CN115821140A - Titanium-containing alloy for metallurgy and low-cost production method thereof - Google Patents
Titanium-containing alloy for metallurgy and low-cost production method thereof Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 104
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 94
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 75
- 239000000956 alloy Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000005272 metallurgy Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 164
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 68
- 239000000843 powder Substances 0.000 claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 34
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 239000012141 concentrate Substances 0.000 claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 28
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 112
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000011449 brick Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000005121 nitriding Methods 0.000 claims description 8
- 239000000523 sample Substances 0.000 claims description 8
- 230000001133 acceleration Effects 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- 238000009417 prefabrication Methods 0.000 claims description 7
- 238000011946 reduction process Methods 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 230000006641 stabilisation Effects 0.000 claims description 7
- 238000011105 stabilization Methods 0.000 claims description 7
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 230000001360 synchronised effect Effects 0.000 claims description 7
- 238000005485 electric heating Methods 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 4
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 24
- 239000010959 steel Substances 0.000 abstract description 24
- 238000005275 alloying Methods 0.000 abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- -1 TiOx titanium oxides Chemical class 0.000 description 1
- 229910000756 V alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a titanium-containing alloy for metallurgy and a low-cost production method thereof, wherein the titanium-containing alloy is prepared from the following raw materials in parts by weight: 100 parts of ilmenite concentrate powder, 50-60 parts of titanium dioxide powder, 50-60 parts of carbonaceous reducing agent, 5-10 parts of sodium carbonate, 20-30 parts of iron powder and 10-20 parts of adhesive; the production method of the titanium-containing alloy comprises the steps of prefabricating reactant raw materials into reaction blocks, adding the reaction blocks into a closed track kiln type heating device, and gradually carrying out carbothermic reaction and nitridation reaction to prepare the titanium-containing alloy; the titanium-containing alloy produced by the invention mainly comprises TiN and TiCN, and can be comprehensively applied in the process of deformed steel bar metallurgy, wherein Ti, N and C are beneficial elements in deformed steel bars, so that the strength and toughness of the deformed steel bars can be effectively improved, the alloy containing vanadium in the deformed steel bars can be partially or completely replaced, and the alloying cost is obviously reduced.
Description
Technical Field
The invention relates to the technical field of ferrous metallurgy industry and titanium-containing alloy production, in particular to a titanium-containing alloy for metallurgy and a low-cost production method thereof.
Background
Titanium is one of the most important alloying elements in steel.
Titanium has a wide range of beneficial effects in steel. Titanium has strong affinity with nitrogen, oxygen and carbon, and is a good deoxidizing and degassing agent and an effective element for fixing nitrogen and carbon. The compound (TiC) of titanium and carbon has strong binding force and high stability, and can be slowly dissolved in the solid solution of iron only by heating to above 1000 ℃, the TiC particles have the function of preventing the steel crystal grains from growing and coarsening, the titanium and the N are also easily combined to form TiN, the particles can be used as heterogeneous cores to promote the increase of nucleation amount of the steel in the solidification process and simultaneously prevent the abnormal coarsening of the crystal grains, and the existence of the TiC and the TiN can form the effect of fine grain strengthening independently and together, thereby obviously improving the strength of the steel.
With the promulgation and implementation of the new national standard GB/T1499.2-2018 of deformed steel bar, the deformed steel bar with HRB400 and above grade can reach the strength required by the national standard only by micro-alloying, the most direct way is the alloying of vanadium and vanadium nitrogen, but the cost of vanadium and the alloy thereof determined by the raw materials and the production process is extremely high, and the unit price per ton is between 16 and 30 ten thousand yuan or even higher. Because titanium has similar action with vanadium in steel, and the price advantage of titanium-containing alloy is obvious, only about one fifth of vanadium alloy, but because deep deoxidation is not carried out in the production of deformed steel bar, the yield is low and extremely unstable after the titanium iron is directly added, the titanium iron is directly added for alloying, the effect fluctuation is obvious, and the application and popularization are greatly limited, therefore, the production process of the deformed steel bar can be added by adopting a composite alloy mode taking TiN or TiCN as the main component, wherein Ti, N and C are necessary elements of the deformed steel bar or elements for improving the strength of finished products, in molten steel, the content of N is increased by the composite, the activity of O can be reduced, the oxidation of Ti is reduced, and therefore, the nitrogen-containing composite of Ti can replace vanadium and the alloy thereof, and the low-cost stable production of HRB400 and HRB 500-grade deformed steel bars is realized. The TiN used in the metallurgical production of deformed steel bar has not very strict requirements on effective content, purity, granularity, density and the like.
In a number of papersAnd the patent mentions the test and the method for producing TiN, tiC and TiCN by carbothermic reduction, and realizes the preparation of titanium nitride with certain purity, for example, the patent with the application number of CN110467160B introduces a raw material composition for preparing titanium nitride by carbothermic reduction nitridation and a preparation method, and the raw material composition can be used for preparing high-purity titanium nitride with the oxygen content of less than 0.5 percent and the carbon content of less than 1.0 percent by taking 100 parts of titanium dioxide, 25 to 29 parts of carbonaceous reducing agent and 0.6 to 1 part of iron and/or iron oxide as the mass of Fe. The method comprises the following steps: and (2) adding the binder into the raw material composition, mixing, pressing, and performing staged antipyresis in a nitrogen atmosphere, wherein the total heating time is 11-19 hours. The method has the main problem that the raw material is pure TiO 2 The method has the advantages of high cost, long graded heating time, high energy cost consumption, high purity of the prepared TiN, high melting point, difficult melting or dissolution in molten steel, and inapplicability to metallurgical processes from the aspects of cost, physical and chemical properties of finished products and the like. The patent of application number CN200610018702.8 introduces a method for synthesizing titanium carbonitride powder by low-temperature molten salt carbothermic reduction, which belongs to the preparation technology of non-oxide ceramics and adopts the technical scheme that: mixing C and TiO in the carbon-containing mixture 2 Mixing according to the molar ratio of 1: 1-5, adding molten salt with the weight percentage content of 0.5-50% of the mixture and 0-30% of binding agent, uniformly mixing, carrying out mechanical compression molding or balling under the pressure of 10-600 MPa, carrying out heat preservation for 30-1200 minutes under the condition of embedding carbon or the protection atmosphere of argon or nitrogen at the temperature of 600-1800 ℃, and naturally cooling to obtain the synthesized titanium carbonitride powder, wherein the content of the titanium carbonitride is more than 85%, the titanium carbonitride powder has a B1-NaCl type crystal structure and the average grain diameter is more than 7 mu m, compared with the simple carbothermal reduction, the synthesis temperature is reduced by 200-500 ℃, the purity is higher, and the grain shape is regular and the grain diameter is larger. The key point of the invention is to control the purity and the grain size of the titanium nitride or the titanium carbonitride, which is difficult to realize under the condition of large-scale industrialized production. Also, the patent of application No. cn200910076143.X describes a method for preparing titanium nitride ceramic powder, in which the titanium source is soluble titanium salt, the aim is to produce high-purity titanium nitride, the cost is too high, and the method has no practical value in the metallurgical industry.
