CN102953029A - Surface treatment method for titanium sponge reactor - Google Patents
Surface treatment method for titanium sponge reactor Download PDFInfo
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- CN102953029A CN102953029A CN2011102494040A CN201110249404A CN102953029A CN 102953029 A CN102953029 A CN 102953029A CN 2011102494040 A CN2011102494040 A CN 2011102494040A CN 201110249404 A CN201110249404 A CN 201110249404A CN 102953029 A CN102953029 A CN 102953029A
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Abstract
The invention provides a surface treatment method for a titanium sponge reactor. The method includes that an electrothermal material containing metal titanium disposed in the titanium sponge reactor is electrified under the condition that the pressure in the titanium sponge reactor is lower than 1Pa, and titanium in the electrothermal material containing the metal titanium is sublimated under the condition of electrification to form a titanized layer on an inner surface of the titanium sponge reactor. The titanized layer of the titanium sponge reactor obtained after being treated by the method covers on the inner surface of the reactor completely and uniformly, so that the content of reactor impurities in titanium sponge is further lowered when the reactor is used for preparing titanium sponge.
Description
Technical field
The present invention relates to smelting field of nonferrous metal, particularly, relate to a kind of surface treatment method of titanium sponge reactor.
Background technology
Titanium metal is owing to having the excellent properties such as high temperature resistant, low temperature resistant, anti-strong acid, anti-highly basic, high strength and low density, have a wide range of applications in every respect, comprise space flight (jet engine, guided missile and spacecraft), military affairs, chemical industry (chemical industry and petroleum product, sea water desaltination and papermaking), automobile, Agrifood, medical science (artifucial limb, orthopaedics transplanting and dental appliance and weighting material), sporting goods, jewelry and mobile phone etc.
The smelting of titanium metal mainly comprises the preparation process of " titanium sponge " (a kind of ventilative titanium metal form) and the step that the fusing titanium sponge forms the titanium metal ingot casting.Particularly, the preparation process of " titanium sponge " (a kind of ventilative titanium metal form) comprising: and the usefulness titanium ore (such as ilmenite, FeTiO
3) the preparation titanium tetrachloride, then with magnesium the titanium elements in the titanium tetrachloride is reduced to prepare titanium sponge.
In detail, the method for preparing titanium sponge comprises: in the titanium sponge reactor, under the temperature about 850 ℃ and under the vacuum condition, magnesium is contacted with titanium tetrachloride, generate titanium sponge and magnesium chloride; Then under the temperature about 1000 ℃ and under the vacuum condition, magnesium chloride and excessive magnesium are removed with gas phase.
Wherein, the material of titanium sponge reactor is generally stainless steel or carbon steel etc., and under 800-1050 ℃ hot conditions, reactor material can permeate in titanium sponge, thereby reduces the purity of titanium sponge.Therefore, must process the surface of titanium sponge reactor, be polluted by reactor material to prevent titanium sponge.
The treatment process of titanium sponge reactor can comprise that the internal surface to the titanium sponge reactor oozes the titanium processing, namely oozes titanium layer in the internal surface formation of titanium sponge reactor; Specifically can comprise: after acid dipping, washing deacidification and drying dewatered, evenly brushing was at the reactor internal surface with titanium valve with reactor, and after ℃ heating of 950-1050 under the vacuum, titanium oozes titanium layer in the internal surface formation of reactor.Aforesaid method helps to reduce the content of reactor impurity in the titanium sponge.
But aforesaid method processes that the titanium sponge reactor obtains, and to ooze titanium layer sufficiently complete and even, so be difficult to further reduce the content of reactor material in the titanium sponge for the preparation of titanium sponge the time.
Summary of the invention
The objective of the invention is to ooze the sufficiently complete and uniform defective of titanium layer for what the surface treatment method that overcomes existing titanium sponge reactor obtained, a kind of surface treatment method that can further reduce the titanium sponge reactor of reactor material content in the titanium sponge for the preparation of titanium sponge the time is provided.
To achieve these goals, the invention provides a kind of surface treatment method of titanium sponge reactor, the method comprises: the pressure in the titanium sponge reactor is lower than under the 1Pa, the thermo electric material that contains metal titanium that is opposite in this titanium sponge reactor is switched on, the condition of energising forms with the internal surface at described titanium sponge reactor and oozes titanium layer so that this contains the titanium distillation in the thermo electric material of metal titanium.
Pass through technique scheme, the titanium sponge reactor that obtains after using the surface treatment method of titanium sponge reactor provided by the invention to process to ooze titanium layer complete and be covered in equably the internal surface of described reactor, thereby for the preparation of titanium sponge the time, further reduced reactor foreign matter content in the titanium sponge.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Description of drawings
Fig. 1 is the schematic diagram of the superficial treatment system of titanium sponge reactor.
