CN114592123B - Chromium ore powder ball and preparation method thereof - Google Patents

Chromium ore powder ball and preparation method thereof Download PDF

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Publication number
CN114592123B
CN114592123B CN202111616607.9A CN202111616607A CN114592123B CN 114592123 B CN114592123 B CN 114592123B CN 202111616607 A CN202111616607 A CN 202111616607A CN 114592123 B CN114592123 B CN 114592123B
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bentonite
parts
ore powder
polyimide
stirring
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CN114592123A (en
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陈杰
陈波
马选坤
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Fujian Tonghai Nickel Industry Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/2406Binding; Briquetting ; Granulating pelletizing
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders
    • C22B1/243Binding; Briquetting ; Granulating with binders inorganic
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders
    • C22B1/244Binding; Briquetting ; Granulating with binders organic
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

The invention relates to the field of smelting materials, and discloses a chromium ore powder ball which comprises the following raw materials in parts by weight: 85-95 parts of chromium mineral powder, 2-3 parts of binder and 2-3 parts of water; the adhesive comprises the following components in parts by weight: 6-7 parts of silane modified polyimide/bentonite composite material, 3-4 parts of silane modified epoxy resin, 0.01-0.03 part of dibutyltin dilaurate and 20-30 parts of tetrahydrofuran. The invention adopts the organic-inorganic composite binder to prepare the chromium ore powder into pellets, can reduce the dosage of the inorganic binder, avoid the influence on the grade of the chromium ore powder, and can improve the strength and the thermal stability of the chromium ore powder pellets.

Description

Chromium ore powder ball and preparation method thereof
Technical Field
The invention relates to the technical field of smelting materials, in particular to a chromium ore powder ball and a preparation method thereof.
Background
The chromium ore is the main raw material for smelting chromium alloy, and in chromium ore required by chromium alloy production, blocky chromium ore is used as the optimal raw material, and in the production process of chromium alloy, the blocky chromium ore and other raw materials enter the furnace, so that the air permeability in the furnace can be improved, the ignition is not easy, the dust is less, the furnace condition can be better controlled, and better economic and technical indexes are obtained. But with the shortage of chromium ore resources, the yield of lump ore is reduced, the grade is reduced, and the price is increased. Correspondingly, the chromium ore powder (particle size is less than 10 mm) obtained by adopting the ore dressing method is more and more, chromium alloy production enterprises gradually start to use the powder ore to produce products such as ferrochrome and the like, and the powder ore use proportion of many enterprises is almost half. However, the direct feeding of the powder ore into the furnace can cause a series of technical problems of poor air permeability, easy ignition, large dust, unstable furnace conditions and the like of the submerged arc furnace. Therefore, the fine ore must be agglomerated or formed into pellets for a large amount of use in electric furnaces for smelting chromium-based alloys.
At present, the method for preparing the chromium ore powder into pellets mainly comprises the cold-pressing pellet process: mixing the chromium mineral powder and the binder, feeding the mixture into a stirrer, conveying the mixture to a ball pressing machine for ball pressing, and airing to obtain the chromium mineral powder balls. For example, the publication No. CN103436694A discloses a method for preparing pellets of powder chrome ore in Chinese patent literature, wherein the preparation process comprises the steps of adding an adhesive, a slag former, a reducing agent and a regulator into the powder chrome ore, uniformly mixing, adding water for humidity adjustment, cold pressing into pellets, natural curing and airing to obtain finished pellets.
However, the chromium ore powder pellets prepared in the prior art have the following disadvantages: 1. the specific gravity of the binder is high, the taste is seriously reduced after balling, and the comprehensive grade of chromium ore entering the furnace is influenced; 2. the pellet has low strength, is easy to damage during transportation and generates secondary pollution; 3. the explosion temperature of the pellets is low, which is not beneficial to stabilizing the furnace condition.
Disclosure of Invention
In order to overcome the problems of the chromium ore powder pellets in the prior art, the invention provides the chromium ore powder pellets and the preparation method thereof, and the organic-inorganic composite binder is adopted to prepare the chromium ore powder into pellets, so that the use amount of the inorganic binder can be reduced, the influence on the grade of the chromium ore powder is avoided, and meanwhile, the strength and the thermal stability of the chromium ore powder pellets can be improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The chromium ore powder ball comprises the following raw materials in parts by weight: 85-95 parts of chromium ore powder, 2-3 parts of binder and 2-3 parts of water; the adhesive comprises the following components in parts by weight: 6 to 7 parts of silane modified polyimide/bentonite composite material, 3 to 4 parts of silane modified epoxy resin, 0.01 to 0.03 part of dibutyl tin dilaurate and 20 to 30 parts of tetrahydrofuran.