The method uses a composite carbothermic method to realize industrialized, low-cost and continuous production of compounds containing TiCN or TiN with stable quality.
Disclosure of Invention
The invention aims to provide a titanium-containing alloy for metallurgy and a low-cost production method thereof, aiming at the problems that the production cost is high, a finished product is not suitable for the metallurgy industry, or the industrial production is difficult to realize in the prior art when the titanium-containing alloy is prepared.
The invention relates to a titanium-containing alloy for metallurgy, which is prepared from the following raw materials in parts by weight:
ferrotitanium concentrate powder 100 parts
50-60 parts of titanium dioxide powder
50-60 parts of carbonaceous reducing agent
5-10 parts of sodium carbonate
20-30 parts of iron powder
10-20 parts of an adhesive.
Preferably, the titanium-containing alloy for metallurgy is prepared from the following raw materials in parts by weight:
ferrotitanium concentrate powder 100 parts
52-58 parts of titanium dioxide powder
52-58 parts of carbonaceous reducing agent
6-9 parts of sodium carbonate
22-28 parts of iron powder
12-18 parts of an adhesive.
Most preferably, the titanium-containing alloy for metallurgy is prepared from the following raw materials in parts by weight:
ferrotitanium concentrate powder 100 parts
55 parts of titanium dioxide powder
55 portions of carbonaceous reducing agent
Sodium carbonate 7 parts
25 portions of iron powder
15 parts of adhesive.
The granularity of the ilmenite concentrate powder is 300-400 meshes, wherein TiO 2 The mass percentage content of the active ingredients is 55-60%; the granularity of the titanium dioxide powder is 400-500 meshes, wherein TiO 2 The mass percentage content of the compound is 92-95%; the carbonaceous reducing agent refers to any one of graphite or coke, and the granularity is 180-200 meshes, the effective C content is more than or equal to 90 percent, and the sodium carbonate is industrial-grade sodium carbonate with the granularity of 450-500 meshes; the granularity of the iron powder is 300-400 meshes, wherein the mass percentage of Fe is more than or equal to 96%; the adhesive is one or two of water glass and aluminum dihydrogen phosphate.
The invention relates to a low-cost production method of titanium-containing alloy for metallurgy, which comprises the following steps:
(1) Prefabrication of raw materials: uniformly mixing ilmenite concentrate powder, titanium dioxide powder, a carbonaceous reducing agent, sodium carbonate, iron powder and an adhesive according to a formula ratio, pressing the mixture into a reaction block under the pressure of 5-10MPa, placing the reaction block in a room, airing the reaction block at normal temperature, placing the reaction block in a low-temperature drying furnace at the temperature of 100-300 ℃ and drying the reaction block until the moisture is less than or equal to 1% for later use;
(2) Charging: adding the reaction block prepared in the step (1) into a closed track kiln type heating device, wherein the feeding amount accounts for 60-70% of the inner volume of the track kiln, and the pressure in the furnace is adjusted to be 0.11-0.115MPa; the inner volume of the track kiln type heating device is 30-40m 3 The system adopts electric heating, a gas discharge device and a gas analyzer are arranged at the head end and the tail end of the track kiln, the gas discharge device is used for keeping micro-positive pressure required by the system and discharging gas generated in the reaction process, and the gas analyzer is respectively provided with a group of sampling probes at the head end and the tail end of the track kiln and is used for detecting the flow rate of the discharged gas and the content of CO in the discharged gas;
(3) And (3) carrying out a carbothermic reduction process:
a. the initial stage of the reaction: electrifying and heating to gradually raise the temperature in the track kiln from room temperature to 500 ℃, wherein the temperature raising rate is 120-150 ℃/h, and at the moment, the air in the kiln begins to be discharged;
b. a rapid temperature rise stage: introducing nitrogen into the track kiln for 10-50L/min, raising the temperature in the track kiln to 1000 ℃ at a temperature rise speed of 200-250 ℃/h, and beginning to generate C and TiO in the reaction block at the stage 2 The reaction of (2) can show that the content of CO in the exhaust gas is gradually increased from a gas analyzer, and meanwhile, the nitriding reaction of Ti is carried out;
c. and (3) a reaction acceleration stage: continuously keeping the nitrogen gas to be introduced into the track kiln for 10-50L/min, heating the temperature in the track kiln to 1500 ℃ at the heating rate of 400-500 ℃/h, continuously increasing the gas emission and the CO content in the gas in the track kiln at the stage, quickly carrying out the carbon thermal reaction, gathering heat in the kiln, and keeping the temperature in the kiln stable through automatic adjustment;
d. and (3) a reaction stabilization stage: continuously keeping the nitrogen gas introduced into the track kiln at 50-80L/min, keeping the temperature in the track kiln at 1520-1580 ℃, keeping the reaction block in the track kiln at a stable carbothermic reaction stage, immediately increasing the nitrogen gas supply to 80-100L/min when detecting that the flow of the discharged gas reaches a peak and tends to be stable through a gas analyzer, gradually transitioning the reaction from the synchronous process of carbothermic reduction and nitridation to a full-nitridation process, and controlling a flow valve of the discharged gas and a pressure stabilizing valve to ensure that the pressure in the track kiln is always at a micro positive pressure of 0.11-0.15 MPa; when the flow rate of the exhaust gas is reduced to be consistent with the flow rate of the nitrogen and the content of CO in the exhaust gas is reduced to 0, the stable reaction stage is finished;
e. and (3) at the end stage of the reaction: keeping the temperature in the rail kiln at 1520-1580 ℃, keeping introducing nitrogen into the rail kiln for 40-50L/min, stopping supplying heat after 2-3 hours, stopping supplying nitrogen after the temperature in the furnace is reduced to 600 ℃, gradually reducing the temperature to room temperature, taking out a reaction block after the reaction is finished, and detecting, wherein the mass percentage of TiN is 35-40%, the mass percentage of TiCN is 15-20%, the mass percentage of TiN + TiCN is 50-60%, the mass percentage of Fe is 30-35%, and the mass percentage of other components is 6-12%, so that the titanium-containing alloy is obtained.
The reaction block prepared in the step (1) is in a square brick shape, the length of the square brick is 20-25cm, the width of the square brick is 12-15cm, and the height of the square brick is 12-15cm. The reaction block can be made into other shapes, and the shape of the reaction block does not influence the quality of the titanium-containing alloy made by the reaction block, so that the titanium-containing alloy is convenient to manufacture and assemble and disassemble.