Description of reference numerals
10 reactor tank bodies, 20 reactor caps, 30 electric heating titanium sublimers
11 thermoscopes, 12 insulation shells, 21 electrodes
22 pneumatic outlets, 23 gas inletes, 24 insulation rings
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
In the present invention, in the situation that do not do opposite explanation, the concept of use " distillation " refers at solid under the condition of the vapour pressure under a certain temperature greater than ambient pressure, is directly become the process of gas phase by solid phase.
The invention provides a kind of surface treatment method of titanium sponge reactor, the method comprises: the pressure in the titanium sponge reactor is below 1Pa, the thermo electric material that contains metal titanium that is opposite in this titanium sponge reactor is switched on, the condition of energising forms with the internal surface at described titanium sponge reactor and oozes titanium layer so that this contains the titanium distillation in the thermo electric material of metal titanium.
Wherein, the selection of titanium sponge reactor does not have special requirement, can be the various titanium sponge reduction distillation reactors of routine, for example, can be document (Zhu Yonghong etc., the selection of titanium sponge reduction distillation reactor, the titanium industrial progress, 2004,21 (6), 40-43 page or leaf) unlike material of being produced by different manufacturers of enumerating in or the titanium sponge reactor of different size.
Wherein, can by conventional air-exhaust method, the pressure in the titanium sponge reactor be remained on below the 1Pa, for example, can be behind airtight titanium sponge reactor, with the pneumatic outlet of vacuum fan by arranging on the described titanium sponge reactor, with the Pressure Drop in the described titanium sponge reactor to 1Pa.
Wherein, the thermo electric material that will contain metal titanium place in the described titanium sponge reactor mode can for: two electrodes are set and are electrically connected on the thermo electric material that contains metal titanium between two described electrodes at the lid of described titanium sponge reactor, the described thermo electric material that contains metal titanium is positioned at the tank body of described titanium sponge reactor.
Wherein, known in the art is that below the fusing point of titanium, when pressure was lower than the saturation vapour pressure of solid titanium, titanium just can distil.The temperature and pressure control of titanium distillation can be the method for routine, the present invention does not repeat them here, for example can with titanium sublimation pump in control method same or similar, namely, be lower than under the ambient pressure of 1Pa, by giving the described mode that contains the thermo electric material energising of metal titanium, the described temperature that contains the thermo electric material of metal titanium is increased to the saturation vapour pressure of titanium more than or equal to the temperature of described ambient pressure.Titanium is pressed in open source literature (P.D.Desai et al. at saturated vapo(u)r at each temperature, Thermodynamic properties of titanium., INTERNATIONAL JOURNAL OF THERMOPHYSICS, 1987,8 (6), on the books 781-794), for example the saturated vapo(u)r of titanium is pressed in 1569 ℃ of lower 0.1Pa of being.
Wherein, the maintenance of the pressure in the titanium sponge reactor can be below 1Pa, preferably below 0.9Pa, more preferably below 0.8Pa, further preferably below 0.7Pa, further preferably below 0.6Pa, below 0.5Pa.
Wherein, after titanium distils from the described thermo electric material that contains titanium, namely can form at the internal surface of described titanium sponge reactor and ooze titanium layer.Particularly, the process that titanium oozes titanium layer in the internal surface formation of described titanium sponge reactor may be: under certain pressure, after the titanium distillation, form titanium tetrachloride vapor, titanium tetrachloride vapor contacts with the internal surface of described titanium sponge reactor, the temperature of the internal surface of described titanium sponge reactor is lower than the titanium sublimation point under this pressure, thereby titanium tetrachloride vapor sublimates in the internal surface of described titanium sponge reactor, and can form by the internal surface that is diffused in described titanium sponge reactor and ooze titanium layer.
The method according to this invention, wherein, the amount of oozing the titanium of titanium layer in the internal surface formation of described titanium sponge reactor does not have special requirement, can control according to actual needs by the method for routine, in order further to improve integrity degree and the homogeneity ooze titanium layer, under the preferable case, the inner surface area of the described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is 45-225g, more preferably 90-180g.
Wherein, the distillation amount of titanium is calculated with the mass loss of thermo electric material, and the quality that namely deducts the thermo electric material before processing with the quality of the thermo electric material after processing is determined.
The method according to this invention, in order further to improve integrity degree and the homogeneity of oozing titanium layer, under the preferable case, wherein, described internal surface at described titanium sponge reactor forms the condition of oozing titanium layer and comprises: the pressure in the titanium sponge reactor is below the 0.1-1Pa, under the condition of carrying out described energising, the temperature of described titanium sponge wall of reactor is remained under 920-1050 ℃, further preferably remain under 950-1020 ℃.Wherein, the method that the temperature of described titanium sponge wall of reactor is remained on above-mentioned scope can realize by the described mode that contains the thermo electric material heating of titanium of indirect heating and/or energising.
