CN113182079B - Method for producing mineralized metallurgical medicament by using low-rank coal for quality improvement, mineralized metallurgical medicament and application - Google Patents

Method for producing mineralized metallurgical medicament by using low-rank coal for quality improvement, mineralized metallurgical medicament and application Download PDF

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CN113182079B
CN113182079B CN202110468205.2A CN202110468205A CN113182079B CN 113182079 B CN113182079 B CN 113182079B CN 202110468205 A CN202110468205 A CN 202110468205A CN 113182079 B CN113182079 B CN 113182079B
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metallurgical
mineralized
coal
medicament
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CN113182079A (en
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韩桂洪
黄艳芳
刘兵兵
苏胜鹏
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Zhengzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/016—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses aThe method for producing the mineralized metallurgical medicament by using the low-rank coal to improve quality, the mineralized metallurgical medicament and the application thereof are characterized in that a low-rank coal material is crushed, subjected to impurity removal and deashing to obtain the beneficiated coal; the fine coal dressing is activated by ultraviolet radiation and then mixed with caustic soda solution and Na 4 P 2 O 7 Stirring the solution for reaction to obtain a solution slurry; and (4) sequentially carrying out acid precipitation treatment, centrifugal treatment, freeze drying and fine grinding treatment on the dissolved slurry, and then irradiating by adopting ultraviolet rays to obtain the mineralized metallurgical medicament. The humic acid active functional groups in the mineralized metallurgical medicament are fully activated, the mineralized metallurgical medicament has better performance when being used for heavy metal ion flotation and metallurgical pellet binding agents compared with the existing humic acid chelating agents and binding agents, and the method takes low-rank coal as a raw material to obtain the high-performance mineralized metallurgical medicament, so that the problem of recycling of a large amount of idle stockpiled low-rank coal can be solved, the performance and the applicability of the mineralized metallurgical medicament can be improved, and the mineralized metallurgical medicament has remarkable economic and social benefits.

Description

Method for producing mineralized metallurgical medicament by using low-rank coal for quality improvement, mineralized metallurgical medicament and application
Technical Field
The invention relates to a mineralized metallurgical medicament, in particular to a mineralized metallurgical medicament which can be used as a heavy metal ion chelating medicament or a metallurgical pellet binder, and also relates to a method for producing the mineralized metallurgical medicament by using low-rank coal for quality improvement, belonging to the technical field of metallurgy.
Background
In the energy structure of China, petroleum and natural gas resources are deficient, the coal reserves are relatively rich, and the coal reserves account for nearly 70 percent of the energy structure and dominate the energy structure. At present, china has found that the coal reserves are 10200 hundred million tons, more than 55% of the low-rank coal with low coalification degree, and the volatile components in the low-rank coal are equivalent to 1000 million tons of oil and gas resources. However, because the water content of the low-rank coal is high, the direct combustion or gasification efficiency is low, and the resource value of the low-rank coal cannot be fully utilized in the prior art, the coal resource is greatly wasted.
The low-rank coal mainly comprises peat, lignite and weathered coal. The coal humic acid resource of China is mainly distributed in lignite, especially young lignite of the late second period, and peat is mainly distributed in Shanxi, inner Mongolia, sichuan, yunnan and the like. According to the relevant data, the proven peat reserves in China are 124.96 hundred million t, and the lignite reserves are 1216.09 million tons. Abundant resource storage lays a foundation for research of coal humic acid and large-scale utilization in production of various industries.
Humic acid medicaments have rich sources and low toxicity, and have better inhibiting and flocculating abilities in mineral separation, thereby generally arousing the attention of people. Research has shown that humic acid is a colloidal polymer composed of multiple structural units. These multi-structural units are composed of single structural units, which in turn are composed of micro-structural units. These microstructure units include a core, a bridge, and a reactive group. The existence of the active groups determines the hydrophilicity, cation exchange performance, complexation capacity and higher adsorption capacity of the humic acid. How to efficiently prepare the mineral mineralizer from low-rank lignite resources is the focus of research in recent years.
