CN101403046A - Method for reduction production of zirconium sponge with double-pot magnesium method - Google Patents
Method for reduction production of zirconium sponge with double-pot magnesium method Download PDFInfo
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- CN101403046A CN101403046A CNA2008102288183A CN200810228818A CN101403046A CN 101403046 A CN101403046 A CN 101403046A CN A2008102288183 A CNA2008102288183 A CN A2008102288183A CN 200810228818 A CN200810228818 A CN 200810228818A CN 101403046 A CN101403046 A CN 101403046A
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Abstract
The invention provides a two-pot magnesium method for restoring and producing sponge zirconium, in particular the control technology for producing the sponge zirconium by adopting large-scale equipment, which comprises the following steps: zirconium tetrachloride and magnesium are respectively loaded to the respective reactors, sublimation, the melting of the magnesium and the reducing reaction are respectively carried out in a subliming reactor and a reduction reactor; an electrothermal channel is coupled between the two reactors, and the temperature of the channel is controlled to be higher than the sublimation temperature of the zirconium tetrachloride; when the magnesium is melt in a crucible, ZrCl4 is sublimated to gas in a subliming furnace; when the channel valve of a pipeline is opened, gaseous ZrCl4 enters the reducing reactor through the channel, and reduces with liquid magnesium under the conditions of 820-920 DEG C of reaction temperature, 8-20KPa of the pressure, 50-80 hours of reaction time and 40-100Kg/h of feeding speed to prepare the sponge zirconium. The method and the equipment have the advantages of realizing ideal technical control of ZrCl4 gas concentration and reaction speed, ensuring the quality stability of the sponge zirconium, improving the recovery rate of the product, reducing environment pollution and reducing the energy consumption of the product.
Description
Technical field
The present invention relates to non-ferrous metal metallurgy, be specifically related to a kind of method of reduction production of zirconium sponge with double-pot magnesium method, particularly adopt the control techniques of large-scale plant reduction production of zirconium sponge with.
Background technology
Tradition is used ZrCl
4The technology of magnesium method reduction system zirconium sponge is: ZrCl
4The reduction reaction of distillation and magnesium is to carry out in same stainless steel reactor, and ZrCl packs in the reactor lower part volatilization bucket
4, thermal baffle is arranged above it, the reduction reaction crucible of dress magnesium is sitting on the thermal baffle, the cover plate cap is arranged, from reactor lower part evaporable ZrCl on the reaction crucible
4Gas carries out gas liquid reaction with molten magnesium in the crucible in the crucible cover plate cap enters the reduction reaction crucible, generate zirconium sponge and magnesium chloride; Single jar of reductive shortcoming is: plant factor is low, the interior temperature top and the bottom of stove influence each other, ZrCl
4Gas concentration and speed of response all be difficult to control, from bottom evaporable ZrCl
4In the process that rises, generate at a low price zirconium and deceive powder, cause product recovery rate low, poor product quality with the outer magnesium generation gas solid/liquid/gas reactions of crucible.Have two jars of equipment of employing at present and carry out magnesium method reduction production of zirconium sponge with, but, also really do not enter the sophisticated suitability for industrialized production stage because the device that reduces, distils less (general diameter is in 1000mm) only limits to test manufacture on a small scale; Do not reach comparatively ideal effect in Technology control, quality product is stable inadequately.
Summary of the invention
In order to solve the shortcoming that existing method exists, the present invention utilizes two jars of equipment, and a kind of method of magnesium method reduction production of zirconium sponge with is provided, and particularly adopts the maximization device to produce the control techniques of zirconium sponge.Adopt this method and apparatus can realize ZrCl
4Gas concentration and speed of response reach ideal control effect, realize sophisticated suitability for industrialized production, thereby guarantee the zirconium sponge steady quality, reduce environmental pollution, reduce product energy consumption.
The method of reduction production of zirconium sponge with double-pot magnesium method provided by the present invention is that zirconium tetrachloride and magnesium are respectively charged in separately the reactor, and zirconium tetrachloride distillation and the fusion and the reduction reaction of magnesium are carried out in distillation reactor and reduction reactor respectively.
Technical scheme of the present invention is to be prepared zirconium sponge in accordance with the following methods:
(1) magnesium of in reduction reactor, packing into, in 260-300 ℃ of low temperature degasification 4-6 hour, the maintenance system was in vacuum state, simultaneously impurity such as C, Mg, Si, Fe in the zirconium tetrachloride was removed; With 750-800 ℃, molten magnesium kept 6-12 hour under the pressure 8-20Kpa condition then;
(2) at the distillation zirconium tetrachloride of packing in the reactor,, carry out the applying argon gas protection, make the zirconium tetrachloride gas of distillation be dense white at 350-400 ℃ in 260-270 ℃ of low temperature degasification 4-6 hour;
(3) open two unicom pipeline valves between the reactor, distillation gas is entered in the reduction reactor, in 820-920 ℃, feed rate is controlled at 40-100Kg/h in zirconium tetrachloride before distilling, made zirconium sponge in 50-80 hour with the molten magnesium reaction under the pressure 8-20KPa condition, single furnace output zirconium sponge is the 0.7-1.2 ton, and technical grade zirconium sponge (Zr+Hf) content is more than 99.4%.
