CN115961163A - Preparation method of high-nitrogen titanium-silicon alloy co-produced titanium nitride powder - Google Patents
Preparation method of high-nitrogen titanium-silicon alloy co-produced titanium nitride powder Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 75
- 229910000676 Si alloy Inorganic materials 0.000 title claims abstract description 49
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 41
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000003723 Smelting Methods 0.000 claims abstract description 68
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 238000005121 nitriding Methods 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000004767 nitrides Chemical class 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims description 100
- 230000008018 melting Effects 0.000 claims description 100
- 239000000428 dust Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 15
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- COGOJRKCCAQAPE-UHFFFAOYSA-N [N].[Si].[Ti] Chemical compound [N].[Si].[Ti] COGOJRKCCAQAPE-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000010309 melting process Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 21
- 229910045601 alloy Inorganic materials 0.000 abstract description 17
- 239000000956 alloy Substances 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010936 titanium Substances 0.000 abstract description 9
- 229910052719 titanium Inorganic materials 0.000 abstract description 9
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 239000010431 corundum Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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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Abstract
The invention belongs to the technical field of metal alloy smelting, and particularly relates to a preparation method of high-nitrogen titanium silicon alloy and titanium nitride powder. According to the invention, sponge titanium and metal silicon are used as raw materials, a split water-cooled copper crucible is used for replacing a corundum crucible to perform suspension smelting on the alloy through a suspension smelting-nitriding method, the generation of titanium oxide is prevented, the low-oxygen high-nitrogen titanium silicon alloy is prepared, the problems of overhigh oxygen (0.1-2 wt%) and overlow nitrogen content (0.001-0.01 wt%) in impurity elements of the traditional titanium silicon alloy are solved, the oxygen content is not higher than 0.04wt%, and the quality of the high-nitrogen titanium silicon alloy is greatly improved. According to the invention, the nitride powder generated in the nitriding process is collected and further calcined to obtain the titanium nitride powder, and the waste dedusting ash generated in the smelting process is refined into the high-purity titanium nitride powder, so that a new direction is provided for recycling the dedusting ash of the high-nitrogen titanium silicon alloy, and the full utilization of resources is realized.
Description
Technical Field
The invention belongs to the technical field of metal alloy smelting, and particularly relates to a preparation method of high-nitrogen titanium silicon alloy and titanium nitride powder.
Background
The high-nitrogen titanium-silicon alloy is used as a novel steel additive, and can effectively improve the strength and corrosion resistance of the alloy (such as iron alloy or titanium alloy). The conventional preparation method of the high-nitrogen titanium-silicon alloy is to use a corundum crucible to smelt the alloy, in the smelting process, titanium reacts with oxygen elements (alumina and a binder) in the crucible at the temperature of more than 1350 ℃ to generate titanium oxide, the titanium oxide is uniformly dispersed in the titanium-silicon alloy through electromagnetic stirring, the oxygen content is more than 0.06wt%, the separation is difficult, and the application of the titanium-silicon alloy and the derivative alloy thereof in the aspect of high-end titanium materials is seriously limited.
Common production processes for high nitrogen silicon titanium alloy are liquid nitriding and gas nitriding. Liquid nitriding is most commonly performed by using cyanide and cyanate, has high toxicity, is easy to cause serious safety accidents, and does not meet the requirements of green chemistry and sustainable development; the gas nitriding mostly takes ammonia gas as a nitrogen source, and takes metal silicon powder and titanium powder as raw materials to perform nitriding reaction at high temperature, but the titanium powder has high oxygen content, and oxygen can not be removed when entering the titanium-silicon alloy in the smelting process, thereby seriously affecting the alloy quality. In summary, how to safely and effectively reduce the oxygen content of the high nitrogen silicon titanium alloy is an urgent problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method for co-producing titanium nitride powder from high-nitrogen titanium-silicon alloy, which is green and safe, and the obtained high-nitrogen titanium-silicon alloy has high nitrogen content of 5-25 wt%, low oxygen content and oxygen content of not higher than 0.04wt%.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of high-nitrogen titanium-silicon alloy co-produced titanium nitride powder, which comprises the following steps:
vacuum melting metal silicon and titanium sponge in a split water-cooled copper crucible, introducing a nitrogen source to nitride the obtained titanium-silicon alloy in the vacuum melting process to obtain a high-nitrogen titanium-silicon alloy, wherein the nitrogen content of the high-nitrogen titanium-silicon alloy is 5-25 wt%;
and removing dust in the nitriding process, wherein the obtained dust is nitride powder, and calcining the nitride powder to obtain the titanium nitride powder.