Humic acid can perform ion exchange, complexation, chelation and other reactions with heavy metal ions in a solution due to the existence of functional acidic groups such as carboxyl, phenolic hydroxyl, amino and the like, so that the humic acid is considered to be a very effective heavy metal ion complexing agent. The ion exchange capacity of humic acid is derived from active functional groups such as carboxyl, phenolic hydroxyl and the like in a molecular structure; the action mechanism of the humic acid carboxyl group as the main binding site of the metal ions and the heavy metal ions is the surface complexation between the humic acid ligand and the metal ions. However, the low-rank coal humic acid contains a large amount of mineral impurities such as silicate, the humic acid is usually purified by an alkali dissolution and acid precipitation method, and the humic acid is activated and modified to prepare the humic acid-based complexing chelating agent after purification. However, under the condition of strong acid and strong alkali treatment, rich functional groups in humic acid cannot be effectively activated, and the advantages of rich oxygen-containing functional groups of humic acid cannot be displayed, so that humic acid prepared by a conventional method cannot show good performance.
In addition, humic acid binders are also used in the field of ferrous metallurgy for the preparation of direct reduction pellets and oxidation pellets. With the continuous progress of metallurgical metals in China, the demand of the steel industry for high-quality pellets is greatly increased. The binder is an essential auxiliary material for producing iron ore pellets, and the quality of the binder directly influences the quality of the pellets. At present, bentonite is generally adopted as a binder to prepare the oxidability pellets in steel plants in China. However, the bentonite in China has poor quality, the coarse fraction content of iron ore concentrate for pellet production is high, and the bentonite with high proportion needs to be added to meet the requirement of industrial production. Because the bentonite is added with a large amount of aluminosilicate and other impurities, the iron grade of the pellet ore is seriously reduced, and the energy consumption and the production cost of iron making are obviously increased. In addition, the inorganic bentonite binder has poor adaptability to iron ore concentrate raw materials, and qualified pellets cannot be prepared from the bentonite for poor iron ore resources. The organic binder is a substance which takes macromolecular organic substances as main components, the binding property of the organic binder is obviously higher than that of bentonite at low temperature, and all or most of the organic binder is combusted and volatilized at medium and high temperature. The organic binder is adopted to replace bentonite, so that the quality of the pellet ore is improved, and the method is an important way for realizing the 'fine material policy' of the blast furnace, and the view is widely accepted by experts in the industry. The humic acid substance is a macromolecular organic polymer containing carboxyl, hydroxyl and benzene ring structures, and has an ideal binder molecular configuration. However, the existing preparation of humic acid mainly uses 'alkali dissolution and acid precipitation' as a principle to extract humic acid from low-rank coal. The humic acid medicament prepared by the alkali dissolution acidification method has the defects that functional groups cannot be effectively activated, good performance cannot be shown and the like.
Disclosure of Invention
Aiming at the problems of low mineralization efficiency, high medicament dosage and the like in the mineralization metallurgy process of humic acid extracted by the conventional method, the invention aims to provide a humic acid mineralization metallurgy medicament with fully activated active functional groups.
The second purpose of the invention is to provide a method for obtaining the high-activity humic acid mineralizing metallurgical medicament by using low-rank coal and the like as raw materials, and the method adopts special ultraviolet irradiation to fully activate functional groups in humic acid and improve the excellent mineralizing metallurgical performance of the humic acid mineralizing metallurgical medicament when the humic acid is extracted from the low-rank coal raw materials. The method has short process flow and convenient operation, takes large-scale low-rank coal as a raw material, can solve the problem of recycling of a large amount of idle stockpiled low-rank coal, can improve the performance and the applicability of the mineralized metallurgical agent, and has remarkable economic and social benefits.
The third purpose of the invention is to provide an application of humic acid mineralized metallurgical medicament, which has strong hydrophilicity, large viscosity and strong coagulation effect, can obviously improve the removal efficiency of metal ions in a solution when being used for ion flotation, has the advantages of low consumption of humic acid binder, good binding property, strong applicability and the like when being used for preparing oxidized pellets, and has the effect superior to that of the humic acid mineralized metallurgical medicament obtained by the existing method.