Dual pot unit of the present invention has reduction reactor, distillation reactor and is located at two unicom pipelines between the reactor, covers in each reactor top evacuation tube and filling tube are installed.With the reduction apparatus enlarged-diameter to more than the 1000mm, the sublimation apparatus enlarged-diameter is provided with reaction crucible to more than the 800mm in reduction reactor, unicom pipeline is equipped with heating control apparatus, make this channel temperature be higher than the sublimation temperature of zirconium tetrachloride, in case low temperature causes obstruction.As magnesium heating and melting in reduction reactor, ZrCl
4Through being sublimed into gas, when gas concentration reaches requirement, open the channel valve on the unicom pipeline, gaseous state ZrCl at subliming furnace
4Enter in the reduction reactor through the passage pipeline, carry out reduction reaction with liquid magnesium and produce zirconium sponge, temperature of reaction is suitable to be controlled at 830-880 ℃, and reaction pressure is controlled at 11-15Kpa, 50-70 hour reduction reaction time, feed rate is controlled at 40-60Kg/h in zirconium tetrachloride before distilling.
The inventive method has solved in the prior art that the product speed of response can not be controlled, many, the poor product quality of the black powder of zirconium, the rate of recovery are hanged down this difficult problem at a low price, adopt this method can realize ZrCl
4Gas concentration and speed of response reach the control of ideal technology, can guarantee the zirconium sponge steady quality, have improved product recovery rate, have reduced environmental pollution, have reduced product energy consumption.The present invention is suitable for the producer with magnesium method reduction production of zirconium sponge with.
Embodiment
Embodiment 1
The method of reduction production of zirconium sponge with double-pot magnesium method, the reduction reactor of equipment choosing stainless steel and distillation reactor, the reduction reactor diameter is designed to 2 meters, and the distillation reactor diameter is designed to 1.8 meters, highly all is designed to 5 meters.With 2 tons of content greater than 99% ZrCl
4Pack in the distillation reactor, temperature is carried out the low temperature degasification at 260 ℃, 4 hours time, be warmed up to 350 ℃ then, and carry out the applying argon gas dividing potential drop, ZrCl after the dividing potential drop
4Gas reaches dense white, at this moment ZrCl
4Gas concentration reaches requirement; Meanwhile in reduction reactor, temperature is carried out the low temperature degasification at 270 ℃, and 4 hours time, temperature is raised to 750 ℃, constant temperature 6 hours, and pressure-controlling 10-13Kpa makes magnesium reach molten state in reduction reactor.Open two unicom pipeline [6] valves between the reactor, gaseous state ZrCl this moment
4Enter in the reduction reactor through the passage pipeline, react with liquid magnesium, temperature of reaction is controlled at 820-890 ℃, reaction pressure is controlled at 11-15Kpa, 50 hours reduction reaction time, feed rate is controlled at 40-42Kg/h, 0.7 ton of single stove salable product output zirconium sponge, technical grade zirconium sponge (Zr+Hf) content 99.5% in zirconium tetrachloride before distilling.
Embodiment 2
The method of reduction production of zirconium sponge with double-pot magnesium method, specification of equipment is with embodiment 1.With 2.8 tons of content greater than 99% ZrCl
4Pack in the distillation reactor, temperature is carried out the low temperature degasification at 270 ℃, 5 hours time, be warmed up to 380 ℃ then, and carry out the applying argon gas dividing potential drop, ZrCl after the dividing potential drop
4Gas reaches dense white, at this moment ZrCl
4Gas concentration reaches requirement; Meanwhile in reduction reactor, temperature is carried out the low temperature degasification at 270 ℃, and 5 hours time, temperature is raised to 760 ℃, constant temperature 7 hours, and pressure-controlling 10-13Kpa makes magnesium reach molten state in reduction reactor.Open two unicom pipeline [6] valves between the reactor, gaseous state ZrCl this moment
4Enter in the reduction reactor through the passage pipeline, react with liquid magnesium, temperature of reaction is controlled at 830-880 ℃, reaction pressure is controlled at 11-15Kpa, 65 hours reduction reaction time, feed rate is controlled at 42-46Kg/h, 0.94 ton of single stove salable product output zirconium sponge, technical grade zirconium sponge (Zr+Hf) content 99.6% in zirconium tetrachloride before distilling.
