CN115676829B - Method for preparing high-quality titanium oxycarbide - Google Patents
Method for preparing high-quality titanium oxycarbide Download PDFInfo
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- CN115676829B CN115676829B CN202210601491.XA CN202210601491A CN115676829B CN 115676829 B CN115676829 B CN 115676829B CN 202210601491 A CN202210601491 A CN 202210601491A CN 115676829 B CN115676829 B CN 115676829B
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- titanium oxycarbide
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- flotation
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 53
- 239000010936 titanium Substances 0.000 title claims abstract description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012535 impurity Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000002023 wood Substances 0.000 claims abstract description 20
- 238000005188 flotation Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000007885 magnetic separation Methods 0.000 claims abstract description 16
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 7
- 229960004889 salicylic acid Drugs 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008396 flotation agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for preparing high-quality titanium oxycarbide, belonging to the technical field of resource processing; the wood powder and the waste resin are used as reducing agents, and are mixed with ilmenite, and then high-power microwaves are adopted for heating and reducing to obtain fluffy products, so that the reduction efficiency can be remarkably improved and the reduction time can be shortened; and then ball milling, flotation, magnetic separation and acid dissolution impurity removal are carried out to obtain high-quality titanium oxycarbide, wherein the titanium oxycarbide content is more than 95%, the iron content is less than 1.2%, and other impurities are less than 3%. The invention utilizes the wood dust and the waste resin as the reducing agent, and can promote the fluffiness of the reduction product while carrying out waste utilization, thereby being beneficial to subsequent ball milling, shortening the conventional ball milling time and obviously reducing the ball milling energy consumption; meanwhile, the flotation, magnetic separation and acid dissolution are combined to remove iron and impurities, so that the high-quality titanium oxycarbide is obtained.
Description
Technical Field
The invention belongs to the technical field of resource processing, and particularly relates to a method for preparing high-quality titanium oxycarbide.
Background
Titanium and its alloy have excellent physical and chemical properties, and are important light structural materials and novel functional materials, and are known as 'future metals', 'third metals'. The existing smelting process has complicated procedures, high energy consumption and high cost, so that the price of the metal titanium is high, and further the wider application of the metal titanium is limited.
The current method for preparing titanium oxycarbide by direct reduction from the mineral angle adopts traditional heating, separates titanium oxycarbide from iron after reduction, has long reduction time, large hardness of a sample for reduction, long subsequent ball milling time, long ball milling time for dissociating titanium oxycarbide, high energy consumption, only research on phase change, no separation of impurity elements and high overall cost, and therefore, a simple and efficient method for obtaining titanium oxycarbide with high purity from ilmenite concentrate is required.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing high-quality titanium oxycarbide, which is characterized in that ilmenite is subjected to microwave reduction, ball milling, flotation, magnetic separation and acid dissolution to prepare the titanium oxycarbide, the operation is simple and convenient, the cost is low, and the high-purity titanium oxycarbide can be efficiently obtained.
The technical scheme of the invention is as follows: a method for preparing high quality titanium oxycarbide comprising the steps of:
(1) Preparation of a reducing agent: crushing wood chips and resin by using a cutter, and then grinding and uniformly mixing by using a planetary ball mill;
(2) Mixing the sample with a reducing agent: grinding and uniformly mixing the reducing agent in the step (1) and ilmenite concentrate in an agate mortar according to a mass ratio of 1:5-1:3;
(3) Microwave heating and reduction: placing the sample uniformly mixed in the step (2) in a graphite crucible, then placing the graphite crucible in microwave heating equipment, and then introducing argon protective atmosphere for microwave heating reduction treatment;
(4) Ball milling: ball milling dissociation is carried out on the sample cooled in the step (3) for 30-40 min hours, and then a 400-450 mesh sieve is adopted for sieving;
(5) And (3) flotation: performing reverse flotation on the sample below 400-450 meshes in the step (4) to remove organic matters, residual carbon and part of impurity elements, wherein sediment is the required titanium oxycarbide sample;
(6) Magnetic separation: carrying out magnetic separation on the sand sediment product obtained in the step (5);
(7) Acid impurity removal: and (3) carrying out acid dissolution and impurity removal on the non-magnetic product obtained in the step (6), and washing with water after removing impurities such as iron, calcium and the like by acid to obtain a titanium oxycarbide product.