In order to realize the technical purpose, the invention provides a method for producing a mineralized metallurgical medicament by using low-rank coal quality improvement, which comprises the steps of crushing low-rank coal materials, and coarsely selecting and removing solid impurities to obtain coarsely selected coal; after the coarse coal dressing is finely ground, the ash content of the coarse coal dressing is carefully selected and removed by a dense medium, and then the fine coal dressing is obtained; irradiating the cleaned coal by adopting ultraviolet rays to obtain activated cleaned coal; the activated cleaned coal, caustic soda solution and Na 4 P 2 O 7 After the solution is stirred and reacts, carrying out centrifugal treatment to obtain solution; and (3) sequentially carrying out acid precipitation treatment, centrifugal treatment, freeze drying and fine grinding treatment on the dissolved pulp, and then irradiating by adopting ultraviolet rays to obtain the ultraviolet-curing resin.
The key point of the technical scheme of the invention is that the humic acid free radicals are generated by adding means such as ultraviolet irradiation and the like in the traditional humic acid alkali dissolution and acidification process, and functional groups in humic acid are thoroughly activated and a considerable amount of active free radicals are generated through a first-stage ultraviolet activation and a second-stage ultraviolet catalysis process, so that the humic acid free radicals have excellent mineralized metallurgical performance, and the separation efficiency and the preparation efficiency of metallurgical ball pellets can be effectively improved.
As a preferable scheme, the conditions of the two times of ultraviolet irradiation are as follows: using 200-500 mu W/cm 2 Irradiating for 5-10 min. The first ultraviolet irradiation mainly plays a role in activation, promotes the oxidation of a humic acid carbon skeleton, reduces the molecular weight of humic acid, and is beneficial to dissolving and extracting humic acid in the clean coal. The second ultraviolet irradiation mainly plays a role in activating functional groups such as carboxyl, phenolic hydroxyl and the like in the humic acid, increases the hydrophilicity of the humic acid,Viscosity and coagulation effect. In addition, the activation effect of humic acid is affected by the ultraviolet irradiation conditions, the extraction efficiency and the activation effect of humic acid are difficult to improve due to too low ultraviolet irradiation power or too short ultraviolet irradiation time, and humic acid is excessively decomposed due to too high ultraviolet irradiation power or too long ultraviolet irradiation time.
As a preferable scheme, the activated cleaned coal is mixed with caustic soda solution and Na 4 P 2 O 7 The solution was mixed at a liquid-solid ratio of 5 to 10mL.
In a preferred embodiment, the concentration of the caustic soda solution is 0.5 to 1mol/L. The caustic soda solution is mainly used for converting humic acid into humic acid salt with high water solubility, so that the humic acid in the low-rank coal material is extracted.
As a preferred embodiment, the Na 4 P 2 O 7 The concentration of the solution is 0.05-0.1 mol/L. Na (Na) 4 P 2 O 7 The addition of the humic acid is beneficial to the extraction of the humic acid complexed with metal ions in the low-rank coal, and the extracted humic acid has more carboxyl and phenolic hydroxyl contents.
As a preferred scheme, the caustic soda solution and the Na 4 P 2 O 7 The volume ratio of the solution is 5:1-2:1.
As a preferred scheme, the conditions of the two centrifugation treatments are as follows: centrifuging at 3000-4000 r/min for 20-40 min. The purpose of the first centrifugation treatment is mainly to remove part of the insoluble impurities. The second centrifugation process mainly promotes the precipitation of humic acid.
As a preferable embodiment, the conditions of the acid precipitation treatment are: adjusting the pH = 1.5-2 of the solution by adopting hydrochloric acid, and standing for 4-8 h. The main purpose of the acidification process is to acidify the humic acid salts, reduce the solubility thereof and realize sedimentation.
As a preferred embodiment, the freeze-drying conditions are: freeze-drying for 8-10 h at-50-20 ℃.
As a preferable scheme, the fine grinding treatment is carried out in a fine grinding mode until the fineness of solid particles in the solution is in a range of 0.001-0.075 mm.
The low-rank coal material is subjected to first-stage medium-stage crushing and second-stage fine crushing by a jaw crusher to be 20-50 mm.
The roughing process of the invention is realized by a jigger, and the crushed low-rank coal material is roughed by the jigger to remove solid impurities such as coal gangue and the like in the material.