Embodiment 3
The method of reduction production of zirconium sponge with double-pot magnesium method, specification of equipment is with embodiment 1.With 3.5 tons of content greater than 99% ZrCl
4Pack in the distillation reactor, temperature is carried out the low temperature degasification at 280 ℃, 6 hours time, be warmed up to 360 ℃ then, and carry out the applying argon gas dividing potential drop, ZrCl after the dividing potential drop
4Gas reaches dense white, at this moment ZrCl
4Gas concentration reaches requirement; Meanwhile in reduction reactor, temperature is carried out the low temperature degasification at 290 ℃, and 6 hours time, temperature is raised to 780 ℃, constant temperature 8 hours, and pressure-controlling makes magnesium reach molten state in reduction reactor at 10-13Kpa.Open two unicom pipeline [6] valves between the reactor, gaseous state ZrCl this moment
4Enter in the reduction reactor through the passage pipeline, react with liquid magnesium, temperature of reaction is controlled at 830-900 ℃, reaction pressure is controlled at 11-15Kpa, 70 hours reduction reaction time, feed rate is controlled at 46-60Kg/h, 1.15 tons of single stove salable product output zirconium sponges, technical grade zirconium sponge (Zr+Hf) content 99.6% in zirconium tetrachloride before distilling.
Claims (3)
1, a kind of method of reduction production of zirconium sponge with double-pot magnesium method, be that zirconium tetrachloride and magnesium are respectively charged in separately the reactor, zirconium tetrachloride distillation and the fusion and the reduction reaction of magnesium are carried out in distillation reactor and reduction reactor respectively, it is characterized in that they are prepared in accordance with the following methods:
(1) magnesium of in reduction reactor, packing into, in 260-300 ℃ of low temperature degasification 4-6 hour, then with 750-800 ℃, molten magnesium kept 6-12 hour under the pressure 8-20Kpa condition;
(2) at the distillation zirconium tetrachloride of packing in the reactor,, carry out the applying argon gas protection, make the zirconium tetrachloride gas of distillation be dense white at 350-400 ℃ in 260-270 ℃ of low temperature degasification 4-6 hour;
(3) open two unicom pipeline valves between the reactor, distillation gas is entered in the reduction reactor, in 820-920 ℃, feed rate is controlled at 40-100Kg/h in zirconium tetrachloride before distilling, and makes zirconium sponge in 50-80 hour with the molten magnesium reaction under the pressure 8-20KPa condition.
2, according to the method for the described reduction production of zirconium sponge with double-pot magnesium method of claim 1, the feed rate that it is characterized in that zirconium tetrachloride is 40-60Kg/h, and reduction reaction pressure is at 11-15KPa, and temperature of reaction is controlled at 830-880 ℃, reaction times 50-70 hour.
3, according to the method for claim 1 or 2 described reduction production of zirconium sponge with double-pot magnesium method, it is characterized in that the reduction reactor diameter greater than 1000mm, the distillation reactor diameter is greater than 800mm.
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| CNA2008102288183A CN101403046A (en) | 2008-11-12 | 2008-11-12 | Method for reduction production of zirconium sponge with double-pot magnesium method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206762A (en) * | 2011-05-18 | 2011-10-05 | 南京佑天金属科技有限公司 | Crystal zirconium growth system with iodine doser |
| CN104583425A (en) * | 2012-08-14 | 2015-04-29 | Ati资产公司 | Methods for reducing impurities in magnesium, purified magnesium, and zirconium metal production |
| CN105063378A (en) * | 2015-09-16 | 2015-11-18 | 西安电炉研究所有限公司 | Split type reduction reaction system for producing zirconium sponge and sponge hafnium |
| CN112430753A (en) * | 2020-11-04 | 2021-03-02 | 宝钛华神钛业有限公司 | Production equipment and process of zirconium sponge |
| CN112941315A (en) * | 2021-03-23 | 2021-06-11 | 宝钛华神钛业有限公司 | Zirconium tetrachloride flow velocity passageway regulation and control device for zirconium sponge reduction |
-
2008
- 2008-11-12 CN CNA2008102288183A patent/CN101403046A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206762A (en) * | 2011-05-18 | 2011-10-05 | 南京佑天金属科技有限公司 | Crystal zirconium growth system with iodine doser |
| CN102206762B (en) * | 2011-05-18 | 2013-09-04 | 南京佑天金属科技有限公司 | Crystal zirconium growth system with iodine doser |
| CN104583425A (en) * | 2012-08-14 | 2015-04-29 | Ati资产公司 | Methods for reducing impurities in magnesium, purified magnesium, and zirconium metal production |
| CN104583425B (en) * | 2012-08-14 | 2016-09-21 | Ati资产公司 | For reducing the method for impurity in magnesium, the magnesium of purification and zirconium Metal Production |
| US10422017B2 (en) | 2012-08-14 | 2019-09-24 | Ati Properties Llc | Methods for reducing impurities in magnesium, purified magnesium, and zirconium metal production methods |
| CN105063378A (en) * | 2015-09-16 | 2015-11-18 | 西安电炉研究所有限公司 | Split type reduction reaction system for producing zirconium sponge and sponge hafnium |
| CN112430753A (en) * | 2020-11-04 | 2021-03-02 | 宝钛华神钛业有限公司 | Production equipment and process of zirconium sponge |
| CN112430753B (en) * | 2020-11-04 | 2021-07-09 | 宝钛华神钛业有限公司 | Production equipment and process of zirconium sponge |
| CN112941315A (en) * | 2021-03-23 | 2021-06-11 | 宝钛华神钛业有限公司 | Zirconium tetrachloride flow velocity passageway regulation and control device for zirconium sponge reduction |
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