Wherein, under the preferable case, described internal surface at described titanium sponge reactor forms the condition of oozing titanium layer and also comprises: carrying out under the condition of described energising, the time of maintenance is 15-35 hour, further preferred 20-30 hour.
Wherein, under the preferable case, the described thermo electric material of titanium that contains is along the internal surface setting of the tank body of described titanium sponge reactor; Particularly, the described thermo electric material of titanium that contains is along the parallel direction setting of the tangent line of the internal surface closest approach of the tank body of described titanium sponge reactor.
Wherein, under the preferable case, the distance between the closest approach of the internal surface of described titanium sponge reactor and the described thermo electric material that contains titanium is that this internal surface is to the 1-10% of distance between another internal surface on the other side.In this distance range, can either guarantee when the thermo electric material that contains titanium is switched on, not damage the inwall of titanium sponge reactor, the titanium of distillation is contacted with the internal surface of titanium sponge reactor fast, form and ooze titanium layer.Described titanium sponge reactor can be different shape, can be the cylindrical cube shaped or square bodily form.When described titanium sponge reactor when being cylindrical, this internal surface of described titanium sponge reactor is the internal diameter of described titanium sponge reactor to distance between another internal surface on the other side.
Wherein, the described thermo electric material that contains metal titanium is used for providing the titanium of distillation, ooze titanium layer with the internal surface formation at described titanium sponge reactor, thereby make described titanium sponge reactor for the preparation of titanium sponge the time, reduce the foreign matter content in the titanium sponge, the particularly content of reactor impurity.Thereby, should avoid the material except titanium in the described thermo electric material that contains metal titanium to mix as far as possible and ooze titanium layer, that is, be chosen under the described titanium sublimation condition, do not produce the thermo electric material that contains metal titanium of other gaseous substance except titanium.
According to method of the present invention, wherein, the described selection that contains the thermo electric material of metal titanium does not have special requirement, get final product so long as can be used for carrying out the titanium distillation, what for example, the described thermo electric material that contains metal titanium can be in electric resistor heating type titanium thermo electric material, thermal conduction formula titanium thermo electric material and the radiant heating type titanium thermo electric material is at least a.
Wherein, electric resistor heating type titanium thermo electric material refers to the metallic substance that contains titanium as resistance; In when energising, this contains in the metallic substance of titanium has electric current to pass through, because the heat effect of electric current, the temperature of described electric resistor heating type titanium thermo electric material raises, until reach the temperature of titanium distillation.
Wherein, thermal conduction formula titanium thermo electric material refers to that the metal that contains titanium is wrapped on the good conductor of heat, and this hot good conductor has electrical insulating property and the inner material that is provided with nichrome wire; When energising, this metal that contains titanium does not have electric current to pass through, and has electric current to pass through in this nichrome wire, because the heat effect of electric current, the temperature of described nichrome wire raises, and by heat conducting mode, the temperature of the metal that contains titanium is raise, until reach the temperature of titanium distillation; For example, thermal conduction formula titanium thermo electric material can be to be provided with the material that parcel titanium band forms on the beryllium oxide ceramics of rhenium tungsten nichrome wire with inside.
Wherein, radiant heating type titanium thermo electric material refers to contain the material that is provided with nichrome wire in the chamber of metal hollow of titanium; When energising, this metal that contains titanium does not have electric current to pass through, and has electric current to pass through in this nichrome wire, because the heat effect of electric current, the temperature of described nichrome wire raises, and by thermal-radiating mode, the temperature of the metal that contains titanium is raise, until reach the temperature of titanium distillation; For example, radiant heating type titanium thermo electric material can be the hollow titanium ball that is provided with tungsten filament in the chamber.
The method according to this invention, wherein, under the preferable case, the described thermo electric material that contains metal titanium is the electric resistor heating type thermo electric material.
Wherein, under the preferable case, described electric resistor heating type thermo electric material is the titaniferous wire and/or is enclosed with titaniferous Metallic rod wiry.Described titaniferous wire is at least a in titanium silk, titanium-tungsten alloy silk, titanium tantalum alloy silk and the titanium maxter alloy silk.Described Metallic rod is at least a in tungsten bar, tantalum bar and the molybdenum rod.