The fine grinding process of the invention adopts an automatic vibration sample grinder to finely grind the rough low-rank coal material to 0.075-0.1 mm.
The dense medium concentration of the invention is realized by an air fluidized bed dense medium separator, and the finely ground low-rank coal material is concentrated to remove the ash content such as silicon, calcium, magnesium and the like in the coal.
The stirring reaction process of the invention mainly promotes the neutralization of humic acid to be converted into humic acid salt, and the reaction can be carried out at room temperature by stirring and can also be carried out by heating and stirring properly to shorten the reaction time. Generally heating and stirring for 20-30 min at 30-50 ℃ until the active components in the clean coal are completely dissolved.
The low-rank coal related by the invention is derived from peat, lignite, weathered coal and the like with abundant reserves.
The invention also provides a mineralized metallurgical medicament prepared by the method.
The invention also provides application of the mineralized metallurgical medicament as a heavy metal ion chelating medicament in a heavy metal ion flotation process. When the mineralized metallurgical agent is used for the flotation of heavy metal ions, 1.5 to 2 times of theoretical chelating amount of the mineralized metallurgical agent is added into the solution containing the heavy metal ions, and the rapid removal of the heavy metal ions is realized through the flotation process.
The invention also provides an application of the mineralized metallurgical agent as a metallurgical pellet binder. When the mineralized metallurgical agent is used for the metallurgical pellet binder, the mineralized metallurgical agent is directly and uniformly mixed with metallurgical mineral powder and water, so that the high-strength metallurgical pellet material can be obtained.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
according to the technical scheme, abundant low-rank coal is used as a raw material, the humic acid mineralized metallurgical medicament with high activity can be extracted and obtained, the problem of recycling of a large amount of idle stockpiled low-rank coal can be solved, the performance and the applicability of the mineralized metallurgical medicament can be improved, and the mineralized metallurgical medicament has remarkable economic and social benefits.
According to the technical scheme, the low-rank coal is used as the raw material, only ultraviolet irradiation is needed to be adopted in the conventional humic acid mineralized metallurgical medicament extraction process to fully activate functional groups in humic acid, a considerable amount of active free radicals are generated, excellent mineralized metallurgical performance is given to the humic acid mineralized metallurgical medicament, and the high-performance humic acid mineralized metallurgical medicament is obtained.
The humic acid mineralized metallurgical medicament obtained by the technical scheme of the invention has high proportion of active groups and higher activity, and can obviously improve the removal efficiency of metal ions in a solution when being used for ion flotation; when the humic acid binding agent is used for preparing the oxidized pellets, the humic acid binding agent has the advantages of low consumption of the humic acid binding agent, good binding performance, strong applicability and the like.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be noted that these examples are only for better understanding of the present invention, and do not limit the scope of the present invention.
Comparative example 1
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; the coarsely sorted lignite is finely ground by an automatic vibration sample grinder to be 0.075mm, and is finely sorted by an air fluidized bed dense-medium sorter to remove ash such as silicon, calcium, magnesium and the like in the lignite, so that clean coal powder is obtained. Adding 1mol/L NaOH and 0.05mol/L Na into the clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) at the temperature of 1: 10 for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at the speed of 3500r/min to obtain a solution containing a large amount of active components. Adding (1+1) HCl into the slurry to adjust the pH of the slurry to be =1.5, standing for 8h to separate out active components in the slurry, centrifuging for 30min at 3500r/min, -50, freeze-drying for 8h, and finely grinding to 0.001mm by a planetary ball mill to obtain the traditional humic acid medicament productThe yield was 52.3%.
Dissolving the humic acid medicament product by using 0.1mol/L NaOH, adjusting the pH of the solution to be =6, and preparing a 1g/L humic acid solution; to the solution containing 500mL of 50mg/L Pb 2+ 、20mg/L Ni 2+ Adding 25mL 1g/L humic acid solution into the mixed solution, stirring for 30min at 400r/min on a constant-temperature magnetic stirrer, transferring to a flotation column, performing flotation for 10min at a gas speed of 40mL/min, and measuring Pb in the flotation raffinate by adopting ICP-OES 2+ 、Ni 2+ The ion concentration. The results show that: pb in flotation raffinate 2+ 、Ni 2+ The concentrations are 5mg/L and 3mg/L respectively, pb 2+ 、Ni 2+ The flotation recovery rates are respectively 90% and 85%.