In the chromium ore powder ball, the silane modified polyimide/bentonite composite material and the silane modified epoxy resin are adopted as main raw materials of the binder, and the water absorption performance of bentonite is utilized to reduce the evaporation rate of water in the chromium ore powder ball, so that the vapor pressure in the pellet is reduced, the bursting temperature of the pellet is improved, the bursting pulverization rate of the chromium ore powder ball after being fed into a furnace is reduced, and the furnace condition is stabilized. However, too much bentonite is added as an inorganic substance to influence the grade of pellets, so that the bentonite and the silane modified polyimide are compounded to prepare the organic-inorganic composite material, the consumption of inorganic bentonite is reduced, the organic components in the binder can be burnt and removed in the smelting process, and the slag amount in the smelting process is reduced. Polyimide in the silane modified polyimide/bentonite composite material has good high temperature resistance, is also beneficial to improving the thermal stability of pellets, reduces the bursting rate of chromium ore powder pellets after being fed into a furnace, but has insufficient bonding performance, so the invention adds silane modified epoxy resin into the adhesive, and improves the bonding performance of the adhesive. In order to improve the strength of the chromium ore powder ball, silane groups are respectively introduced into polyimide and epoxy resin, and after the adhesive is mixed with water, the silane groups in the silane modified polyimide and the silane modified epoxy resin are hydrolyzed under the catalysis of dibutyltin dilaurate, so that the polyimide and the epoxy resin are crosslinked and cured at room temperature, the curing temperature is reduced, and the curing time is shortened; and the strength of the chromium ore powder ball is improved through the co-crosslinking of polyimide and epoxy resin, so that the damage of the ball in the transportation and use processes can be effectively reduced.
Preferably, the particle size of the chromium ore powder is 0 to 1mm. Although the smaller the granularity of the chromium mineral powder is, the easier the pelletization is, but the smaller the granularity is, the denser the prepared pellet is, the water in the pellet is not easy to evaporate, and the vapor pressure in the pellet is larger, so the pellet prepared from the chromium mineral powder with smaller granularity is usually easy to burst and pulverize, and is unfavorable for the stability of furnace conditions. According to the invention, through optimizing the binder component, the chromium ore powder balls with higher bursting temperature can be prepared by using the chromium ore powder with smaller granularity, so that the application of the chromium ore powder balls is facilitated.
Preferably, the preparation method of the silane modified polyimide/bentonite composite material comprises the following steps:
a) Adding bentonite into octadecyl trimethyl ammonium bromide solution, stirring uniformly, performing ultrasonic oscillation reaction for 2-4 hours, separating and drying the product to obtain primarily intercalated bentonite;
b) Dissolving the primarily intercalated bentonite in DMF to obtain DMF solution of bentonite;
c) Dissolving 4,4' -diaminodiphenyl ether in DMF, stirring uniformly, adding hexafluorodianhydride into the solution, stirring to react for 3-4 hours, adding DMF solution of bentonite and isoquinoline, heating to 185-195 ℃ and continuing stirring to react for 8-10 hours; transferring the product to ethanol for precipitation, separating and cleaning the precipitation, and drying to obtain a polyimide/bentonite composite material;
D) Dissolving the polyimide/bentonite composite material in DMF, adding gamma-aminopropyl triethoxysilane into the solution under the protection of nitrogen at 0-4 ℃, stirring and reacting for 2-4 hours, heating to 45-55 ℃, adding isoquinoline and pyridine acetic anhydride, stirring and reacting for 8-10 hours, transferring the product into petroleum ether for precipitation, separating the precipitate, cleaning and drying to obtain the silane modified polyimide/bentonite composite material.
Firstly, intercalating bentonite through octadecyl trimethyl ammonium bromide, primarily expanding the interlayer spacing of the bentonite, and then intercalating polyimide between bentonite layers by using 4,4' -diaminodiphenyl ether and hexafluorodianhydride as monomers through a solution polymerization in-situ intercalation method to obtain a polyimide/bentonite composite material; and finally, capping the polyimide with gamma-aminopropyl triethoxy silane to obtain the silane modified polyimide/bentonite composite material.
According to the invention, the silane modified polyimide is inserted between layers of the bentonite, and then the silane modified polyimide is co-crosslinked with the silane modified epoxy resin, so that the limiting effect of the lamellar structure of the bentonite on polyimide molecules can be further improved, and the high temperature resistance of the pellets can be further improved; meanwhile, bentonite dissociated into nano-structures can be used as a crosslinking point, so that the strength of the pellets is further improved. Therefore, the invention can lead the prepared chromium ore powder ball to have good strength and thermal stability under the condition of less bentonite addition.
Preferably, the concentration of the octadecyl trimethyl ammonium bromide solution in the step A) is 0.5-1.0 mol/L, and the mass volume ratio of bentonite to the octadecyl trimethyl ammonium bromide solution is 1 g:50-100 mL; the mass concentration of the DMF solution of the bentonite obtained in the step B) is 1-3%.