Preferably, the calcining temperature is 1900-2200 ℃, and the holding time is 5-20 min.
Preferably, the mass ratio of the metal silicon to the titanium sponge is 0.7-1.3.
Preferably, the pressure rise rate of the vacuum melting is less than 30Pa/min.
Preferably, the vacuum melting comprises first vacuum melting, second vacuum melting, third vacuum melting, fourth vacuum melting, fifth vacuum melting and sixth vacuum melting in sequence;
the smelting power of the first vacuum smelting is 80-90 kW, and the smelting time is 10-30 min;
the smelting power of the second vacuum smelting is 120-135 kW, and the smelting time is 20-40 min;
the smelting power of the third vacuum smelting is 140-150 kW, and the smelting time is 10-20 min;
the smelting power of the fourth vacuum smelting is 160-180 kW, and the smelting time is 60-360 min;
the melting power of the fifth vacuum melting is 140-150 kW, and the melting time is 5-10 min;
the melting power of the sixth vacuum melting is 100-120 kW, and the melting time is 10-20 min.
Preferably, nitrogen sources are introduced during the third vacuum melting and the fourth vacuum melting; the vacuum degree of the third vacuum melting is 10 2 ～10 3 Pa, the flow rate of the nitrogen source introduced during the third vacuum melting is 10-20L/min;
the vacuum degree of the fourth vacuum melting is not higher than 1.5 multiplied by 10 4 Pa, wherein the flow rate of the introduced nitrogen source during the fourth vacuum melting is 25-50L/min;
and dedusting in the fourth vacuum melting process.
Preferably, the nitrogen source is closed during the fifth vacuum melting; the vacuum degree of the fifth vacuum melting is not higher than 50Pa;
the vacuum degree of the first vacuum melting is less than 15Pa;
the vacuum degree of the second vacuum melting is less than 15Pa;
the vacuum degree of the sixth vacuum melting is not higher than 50Pa.
Preferably, the nitrogen source is nitrogen-ammonia mixed gas; the mass fraction of ammonia in the nitrogen-ammonia mixed gas is 20-70%, and the total mass fraction of nitrogen and ammonia is more than 99.99%.
Preferably, the nitriding time is 2 to 6 hours.
Preferably, the vacuum melting equipment is a cold crucible suspension melting furnace.
The invention provides a preparation method of titanium nitride powder with the co-production of high-nitrogen titanium silicon alloy. The invention takes titanium sponge and metallic silicon as raw materials, and adopts a split water-cooled copper crucible to replace a corundum crucible to carry out suspension smelting on the alloy by a suspension smelting-nitriding method, thereby preventing the metallic titanium from reacting with alumina (the product is Al) compared with the corundum crucible of the traditional intermediate frequency furnace 2 TiO 5 ) The quality and yield of the alloy are improved, the low-oxygen high-nitrogen titanium-silicon alloy is prepared by blowing a nitrogen source at a high temperature, the problems of overhigh oxygen (0.1-2 wt%) and overlow nitrogen content (0.001-0.01 wt%) in the impurity elements of the traditional titanium-silicon alloy are solved, and the quality of the high-nitrogen titanium-silicon alloy is greatly improved. The high nitrogen titanium silicon alloy prepared by the inventionThe components are as follows: n:5 to 25wt%, ti: 60-85 wt%, O not higher than 0.04wt% and Si in balance. According to the invention, the waste nitride powder generated in the nitriding process is calcined to obtain the high-purity titanium nitride powder, so that a new direction is provided for recycling the dedusting ash of the high-nitrogen titanium silicon alloy, the full utilization of resources is realized, and the concept of green chemistry and sustainable development is met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a cold crucible suspension smelting furnace used in the preparation method of the high nitrogen titanium silicon alloy co-production titanium nitride powder provided by the invention; wherein, 1 is a dust removal channel, 2 is a nitrogen source channel, and 3 is a split water-cooled copper crucible.