Comparative example 2
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the cleaned coal is 200 mu W/cm 2 Irradiating with ultraviolet ray for 10min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the clean coal powder in sequence 4 P 2 O 7 And (3) heating and stirring the solution (with the volume ratio of 3:1) at the temperature of 1 ℃ for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution at 3500r/min for 30min to obtain the slurry containing a large amount of active components. Adding (1+1) HCl into the dissolving pulp to adjust the pH of the dissolving pulp to be =1.5, standing for 8h to separate out active components in the dissolving pulp, centrifuging for 30min at 3500r/min, freeze-drying for 8h at-50, and finely grinding to 0.001mm by a planetary ball mill to obtain a humic acid medicament product, wherein the yield of the humic acid medicament is 65.8%.
Dissolving the humic acid medicament product by using 0.1mol/L NaOH, adjusting the pH of the solution to be =6, and preparing a 1g/L humic acid solution; to 500mL of 100mg/L Zn 2+ 、40mg/L Cd 2+ Adding 50mL 1g/L humic acid solution into the mixed solution, stirring for 30min at 400r/min on a constant-temperature magnetic stirrer, transferring to a flotation column, performing flotation for 10min at a gas velocity of 40ml/min, and measuring Zn in the flotation raffinate by adopting ICP-OES 2+ 、Cd 2+ The ion concentration. The results show that: zn in flotation raffinate 2+ 、Cd 2+ Concentration ofRespectively 13mg/L and 8mg/L, zn 2+ 、Cd 2+ The flotation recovery rates were 87% and 80%, respectively.
Comparative example 3
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the cleaned coal is 50 mu W/cm 2 Irradiating with ultraviolet ray for 3min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) at the temperature of 1: 10 for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at the speed of 3500r/min to obtain a solution containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components, centrifuging at 3500r/min for 30min, -50 freeze drying for 8h, fine grinding to 0.001mm with planetary ball mill, and passing through 100 μ W/cm 2 Irradiating with ultraviolet ray for 3min to obtain the conventional humic acid product with a humic acid product yield of 58.1%.
The magnetite concentrate with the grain size of-0.074 mm not less than 80 percent (mass percentage) and the humic acid medicament product accounting for 2.0 percent of the mass percentage of the iron concentrate are mixed, mixed and pelletized. The green ball forming rate is 75%, the green ball falling strength is 4.8 times/0.5 m, and the green ball compressive strength is 10.5N/piece. The dry ball has a compressive strength of 150N/piece at a drying temperature of 105 deg.C for 120 min. Under the conditions of the preheating temperature of 950 ℃, the preheating time of 10min, the roasting temperature of 1250 ℃ and the roasting time of 10min, the compressive strength of the preheated balls is 500N/piece, and the AC rotary drum is 3.43 percent; the compression strength of the baked pellets is 2300N/pellet.
Comparative example 4
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the fine coal dressing process is 800 mu W/cm 2 Ultraviolet irradiation of 20miAnd n, obtaining the activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the clean coal powder in sequence 4 P 2 O 7 And (3) heating and stirring the solution (with the volume ratio of 3:1) at the temperature of 1 ℃ for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution at 3500r/min for 30min to obtain the slurry containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components in the slurry, centrifuging at 3500r/min for 30min, -50, freeze drying for 8h, fine grinding to 0.001mm with a planetary ball mill, and passing through 800 μ W/cm 2 Ultraviolet irradiation is carried out for 30min to obtain the traditional humic acid medicament product, and the yield of the humic acid medicament is 59.7 percent.
