid leaching residue of stone coal vanadium ore, coke dust, and water to obtain a combined grinding slurry; 2) Add the combined grinding slurry to the flotation machine, add the inhibitor, frother and collector in sequence for stirring and mineralization, and then carry out multi-stage flotation to obtain clean coal products and micro-carbon tailings.

2. The carrier flotation method of combined grinding pulp according to claim 1, characterized in that: The coke dust and water are premixed in a mass ratio of 1: (1-10) to prepare a premixed slurry; the premixed slurry is subjected to a combined grinding treatment with stone coal vanadium ore acid leaching residue to obtain a combined grinding slurry.

3. The carrier flotation method of combined grinding pulp according to claim 1 or 2, characterized in that: In the composition of stone coal vanadium ore acid leaching residue and coke dust, the coke dust accounts for 20-85wt%.

4. The carrier flotation method of combined grinding pulp according to claim 3, characterized in that: In the composition of stone coal vanadium ore acid leaching residue and coke dust, the coke dust accounts for 20-35wt%.

5. The carrier flotation method of combined grinding slurry according to claim 1 or 2, characterized in that: The stone coal vanadium ore acid leaching residue has an ash content of 40-90% and a calorific value of 2-10 MJ / Kg.

6. The carrier flotation method of combined grinding pulp according to claim 5, characterized in that: The mass proportion of the coke residue with a particle size between 0.1 and 0.3 mm is greater than 70%, the ash content is 5 to 15%, and the calorific value is 25 to 31 MJ / kg.

7. The carrier flotation method of combined grinding pulp according to claim 6, characterized in that: The ash content is 8-12%, and the calorific value is 28-30 MJ / kg.

8. The carrier flotation method of combined grinding slurry according to claim 1, characterized in that: The concentration of the combined grinding slurry is 20-70%.

9. The carrier flotation method of combined grinding pulp according to claim 8, characterized in that: In the combined grinding slurry, particles smaller than 0.075 mm account for 60-98%.

10. The carrier flotation method of combined grinding pulp according to claim 9, characterized in that: The inhibitor is water glass, and the dosage of the inhibitor is 100 g / t to 5000 g / t; the foaming agent is wash oil, and the dosage of the foaming agent is 50 g / t to 5000 g / t; the collector is wash oil, and the dosage of the collector is 100 g / t to 3000 g / t.

11. The carrier flotation method of combined grinding pulp according to claim 10, characterized in that: The multi-stage flotation in step 2) specifically comprises one roughing operation, one to three cleaning operations, and one to two scavenging operations.

Images