The method according to this invention, wherein, in order further to improve integrity degree and the homogeneity of oozing titanium layer, under the preferable case, described method also comprises: before the temperature of distillation occurs the described thermo electric material that contains metal titanium of heating to the titanium in the described thermo electric material that contains metal titanium, be lower than under the pressure of 1Pa, heat de-airing carried out in the inside of described titanium sponge reactor process; Described heat de-airing is processed at least one in may further comprise the steps: the temperature of the described titanium sponge wall of reactor of (1) heating is to 190-210 ℃ and kept 2-4 hour; (2) temperature of the described titanium sponge wall of reactor of heating is to 390-410 ℃ and kept 3-5 hour; (3) temperature of the described titanium sponge wall of reactor of heating is to 790-810 ℃ and kept 1-2 hour.In the preferred situation, described heat de-airing is processed the step that comprises above-mentioned (1) to (3) of carrying out successively.Wherein, the method that the temperature of described titanium sponge wall of reactor is remained on above-mentioned scope can realize by the described mode that contains the thermo electric material heating of titanium of indirect heating and/or energising.
Wherein, in order further to improve integrity degree and the homogeneity of oozing titanium layer, under the preferable case, described method also comprises: before the inside of described titanium sponge reactor being carried out the heat de-airing processing, inwall to described titanium sponge reactor carries out pickling, washing and dry operation, with the corrosion thing on the inwall of removing described titanium sponge reactor, oil and other pollutent.
The method according to this invention, wherein, to ooze titanium layer more complete and even in order to make, described method also comprises: the internal surface of described titanium sponge reactor form ooze titanium layer after, under protection of inert gas, with described titanium sponge reactor cooling to 25-50 ℃.
Wherein, the amount of being filled with of rare gas element does not have special requirement, and for example, the amount of being filled with of rare gas element can be so that the pressure in the described titanium sponge reactor raises gets final product for 4.9-24.5kPa.Described rare gas element can be in helium, neon, argon, krypton and the xenon at least a, be preferably argon.
The method provided by the invention preferably superficial treatment system of a kind of titanium sponge reactor by is as schematically shown in Figure 1 carried out, and with reference to figure 1, this system comprises: reactor tank body 10 and reactor cap 20, and described reactor tank body 10 has opening; Described reactor cap 20 removably connects described reactor tank body 10, to seal described opening; Be provided with at least two electrodes 21 and at least one electric heating titanium sublimer 30 on the described reactor cap 20, each electric heating titanium sublimer 30 is electrically connected with two described electrodes 21; Described electric heating titanium sublimer 30 is positioned at described reactor tank body 10.
Preferably, described electrode 21 circumferentially evenly distributes, and is projected in the described reactor tank body 10 along described reactor cap 20, can make the connection of electric heating titanium sublimer 30 and arrange more convenient.
Preferably, described electric heating titanium sublimer 30 is along the internal surface setting of described reactor tank body 10; Particularly, the described thermo electric material of titanium that contains is along the parallel direction setting of the tangent line of the internal surface closest approach of the tank body of described titanium sponge reactor; And the distance between the closest approach of the internal surface of described reactor tank body 10 and described electric heating titanium sublimer 30 is that this internal surface of described titanium sponge reactor is to the 1-10% of distance between another internal surface on the other side, in this distance range, can either guarantee to 30 energising of electric heating titanium sublimer the time, not damage the inwall of titanium sponge reactor, the titanium of distillation is contacted with the internal surface of described reactor tank body 10 fast, form and ooze titanium layer.Described titanium sponge reactor can be different shape, can be the cylindrical cube shaped or square bodily form.When described titanium sponge reactor when being cylindrical, this internal surface of described titanium sponge reactor is the internal diameter of described titanium sponge reactor to distance between another internal surface on the other side.
Preferably, described electric heating titanium sublimer 30 contains the described thermo electric material that contains titanium.Particularly, can be in electric resistor heating type titanium sublimer, thermal conduction formula electric heating titanium sublimer and the radiant heating type electric heating titanium sublimer at least a.
Wherein, electric resistor heating type titanium sublimer refers to contain the metallic substance of titanium as the titanium sublimer of resistance; In when energising, this contains in the metallic substance of titanium has electric current to pass through, because the heat effect of electric current, the temperature of described electric resistor heating type titanium sublimer raises, until reach the temperature of titanium distillation.
Preferably, described electric heating titanium sublimer 30 is electric resistor heating type titanium sublimer, and described electric resistor heating type titanium sublimer is titanium metal silk and/or the Metallic rod that is enclosed with the titanium metal silk; Described titanium metal silk is at least a in titanium silk, titanium-tungsten alloy silk, titanium tantalum alloy silk and the titanium maxter alloy silk; Described Metallic rod is at least a in tungsten bar, tantalum bar and the molybdenum rod.
Preferably, described system also comprises the pneumatic outlet 22 that is arranged on the described reactor cap 20, is beneficial to extract the gas in the described system out and reduces pressure near vacuum.