Preferably, the molar ratio of 4,4' -diaminodiphenyl ether to hexafluorodianhydride added in step C) is 1-1.5:1; the mass ratio of the 4,4' -diaminodiphenyl ether to the bentonite is 3-4:1; the solid content of the reaction system is 10-15 wt%, and the addition amount of isoquinoline is 3-5% of the total mass of the reaction system.
Preferably, the mass ratio of the polyimide/bentonite composite material added in the step D) to the gamma-aminopropyl triethoxysilane is 12-15:1, the solid content of the reaction system is 10-15 wt%, the addition of isoquinoline is 3-5% of the total mass of the reaction system, and the addition of pyridine acetate anhydride is 0.3-0.5% of the total mass of reactants.
Preferably, the preparation method of the silane modified epoxy resin comprises the following steps: heating epoxy resin to 100-105 ℃, vacuumizing to remove water vapor under a stirring state, adding a solvent for dissolution, uniformly stirring, and then adding methyltrimethoxysilane and dibutyltin dilaurate, wherein the mass ratio of the epoxy resin to the methyltrimethoxysilane is 15-20:1, and the addition amount of the dibutyltin dilaurate is 0.3-0.5% of the total mass of reactants; stirring and reacting for 3-5 h at 85-95 ℃, and vacuumizing to remove the solvent to obtain the silane modified epoxy resin.
The invention also discloses a preparation method of the chromium ore powder ball, which comprises the following steps: mixing the chromium ore powder and each component in the binder in proportion, adding atomized water, uniformly stirring, cold-pressing to form pellets, and drying the pellets to obtain the chromium ore powder pellets.
Preferably, the pressure during cold press molding is 100 to 500 tons.
Preferably, the pellet particle size after cold press molding is 30-50 mm.
Therefore, the invention has the following beneficial effects:
(1) The bentonite, polyimide and epoxy resin are matched, so that the adhesive does not greatly influence the grade of the chromium ore powder, and meanwhile, the prepared chromium ore powder ball has good strength and thermal stability;
(2) The silane groups are modified on the polyimide and epoxy resin molecules, and the polyimide and the epoxy resin can be crosslinked together through the hydrolysis of the silane groups, so that the curing temperature is reduced, the curing time is shortened, and the strength of the pellets is improved;
(3) The silane modified polyimide is inserted between the layers of the bentonite, so that the high temperature resistance of the pellets and the strength of the pellets are further improved.
Detailed Description
The invention is further described below in connection with the following detailed description.
Example 1:
The chromium ore powder ball comprises the following raw materials in parts by weight: 90 parts of chromium ore powder with the granularity of 0-1 mm, 2.5 parts of binder and 2.5 parts of water. The binder comprises the following components in parts by weight: 6.5 parts of silane modified polyimide/bentonite composite material, 3.5 parts of silane modified epoxy resin, 0.02 part of dibutyltin dilaurate and 40 parts of tetrahydrofuran.
The preparation method of the silane modified polyimide/bentonite composite material comprises the following steps:
a) Adding bentonite into octadecyl trimethyl ammonium bromide solution with the concentration of 0.8mol/L, wherein the mass volume ratio of the bentonite to the octadecyl trimethyl ammonium bromide solution is 1g to 80mL; stirring uniformly, performing ultrasonic oscillation reaction for 3 hours, separating and drying the product to obtain the preliminary intercalated bentonite;
B) Adding the primarily intercalated bentonite into DMF, and stirring for 4 hours at 95 ℃ to obtain DMF solution of bentonite with mass concentration of 2%;
C) Dissolving 4,4 '-diaminodiphenyl ether in DMF, stirring uniformly, and adding hexafluorodianhydride into the solution, wherein the molar ratio of the 4,4' -diaminodiphenyl ether to the hexafluorodianhydride is 1.2:1; stirring and reacting for 3.5h, then adding DMF solution of bentonite and isoquinoline, wherein the mass ratio of 4,4' -diaminodiphenyl ether to bentonite is 3.5:1, the solid content of the reaction system is 12wt%, and the addition amount of isoquinoline is 4% of the total mass of the reaction system; heating to 190 ℃ and continuing stirring to react for 9 hours; transferring the product to ethanol for precipitation, separating and cleaning the precipitation, and drying to obtain a polyimide/bentonite composite material;
D) Dissolving polyimide/bentonite composite material in DMF, adding gamma-aminopropyl triethoxysilane into the solution under the protection of nitrogen at 0 ℃, wherein the mass ratio of the polyimide/bentonite composite material to the gamma-aminopropyl triethoxysilane is 13:1, the solid content of the reaction system is 12wt%, stirring and reacting for 3 hours, heating to 50 ℃, adding isoquinoline and pyridine acetate, wherein the addition amount of isoquinoline is 4% of the total mass of the reaction system, the addition amount of pyridine acetate is 0.4% of the total mass of the reactants, stirring and reacting for 9 hours, transferring the product into petroleum ether for precipitation, separating the precipitate, cleaning and drying to obtain the silane modified polyimide/bentonite composite material.