The density of the titanium-containing alloy prepared by the invention is 3.0-4.0g/cm 3 When in use, the mixture is prepared into blocks, granules or powder; the granular or powdery titanium-containing alloy can be wrapped by iron sheet to be made into cored wire. The blocky titanium-containing alloy can be put into a steel refining link or added into a bin for a refining process; the cored wire made of the granular or powdery titanium-containing alloy can be fed and used in the smelting link by a wire feeder.
The various raw materials used in the present invention function in the present invention as follows: ilmenite concentrate powder: is one of the sources of titanium in the titanium-containing alloy, has moderate titanium content, large density and easy volume pressing; titanium dioxide powder: the titanium is one of the sources of titanium in the titanium-containing alloy, the titanium content is high, but the titanium is not easy to be compacted; carbonaceous reducing agent: is the only reducing agent for reducing oxides in the titaniferous ore; sodium carbonate: the reaction catalyst is a substance forming a porous structure, and is beneficial to discharging CO generated by carbothermic reaction; iron powder: the framework material is beneficial to heat transfer and heat storage in the reaction process and promotes the reaction to be continuously carried out; adhesive: binding multiple composite minerals into blocks.
The preparation method of the titanium-containing alloy basically comprises the following reaction steps:
2TiO 2 +4C+N 2 = 2TiN+4CO （1）
2TiO 2 +6C+N 2 = 2TiCN+4CO （2）
the reactions (1) and (2) are carried out simultaneously within the range of 1500 to 1600 ℃, the invention produces the titanium-containing TiN or TiCN composite alloy with high efficiency and low cost by combining composite carbothermic reduction and a nitriding method, and mainly solves the following problems:
(1) Compared with the traditional process route for producing the titanium alloy and the titanium-containing composite alloy by complex long flows of reduction, chlorination, electrolysis and the like, the process flow is short, the cost is obviously reduced, and toxic waste is not discharged.
(2) Both the reduction and nitridation reaction processes of Ti-containing oxides need to be performed at high temperatures, and thus, in addition to a fixed raw material cost, heat source cost control significantly affects the overall cost control level, and it is required to efficiently provide a heat source and to promote the reaction to be rapidly performed.
(3) The properties of reactants, the proportion of carbon, the heating rate, the pressure in a reaction container and the like need to be properly controlled so as to achieve the purposes of high efficiency and stability of the reaction process and total stability of the product cost.
The titanium-iron alloy produced by the invention has slightly lower purity than the titanium-containing minerals generated by the traditional long process, mainly comprises TiN and TiCN, but has good application prospect in the production of deformed steel bars, wherein Ti, N and C are beneficial elements, the alloying cost of the deformed steel bars can be obviously reduced, and for China which is still in a high-quality development period and is still an important engine for economic development of capital construction, the annual yield of the deformed steel bars is measured in billions of tons.
Drawings
FIG. 1 is a micro-area morphology image of a titanium-containing alloy finished product obtained in example 1 of the present invention, which is analyzed by Scanning Electron Microscopy (SEM);
FIG. 2 is a partial compositional result of an analysis of binding energy spectrum (EDS) points at the cross-hair of FIG. 1;
FIG. 3 is a micro-area morphology image of a titanium-containing alloy finished product obtained in example 3 of the present invention, which is analyzed by Scanning Electron Microscopy (SEM);
FIG. 4 is a partial compositional result of an analysis of binding energy spectroscopy (EDS) points at the cross-hair marker of FIG. 2;
FIG. 5 shows the XRD partial component analysis results of multiple groups of samples of the finished Ti-containing alloy product obtained in example 5 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following specific examples, which are only for illustrating the present invention and are not to be construed as limiting the present invention in any way.
Example 1
The titanium-containing alloy for metallurgy is prepared from the following raw materials in parts by weight: 100 parts of ilmenite concentrate powder, 55 parts of titanium dioxide powder, 55 parts of carbonaceous reducing agent, 7 parts of sodium carbonate, 25 parts of iron powder and 15 parts of adhesive.
The particle size of the ilmenite concentrate powder in this example was 400 mesh, wherein TiO 2 The mass percentage content of the active carbon is 58.2 percent; the granularity of the titanium dioxide powder is 500 meshes, wherein the TiO powder 2 The mass percentage content of (A) is 95.4%; the carbonaceous reducing agent is graphite with the granularity of 200 meshes, the effective C content is 95.3 percent, and the sodium carbonate is industrial-grade sodium carbonate with the granularity of 500 meshes; the granularity of the iron powder is 400 meshes, wherein the mass percent of FeThe content is 98.2%; the adhesive is water glass.
The low-cost production method of the titanium-containing alloy comprises the following steps:
(1) Prefabrication of raw materials: uniformly mixing ferrotitanium concentrate powder, titanium dioxide powder, a carbonaceous reducing agent, sodium carbonate, iron powder and an adhesive, namely water glass according to a formula ratio, pressing into a reaction block (the reaction block is in a square brick shape, and the size of the reaction block is 20cm x 12cm), placing the reaction block in a room, airing at normal temperature, and then placing the reaction block in a low-temperature drying furnace at the temperature of 200 ℃ for drying until the moisture is 0.6% for later use;
(2) Charging: adding the reaction block prepared in the step (1) into a closed track kiln type heating device, wherein the feeding amount accounts for 65% of the inner volume of the track kiln, and the pressure in the furnace is adjusted to be 0.11-0.115MPa; the inner volume of the track kiln type heating device is 40m 3 The system adopts electric heating, a gas discharge device and a gas analyzer are arranged at the head end and the tail end of the track kiln, the gas discharge device is used for keeping micro-positive pressure required by the system and discharging gas generated in the reaction process, and the gas analyzer is respectively provided with a group of sampling probes at the head end and the tail end of the track kiln and is used for detecting the flow rate of the discharged gas and the content of CO in the discharged gas;
(3) And (3) carrying out a carbothermic reduction process:
a. the initial stage of the reaction: electrifying for heating, gradually raising the temperature in the track kiln from room temperature to 500 ℃, wherein the temperature raising rate is 135 ℃/h, and at the moment, the air in the kiln begins to be discharged;
b. a rapid temperature rise stage: introducing nitrogen into the track kiln for 30L/min, raising the temperature in the track kiln to 1000 ℃ at a temperature rise speed of 225 ℃/h, and beginning to generate C and TiO in the reaction block at the stage 2 The reaction of (2) can show that the content of CO in the exhaust gas is gradually increased from a gas analyzer, and meanwhile, the nitriding reaction of Ti is carried out;
c. and (3) a reaction acceleration stage: continuously keeping the nitrogen gas introduced into the track kiln for 30L/min, heating the temperature in the track kiln to 1500 ℃ at the heating rate of 450 ℃/h, continuously increasing the gas emission of the track kiln and the CO content in the gas at the stage, rapidly carrying out the carbon thermal reaction, gathering heat in the kiln, and keeping the temperature in the kiln stable through automatic adjustment;
d. and (3) a reaction stabilization stage: continuously keeping 65L/min of nitrogen introduced into the rail kiln, keeping the temperature in the rail kiln at 1530-1550 ℃, enabling a reaction block in the rail kiln to be in a stable carbothermic reaction stage, immediately increasing the nitrogen supply to 90L/min when detecting that the flow of the discharged gas reaches a peak and tends to be stable through a gas analyzer, gradually transitioning the reaction from a carbothermic reduction and nitridation synchronous process to a full-nitridation process, and controlling a discharged gas flow valve and a pressure stabilizing valve to ensure that the pressure in the rail kiln is always at a micro-positive pressure of 0.11-0.15 MPa; when the flow rate of the exhaust gas is reduced to be consistent with the flow rate of the nitrogen and the content of CO in the exhaust gas is reduced to 0, ending the stable reaction stage;
e. and (3) at the end stage of the reaction: keeping the temperature in the rail kiln at 1530-1550 ℃, keeping the nitrogen introduced into the rail kiln for 45L/min, stopping heat supply after 3 hours, stopping nitrogen supply after the temperature in the furnace is reduced to 600 ℃, gradually cooling to room temperature, taking out a reaction block after the reaction is finished, and detecting, wherein the mass percentage of TiN is 38.2%, the mass percentage of TiCN is 18.6%, the mass percentage of TiN + TiCN is 56.8%, the mass percentage of Fe is 32.2%, and the mass percentage of other components is 11%, so that the titanium-containing alloy is obtained. The density of the titanium-containing alloy prepared by the method is 3.6g/cm 3 The product is made into a cuboid shape.