Preferably, described system also comprises the gas inlet 23 that is arranged on the described reactor cap 20, is beneficial to pass into the titanium layer that oozes that rare gas element is protected formation.
Preferably, described system also comprises the thermoscope 11 that is arranged on the described reactor tank body 10, is beneficial to measure the temperature of described reactor tank body 10, thereby the process that titanium is processed is oozed in control.
Preferably, described system also comprises insulation shell 12, and described insulation shell 12 holds described reactor tank body 10, is beneficial to described reactor tank body 10 and keeps oozing the temperature that titanium is processed.
Preferably, the edge of described reactor cap 20 is connected with insulation ring 24, and described insulation ring 24 removably is connected with described insulation shell 12, is beneficial to described reactor tank body 10 and keeps oozing the temperature that titanium is processed.
Preferably, described reactor cap 20 removably connects described reactor tank body 10 by flange.
More than describe preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can make up by any suitable mode, for example under the condition of carrying out described energising, the temperature of described titanium sponge wall of reactor is remained on 920-1050 ℃ of lower 15-35 hour.For fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Further describe by the following examples the present invention, but scope of the present invention is not limited in following examples.
Embodiment 1
Will available from the tank body of the I type titanium sponge reactor of climbing steel company (trade mark 1Cr18Ni9Ti, specification is erected type, internal diameter 0.18m, inner surface area are 2.12m
2, material is stainless steel) inwall after overpickling, washing and drying, by flange be used for the lid that this titanium sponge reactor cooperates and be connected.Be provided with two electrodes on this lid, (titanium content is greater than 98 % by weight to be connected with the titanium silk between described two electrodes, gross weight 2000g, diameter is 5mm), described titanium silk arranges evenly distributedly along the internal surface of the tank body of described titanium sponge reactor, and the distance between the closest approach of the internal surface of the tank body of described titanium sponge reactor and described titanium silk is 0.9cm.Also be provided with a gas feed and a pneumatic outlet on the lid of this reactor.
By described pneumatic outlet, with vacuum pump with the Pressure Drop in the tank body of described titanium sponge reactor to 1Pa, and stable to 0.5Pa.Then under 0.5Pa, (starting voltage is 15V to give described titanium silk energising, initial current is 600A), by regulating voltage and electric current the temperature of described titanium sponge wall of reactor was kept 3 hours successively under 200 ℃, keeping under 400 ℃ 4 hours and under 800 ℃, keeping 1.5 hours, then under 950-1020 ℃, kept 25 hours, when the temperature of wall of reactor is 950-1020 ℃, at this moment, the saturation vapour pressure that the temperature of titanium silk is higher than titanium is the temperature of 0.5Pa and the fusing point that is lower than titanium, thereby, titanium in the titanium silk distils, and the titanium of distillation forms on the wall surface of reactor and oozes titanium layer.After keeping 15 hours under 950-1020 ℃, by the gas inlet, passing into argon gas to pressure in the reactor is 12kPa, and then reactor being inserted and being cooled to the wall temperature in the condenser is 40 ℃, the titanium sponge reactor after namely obtaining processing.Take off the titanium silk in the titanium sponge reactor after the processing, claim to such an extent that weight is 1809.2g, i.e. the inner surface area of the described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is 90g.
According to document (Li Dacheng etc., the magnesiothermy titanium sponge is produced, metallurgical industry press, 2008) method in, use titanium sponge reactor after the processing that the present embodiment obtains to prepare label and be the Sponge Titanium of TG-100, the content of Ti is 99.78 % by weight in this Sponge Titanium, and the content of iron is 0.03 % by weight.
Embodiment 2
Will available from the tank body of the I type titanium sponge reactor of climbing steel company (trade mark 1Cr18Ni9Ti, specification is erected type, internal diameter 0.18m, inner surface area are 2.12m
2, material is stainless steel) inwall after overpickling, washing and drying, by flange be used for the lid that this titanium sponge reactor cooperates and be connected.Be provided with two electrodes on this lid, (titanium content is greater than 98 % by weight to be connected with the titanium silk between described two electrodes, gross weight 2000g, diameter is 5mm), described titanium silk arranges evenly distributedly along the internal surface of the tank body of described titanium sponge reactor, and the distance between the closest approach of the internal surface of the tank body of described titanium sponge reactor and described titanium silk is 0.3cm.Also be provided with a gas feed and a pneumatic outlet on the lid of this reactor.