The hematite concentrate with the grain size of-0.074 mm not less than 80 percent (mass percentage) and the humic acid medicament product accounting for 2.0 percent of the mass percentage of the hematite concentrate are mixed and pelletized. The green ball forming rate was 65%, the green ball dropping strength was 3.6 times/0.5 m, and the green ball compressive strength was 11.0N/piece. The dry ball has a compressive strength of 180N/piece at a drying temperature of 105 ℃ for 120 min. Under the conditions of the preheating temperature of 950 ℃, the preheating time of 10min, the roasting temperature of 1280 ℃ and the roasting time of 10min, the compressive strength of the preheated balls is 450N/ball, and the AC rotary drum is 3.85%; the compressive strength of the baked pellets is 2520N/pellet.
Example 1
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the cleaned coal is processed by 200 mu W/cm 2 Irradiating with ultraviolet ray for 10min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the activated clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) with the liquid-solid ratio of 10 for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at 3500r/min to obtain a slurry containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components in the slurry, centrifuging at 3500r/min for 30min, -50 freeze drying for 8h, fine grinding to 0.001mm with a planetary ball mill, and passing through 500 μ W/cm 2 The ultraviolet ray is irradiated for 10min,the mineralized metallurgical medicament product is obtained, and the medicament yield is 68.4 percent.
Dissolving the mineralized metallurgical agent by using 0.1mol/L NaOH, adjusting the pH of the solution to be =6, and preparing 1g/L humic acid solution; to the solution containing 500mL of 50mg/L Pb 2+ 、20mg/L Ni 2+ Adding 25mL 1g/L humic acid solution into the mixed solution, stirring for 30min at 400r/min on a constant-temperature magnetic stirrer, transferring to a flotation column, performing flotation for 10min at a gas velocity of 40ml/min, and measuring Pb in the flotation raffinate by adopting ICP-OES 2+ 、Ni 2+ The ion concentration. The results show that: pb in flotation raffinate 2+ 、Ni 2+ The concentrations are 0.5mg/L and 0.2mg/L, respectively, pb 2+ 、Ni 2+ The flotation recovery rates are 99% and 99.5% respectively.
Example 2
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the fine coal dressing process is 300 mu W/cm 2 Irradiating with ultraviolet ray for 8min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the activated clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) with the liquid-solid ratio of 8:1 for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at 3500r/min to obtain a dissolving pulp containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components in the slurry, centrifuging at 3500r/min for 30min, -50 freeze drying for 8h, fine grinding to 0.001mm with a planetary ball mill, and passing through 400 μ W/cm 2 Irradiating with ultraviolet for 10min to obtain mineralized metallurgical chemical product with a chemical yield of 71.5%.
Dissolving the mineralized metallurgical agent by using 0.1mol/L NaOH, adjusting the pH of the solution to be =6, and preparing 1g/L humic acid solution; to 500mL of 100mg/L Zn 2+ 、40mg/L Cd 2+ Adding 50mL 1g/L humic acid solution into the mixed solution, stirring for 30min at 400r/min on a constant-temperature magnetic stirrer, transferring to a flotation column, performing flotation for 10min at a gas velocity of 40ml/min, and measuring Zn in the flotation raffinate by adopting ICP-OES 2+ 、Cd 2+ Ion concentration. The results show that: zn in flotation raffinate 2+ 、Cd 2+ The concentrations are 1.2mg/L and 0.7mg/L respectively, zn 2+ 、Cd 2+ The flotation recovery rates are respectively 98.8% and 98.25%.
Example 3
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the refined coal is treated by 250 mu W/cm 2 Irradiating with ultraviolet ray for 10min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the activated clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) with the liquid-solid ratio of 10 for 30min until active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at 3500r/min to obtain a solution containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components in the slurry, centrifuging at 3500r/min for 30min, -50 freeze drying for 8h, fine grinding to 0.001mm with a planetary ball mill, and passing through 500 μ W/cm 2 Irradiating with ultraviolet ray for 5min to obtain mineralized metallurgical chemical product with yield of 67.8%.
The magnetite concentrate with the grain size of-0.074 mm and the grain size of more than 80 percent (mass percentage) and the mineralized metallurgical medicament product accounting for 0.75 percent of the mass percentage of the iron concentrate are mixed, mixed and pelletized. The green ball forming rate is 85%, the green ball falling strength is 4.5 times/0.5 m, and the green ball compressive strength is 11.2N/piece. The dry ball has a compressive strength of 280N/piece under the conditions of a drying temperature of 105 ℃ and a drying time of 120 min. Under the conditions of the preheating temperature of 950 ℃, the preheating time of 10min, the roasting temperature of 1250 ℃ and the roasting time of 10min, the compressive strength of the preheated balls is 512N/ball, and the AC rotary drum is 3.20%; the compression strength of the baked pellets is 3310N/pellet.