The preparation method of the silane modified epoxy resin comprises the following steps: heating the epoxy resin E51 to 101 ℃, vacuumizing in a stirring state, adding toluene for dissolution, uniformly stirring, and then adding methyltrimethoxysilane and dibutyltin dilaurate, wherein the mass ratio of the epoxy resin to the methyltrimethoxysilane is 19:1, and the adding amount of the dibutyltin dilaurate is 0.4% of the total mass of reactants; stirring and reacting for 4 hours at 90 ℃, and vacuumizing to remove the solvent to obtain the silane modified epoxy resin.
The preparation method of the chromium ore powder ball comprises the following steps: uniformly mixing the components in the binder according to a proportion; mixing chromium ore powder with a binder, adding atomized water, uniformly stirring, pressing into pellets with the particle size of 50mm by using 300 tons of pressure of a ball press, and naturally airing the pellets to obtain the chromium ore powder pellets.
Example 2:
The chromium ore powder ball comprises the following raw materials in parts by weight: 85 parts of chromium ore powder with the granularity of 0-1 mm, 2 parts of binder and 2 parts of water. The binder comprises the following components in parts by weight: 6 parts of silane modified polyimide/bentonite composite material, 3 parts of silane modified epoxy resin, 0.03 part of dibutyltin dilaurate and 20 parts of tetrahydrofuran.
The preparation method of the silane modified polyimide/bentonite composite material comprises the following steps:
A) Adding bentonite into octadecyl trimethyl ammonium bromide solution with the concentration of 0.5mol/L, wherein the mass volume ratio of the bentonite to the octadecyl trimethyl ammonium bromide solution is 1g:50mL; stirring uniformly, performing ultrasonic oscillation reaction for 2 hours, separating and drying the product to obtain the preliminary intercalated bentonite;
B) Adding the primarily intercalated bentonite into DMF, and stirring for 5 hours at 90 ℃ to obtain DMF solution of bentonite with the mass concentration of 1%;
C) Dissolving 4,4 '-diaminodiphenyl ether in DMF, stirring uniformly, and adding hexafluorodianhydride into the solution, wherein the molar ratio of the 4,4' -diaminodiphenyl ether to the hexafluorodianhydride is 1:1; stirring and reacting for 3 hours, and then adding DMF solution of bentonite and isoquinoline, wherein the mass ratio of 4,4' -diaminodiphenyl ether to bentonite is 3:1, the solid content of the reaction system is 10wt%, and the addition amount of isoquinoline is 3% of the total mass of the reaction system; heating to 185 ℃ and continuing stirring to react for 10 hours; transferring the product to ethanol for precipitation, separating and cleaning the precipitation, and drying to obtain a polyimide/bentonite composite material;
D) Dissolving polyimide/bentonite composite material in DMF, adding gamma-aminopropyl triethoxysilane into the solution under the protection of nitrogen at 0 ℃, wherein the mass ratio of the polyimide/bentonite composite material to the gamma-aminopropyl triethoxysilane is 12:1, the solid content of the reaction system is 10wt%, stirring and reacting for 2 hours, heating to 45 ℃, adding isoquinoline and pyridine acetate, wherein the addition amount of isoquinoline is 3% of the total mass of the reaction system, the addition amount of pyridine acetate is 0.3% of the total mass of the reactants, stirring and reacting for 10 hours, transferring the product into petroleum ether for precipitation, separating the precipitation, cleaning and drying to obtain the silane modified polyimide/bentonite composite material.
The preparation method of the silane modified epoxy resin comprises the following steps: heating epoxy resin E51 to 100 ℃, vacuumizing to remove water vapor under a stirring state, adding toluene for dissolution, uniformly stirring, and then adding methyltrimethoxysilane and dibutyltin dilaurate, wherein the mass ratio of the epoxy resin to the methyltrimethoxysilane is 15:1, and the adding amount of the dibutyltin dilaurate is 0.3% of the total mass of reactants; stirring and reacting for 5 hours at 85 ℃, and vacuumizing to remove the solvent to obtain the silane modified epoxy resin.
The preparation method of the chromium ore powder ball comprises the following steps: uniformly mixing the components in the binder according to a proportion; mixing chromium ore powder with a binder, adding atomized water, uniformly stirring, pressing into pellets with the particle size of 30mm by 100 ton pressure of a ball press, and naturally airing the pellets to obtain the chromium ore powder pellets.