Referring to fig. 1 and 2, a part of the sample prepared in example 1 is taken, and SEM scanning analysis is performed to obtain a micro-topography as shown in fig. 1, it can be seen from fig. 1 that the finished product of the titanium-containing alloy prepared in this example is tightly bonded and relatively uniform overall, and the composition result is shown in fig. 2 by analyzing the cross-shaped bonding energy spectrum (EDS) points in fig. 1, and it can be seen from fig. 2 that the titanium-containing alloy prepared in this example has regions rich in Ti, N and C, and O in the reactant is completely removed to form titanium nitride and carbonitride.
Example 2
The titanium-containing alloy for metallurgy is prepared from the following raw materials in parts by weight: 100 parts of ilmenite concentrate powder, 50 parts of titanium dioxide powder, 50 parts of carbonaceous reducing agent, 5 parts of sodium carbonate, 20 parts of iron powder and 10 parts of adhesive.
Ferrotitanium described in this exampleThe particle size of the concentrate powder is 350 meshes, wherein the particle size of the concentrate powder is TiO 2 The mass percentage content of the compound is 55.6 percent; the granularity of the titanium dioxide powder is 400 meshes, wherein the TiO powder 2 The mass percentage content of (A) is 92.3%; the carbonaceous reducing agent is coke, the granularity is 180 meshes, the effective C content is 90.5 percent, the sodium carbonate is industrial grade sodium carbonate, and the granularity is 450 meshes; the granularity of the iron powder is 300 meshes, wherein the mass percentage of Fe is 96.4%; the adhesive is 5 parts of water glass and 5 parts of aluminum dihydrogen phosphate.
The low-cost production method of the titanium-containing alloy comprises the following steps:
(1) Prefabrication of raw materials: uniformly mixing ferrotitanium concentrate powder, titanium dioxide powder, a carbonaceous reducing agent, sodium carbonate, iron powder and an adhesive according to a formula proportion, pressing the mixture into a reaction block (the reaction block is in a square brick shape, and the size of the reaction block is 20cm x 10cm), placing the reaction block in a room, airing the reaction block at normal temperature, and then placing the reaction block in a low-temperature drying furnace at 100 ℃ to dry the reaction block until the water content is 1% for later use;
(2) Charging: adding the reaction block prepared in the step (1) into a closed track kiln type heating device, wherein the feeding amount accounts for 70% of the inner volume of the track kiln, and the pressure in the furnace is adjusted to be 0.11-0.115MPa; the inner volume of the track kiln type heating device is 30m 3 The system adopts electric heating, a gas discharge device and a gas analyzer are arranged at the head end and the tail end of the track kiln, the gas discharge device is used for keeping micro-positive pressure required by the system and discharging gas generated in the reaction process, and the gas analyzer is respectively provided with a group of sampling probes at the head end and the tail end of the track kiln and is used for detecting the flow rate of the discharged gas and the content of CO in the discharged gas;
(3) And (3) carrying out a carbothermic reduction process:
a. the initial stage of the reaction: electrifying for heating, gradually raising the temperature in the track kiln from room temperature to 500 ℃, wherein the temperature raising rate is 150 ℃/h, and at the moment, the air in the kiln begins to be discharged;
b. a rapid temperature rise stage: introducing nitrogen into the rail kiln for 10L/min, raising the temperature in the rail kiln to 1000 ℃ at a temperature rise speed of 250 ℃/h, and beginning to generate C and TiO in the reaction block at the stage 2 From the gas analyzer, it was revealed that the CO content in the exhaust gas was gradually increased with the progress of the nitriding reaction of TiA row;
c. a reaction acceleration stage: continuously keeping the nitrogen gas introduced into the track kiln for 10L/min, heating the temperature in the track kiln to 1500 ℃ at the heating rate of 500 ℃/h, continuously increasing the gas emission of the track kiln and the CO content in the gas at the stage, rapidly carrying out the carbon thermal reaction, gathering heat in the kiln, and keeping the temperature in the kiln stable through automatic adjustment;
d. and (3) a reaction stabilization stage: continuously keeping the nitrogen gas introduced into the track kiln for 50L/min, keeping the temperature in the track kiln at 1520-1540 ℃, immediately increasing the nitrogen gas supply to 80L/min when the reaction block in the track kiln is in a stable carbothermic reaction stage, detecting that the flow of the discharged gas reaches the peak and tends to be stable through a gas analyzer, gradually transitioning the reaction from the synchronous process of carbothermic reduction and nitridation to a full-nitridation process, and controlling a flow valve of the discharged gas and a pressure stabilizing valve to ensure that the pressure in the track kiln is always at a micro-positive pressure of 0.11-0.15 MPa; when the flow rate of the exhaust gas is reduced to be consistent with the flow rate of the nitrogen and the content of CO in the exhaust gas is reduced to 0, the stable reaction stage is finished;
e. and (3) at the end stage of the reaction: keeping the temperature in the rail kiln at 1520-1540 ℃, keeping introducing nitrogen into the rail kiln for 40L/min, stopping supplying heat after 2 hours, stopping supplying nitrogen after the temperature in the furnace is reduced to 600 ℃, gradually cooling to room temperature, taking out a reaction block after the reaction is finished, and detecting, wherein the mass percentage of TiN is 40%, the mass percentage of TiCN is 15.2%, the mass percentage of TiN and TiCN is 55.2%, the mass percentage of Fe is 33.5%, and the mass percentage of other components is 11.3%, so that the titanium-containing alloy is obtained. The density of the titanium-containing alloy prepared by the method is 4.0g/cm 3 And making into cuboid shape.