Preferably, in the step (1), the particle size of the wood chips is controlled to be 0.5-1 mm, the particle size of the resin is controlled to be 0.05-0.5 mm, and the ratio of the wood chips to the resin is 1:1-1:3. The particle size of the wood dust and the resin is controlled within a certain range, so that the contact between the reducing agent and ilmenite is promoted, and meanwhile, a reduction product can form a loose state in the particle size range, so that the energy consumption is saved during the subsequent ball milling dissociation, and the ball milling time is reduced; in addition, the granularity is controlled in the range, and in the high-temperature reduction process, the diffusion of CO and CH 4 in the reducing atmosphere is facilitated, the reduction is promoted, and meanwhile, the reduced iron can be diffused and aggregated to form large liquid drops, so that the subsequent separation of iron and titanium is facilitated; the proportion selection in the range is beneficial to the generation of pores by fully utilizing pyrolysis reduction of respective materials when wood chips and resin are used as reducing agents, the wood chips and the resin can be matched with each other to complement respective contact with ilmenite, the synergistic effect is formed to promote reduction, the reduction products are promoted to be fluffy and the reduced iron liquid drops are gathered, and the subsequent separation is utilized.
Preferably, in the step (3), the microwave heating reduction treatment parameters are set as follows: the microwave opening time is 40-100 min, the microwave power is 1-2.8 kW, and the heat preservation is 40-100 min after the microwave is stopped. Unlike traditional electric furnace heating, the microwave heating needs to be from the outside to the inside, and has the characteristics of bulk heating, penetrating integral heating, selective heating, high heating speed, non-thermal effect and the like. Therefore, the larger the microwave power is, the smaller the microwave starting time is, the heating reduction time is reduced, the energy consumption is saved, the microwave reduction cost is reduced, compared with the reduction time of 4-8 hours of the traditional electric furnace heating, the microwave heating obviously reduces the microwave heating and reduction time, the energy consumption is reduced from the source, and the cost is saved; in addition, the non-thermal effect of the microwaves is beneficial to the overall improvement, promotes the reduction effect and improves the reduction efficiency.
Preferably, in the step (5), the flotation agent is MY, and the air bubble agent is No. 2 oil. MY is a mixture of kerosene, oleic acid, sodium oleate and salicylic acid, and is formed according to a certain proportion. The mixture ratio can be kerosene: oleic acid: sodium oleate: salicylic acid=4:1:1:1, the substances such as calcium, magnesium and aluminum are removed by utilizing the affinities of kerosene and carbon substances and oleic acid, sodium oleate and salicylic acid, the purity of titanium oxycarbide is improved, the No. 2 oil serves as a good foaming agent to play a role in bubble in mineral flotation, and impurity minerals are promoted to be combined with bubbles to remove impurities.
Preferably, in the step (6), the magnetic separation strength is 10 to 20Ka/m. The magnetic field has the strength favorable for removing metallic iron, and the iron reacts in the magnetic field strength, so that the received magnetic force is strong, and the removal can be effectively realized through magnetic separation.
Preferably, in the step (7), the non-magnetic product is treated by hydrochloric acid and a solution with the nitric acid concentration of 0.5-3 mol/L, the temperature is 25-80 ℃ and the time is 1-3 h. Hydrochloric acid has strong aggressivity to iron, can be used as a good iron removal reagent, and can effectively remove residual impurity iron in titanium oxycarbide; nitric acid has certain oxidizing property, can destroy impurity structure and promote dissolution and removal of impurity elements of calcium, magnesium and aluminum.
The beneficial effects of the invention are as follows:
1. according to the invention, wood dust and waste resin are used as reducing agents, waste materials are utilized, the reducing agents and ilmenite can absorb microwaves to quickly heat up after being heated by microwaves in the reduction process, the reduction time is obviously short, the reduction energy consumption is low, meanwhile, a reduced sample is loose, the subsequent ball milling time is reduced, and then the impurity is removed by flotation, magnetic separation, acid dissolution and other methods, so that high-quality titanium oxycarbide is obtained; the content of titanium oxycarbide is more than 95%, the content of iron is less than 1.2%, and other impurities are less than 3%.
2. The sample container adopted by the invention is a graphite crucible, the ilmenite sample and the reduction self-absorption microwave energy are used for differential heating, and meanwhile, the graphite crucible can absorb microwaves to generate auxiliary heating, so that the internal and external heating of the whole sample is simultaneously carried out, the sample reducing agent is heated to generate decomposition and gas inside, a pore canal is formed to promote the diffusion of the reducing agent CO to promote the reduction, the sample is fluffy finally, the subsequent ball milling is facilitated, the ball milling time is shortened, and meanwhile, the sample reduction time is shortened by 2-3 hours compared with the traditional electric furnace, and the ball milling energy consumption can be obviously reduced.
3. Titanium oxycarbide is applied to preparing metallic titanium by electrolysis and is used as a front-end raw material for producing the metallic titanium; when the metallic titanium is electrolyzed, purer and high-quality titanium oxycarbide is needed to be used as a raw material so as to obtain the high-purity metallic titanium through electrolysis.