Example 3:
The chromium ore powder ball comprises the following raw materials in parts by weight: 95 parts of chromium mineral powder with the granularity of 0-1 mm, 3 parts of binder and 3 parts of water. The binder comprises the following components in parts by weight: 7 parts of silane modified polyimide/bentonite composite material, 4 parts of silane modified epoxy resin, 0.01 part of dibutyltin dilaurate and 30 parts of tetrahydrofuran.
The preparation method of the silane modified polyimide/bentonite composite material comprises the following steps:
a) Adding bentonite into octadecyl trimethyl ammonium bromide solution with the concentration of 1.0mol/L, wherein the mass volume ratio of the bentonite to the octadecyl trimethyl ammonium bromide solution is 1g:100mL; stirring uniformly, performing ultrasonic oscillation reaction for 4 hours, separating and drying the product to obtain the preliminary intercalated bentonite;
b) Adding the primarily intercalated bentonite into DMF, and stirring for 4 hours at 100 ℃ to obtain DMF solution of bentonite with mass concentration of 3%;
C) Dissolving 4,4 '-diaminodiphenyl ether in DMF, stirring uniformly, and adding hexafluorodianhydride into the solution, wherein the molar ratio of the 4,4' -diaminodiphenyl ether to the hexafluorodianhydride is 1.5:1; stirring and reacting for 4 hours, and then adding DMF solution of bentonite and isoquinoline, wherein the mass ratio of 4,4' -diaminodiphenyl ether to bentonite is 4:1, the solid content of the reaction system is 15wt%, and the addition amount of isoquinoline is 5% of the total mass of the reaction system; heating to 195 ℃ and continuing stirring for reaction for 8 hours; transferring the product to ethanol for precipitation, separating and cleaning the precipitation, and drying to obtain a polyimide/bentonite composite material;
D) Dissolving polyimide/bentonite composite material in DMF, adding gamma-aminopropyl triethoxysilane into the solution under the protection of nitrogen at 4 ℃, wherein the mass ratio of the polyimide/bentonite composite material to the gamma-aminopropyl triethoxysilane is 15:1, the solid content of the reaction system is 15wt%, stirring and reacting for 4 hours, heating to 55 ℃, adding isoquinoline and pyridine acetate, wherein the addition of isoquinoline is 5% of the total mass of the reaction system, the addition of pyridine acetate is 0.5% of the total mass of the reactants, stirring and reacting for 8 hours, transferring the product into petroleum ether for precipitation, separating the precipitate, cleaning and drying to obtain the silane modified polyimide/bentonite composite material.
The preparation method of the silane modified epoxy resin comprises the following steps: heating the epoxy resin E51 to 105 ℃, vacuumizing in a stirring state, adding toluene for dissolution, uniformly stirring, and then adding methyltrimethoxysilane and dibutyltin dilaurate, wherein the mass ratio of the epoxy resin to the methyltrimethoxysilane is 20:1, and the adding amount of the dibutyltin dilaurate is 0.5% of the total mass of reactants; stirring and reacting for 3 hours at 95 ℃, and vacuumizing to remove the solvent to obtain the silane modified epoxy resin.
The preparation method of the chromium ore powder ball comprises the following steps: uniformly mixing the components in the binder according to a proportion; mixing chromium ore powder with a binder, adding atomized water, uniformly stirring, pressing into pellets with the particle size of 40mm by using 500 tons of pressure of a ball press, and naturally airing the pellets to obtain the chromium ore powder pellets.
Comparative example 1 (bentonite was not intercalated):
the binder in comparative example 1 comprises the following components in parts by weight: 6 parts of silane modified polyimide, 0.5 part of bentonite, 3.5 parts of silane modified epoxy resin, 0.02 part of dibutyltin dilaurate and 40 parts of tetrahydrofuran.
The preparation method of the silane modified polyimide comprises the following steps:
A) Dissolving 4,4 '-diaminodiphenyl ether in DMF, stirring uniformly, adding hexafluorodianhydride into the solution, wherein the molar ratio of the 4,4' -diaminodiphenyl ether to the hexafluorodianhydride is 1.2:1, stirring and reacting for 3.5 hours, then adding isoquinoline, wherein the solid content of the reaction system is 12wt%, and the adding amount of the isoquinoline is 4% of the total mass of the reaction system; heating to 190 ℃ and continuing stirring to react for 9 hours; transferring the product to ethanol for precipitation, separating and cleaning the precipitate, and drying to obtain polyimide;
B) Dissolving polyimide in DMF, adding gamma-aminopropyl triethoxysilane into the solution under the protection of nitrogen at 0 ℃, wherein the mass ratio of the polyimide to the gamma-aminopropyl triethoxysilane is 13:1, stirring and reacting for 3 hours, heating to 50 ℃, adding isoquinoline and pyridine acetic anhydride, wherein the addition amount of isoquinoline is 4% of the total mass of the reaction system, the addition amount of pyridine acetic anhydride is 0.4% of the total mass of reactants, stirring and reacting for 9 hours, transferring the product into petroleum ether for precipitation, separating the precipitate, cleaning and drying to obtain the silane modified polyimide.