Example 3
The titanium-containing alloy for metallurgy is prepared from the following raw materials in parts by weight: 100 parts of ilmenite concentrate powder, 100 parts of titanium dioxide powder, 60 parts of carbonaceous reducing agent, 10 parts of sodium carbonate, 30 parts of iron powder and 20 parts of adhesive.
The particle size of the ilmenite concentrate powder in the example is 300 meshes, wherein TiO is 2 The mass percentage content of the active carbon is 60.2 percent; the granularity of the titanium dioxide powder is 480 meshes, wherein the TiO powder 2 The mass percentage content of (A) is 94.5%; the carbonaceous reducing agent is graphite with the granularity of 200 meshes, the effective C content is 94.5 percent, and the sodium carbonate is industrial-grade sodium carbonate with the granularity of 500 meshes; the granularity of the iron powder is 350 meshes, wherein the mass percentage of Fe is 96.3%; the adhesive is water glass.
The low-cost production method of the titanium-containing alloy comprises the following steps:
(1) Prefabrication of raw materials: uniformly mixing ilmenite concentrate powder, titanium dioxide powder, a carbonaceous reducing agent, sodium carbonate, iron powder and an adhesive according to a formula ratio, pressing into a reaction block (the reaction block is 25 x 12 x 12cm) under the pressure of 10MPa, placing the reaction block in a room, airing at normal temperature, placing the reaction block in a low-temperature drying furnace at the temperature of 300 ℃, and drying until the moisture is 0.4% for later use;
(2) Charging: adding the reaction block prepared in the step (1) into a closed track kiln type heating device, wherein the feeding amount accounts for 60% of the inner volume of the track kiln, and the pressure in the furnace is adjusted to be 0.11-0.115MPa; the inner volume of the track kiln type heating device is 40m 3 The system adopts electric heating, a gas discharge device and a gas analyzer are arranged at the head end and the tail end of the track kiln, the gas discharge device is used for keeping micro-positive pressure required by the system and discharging gas generated in the reaction process, and the gas analyzer is respectively provided with a group of sampling probes at the head end and the tail end of the track kiln and is used for detecting the flow rate of the discharged gas and the content of CO in the discharged gas;
(3) C, carbon thermal reduction process:
a. the initial stage of the reaction: electrifying for heating, gradually raising the temperature in the track kiln from room temperature to 500 ℃, wherein the temperature raising rate is 120 ℃/h, and at the moment, the air in the kiln begins to be discharged;
b. a rapid temperature rise stage: introducing nitrogen into the track kiln for 50L/min, raising the temperature in the track kiln to 1000 ℃ at a temperature rise speed of 200 ℃/h, and beginning to generate C and TiO in the reaction block at the stage 2 The reaction of (2) can show that the content of CO in the exhaust gas is gradually increased from a gas analyzer, and meanwhile, the nitriding reaction of Ti is carried out;
c. and (3) a reaction acceleration stage: continuously keeping the nitrogen gas introduced into the track kiln for 50L/min, heating the temperature in the track kiln to 1500 ℃ at the heating rate of 400 ℃/h, continuously increasing the gas emission of the track kiln and the CO content in the gas at the stage, rapidly carrying out the carbon thermal reaction, gathering heat in the kiln, and keeping the temperature in the kiln stable through automatic adjustment;
d. and (3) a reaction stabilization stage: continuously keeping the nitrogen gas introduced into the rail kiln at 80L/min, keeping the temperature in the rail kiln at 1560-1580 ℃, immediately increasing the nitrogen gas supply to 100L/min when the reaction block in the rail kiln is in a stable carbothermic reaction stage, detecting that the flow of the discharged gas reaches the peak and tends to be stable through a gas analyzer, gradually transitioning the reaction from the synchronous process of carbothermic reduction and nitridation to a full-nitridation process, and controlling a flow valve of the discharged gas and a pressure stabilizing valve to ensure that the pressure in the rail kiln is always at a micro positive pressure of 0.11-0.15 MPa; when the flow rate of the exhaust gas is reduced to be consistent with the flow rate of the nitrogen and the content of CO in the exhaust gas is reduced to 0, the stable reaction stage is finished;
e. and (3) at the end stage of the reaction: keeping the temperature in the rail kiln at 1560-1580 ℃, keeping the nitrogen gas introduced into the rail kiln for 50L/min, stopping heat supply after 3 hours, stopping nitrogen supply after the temperature in the furnace is reduced to 600 ℃, gradually cooling to room temperature, taking out a reaction block after the reaction is finished, and detecting, wherein the mass percentage of TiN is 39.8%, the mass percentage of TiCN is 19.6%, the mass percentage of TiN + TiCN is 59.4%, the mass percentage of Fe is 34.5%, and the mass percentage of other components is 6.1%, thus obtaining the titanium-containing alloy. The density of the titanium-containing alloy prepared by the method is 3.2g/cm 3 And making into cuboid shape.
Referring to fig. 3 and fig. 4, a part of the samples prepared in example 3 is taken, and SEM scanning analysis shows that the obtained microscopic morphology is as shown in fig. 3, as can be seen from fig. 3, the titanium-containing alloy prepared in this example has tightly and densely bonded interior, relatively uniform overall, and crystalline substances exist in a part of the area, and as can be seen from fig. 3, the composition result is as shown in fig. 4 by analyzing the point of cross-shaped bonding spectrum (EDS) at the cross mark, as can be seen from fig. 4, the titanium-containing alloy prepared in this example has high purity crystalline substances of Ti, N, and C, and as can be seen from fig. 1~4, the titanium-containing alloy finished product prepared in this example has compounds of TiN and TiCN, and the contents of each substance in different batches of finished products are slightly different.
Example 4
The titanium-containing alloy for metallurgy is prepared from the following raw materials in parts by weight: 100 parts of ilmenite concentrate powder, 52 parts of titanium dioxide powder, 58 parts of carbonaceous reducing agent, 6 parts of sodium carbonate, 26 parts of iron powder and 10 parts of adhesive.