By described pneumatic outlet, with vacuum pump with the Pressure Drop in the tank body of described titanium sponge reactor to 1Pa, and stable to 0.7Pa.Then under 0.7Pa, (starting voltage is 15V to give described titanium silk energising, initial current is 600A), the temperature that makes described titanium sponge wall of reactor by regulating voltage and electric current successively keep under 200 ℃ 3 hours, keeping under 400 ℃ 4 hours and under 800 ℃, keeping 1.5 hours, then under 950-1020 ℃, kept 25 hours, at this moment, the saturation vapour pressure that the temperature of titanium silk is higher than titanium is the temperature of 0.7Pa and the fusing point that is lower than titanium, thereby, titanium in the titanium silk under this temperature distils, and the titanium of distillation forms on the wall surface of reactor and oozes titanium layer.After keeping 35 hours under 950-1020 ℃, by the gas inlet, passing into argon gas to pressure in the reactor is 4.5kPa, and then reactor being inserted and being cooled to the wall temperature in the condenser is 25 ℃, the titanium sponge reactor after namely obtaining processing.Take off the titanium silk in the titanium sponge reactor after the processing, claim to such an extent that weight is 1718.4g, i.e. the inner surface area of the described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is 180g.
According to document (Li Dacheng etc., the magnesiothermy titanium sponge is produced, metallurgical industry press, 2008) method in, use titanium sponge reactor after the processing that the present embodiment obtains to prepare label and be the Sponge Titanium of TG-100, the content of Ti is 99.8 % by weight in this Sponge Titanium, and the content of iron is 0.03 % by weight.
Embodiment 3
Will available from the tank body of the I type titanium sponge reactor of climbing steel company (trade mark 1Cr18Ni9Ti, specification is erected type, internal diameter 0.18m, inner surface area are 2.12m
2, material is stainless steel) inwall after overpickling, washing and drying, by flange be used for the lid that this titanium sponge reactor cooperates and be connected.Be provided with two electrodes on this lid, (titanium content is greater than 98 % by weight to be connected with the titanium silk between described two electrodes, gross weight 2000g, diameter is 5mm), described titanium silk arranges evenly distributedly along the internal surface of the tank body of described titanium sponge reactor, and the distance between the closest approach of the internal surface of the tank body of described titanium sponge reactor and described titanium silk is 1.5cm.Also be provided with a gas feed and a pneumatic outlet on the lid of this reactor.
By described pneumatic outlet, with vacuum pump with the Pressure Drop in the tank body of described titanium sponge reactor to 1Pa, and stable to 0.2Pa.Then under 0.2Pa, (starting voltage is 15V to give described titanium silk energising, initial current is 600A), by regulating voltage and electric current the temperature of described titanium sponge wall of reactor was kept 3 hours successively under 200 ℃, keeping under 400 ℃ 4 hours and under 800 ℃, keeping 1.5 hours, then under 950-1020 ℃, kept 25 hours, when the temperature of wall of reactor is 950-1020 ℃, the saturation vapour pressure that the temperature of titanium silk is higher than titanium is the temperature of 0.2Pa and the fusing point that is lower than titanium, thereby, titanium in the titanium silk under this temperature distils, and the titanium of distillation forms on the wall surface of reactor and oozes titanium layer.After keeping 25 hours under 950-1020 ℃, by the gas inlet, passing into argon gas to pressure in the reactor is 22.5kPa, and then reactor being inserted and being cooled to the wall temperature in the condenser is 50 ℃, the titanium sponge reactor after namely obtaining processing.Take off the titanium silk in the titanium sponge reactor after the processing, claim to such an extent that weight is 1713g, i.e. the inner surface area of the described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is 135g.
According to document (Li Dacheng etc., the magnesiothermy titanium sponge is produced, metallurgical industry press, 2008) method in, use titanium sponge reactor after the processing that the present embodiment obtains to prepare label and be the Sponge Titanium of TG-100, the content of Ti is 99.75 % by weight in this Sponge Titanium, and the content of iron is 0.03 % by weight.
Embodiment 4
Will available from the tank body of the I type titanium sponge reactor of climbing steel company (trade mark 1Cr18Ni9Ti, specification is erected type, internal diameter 0.18m, inner surface area are 2.12m
2, material is stainless steel) inwall after overpickling, washing and drying, by flange be used for the lid that this titanium sponge reactor cooperates and be connected.Be provided with two electrodes on this lid, (titanium content is greater than 98 % by weight to be connected with the titanium silk between described two electrodes, gross weight 2000g, diameter is 5mm), described titanium silk arranges evenly distributedly along the internal surface of the tank body of described titanium sponge reactor, and the distance between the closest approach of the internal surface of the tank body of described titanium sponge reactor and described titanium silk is 1.5cm.Also be provided with a gas feed and a pneumatic outlet on the lid of this reactor.