Drawings
FIG. 1 is a flow chart of the preparation of high quality titanium oxycarbide in accordance with the present invention;
FIG. 2 is a phase of the reduction product of example 1 of the present invention;
FIG. 3 is a scanning electron microscope and energy spectrum of the reduction product titanium oxycarbide of example 1 of the present invention;
FIG. 4 is a flotation froth product phase of example 1 of the present invention;
FIG. 5 is a magnetic separation magnetic product phase of example 1 of the present invention;
FIG. 6 is a magnetic separation of a non-magnetic product phase according to example 1 of the present invention;
FIG. 7 shows the product phase of hydrochloric acid after impurity removal in example 1 of the present invention;
FIG. 8 is a scanning electron microscope and energy spectrum of the product of hydrochloric acid impurity removal in example 1 of the present invention.
Detailed Description
In order to facilitate a better understanding of the present invention, the following description will be given with reference to examples. It is to be understood that the examples are merely to aid in the understanding of the present invention and are not to be construed as a specific limitation thereof.
Example 1
A method for preparing high-quality titanium oxycarbide comprises the following specific preparation processes shown in figure 1: crushing wood chips and resin by using a cutting machine, controlling the granularity of the wood chips of a reducing agent to be 0.5-1 mm, controlling the granularity of the resin to be 0.05-0.5 mm, and mixing the wood chips and the resin to be 1:1; the reducing agent and ilmenite concentrate are ground and mixed in an agate mortar in a mass ratio of 1:5 (5 g of reducing agent, 25g of ilmenite).
Filling a uniformly mixed sample into a graphite crucible, carrying out microwave heating reduction, carrying out microwave power 2kW, carrying out microwave heating for 30 min hours, and carrying out heat preservation for 50 min; after cooling, ball milling time was 30 min, and then sieving with 400 mesh sieve, the phase of the sieved product is shown in FIG. 2. The phase XRD pattern of FIG. 2 shows that ilmenite is reduced to produce titanium oxycarbide and iron, the reduced product of FIG. 2 is reduced with conventional carbon to obtain a compact product, and wood chips and resin are porous and fluffy; fig. 3 shows a scanning electron microscope and an energy spectrum of a reduction product, wherein particles in the morphology of the product are in an aggregated state, which is similar to a porous state, smooth particles on the surface are piled up, part of titanium oxycarbide is aggregated into a strip-shaped tadpole shape, main elements on the surface of the particle aggregate are Ti, C and O, a small amount of impurity elements Fe, mg, ca, mg, al, mg, si are used for explaining that the elements of the original product are mainly titanium and iron, and the impurity elements are calcium, aluminum, magnesium and the like.
Carrying out flotation decarburization impurity removal on the undersize product, wherein a flotation reagent is MY, and the ratio is kerosene: oleic acid: sodium oleate: salicylic acid = 4:1:1:1; the bubble agent is No. 2 oil, the phase of the flotation foam product is shown in fig. 4, the impurity element content of the product is high, and the flotation can remove carbon, calcium aluminate, magnesium aluminate, calcium titanate and other impurities.
The settled sand after flotation is magnetically separated, the magnetic separation strength is 12 Ka/m, the magnetic product is a substance with high iron content as shown in figure 5, and the non-magnetic product is titanium oxycarbide as shown in figure 6.
Finally, acid impurity removal is carried out: the obtained nonmagnetic product is subjected to acid dissolution and impurity removal, the nonmagnetic product is treated by using a solution with the hydrochloric acid concentration of 1 mol/L, the temperature is 25 ℃ and the time is 2 hours, and the titanium oxycarbide product is obtained by washing with water after removing impurities such as iron, calcium and the like by acid, as shown in fig. 7 and 8, the titanium oxycarbide concentrate sample after acid dissolution and impurity removal shows an irregular shape, and as can be seen from an energy spectrum element analysis table of EDS, the main substance in the sample is TiCxOy, the content of main elements Ca and Fe of impurity elements is obviously reduced, the total amount of impurities is also obviously reduced, and the acid dissolution and impurity removal effects are obvious.
The quality of the titanium oxycarbide is improved through assay, the total impurity amount is reduced to 4.63%, the contents of main impurity elements Ca, mg and Fe are obviously reduced to 0.68% and 0.86%, and the final titanium oxycarbide content is 96.26%.
The time required by the microwave heating reduction and the traditional electric furnace reduction process under the same conditions is obviously shortened, and comparative experiments show that the time required by the electric furnace reduction is 8 hours (temperature rise, heat preservation and temperature reduction), the microwave wood chip and waste resin reduction product is fluffy, the ore grinding time is only 30 minutes, and if the required amount of graphite and activated carbon is large, the hardness of the reduced sample is large, and the subsequent ball milling dissociation is not facilitated.