Detailed Description
The invention provides a preparation method of high-nitrogen titanium-silicon alloy co-produced titanium nitride powder, which comprises the following steps:
vacuum melting metal silicon and titanium sponge in a split water-cooled copper crucible, introducing a nitrogen source to nitrify the obtained titanium-silicon alloy in the vacuum melting process to obtain a high-nitrogen titanium-silicon alloy, wherein the nitrogen content of the high-nitrogen titanium-silicon alloy is 5-25 wt%;
and removing dust in the nitriding process, wherein the obtained dust is nitride powder, and calcining the nitride powder to obtain titanium nitride powder.
In the present invention, the mass ratio of the metallic silicon to the titanium sponge is preferably 0.7 to 1.3, more preferably 0.8 to 1.2; the initial vacuum degree of the invention is limited in the range, and the oxidation reaction between oxygen in the air and titanium can be prevented, thereby being beneficial to reducing the oxygen content of the high-nitrogen titanium-silicon alloy; the vacuum degree of the vacuum melting is preferably obtained by pumping a Roots pump; the vacuum smelting equipment is preferably a cold crucible suspension smelting furnace; the charging process of the metal silicon and the titanium sponge is preferably as follows: the method comprises the following steps of (1) loading metal silicon in the middle part of a split type water-cooled copper crucible, and loading titanium sponge close to the wall part of the split type water-cooled copper crucible; by utilizing the charging mode, the metal silicon is placed in the middle part of the induction coil because the melting point of the metal silicon is low, so that the melting time is shortened, and the energy consumption is reduced.
The cold crucible suspension smelting furnace adopted for preparing the high-nitrogen titanium silicon alloy is shown in figure 1. According to the figure 1, the cold crucible suspension smelting furnace adopted by the invention comprises 3 main parts, namely a dust removal channel, a nitrogen source channel and a split water-cooled copper crucible, wherein the dust removal channel is positioned above the split water-cooled copper crucible, the nitrogen source channel is communicated with the bottom of the split water-cooled copper crucible, the nitrogen source enters chlorinated electrolyte in the split water-cooled copper crucible through the nitrogen source channel during working, and nitride powder generated in the vacuum smelting process enters a collecting device for later use through the dust removal channel.
In the invention, the vacuum melting preferably comprises sequentially carrying out first vacuum melting, second vacuum melting, third vacuum melting, fourth vacuum melting, fifth vacuum melting and sixth vacuum melting; the smelting power of the first vacuum smelting is preferably 80-90 kW, more preferably 85kW, and the smelting time is preferably 10-30 min, more preferably 15-25 min; the vacuum degree of the first vacuum melting is preferably less than 15Pa, and more preferably less than 10Pa; the smelting power of the second vacuum smelting is preferably 120-135 kW, more preferably 125-130 kW, and the smelting time is preferably 20-40 min, more preferably 30min; the vacuum degree of the second vacuum melting is preferably less than 15Pa, and more preferably less than 10Pa; the smelting power of the third vacuum smelting is preferably 140-150 kW, more preferably 145kW, and the smelting time is preferably 10-20 min, more preferably 15min; the vacuum degree of the third vacuum melting is preferably 10 2 ～10 3 Pa, more preferably 0.5X 10 3 Pa。
In the invention, the melting power of the fourth vacuum melting is preferably 160-180 kW, more preferably 170-175 kW, and the melting time is preferably 60-360 min, more preferablyPreferably 120-360 min; the degree of vacuum of the fourth vacuum melting is preferably not higher than 1.5X 10 4 Pa, more preferably not higher than 1.0X 10 4 Pa; the melting power of the fifth vacuum melting is preferably 140-150 kW, more preferably 145kW, and the melting time is preferably 5-10 min, more preferably 7min; the vacuum degree of the fifth vacuum melting is preferably not higher than 50Pa, and more preferably not higher than 30Pa; the melting power of the sixth vacuum melting is preferably 100-120 kW, more preferably 105-115 kW, and the melting time is preferably 10-20 min, more preferably 15min; the vacuum degree of the sixth vacuum melting is preferably not higher than 50Pa, and more preferably not higher than 30Pa; the pressure rise rate of the vacuum melting is preferably less than 30Pa/min, and more preferably less than 20Pa/min.