By described pneumatic outlet, with vacuum pump with the Pressure Drop in the tank body of described titanium sponge reactor to 1Pa, and stable to 0.7Pa.Then under 0.7Pa, (starting voltage is 15V to give described titanium silk energising, initial current is 600A), the temperature of described titanium sponge wall of reactor was kept under 950-1020 ℃ 25 hours, when the temperature of wall of reactor is 950-1020 ℃, at this moment, the saturation vapour pressure that the temperature of titanium silk is higher than titanium is the temperature of 0.7Pa and the fusing point that is lower than titanium, thereby the titanium in the titanium silk under this temperature distils, and the titanium of distillation forms on the wall surface of reactor and oozes titanium layer.After keeping 25 hours under 950-1020 ℃, by the gas inlet, passing into argon gas to pressure in the reactor is 12kPa, and then reactor being inserted and being cooled to the wall temperature in the condenser is 40 ℃, the titanium sponge reactor after namely obtaining processing.Take off the titanium silk in the titanium sponge reactor after the processing, claim to such an extent that weight is 1682g, i.e. the inner surface area of the described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is 150g.
According to document (Li Dacheng etc., the magnesiothermy titanium sponge is produced, metallurgical industry press, 2008) method in, use titanium sponge reactor after the processing that the present embodiment obtains to prepare label and be the Sponge Titanium of TG-100, the content of Ti is 99.7 % by weight in this Sponge Titanium, and the content of iron is 0.05 % by weight.
Embodiment 5
Will available from the tank body of the I type titanium sponge reactor of climbing steel company (trade mark 1Cr18Ni9Ti, specification is erected type, internal diameter 0.18m, inner surface area are 2.12m
2, material is stainless steel) inwall after overpickling, washing and drying, by flange be used for the lid that this titanium sponge reactor cooperates and be connected.Be provided with two electrodes on this lid, (titanium content is greater than 98 % by weight to be connected with the titanium silk between described two electrodes, gross weight 2000g, diameter is 5mm), described titanium silk arranges evenly distributedly along the internal surface of the tank body of described titanium sponge reactor, and the distance between the closest approach of the internal surface of the tank body of described titanium sponge reactor and described titanium silk is 1.5cm.Also be provided with a gas feed and a pneumatic outlet on the lid of this reactor.
By described pneumatic outlet, with vacuum pump with the Pressure Drop in the tank body of described titanium sponge reactor to 1Pa, and stable to 0.2Pa.Then under 0.2Pa, (starting voltage is 15V to give described titanium silk energising, initial current is 600A), by regulating voltage and electric current the temperature of described titanium sponge wall of reactor was kept 3 hours successively under 200 ℃, keeping under 400 ℃ 4 hours and under 800 ℃, keeping 1.5 hours, then under 950-1020 ℃, kept 25 hours, when the temperature of wall of reactor is 950-1020 ℃, the saturation vapour pressure that the temperature of titanium silk is higher than titanium is the temperature of 0.2Pa and the fusing point that is lower than titanium, thereby, titanium in the titanium silk under this temperature distils, and the titanium of distillation forms on the wall surface of reactor and oozes titanium layer.After keeping 10 hours under 950-1020 ℃, by the gas inlet, passing into argon gas to pressure in the reactor is 22.5kPa, and then reactor being inserted and being cooled to the wall temperature in the condenser is 50 ℃, the titanium sponge reactor after namely obtaining processing.Take off the titanium silk in the titanium sponge reactor after the processing, claim to such an extent that weight is 1925g, i.e. the inner surface area of the described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is 35g.
According to document (Li Dacheng etc., the magnesiothermy titanium sponge is produced, metallurgical industry press, 2008) method in, use titanium sponge reactor after the processing that the present embodiment obtains to prepare label and be the Sponge Titanium of TG-100, the content of Ti is 99.75 % by weight in this Sponge Titanium, and the content of iron is 0.05 % by weight.
Comparative Examples 1
Will available from the tank body of the I type type titanium sponge reactor of climbing steel company (trade mark 1Cr18Ni9Ti, specification is erected type, internal diameter 0.18m, inner surface area are 2.12m
2, material is stainless steel) inwall after overpickling, washing and drying, titanium valve (available from climbing steel company, trade mark PTi2) is brushed equably on the inwall of tank body, the thickness of brushing is 0.05 millimeter, and tank body is connected with reactor cap by flange.Also be provided with a gas feed and a pneumatic outlet on the lid of this reactor.
By described pneumatic outlet, with vacuum pump with the Pressure Drop in the tank body of described titanium sponge reactor to 1Pa, and stable to 0.5Pa.Then under 0.5Pa, described titanium sponge reactor is placed process furnace, the temperature that makes described titanium sponge wall of reactor successively keep under 200 ℃ 3 hours, keeping under 400 ℃ 4 hours and under 800 ℃, keeping 1.5 hours, then after keeping 25 hours under 950-1020 ℃, pass through the gas inlet, passing into argon gas to pressure in the reactor is 22.5Pa, and then reactor being inserted and being cooled to the wall temperature in the condenser is 50 ℃, the titanium sponge reactor after namely obtaining processing.