The particle size of the ilmenite concentrate powder in this example is 380 mesh, wherein TiO 2 The mass percentage content of (A) is 56%; the granularity of the titanium dioxide powder is 430 meshes, wherein the TiO powder 2 The mass percentage content of the compound is 94 percent; the carbonaceous reducing agent is coke, the granularity is 200 meshes, the effective C content is 95.2 percent, the sodium carbonate is industrial grade sodium carbonate, and the granularity is 480 meshes; the granularity of the iron powder is 360 meshes, wherein the mass percentage of Fe is 97.5%; the adhesive is aluminum dihydrogen phosphate.
The low-cost production method of the titanium-containing alloy comprises the following steps:
(1) Prefabrication of raw materials: uniformly mixing ilmenite concentrate powder, titanium dioxide powder, a carbonaceous reducing agent, sodium carbonate, iron powder and an adhesive according to a formula ratio, pressing into a reaction block (the reaction block is in a square brick shape, and the size of the reaction block is 22cm by 11cm) under the pressure of 9MPa, placing the reaction block in a room, airing at normal temperature, and then placing the reaction block in a low-temperature drying furnace at the temperature of 240 ℃ for drying until the moisture is 0.7% for later use;
(2) Charging: adding the reaction block prepared in the step (1) into a closed rail kiln type heating device, wherein the feeding amount accounts for 66% of the inner volume of the rail kiln, and the pressure in the furnace is adjusted to be 0.11-0.115MPa; the inner volume of the track kiln type heating device is 38m 3 The system is electrically heated, and a gas discharge device and a gas analyzer are arranged at the head end and the tail end of the rail kiln, wherein the gas discharge device is used for keeping micro-positive pressure required by the system and discharging gas generated in the reaction process, and the gas analyzer is provided with a group of sampling probes at the head end and the tail end of the rail kiln respectively and used for detecting the flow rate of the discharged gas and the content of CO in the discharged gas;
(3) And (3) carrying out a carbothermic reduction process:
a. the initial stage of the reaction: electrifying for heating, gradually raising the temperature in the track kiln from room temperature to 500 ℃, wherein the temperature raising rate is 140 ℃/h, and at the moment, the air in the kiln begins to be discharged;
b. a rapid temperature rise stage:introducing nitrogen into the track kiln for 35L/min, raising the temperature in the track kiln to 1000 ℃ at a temperature rise speed of 240 ℃/h, and beginning to generate C and TiO in the reaction block at the stage 2 The reaction of (2) can show that the content of CO in the exhaust gas is gradually increased from a gas analyzer, and meanwhile, the nitriding reaction of Ti is carried out;
c. a reaction acceleration stage: continuously keeping introducing nitrogen into the track kiln for 45L/min, heating the temperature in the track kiln to 1500 ℃ at a heating rate of 420 ℃/h, continuously increasing the gas emission of the track kiln and the CO content in the gas at the stage, rapidly carrying out carbon thermal reaction, gathering heat in the kiln, and keeping the temperature in the kiln stable through automatic adjustment;
d. and (3) a reaction stabilization stage: continuously keeping the nitrogen gas introduced into the track kiln for 60L/min, keeping the temperature in the track kiln at 1550-1570 ℃, immediately increasing the nitrogen gas supply to 80L/min when the reaction block in the track kiln is in a stable carbothermic reaction stage, detecting that the flow of the discharged gas reaches the peak and tends to be stable through a gas analyzer, gradually transitioning the reaction from the carbothermic reduction and nitridation synchronous process to a full nitridation process, and controlling a flow valve of the discharged gas and a pressure stabilizing valve to ensure that the pressure in the track kiln is always at a micro positive pressure of 0.11-0.15 MPa; when the flow rate of the exhaust gas is reduced to be consistent with the flow rate of the nitrogen and the content of CO in the exhaust gas is reduced to 0, the stable reaction stage is finished;
e. and (3) at the end stage of the reaction: keeping the temperature in the rail kiln at 1550-1570 ℃, keeping the nitrogen gas introduced into the rail kiln for 48L/min, stopping heat supply after 2.5 hours, stopping nitrogen supply after the temperature in the furnace is reduced to 600 ℃, gradually cooling to room temperature, taking out a reaction block after the reaction is finished, and detecting, wherein the mass percentage of TiN is 35.6%, the mass percentage of TiCN is 19.8%, the mass percentage of TiN + TiCN is 55.4%, the mass percentage of Fe is 34.6%, and the other components are 10%, so as to obtain the titanium-containing alloy. The density of the titanium-containing alloy prepared by the method is 3.5g/cm 3 And making into cuboid shape.
Example 5
The titanium-containing alloy for metallurgy is prepared from the following raw materials in parts by weight: 100 parts of ilmenite concentrate powder, 52 parts of titanium dioxide powder, 59 parts of carbonaceous reducing agent, 7 parts of sodium carbonate, 22 parts of iron powder and 10 parts of adhesive.
The particle size of the ilmenite concentrate powder in this example is 320 mesh, wherein TiO 2 The mass percentage content of (A) is 57%; the granularity of the titanium dioxide powder is 440 meshes, wherein the TiO powder is TiO 2 The mass percentage content of the compound is 94 percent; the carbonaceous reducing agent is graphite with the granularity of 200 meshes, the effective C content is 93.5 percent, and the sodium carbonate is industrial-grade sodium carbonate with the granularity of 500 meshes; the granularity of the iron powder is 320 meshes, wherein the mass percentage of Fe is 98%; the adhesive is water glass.