Example 2
A method for preparing high-quality titanium oxycarbide comprises the following specific preparation processes shown in figure 1: the wood chips and the resin are crushed by a cutter, the granularity of the wood chips of the reducing agent is controlled to be 0.5-1 mm, the granularity of the resin is controlled to be 0.05-0.5 mm, and the ratio of the wood chips to the resin is 1:1. The reducing agent and ilmenite concentrate are ground and mixed in an agate mortar in a mass ratio of 1:4 (5 g of reducing agent, 20g of ilmenite). And (3) filling a uniformly mixed sample by using a graphite crucible, and carrying out microwave heating reduction, wherein the microwave power is 2.5kW, the microwave heating time is 25 min, and the heat preservation is 50 min.
Ball milling time is 30min after cooling, then sieving by a 400-mesh sieve, carrying out flotation decarburization impurity removal on the undersize product, wherein the flotation agent is MY, and the proportion is kerosene: oleic acid: sodium oleate: salicylic acid = 4:1:1:1; the air bubble agent is No. 2 oil; carrying out magnetic separation on the settled sand after flotation, wherein the magnetic separation strength is 10 Ka/m, finally carrying out acid dissolution and impurity removal on the obtained non-magnetic product, treating the non-magnetic product by using a solution with the nitric acid concentration of 2 mol/L, wherein the temperature is 30 ℃, the time is 3 hours, removing impurities such as iron, calcium and the like through acid, then washing with water to obtain a titanium oxycarbide product, obtaining the titanium oxycarbide product through assay, improving the quality of the titanium oxycarbide product, reducing the total amount of impurities to 4.83%, obviously reducing the contents of main impurity elements Ca, mg and Fe to 0.78% and 0.94%, and finally obtaining the titanium oxycarbide with the content of 96.48%.
The above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or simple substitutions that do not undergo the inventive work should be covered in the scope of the present invention.
Claims (3)
1. A method for preparing high quality titanium oxycarbide comprising the steps of:
(1) Preparation of a reducing agent: crushing wood chips and resin by using a cutter, and then grinding and uniformly mixing by using a planetary ball mill;
(2) Mixing the sample with a reducing agent: grinding and uniformly mixing the reducing agent in the step (1) and ilmenite concentrate in an agate mortar according to a mass ratio of 1:5-1:3;
(3) Microwave heating and reduction: placing the sample uniformly mixed in the step (2) in a graphite crucible, then placing the graphite crucible in microwave heating equipment, and then introducing argon protective atmosphere for microwave heating reduction treatment;
(4) Ball milling: ball milling dissociation is carried out on the sample cooled in the step (3) for 30-40 min hours, and then a 400-450 mesh sieve is adopted for sieving;
(5) And (3) flotation: performing reverse flotation on the sample below 400-450 meshes in the step (4) to remove organic matters, residual carbon and part of impurity elements, wherein sediment is the required titanium oxycarbide sample;
(6) Magnetic separation: carrying out magnetic separation on the sand sediment product obtained in the step (5);
(7) Acid impurity removal: carrying out acid dissolution and impurity removal on the non-magnetic product obtained in the step (6), and washing with water after removing impurities such as iron, calcium and the like by acid to obtain a titanium oxycarbide product;
In the step (1), the particle size of the wood chips is controlled to be 0.5-1 mm, the particle size of the resin is controlled to be 0.05-0.5 mm, and the ratio of the wood chips to the resin is 1:1-1:3;
in the step (3), the parameters of the microwave heating reduction treatment are set as follows: the microwave opening time is 40-100 min, the microwave power is 1-2.8 kW, and the heat preservation is 40-100 min after the microwave is stopped;
In the step (5), the flotation reagent is MY, and MY is a mixture of kerosene, oleic acid, sodium oleate and salicylic acid; the air bubble agent is No. 2 oil;
in the step (5), the flotation reagent is kerosene with the following MY ratio: oleic acid: sodium oleate: salicylic acid=4:1:1:1.
2. A method for producing high quality titanium oxycarbide according to claim 1, wherein: in the step (6), the magnetic separation strength is 10-20 Ka/m.
3. A method for producing high quality titanium oxycarbide according to claim 1, wherein: in the step (7), the non-magnetic product is treated by hydrochloric acid or solution with the nitric acid concentration of 0.5-3 mol/L, the temperature is 25-80 ℃, and the time is 1-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210601491.XA CN115676829B (en) | 2022-05-30 | 2022-05-30 | Method for preparing high-quality titanium oxycarbide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210601491.XA CN115676829B (en) | 2022-05-30 | 2022-05-30 | Method for preparing high-quality titanium oxycarbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115676829A CN115676829A (en) | 2023-02-03 |
| CN115676829B true CN115676829B (en) | 2024-04-19 |
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