According to document (Li Dacheng etc., the magnesiothermy titanium sponge is produced, metallurgical industry press, 2008) method in, use titanium sponge reactor after the processing that Comparative Examples obtains to prepare label and be the Sponge Titanium of TG-100, the content of Ti is 99.7 % by weight in this Sponge Titanium, and the content of iron is 0.07 % by weight.
Comparison by above-described embodiment 1-5 and Comparative Examples 1, can find out, the titanium sponge reactor that obtains after using the surface treatment method of titanium sponge reactor provided by the invention to process to ooze titanium layer complete and be covered in equably the internal surface of described reactor, thereby for the preparation of titanium sponge the time, further reduced reactor foreign matter content in the titanium sponge.
And at the inner surface area of preferred described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is in the situation of 45-225g, can further reduce reactor foreign matter content in the titanium sponge for the preparation of titanium sponge the time.
Claims (10)
1. the surface treatment method of a titanium sponge reactor, the method comprises: the pressure in the titanium sponge reactor is below the 1Pa, the thermo electric material that contains metal titanium that is opposite in this titanium sponge reactor is switched on, the condition of energising forms with the internal surface at described titanium sponge reactor and oozes titanium layer so that this contains the titanium distillation in the thermo electric material of metal titanium.
2. method according to claim 1, wherein, the inner surface area of the described titanium sponge reactor with respect to every square metre, the distillation amount of titanium is 45-225g.
3. method according to claim 1 and 2, wherein, described internal surface at described titanium sponge reactor forms the condition of oozing titanium layer and comprises: the pressure in the titanium sponge reactor is below the 0.1-1Pa, under the condition of carrying out described energising, the temperature of the wall of described titanium sponge reactor is remained on 920-1050 ℃ of lower 15-35 hour.
4. method according to claim 3, wherein, described internal surface at described titanium sponge reactor forms the condition of oozing titanium layer and comprises: the pressure in the titanium sponge reactor is below the 0.1-1Pa, under the condition of carrying out described energising, the temperature of the wall of described titanium sponge reactor is remained on 950-1020 ℃ of lower 20-30 hour.
5. according to claim 1, the described method of any one in 2 and 4, wherein, the described thermo electric material of titanium that contains is along the internal surface setting of described titanium sponge reactor, and the distance between the closest approach of the internal surface of described titanium sponge reactor and the described thermo electric material that contains titanium is that this internal surface is to the 1-10% of distance between another internal surface on the other side.
6. according to claim 1, the described method of any one in 2 and 4, wherein, the described thermo electric material that contains metal titanium is at least a in electric resistor heating type titanium thermo electric material, thermal conduction formula titanium thermo electric material and the radiant heating type titanium thermo electric material.
7. method according to claim 6, wherein, the described thermo electric material that contains metal titanium is electric resistor heating type titanium thermo electric material; Described electric resistor heating type titanium thermo electric material is the titaniferous wire and/or is enclosed with titaniferous Metallic rod wiry; Described titaniferous wire is at least a in titanium silk, titanium-tungsten alloy silk, titanium tantalum alloy silk and the titanium maxter alloy silk; Described Metallic rod is at least a in tungsten bar, tantalum bar and the molybdenum rod.
8. method according to claim 1, wherein, described method also comprises: before the temperature of distillation occurs the described thermo electric material that contains metal titanium of heating to the titanium in the described thermo electric material that contains metal titanium, be lower than under the pressure of 1Pa, heat de-airing carried out in the inside of described titanium sponge reactor process; Described heat de-airing is processed at least one in may further comprise the steps:
(1) temperature of the described titanium sponge wall of reactor of heating is to 190-210 ℃ and kept 2-4 hour;
(2) temperature of the described titanium sponge wall of reactor of heating is to 390-410 ℃ and kept 3-5 hour;
(3) temperature of the described titanium sponge wall of reactor of heating is to 790-810 ℃ and kept 1-2 hour.
9. method according to claim 8, wherein, described heat de-airing is processed and is comprised the following steps of carrying out successively:
(1) temperature of the described titanium sponge wall of reactor of heating is to 190-210 ℃ and kept 2-4 hour;
(2) temperature of the described titanium sponge wall of reactor of heating is to 390-410 ℃ and kept 3-5 hour;
(3) temperature of the described titanium sponge wall of reactor of heating is to 790-810 ℃ and kept 1-2 hour.
10. method according to claim 1, wherein, described method also comprises: the internal surface of described titanium sponge reactor form ooze titanium layer after, under protection of inert gas, with described titanium sponge reactor cooling to 25-50 ℃.
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