In the invention, nitrogen sources are preferably introduced during the third vacuum melting and the fourth vacuum melting; according to the invention, titanium-silicon alloy is melted into alloy melt through the first vacuum melting and the second vacuum melting, and then the melting power of the vacuum melting is increased (namely, the third vacuum melting and the fourth vacuum melting are carried out in two stages), so that the superheat degree of the alloy is improved, and the nitridation reaction of the titanium-silicon alloy is accelerated; the nitrogen source is preferably nitrogen-ammonia mixed gas; the mass fraction of ammonia in the nitrogen-ammonia mixed gas is preferably 20-70%, more preferably 40-60%, and the total mass fraction of nitrogen and ammonia is preferably more than 99.99%, more preferably more than 99.999%; the reaction rate of the nitridation reaction is high at high temperature, and the nitrogen-ammonia mixed gas is used for replacing the commonly used ammonia gas, so that the phenomenon of explosion and splashing caused by too violent nitridation reaction can be prevented, and the alloy recovery rate and the purity of the titanium nitride powder are prevented from being influenced; the flow rate of the nitrogen source introduced during the third vacuum melting is preferably 10 to 20L/min, and more preferably 12 to 18L/min; the flow rate of the nitrogen source introduced during the fourth vacuum melting is preferably 25 to 50L/min, more preferably 30 to 45L/min, and further preferably 35 to 40L/min; the nitrogen source flow introduced during the fourth vacuum melting limited by the invention can ensure that the alloy melt does not splash, and simultaneously improve the reaction rate of the nitridation reaction; preferably, dust is removed in the fourth vacuum melting process; the dust removing equipment is preferably a roots pump; preferably, the nitrogen source is closed during the fifth vacuum melting; preferably, the dust removal is stopped after the nitrogen source is closed; the nitriding time is preferably 2 to 6 hours, more preferably 3 to 5 hours when the nitrogen gas is started to be introduced, and the content of nitrogen elements in the high-nitrogen titanium silicon alloy can be ensured in the nitriding time. The invention reduces the power step by step, can prevent the suspended alloy melt from directly falling to the crucible or the magnetic coil after direct power-off, and then the alloy falls into the split water-cooled copper crucible after cooling, and then the temperature is cooled by water.
In the present invention, it is preferable that the cold crucible suspension melting furnace is cooled after the vacuum melting by cutting off the power. The high-nitrogen titanium-silicon alloy prepared by the invention comprises the following components: n: 5-25 wt%, ti: 60-85 wt%, O not higher than 0.04wt% and Si in balance.
In the invention, dust is removed in the nitriding process (namely, the fourth vacuum melting stage), the obtained dust is nitride powder, and the nitride powder is calcined to obtain the titanium nitride. In the invention, the calcination temperature is preferably 1900-2200 ℃, more preferably 2000-2100 ℃, and the heat preservation time is preferably 5-20 min, more preferably 10-15 min; the calcining apparatus is preferably a high temperature calciner. The invention carries out calcination treatment on nitride powder (comprising silicon nitride and titanium nitride), the silicon nitride can be rapidly decomposed at the temperature of more than 1900 ℃ and biochemically changed into nitrogen and gaseous silicon, thereby obtaining pure titanium nitride powder, and the titanium nitride (TiN) powder comprises the following components: 99wt% or more of TiN, 0.1wt% of Si and 0.1wt% of C.