The remainder was the same as in example 1.
Comparative example 2 (no silane modification of polyimide/bentonite composite):
the binder in comparative example 2 comprises the following components in parts by weight: 6.5 parts of polyimide/bentonite composite material, 3.5 parts of silane modified epoxy resin, 0.02 part of dibutyl tin dilaurate and 40 parts of tetrahydrofuran.
The preparation method of the polyimide/bentonite composite material comprises the following steps:
a) Adding bentonite into octadecyl trimethyl ammonium bromide solution with the concentration of 0.8mol/L, wherein the mass volume ratio of the bentonite to the octadecyl trimethyl ammonium bromide solution is 1g to 80mL; stirring uniformly, performing ultrasonic oscillation reaction for 3 hours, separating and drying the product to obtain the preliminary intercalated bentonite;
B) Adding the primarily intercalated bentonite into DMF, and stirring for 4 hours at 95 ℃ to obtain DMF solution of bentonite with mass concentration of 2%;
C) Dissolving 4,4 '-diaminodiphenyl ether in DMF, stirring uniformly, and adding hexafluorodianhydride into the solution, wherein the molar ratio of the 4,4' -diaminodiphenyl ether to the hexafluorodianhydride is 1.2:1; stirring and reacting for 3.5h, then adding DMF solution of bentonite and isoquinoline, wherein the mass ratio of 4,4' -diaminodiphenyl ether to bentonite is 3.5:1, the solid content of the reaction system is 12wt%, and the addition amount of isoquinoline is 4% of the total mass of the reaction system; heating to 190 ℃ and continuing stirring to react for 9 hours; transferring the product into ethanol for precipitation, separating and cleaning the precipitate, and drying to obtain the polyimide/bentonite composite material.
The remainder was the same as in example 1.
Comparative example 3 (no silane modification of epoxy resin):
the binder in comparative example 3 comprises the following components in parts by weight: 6.5 parts of silane modified polyimide/bentonite composite material, 3.5 parts of epoxy resin E51,0.02 part of dibutyltin dilaurate and 40 parts of tetrahydrofuran. The remainder was the same as in example 1.
The properties of the chromium ore powder balls prepared in the above examples and comparative examples were tested and the results are shown in table 1. Wherein, the dropping strength refers to the number of times that the chromium ore powder balls are freely dropped from a height of 1.5m to the cement floor without fragmentation, and 10 chromium ore powder balls are tested in each group, and the dropping strength is averaged.
Table 1: and (5) testing the performance of the chromium ore powder ball.
Compressive strength (MPa) Drop strength (times) Burst temperature (. Degree. C.)
Example 1 20.6 26.7 793
Example 2 21.1 28.2 775
Example 3 20.0 26.1 784
Comparative example 1 16.2 17.8 673
Comparative example 2 10.8 12.5 568
Comparative example 3 12.4 13.9 581
As can be seen from Table 1, the chromium ore powder balls prepared by the method of the invention in examples 1 to 3 have high compressive strength and dropping strength, and are convenient for transportation; meanwhile, the furnace has higher bursting temperature, and burst and pulverization phenomena are not easy to occur after the furnace is charged. In comparative example 1, the silane-modified polyimide was not inserted between bentonite layers, but bentonite was directly blended with the silane-modified polyimide and the silane-modified epoxy resin, and the pellet strength and high temperature resistance were reduced as compared with those in example 1; the polyimide or epoxy resin in comparative examples 2 and 3 was not modified with silane, and the polyimide and epoxy resin could not be co-crosslinked, resulting in a significant decrease in pellet strength and high temperature resistance.

Claims (10)

1. The chromium ore powder ball is characterized by comprising the following raw materials in parts by weight: 85-95 parts of chromium mineral powder, 2-3 parts of binder and 2-3 parts of water; the adhesive comprises the following components in parts by weight: 6-7 parts of silane modified polyimide/bentonite composite material, 3-4 parts of silane modified epoxy resin, 0.01-0.03 part of dibutyltin dilaurate and 20-30 parts of tetrahydrofuran;
Firstly, intercalation is carried out on bentonite through octadecyl trimethyl ammonium bromide, the interlayer spacing of the bentonite is enlarged preliminarily, then 4,4' -diaminodiphenyl ether and hexafluorodianhydride are taken as monomers, polyimide is intercalated between bentonite layers through a solution polymerization in-situ intercalation method, and a polyimide/bentonite composite material is obtained; and finally, capping the polyimide with gamma-aminopropyl triethoxy silane to obtain the silane modified polyimide/bentonite composite material.