Example 4
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; the coarsely-selected brown coal is finely ground by an automatic vibration sample grinder to 0.075mm, and is finely selected by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the coal to obtain fine coal powderGrinding; the fine coal dressing process is 320 mu W/cm 2 Irradiating with ultraviolet ray for 6min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the activated clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) with the liquid-solid ratio of 10 for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at 3500r/min to obtain a slurry containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components in the slurry, centrifuging at 3500r/min for 30min, -50, freeze drying for 8h, fine grinding to 0.001mm with a planetary ball mill, and passing through 450 μ W/cm 2 Irradiating with ultraviolet ray for 5min to obtain mineralized metallurgical chemical product with a chemical yield of 70.9%.
The hematite concentrate with the grain size of-0.074 mm which is more than 80 percent (mass percentage) and the mineralized metallurgical medicament product which accounts for 1.0 percent of the mass percentage of the hematite concentrate are mixed, mixed and pelletized. The green ball forming rate is 83%, the green ball falling strength is 3.9 times/0.5 m, and the green ball compressive strength is 12.6N/piece. The dry ball has a compressive strength of 310N/piece under the conditions of a drying temperature of 105 ℃ and a drying time of 120 min. Under the conditions of the preheating temperature of 950 ℃, the preheating time of 10min, the roasting temperature of 1280 ℃ and the roasting time of 10min, the compressive strength of the preheated balls is 490N/piece, and the AC rotary drum is 3.30 percent; the compression strength of the baked pellets is 2840N/pellet.
Example 5
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the fine coal dressing process is 380 mu W/cm 2 Irradiating with ultraviolet ray for 5min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the activated clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) with the liquid-solid ratio of 10 for 30min until active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at 3500r/min to obtain a solution containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components, centrifuging at 3500r/min for 30min, -50, freeze drying for 8h, fine grinding to 0.001mm with planetary ball mill, and grindingAt a speed of 300. Mu.W/cm 2 Ultraviolet irradiation is carried out for 10min, and the mineralized metallurgical medicament product is obtained, wherein the medicament yield is 69.3%.
The magnetite concentrate with the grain size of-0.074 mm and larger than 80 percent (mass percent) and the mineralized metallurgical medicament product accounting for 1.0 percent of the mass percent of the iron concentrate are mixed, mixed and pelletized. The green ball forming rate is 75%, the green ball falling strength is 4.0 times/0.5 m, and the green ball compressive strength is 11.8N/piece. The dry ball has a compressive strength of 265N/piece at a drying temperature of 105 ℃ for 120 min. Under the conditions of the preheating temperature of 950 ℃, the preheating time of 10min, the roasting temperature of 1250 ℃ and the roasting time of 10min, the compressive strength of the preheated balls is 524N/each, and the AC rotary drum is 3.35 percent; the compressive strength of the baked pellets is 3432N/pellet.
Example 6
Crushing the low-order lignite in a first section by a jaw crusher, finely crushing the low-order lignite in a second section to 30mm, and removing coal gangue in the materials by a jigger; finely grinding the coarsely-selected lignite by an automatic vibration sample grinder for 0.075mm, and finely selecting by an air fluidized bed dense-medium separator to remove ash such as silicon, calcium, magnesium and the like in the lignite to obtain clean coal powder; the cleaned coal is processed by 450 mu W/cm 2 Irradiating with ultraviolet ray for 8min to obtain activated clean coal powder. Adding 1mol/L NaOH and 0.05mol/L Na into the activated clean coal powder in sequence 4 P 2 O 7 Heating and stirring the solution (the volume ratio is 3:1) with the liquid-solid ratio of 10 for 30min until the active components in the clean coal are completely dissolved, and centrifuging the solution for 30min at 3500r/min to obtain a slurry containing a large amount of active components. Adding (1+1) HCl to the slurry to adjust pH =1.5, standing for 8h to separate out active components in the slurry, centrifuging at 3500r/min for 30min, -50, freeze drying for 8h, fine grinding to 0.001mm with a planetary ball mill, and passing through 200 μ W/cm 2 Irradiating with ultraviolet ray for 10min to obtain mineralized metallurgical chemical product with chemical yield of 72.6%.