In order to further illustrate the invention, the following detailed description of the aspects of the invention is given in conjunction with the accompanying drawings and examples, which are not to be construed as limiting the scope of the invention.
Example 1
A preparation method of high-nitrogen titanium silicon alloy co-production titanium nitride powder comprises the following steps:
(1) 25kg of metal silicon and 70kg of sponge titanium are loaded into a cold crucible suspension smelting furnace, the metal silicon is loaded in the middle part of the cold crucible, the sponge titanium is distributed near the wall of a split type water-cooled copper crucible, a furnace body is closed, a roots pump is started, the suspension smelting furnace is vacuumized, the vacuum degree of the suspension smelting furnace is 9Pa, and the pressure rise rate is 17Pa/min;
(2) Electrifying, smelting for 10min after the smelting power reaches 85kW, increasing the power to 120kW, smelting for 30min, increasing the power to 145kW after the alloy is completely melted, simultaneously opening an electromagnetic valve, introducing a nitrogen-ammonia mixed gas (ammonia gas is 50 wt%) at a flow rate of 20L/min, smelting for 15min, increasing the power to 165kW, introducing the nitrogen-ammonia mixed gas (ammonia gas is 50 wt%) at a flow rate of 50L/min, opening a dust removal pump and a dust removal channel electromagnetic valve, extracting titanium nitride and silicon nitride powder, and smelting for 4h; and after the alloy nitridation is finished, closing a nitrogen-ammonia mixed gas electromagnetic valve, closing a dust removal channel electromagnetic valve, reducing the vacuum degree in the suspension smelting furnace to 32Pa at the moment, reducing the power to 140kW, reducing the vacuum degree to 100kW after smelting for 15min, smelting for 10min, and cutting off the power to finish the smelting to obtain 98.5kg of the high-nitrogen titanium-silicon alloy.
(3) 24.5kg of powder in the dust removal bag is collected and calcined in a high-temperature calciner, and 13.9kg of high-purity titanium nitride powder is obtained.
Through detection:
the high-nitrogen titanium-silicon alloy comprises the following components: ti:60.8wt%, N:20.9wt%, O:0.017wt% and the balance of Si;
the titanium nitride powder comprises the following components: tiN:99.62wt%, si:0.085wt%, C:0.012wt%, and the balance of impurities.
Example 2
A preparation method of high-nitrogen titanium silicon alloy co-production titanium nitride powder comprises the following steps:
(1) 30kg of metal silicon and 80kg of sponge titanium are loaded into a cold crucible suspension smelting furnace, the metal silicon is loaded in the middle part of the cold crucible, the sponge titanium is distributed near the wall of a split type water-cooled copper crucible, a furnace body is closed, a roots pump is started, the suspension smelting furnace is vacuumized, the vacuum degree of the suspension smelting furnace is 12Pa, and the pressure rise rate is 20Pa/min;
(2) Electrifying, smelting for 15min after the smelting power reaches 80kW, increasing the power to 130kW, smelting for 20min, after the alloy is completely melted, increasing the power to 140kW, simultaneously opening the electromagnetic valve, introducing a nitrogen-ammonia mixed gas (ammonia gas is 55 wt%) at a flow rate of 20L/min, smelting for 12min, increasing the power to 170kW, introducing the nitrogen-ammonia mixed gas (ammonia gas is 50 wt%) at a flow rate of 50L/min, opening the dust removal pump and the electromagnetic valve of the dust removal channel, extracting titanium nitride and silicon nitride powder, and smelting for 3.5h; and after the alloy nitridation is finished, closing a nitrogen-ammonia mixed gas electromagnetic valve, closing a dust removal channel electromagnetic valve, reducing the vacuum degree in the suspension smelting furnace to 40Pa at the moment, reducing the power to 140kW, reducing the vacuum degree to 110kW after smelting for 8min, smelting for 10min, and cutting off the power to finish the smelting to obtain 103.4kg of the high-nitrogen titanium-silicon alloy.