The low-cost production method of the titanium-containing alloy comprises the following steps:
(1) Prefabrication of raw materials: uniformly mixing ferrotitanium concentrate powder, titanium dioxide powder, a carbonaceous reducing agent, sodium carbonate, iron powder and an adhesive according to a formula ratio, pressing into a reaction block (the reaction block is in a square brick shape, and the size of the reaction block is 25cm 10 cm) under the pressure of 7MPa, placing the reaction block in a room, airing at normal temperature, placing the reaction block in a low-temperature drying furnace at the temperature of 150 ℃, and drying until the moisture is 0.8% for later use;
(2) Charging: adding the reaction block prepared in the step (1) into a closed track kiln type heating device, wherein the feeding amount accounts for 62% of the inner volume of the track kiln, and the pressure in the furnace is adjusted to be 0.11-0.115MPa; the inner volume of the track kiln type heating device is 40m 3 The system adopts electric heating, a gas discharge device and a gas analyzer are arranged at the head end and the tail end of the track kiln, the gas discharge device is used for keeping micro-positive pressure required by the system and discharging gas generated in the reaction process, and the gas analyzer is respectively provided with a group of sampling probes at the head end and the tail end of the track kiln and is used for detecting the flow rate of the discharged gas and the content of CO in the discharged gas;
(3) And (3) carrying out a carbothermic reduction process:
a. the initial stage of the reaction: electrifying for heating, gradually raising the temperature in the track kiln from room temperature to 500 ℃, wherein the temperature raising rate is 125 ℃/h, and at the moment, the air in the kiln begins to be discharged;
b. a rapid temperature rise stage: introducing nitrogen into the track kiln for 20L/min, raising the temperature in the track kiln to 1000 ℃ at the temperature rise speed of 210 ℃/h, and beginning to generate C and TiO in the reaction block at the stage 2 FromThe gas analyzer can display that the content of CO in the exhaust gas is gradually increased, and meanwhile, the nitriding reaction of Ti is carried out;
c. and (3) a reaction acceleration stage: continuously keeping the nitrogen gas introduced into the track kiln for 20L/min, heating the temperature in the track kiln to 1500 ℃ at the heating rate of 430 ℃/h, continuously increasing the gas emission of the track kiln and the CO content in the gas at the stage, rapidly carrying out the carbon thermal reaction, gathering heat in the kiln, and keeping the temperature in the kiln stable through automatic adjustment;
d. and (3) a reaction stabilization stage: continuously keeping introducing 55L/min of nitrogen into the rail kiln, keeping the temperature in the rail kiln at 1530-1550 ℃, enabling a reaction block in the rail kiln to be in a stable carbothermic reaction stage, immediately increasing the nitrogen supply to 85L/min when detecting that the flow of the discharged gas reaches a peak and tends to be stable through a gas analyzer, gradually transitioning the reaction from a carbothermic reduction and nitridation synchronous process to a full-nitridation process, and controlling a discharged gas flow valve and a pressure stabilizing valve to ensure that the pressure in the rail kiln is always at a micro-positive pressure of 0.11-0.15 MPa; when the flow rate of the exhaust gas is reduced to be consistent with the flow rate of the nitrogen and the content of CO in the exhaust gas is reduced to 0, the stable reaction stage is finished;
e. and (3) at the end stage of the reaction: keeping the temperature in the rail kiln at 1530-1550 ℃, keeping the nitrogen gas introduced into the rail kiln at 42L/min, stopping heat supply after 2 hours, stopping nitrogen supply after the temperature in the furnace is reduced to 600 ℃, gradually cooling to room temperature, taking out a reaction block after the reaction is finished, and detecting, wherein the mass percent of TiN is 39.6%, the mass percent of TiCN is 19.5%, the mass percent of TiN + TiCN is 59.1%, the mass percent of Fe is 30.7%, and the mass percent of other components is 11.2%, so as to obtain the titanium-containing alloy. The density of the titanium-containing alloy prepared by the method is 3.3g/cm 3 And making into cuboid shape.
Referring to FIG. 5, FIG. 5 is an XRD spectrum of the composition analysis of part of the finished product containing titanium alloy obtained in example 5 of the present invention.
As can be seen from FIG. 5, the titanium-containing alloy finished product mainly contains TiN and TiCN, and does not contain TiOx titanium oxides, and the reaction is complete and complete.
The titanium-containing alloy prepared by the embodiment is used for screw-thread steel smelting, and can replace 0.4-0.5kg of 70 ferrovanadium (namely 70% of vanadium) when 1kg of the titanium-containing alloy is added, and the cost of the ferrovanadium is about 5-8 times of that of the titanium-containing alloy according to the conventional preparation cost, so that the advantage of the cost of the titanium-containing alloy is obvious, the production flow is short, and the method is more environment-friendly.
Claims (8)
1. The titanium-containing alloy for metallurgy is characterized by being prepared from the following raw materials in parts by weight:
ferrotitanium concentrate powder 100 parts
50-60 parts of titanium dioxide powder
50-60 parts of carbonaceous reducing agent
5-10 parts of sodium carbonate
20-30 parts of iron powder
10-20 parts of an adhesive.
2. The titanium-containing alloy for metallurgy according to claim 1, which is prepared from the following raw materials in parts by weight:
ferrotitanium concentrate powder 100 parts
52-58 parts of titanium dioxide powder
52-58 parts of carbonaceous reducing agent
6-9 parts of sodium carbonate
22-28 parts of iron powder
12-18 parts of an adhesive.
3. The titanium-containing alloy for metallurgy according to claim 1, which is prepared from the following raw materials in parts by weight:
ferrotitanium concentrate powder 100 parts
55 parts of titanium dioxide powder
55 portions of carbonaceous reducing agent
Sodium carbonate 7 parts
Iron powder 25 parts
15 parts of adhesive.
4. A metallurgical titanium-containing alloy according to any one of claims 1 to 3, wherein: the granularity of the ilmenite concentrate powder is 300-400 meshes, whereinTiO 2 The mass percentage content of the compound is 55-60%; the granularity of the titanium dioxide powder is 400-500 meshes, wherein TiO 2 The mass percentage content of the active ingredients is 92-95 percent; the carbonaceous reducing agent is any one of graphite or coke, the granularity is 180-200 meshes, the effective C content is more than or equal to 90%, the sodium carbonate is industrial-grade sodium carbonate, and the granularity is 450-500 meshes; the granularity of the iron powder is 300-400 meshes, wherein the mass percentage of Fe is more than or equal to 96%; the adhesive is one or two of water glass and aluminum dihydrogen phosphate.