2. The chromium ore powder ball according to claim 1, wherein the particle size of the chromium ore powder is 0 to 1mm.
3. The chrome ore powder ball according to claim 1, wherein the preparation method of the silane modified polyimide/bentonite composite material comprises the following steps:
a) Adding bentonite into octadecyl trimethyl ammonium bromide solution, uniformly stirring, performing ultrasonic oscillation reaction for 2-4 hours, separating and drying a product to obtain primarily intercalated bentonite;
b) Dissolving the primarily intercalated bentonite in DMF to obtain DMF solution of bentonite;
C) Dissolving 4,4' -diaminodiphenyl ether in DMF, stirring uniformly, adding hexafluorodianhydride into the solution, stirring to react for 3-4 hours, adding DMF solution of bentonite and isoquinoline, heating to 185-195 ℃ and continuing stirring to react for 8-10 hours; transferring the product to ethanol for precipitation, separating and cleaning the precipitation, and drying to obtain a polyimide/bentonite composite material;
d) And dissolving the polyimide/bentonite composite material in DMF, adding gamma-aminopropyl triethoxysilane into the solution under the protection of nitrogen at 0-4 ℃, stirring and reacting for 2-4 hours, heating to 45-55 ℃, adding isoquinoline and pyridine acetic anhydride, stirring and reacting for 8-10 hours, transferring the product into petroleum ether for precipitation, separating the precipitate, cleaning and drying to obtain the silane modified polyimide/bentonite composite material.
4. The chromium ore powder ball according to claim 3, wherein the concentration of the octadecyl trimethyl ammonium bromide solution in the step A) is 0.5-1.0 mol/L, and the mass volume ratio of bentonite to the octadecyl trimethyl ammonium bromide solution is 1 g:50-100 mL; the mass concentration of the DMF solution of the bentonite obtained in the step B) is 1-3%.
5. The chromium ore powder ball according to claim 3, wherein the molar ratio of the 4,4' -diaminodiphenyl ether to the hexafluorodianhydride added in the step C) is 1 to 1.5:1; the mass ratio of the 4,4' -diaminodiphenyl ether to the bentonite is 3-4:1; the solid content of the reaction system is 10-15 wt%, and the addition amount of isoquinoline is 3-5% of the total mass of the reaction system.
6. The chromium ore powder ball according to claim 3, wherein the mass ratio of the polyimide/bentonite composite material added in the step D) to the gamma-aminopropyl triethoxysilane is 12-15:1, the solid content of the reaction system is 10-15 wt%, the addition amount of isoquinoline is 3-5% of the total mass of the reaction system, and the addition amount of pyridine acetate anhydride is 0.3-0.5% of the total mass of reactants.
7. The chrome ore powder ball according to claim 3, wherein the preparation method of the silane-modified epoxy resin comprises the following steps: heating epoxy resin to 100-105 ℃, vacuumizing to remove water vapor under a stirring state, adding a solvent for dissolution, uniformly stirring, and then adding methyltrimethoxysilane and dibutyltin dilaurate, wherein the mass ratio of the epoxy resin to the methyltrimethoxysilane is 15-20:1, and the addition amount of the dibutyltin dilaurate is 0.3-0.5% of the total mass of reactants; stirring and reacting for 3-5 hours at the temperature of 85-95 ℃, and vacuumizing to remove the solvent to obtain the silane modified epoxy resin.
8. A method for preparing the chromium ore powder ball according to claim 1, comprising the steps of: mixing the chromium ore powder and each component in the binder in proportion, adding atomized water, uniformly stirring, cold-pressing to form pellets, and drying the pellets to obtain the chromium ore powder pellets.