(3) And collecting 34.2kg of powder in the dust removal bag, and calcining the powder in a high-temperature calciner to obtain 19.6kg of high-purity titanium nitride powder.
Through detection:
the high-nitrogen titanium-silicon alloy comprises the following components: ti:65.2wt%, N:13.6wt%, O:0.014wt%, the balance being Si;
the titanium nitride powder comprises the following components: tiN:99.88wt%, si:0.045wt%, C:0.009wt%, and the balance impurities.
From the above embodiments, it can be known that the oxygen content of the high nitrogen titanium silicon alloy prepared by the invention is not higher than 0.04wt%, even can be as low as 0.01wt%, and the nitrogen content is 5-25 wt%, so that the oxygen content is reduced on the premise of ensuring the nitrogen content of the high nitrogen titanium silicon alloy, the problem of too high oxygen content of the high nitrogen titanium silicon alloy is solved, and the titanium nitride is fully utilized.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A preparation method of titanium nitride powder with high nitrogen titanium silicon alloy co-production is characterized by comprising the following steps:
vacuum melting metal silicon and titanium sponge in a split water-cooled copper crucible, introducing a nitrogen source to nitride the obtained titanium-silicon alloy in the vacuum melting process to obtain a high-nitrogen titanium-silicon alloy, wherein the nitrogen content of the high-nitrogen titanium-silicon alloy is 5-25 wt%;
and removing dust in the nitriding process, wherein the obtained dust is nitride powder, and calcining the nitride powder to obtain the titanium nitride powder.
2. The preparation method according to claim 1, wherein the calcination temperature is 1900-2200 ℃ and the holding time is 5-20 min.
3. The preparation method according to claim 1, wherein the mass ratio of the metallic silicon to the titanium sponge is 0.7 to 1.3.
4. The production method according to claim 1, wherein a pressure rise rate of the vacuum melting is less than 30Pa/min.
5. The production method according to claim 1 or 4, wherein the vacuum melting includes sequentially performing first vacuum melting, second vacuum melting, third vacuum melting, fourth vacuum melting, fifth vacuum melting, and sixth vacuum melting;
the smelting power of the first vacuum smelting is 80-90 kW, and the smelting time is 10-30 min;
the smelting power of the second vacuum smelting is 120-135 kW, and the smelting time is 20-40 min;
the smelting power of the third vacuum smelting is 140-150 kW, and the smelting time is 10-20 min;
the melting power of the fourth vacuum melting is 160-180 kW, and the melting time is 60-360 min;
the melting power of the fifth vacuum melting is 140-150 kW, and the melting time is 5-10 min;
the melting power of the sixth vacuum melting is 100-120 kW, and the melting time is 10-20 min.
6. The production method according to claim 5, wherein a nitrogen source is introduced during the third vacuum melting and the fourth vacuum melting; the vacuum degree of the third vacuum melting is 10 2 ～10 3 Pa, the flow rate of the introduced nitrogen source during the third vacuum melting is 10-20L/min;
the vacuum degree of the fourth vacuum melting is not higher than 1.5 multiplied by 10 4 Pa, the fourth vacuumThe flow rate of the introduced nitrogen source during smelting is 25-50L/min;
and dedusting in the fourth vacuum melting process.
7. The production method according to claim 5, wherein the nitrogen source is turned off at the time of the fifth vacuum melting; the vacuum degree of the fifth vacuum melting is not higher than 50Pa;
the vacuum degree of the first vacuum melting is less than 15Pa;
the vacuum degree of the second vacuum melting is less than 15Pa;
the vacuum degree of the sixth vacuum melting is not higher than 50Pa.
8. The production method according to claim 1 or 6, wherein the nitrogen source is a nitrogen-ammonia mixed gas; the mass fraction of ammonia in the nitrogen-ammonia mixed gas is 20-70%, and the total mass fraction of nitrogen and ammonia is more than 99.99%.
9. The method according to claim 1 or 6, wherein the nitriding is carried out for a time of 2 to 6 hours.
10. The production method according to claim 1 or 4, wherein the vacuum melting apparatus is a cold crucible suspension melting furnace.
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