5. A low cost process for the production of a metallurgical titanium-containing alloy according to any one of claims 1 to 3, comprising the steps of:
(1) Prefabrication of raw materials: uniformly mixing ilmenite concentrate powder, titanium dioxide powder, a carbonaceous reducing agent, sodium carbonate, iron powder and an adhesive according to a formula ratio, pressing the mixture into a reaction block under the pressure of 5-10MPa, placing the reaction block in a room, airing the reaction block at normal temperature, placing the reaction block in a low-temperature drying furnace at the temperature of 100-300 ℃ and drying the reaction block until the moisture is less than or equal to 1% for later use;
(2) Charging: adding the reaction block prepared in the step (1) into a closed track kiln type heating device, wherein the feeding amount accounts for 60-70% of the inner volume of the track kiln, and the pressure in the furnace is adjusted to be 0.11-0.115MPa; the inner volume of the track kiln type heating device is 30-40m 3 The system adopts electric heating, a gas discharge device and a gas analyzer are arranged at the head end and the tail end of the track kiln, the gas discharge device is used for keeping micro-positive pressure required by the system and discharging gas generated in the reaction process, and the gas analyzer is respectively provided with a group of sampling probes at the head end and the tail end of the track kiln and used for detecting the flow rate of the discharged gas and the content of CO in the discharged gas;
(3) And (3) carrying out a carbothermic reduction process:
a. the initial stage of the reaction: electrifying and heating to gradually raise the temperature in the track kiln from room temperature to 500 ℃, wherein the temperature raising rate is 120-150 ℃/h, and at the moment, the air in the kiln begins to be discharged;
b. a rapid temperature rise stage: introducing nitrogen into the track kiln for 10-50L/min, raising the temperature in the track kiln to 1000 ℃ at a temperature rise speed of 200-250 ℃/h, and beginning to generate C and TiO in the reaction block at the stage 2 ToIt should be noted that the CO content in the exhaust gas was gradually increased as it was shown from the gas analyzer, accompanied by the nitriding reaction of Ti;
c. and (3) a reaction acceleration stage: continuously keeping the nitrogen gas to be introduced into the track kiln for 10-50L/min, heating the temperature in the track kiln to 1500 ℃ at the heating rate of 400-500 ℃/h, continuously increasing the gas emission and the CO content in the gas in the track kiln at the stage, quickly carrying out the carbon thermal reaction, gathering heat in the kiln, and keeping the temperature in the kiln stable through automatic adjustment;
d. and (3) a reaction stabilization stage: continuously keeping the nitrogen gas introduced into the track kiln at 50-80L/min, keeping the temperature in the track kiln at 1520-1580 ℃, keeping the reaction block in the track kiln at a stable carbothermic reaction stage, immediately increasing the nitrogen gas supply to 80-100L/min when detecting that the flow of the discharged gas reaches a peak and tends to be stable through a gas analyzer, gradually transitioning the reaction from the synchronous process of carbothermic reduction and nitridation to a full-nitridation process, and controlling a flow valve of the discharged gas and a pressure stabilizing valve to ensure that the pressure in the track kiln is always at a micro positive pressure of 0.11-0.15 MPa; when the flow rate of the exhaust gas is reduced to be consistent with the flow rate of the nitrogen and the content of CO in the exhaust gas is reduced to 0, the stable reaction stage is finished;
e. and (3) at the end stage of the reaction: keeping the temperature in the rail kiln at 1520-1580 ℃, keeping introducing nitrogen into the rail kiln for 40-50L/min, stopping supplying heat after 2-3 hours, stopping supplying nitrogen after the temperature in the furnace is reduced to 600 ℃, gradually reducing the temperature to room temperature, taking out a reaction block after the reaction is finished, and detecting, wherein the mass percentage of TiN is 35-40%, the mass percentage of TiCN is 15-20%, the mass percentage of TiN and TiCN is 50-60%, the mass percentage of Fe is 30-35%, and the mass percentage of other components is 6-12%, so that the titanium-containing alloy is obtained.
6. A low cost process according to claim 5, wherein the titanium alloy is produced by: the reaction block prepared in the step (1) is in a square brick shape, the length of the square brick is 20-25cm, the width of the square brick is 12-15cm, and the height of the square brick is 12-15cm.
7. The low cost titanium-containing alloy of claim 5The production method is characterized in that: the density of the titanium-containing alloy is 3.0-4.0g/cm 3 It can be made into block, granule or powder.
8. A low cost process for the production of titanium-containing alloys as claimed in claim 7 wherein: the granular or powdery titanium-containing alloy can be wrapped by iron sheet to make into cored wire.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6855290A (en) * | 1989-12-30 | 1991-07-11 | Industrial Research Limited | Process for manufacturing ceramic-metal composites |
| CN102153135A (en) * | 2010-12-30 | 2011-08-17 | 重庆大学 | Method for preparing titanium carbonitride from ilmenite with high impurity content |
| CN102277522A (en) * | 2011-07-28 | 2011-12-14 | 四川省川威集团有限公司 | Method for producing vanadium and nitrogen alloy |
| CN104313310A (en) * | 2014-10-10 | 2015-01-28 | 昆明理工大学 | Method for adding silicon iron powder to increase carbon thermal reduction velocity of vanadium-titanium magnetite concentrate |
| CN104846258A (en) * | 2015-05-29 | 2015-08-19 | 攀枝花学院 | Method for preparing iron-based (V, Ti) CN compound powder |
| CN106498108A (en) * | 2016-09-30 | 2017-03-15 | 江西理工大学 | DRI and nitrogen are produced with titanomagnetite concentrate（Carbon）The method for changing titanium |
| CN108080648A (en) * | 2017-12-18 | 2018-05-29 | 北京科技大学 | A kind of method that Fe/TiC composite granules are prepared in situ in vacuum carbothermal reduction |
| CN108424147A (en) * | 2018-02-12 | 2018-08-21 | 吉林长玉特陶新材料技术股份有限公司 | A kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve |
| CN109694982A (en) * | 2019-03-13 | 2019-04-30 | 湖北晶洋科技股份有限公司 | The preparation process of VN alloy |
| WO2020170223A1 (en) * | 2019-02-22 | 2020-08-27 | University Of Johannesburg | Titanium carbonitride |
| CN113462842A (en) * | 2021-05-31 | 2021-10-01 | 钢研晟华科技股份有限公司 | Method for preparing high-titanium slag powder and metal iron powder by reducing ilmenite concentrate powder at low temperature |
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6855290A (en) * | 1989-12-30 | 1991-07-11 | Industrial Research Limited | Process for manufacturing ceramic-metal composites |
| CN102153135A (en) * | 2010-12-30 | 2011-08-17 | 重庆大学 | Method for preparing titanium carbonitride from ilmenite with high impurity content |
| CN102277522A (en) * | 2011-07-28 | 2011-12-14 | 四川省川威集团有限公司 | Method for producing vanadium and nitrogen alloy |
| CN104313310A (en) * | 2014-10-10 | 2015-01-28 | 昆明理工大学 | Method for adding silicon iron powder to increase carbon thermal reduction velocity of vanadium-titanium magnetite concentrate |
| CN104846258A (en) * | 2015-05-29 | 2015-08-19 | 攀枝花学院 | Method for preparing iron-based (V, Ti) CN compound powder |
| CN106498108A (en) * | 2016-09-30 | 2017-03-15 | 江西理工大学 | DRI and nitrogen are produced with titanomagnetite concentrate（Carbon）The method for changing titanium |
| CN108080648A (en) * | 2017-12-18 | 2018-05-29 | 北京科技大学 | A kind of method that Fe/TiC composite granules are prepared in situ in vacuum carbothermal reduction |
| CN108424147A (en) * | 2018-02-12 | 2018-08-21 | 吉林长玉特陶新材料技术股份有限公司 | A kind of method that Rapid Nitriding produces titanium carbonitride, nitrogenizes titanium valve |
| WO2020170223A1 (en) * | 2019-02-22 | 2020-08-27 | University Of Johannesburg | Titanium carbonitride |
| CN109694982A (en) * | 2019-03-13 | 2019-04-30 | 湖北晶洋科技股份有限公司 | The preparation process of VN alloy |
| CN113462842A (en) * | 2021-05-31 | 2021-10-01 | 钢研晟华科技股份有限公司 | Method for preparing high-titanium slag powder and metal iron powder by reducing ilmenite concentrate powder at low temperature |
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