9. The method according to claim 8, wherein the pressure during cold press molding is 100 to 500 tons.
10. The preparation method of claim 8, wherein the particle size of the pellets after cold press molding is 30-50 mm.
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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB747483A (en) * 1953-01-23 1956-04-04 British Thomson Houston Co Ltd A bonded boride composite material
AU6295973A (en) * 1972-12-04 1975-05-29 Ici Australia Limited Reductive roasting of ores
CN1441697A (en) * 2000-07-12 2003-09-10 阿克佐诺贝尔股份有限公司 Mixed metal catalyst comprising combustible binder
JP2004010434A (en) * 2002-06-07 2004-01-15 Kuraray Chem Corp Granulated carbon and its production method
CN102051474A (en) * 2010-12-17 2011-05-11 兰州三普电力有限公司 Cr-Fe powder ore cold-hardened pellet binder and process for pelleting by using same
CN102268543A (en) * 2011-08-30 2011-12-07 北京科技大学 Shaping adhesive for chromium powder ore cold-pressed pellets and using method of shaping adhesive
CN102822256A (en) * 2010-01-26 2012-12-12 苏舍美特科(美国)公司 Abradable composition and method of manufacture
CN103436694A (en) * 2013-09-04 2013-12-11 宁夏天元锰业有限公司 Method for preparing chrome ore pellets
KR101367834B1 (en) * 2013-03-22 2014-02-28 주식회사 제철세라믹 Production method of granulating binder for nickel ore reduction dust and binder produced by this method
CN104451131A (en) * 2015-01-09 2015-03-25 山东鑫海科技股份有限公司 Powder chrome ore reducing sintering agglomeration technique
CN105506271A (en) * 2014-09-24 2016-04-20 宝钢不锈钢有限公司 Chromium ore composite pellet used for reduction in argon-oxygen refining furnace, production method and application thereof
CN107881334A (en) * 2017-11-07 2018-04-06 江苏省冶金设计院有限公司 A kind of ferrochrome Pellet production method and system
CN108754133A (en) * 2018-06-14 2018-11-06 攀钢集团攀枝花钢铁研究院有限公司 A kind of high titanium solvent borne pelletizing of high chromium and the preparation method and application thereof
KR20180127105A (en) * 2017-05-19 2018-11-28 국민대학교산학협력단 Method for manufacturing pre-reduced chromium ore and pre-reduced chromium ore
CN109266848A (en) * 2018-11-29 2019-01-25 攀钢集团攀枝花钢铁研究院有限公司 Prepare the binder of oxidation of chromite pelletizing
EP3760748A1 (en) * 2019-07-02 2021-01-06 Brother Group (Hong Kong) Limited Process for preparing optimized calcined, iron- and chrome-containing pellets

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009128425A1 (en) * 2008-04-15 2009-10-22 東邦亜鉛株式会社 Composite magnetic material and manufacturing method thereof

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB747483A (en) * 1953-01-23 1956-04-04 British Thomson Houston Co Ltd A bonded boride composite material
AU6295973A (en) * 1972-12-04 1975-05-29 Ici Australia Limited Reductive roasting of ores
CN1441697A (en) * 2000-07-12 2003-09-10 阿克佐诺贝尔股份有限公司 Mixed metal catalyst comprising combustible binder
JP2004010434A (en) * 2002-06-07 2004-01-15 Kuraray Chem Corp Granulated carbon and its production method
CN102822256A (en) * 2010-01-26 2012-12-12 苏舍美特科(美国)公司 Abradable composition and method of manufacture
CN102051474A (en) * 2010-12-17 2011-05-11 兰州三普电力有限公司 Cr-Fe powder ore cold-hardened pellet binder and process for pelleting by using same
CN102268543A (en) * 2011-08-30 2011-12-07 北京科技大学 Shaping adhesive for chromium powder ore cold-pressed pellets and using method of shaping adhesive
KR101367834B1 (en) * 2013-03-22 2014-02-28 주식회사 제철세라믹 Production method of granulating binder for nickel ore reduction dust and binder produced by this method
CN103436694A (en) * 2013-09-04 2013-12-11 宁夏天元锰业有限公司 Method for preparing chrome ore pellets
CN105506271A (en) * 2014-09-24 2016-04-20 宝钢不锈钢有限公司 Chromium ore composite pellet used for reduction in argon-oxygen refining furnace, production method and application thereof
CN104451131A (en) * 2015-01-09 2015-03-25 山东鑫海科技股份有限公司 Powder chrome ore reducing sintering agglomeration technique
KR20180127105A (en) * 2017-05-19 2018-11-28 국민대학교산학협력단 Method for manufacturing pre-reduced chromium ore and pre-reduced chromium ore
CN107881334A (en) * 2017-11-07 2018-04-06 江苏省冶金设计院有限公司 A kind of ferrochrome Pellet production method and system
CN108754133A (en) * 2018-06-14 2018-11-06 攀钢集团攀枝花钢铁研究院有限公司 A kind of high titanium solvent borne pelletizing of high chromium and the preparation method and application thereof
CN109266848A (en) * 2018-11-29 2019-01-25 攀钢集团攀枝花钢铁研究院有限公司 Prepare the binder of oxidation of chromite pelletizing
EP3760748A1 (en) * 2019-07-02 2021-01-06 Brother Group (Hong Kong) Limited Process for preparing optimized calcined, iron- and chrome-containing pellets

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
铬铁粉矿球团烧结新工艺及固结机理研究;朱德庆;仉宏亮;潘建;;金属矿山;20100515(第05期);第105-109页 *
铬铁粉矿球团烧结新工艺及固结机理研究;朱德庆等;《金属矿山》;20100531(第第5期期);第105-109页 *

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