The hematite concentrate with the grain size of-0.074 mm which is more than 80 percent (mass percentage) and the mineralized metallurgical medicament product which accounts for 0.75 percent of the mass percentage of the hematite concentrate are mixed, mixed and pelletized. The green ball forming rate is 76%, the green ball falling strength is 3.6 times/0.5 m, and the green ball compressive strength is 12.2N/piece. The dry ball has a compressive strength of 294N/ball under the conditions of a drying temperature of 105 ℃ and a drying time of 120 min. Under the conditions of the preheating temperature of 950 ℃, the preheating time of 10min, the roasting temperature of 1280 ℃ and the roasting time of 10min, the compressive strength of the preheated balls is 476N/ball, and the AC rotary drum is 3.13%; the compressive strength of the roasted pellets was 2920N/pellet.

Claims (9)

1. A method for producing a mineralized metallurgical medicament by using low-rank coal for quality improvement is characterized by comprising the following steps: crushing a low-rank coal material, and performing rough separation to remove solid impurities to obtain rough separated coal; after the coarse coal dressing is finely ground, the ash content of the coarse coal dressing is carefully selected and removed by a dense medium, and then the fine coal dressing is obtained; irradiating the cleaned coal by adopting ultraviolet rays to obtain activated cleaned coal; the activated cleaned coal, caustic soda solution and Na 4 P 2 O 7 After the solution is stirred and reacts, carrying out centrifugal treatment to obtain solution slurry; performing acidification treatment, centrifugation treatment, freeze drying and fine grinding treatment on the dissolved pulp in sequence, and then irradiating by using ultraviolet rays to obtain the ultraviolet-cured resin; wherein, the conditions of the two times of ultraviolet irradiation are as follows: using 200-500 mu W/cm 2 Irradiating for 5-10 min.
2. The method for producing the mineralized metallurgical agent by using the low-rank coal for quality improvement according to claim 1, wherein the method comprises the following steps:
the activated cleaned coal, caustic soda solution and Na 4 P 2 O 7 Mixing the solution according to the liquid-solid ratio of 5-10mL;
the concentration of the caustic soda solution is 0.5-1 mol/L;
the Na is 4 P 2 O 7 The concentration of the solution is 0.05-0.1 mol/L;
the caustic soda solution and the Na 4 P 2 O 7 The volume ratio of the solution is 5:1-2:1.
3. The method for producing the mineralized metallurgical agent by using the low-rank coal for quality improvement according to claim 1, wherein the method comprises the following steps: the conditions of the two centrifugation treatments are as follows: centrifuging at 3000-4000 r/min for 20-40 min.
4. The method for producing the mineralized metallurgical agent by using the low-rank coal for quality improvement according to claim 1, wherein the method comprises the following steps: the conditions of the acid precipitation treatment are as follows: adjusting the pH = 1.5-2 of the solution by adopting hydrochloric acid, and standing for 4-8 h.
5. The method for producing the mineralized metallurgical agent by using the low-rank coal for quality improvement according to claim 1, wherein the method comprises the following steps: the conditions of freeze drying are as follows: freeze-drying for 8-10 h at-50-20 ℃.
6. The method for producing the mineralized metallurgical agent by using the low-rank coal for quality improvement according to claim 1, wherein the method comprises the following steps: the fine grinding treatment is to grind the mixture until the fineness of solid particles in the dissolved pulp is within the range of 0.001-0.075 mm.
7. A mineralizing metallurgical agent, characterized by: prepared by the method of any one of claims 1 to 6.
8. Use of a mineralogical metallurgical agent according to claim 7, wherein: the chelating agent is used as a heavy metal ion chelating agent in the heavy metal ion flotation process.
9. Use of a mineralogical metallurgical agent according to claim 7, wherein: the composite material is applied as a metallurgical pellet binder.
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