JP2008137890A - Device for producing titanium tetrachloride - Google Patents

Device for producing titanium tetrachloride Download PDF

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JP2008137890A
JP2008137890A JP2008011025A JP2008011025A JP2008137890A JP 2008137890 A JP2008137890 A JP 2008137890A JP 2008011025 A JP2008011025 A JP 2008011025A JP 2008011025 A JP2008011025 A JP 2008011025A JP 2008137890 A JP2008137890 A JP 2008137890A
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transfer pipe
titanium tetrachloride
cooling
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cooling means
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JP4958306B2 (en
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Haruyuki Okamura
治幸 岡村
Tadao Araike
忠男 荒池
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Osaka Titanium Technologies Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a device for producing titanium tetrachloride which prevents the blocking due to the flocculation of ferrous chloride in transportation piping and the change of the production rate without reducing production efficiency. <P>SOLUTION: Generated gas is sent from a reactor 10 to produce titanium tetrachloride by fluidized layer reaction via the transportation piping 20 to a condenser. A cooling means 31 is a spray device to spray liquid titanium tetrachloride in the transportation piping and forces high temperature generated gas to cool to lower temperature than the flocculation temperature range of ferrous chloride. A removing means 32 is provided in the piping together with the cooling means 31, to remove a ferrous oxide flocculated and adhered to inner surface of the piping by gas cooling by the cooling means 31. The removing means 32 is a hammer to remove flocculation adherent by blow in an axial direction. A pressure control valve 40 is provided downstream of the cooling means 31 and removing means 32 to prevent malfunction of a pressure control valve 40 due to flocculation adhesion. Variation of superficial linear velocity accompanying the change in the raw gas amount to be introduced is prevented by controlling the pressure in the reactor by the pressure control valve 40. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、スポンジチタンの製造原料等に使用される四塩化チタンの製造装置に関する。   The present invention relates to an apparatus for producing titanium tetrachloride used as a raw material for producing sponge titanium.

スポンジチタンの製造原料である四塩化チタンは、チタン、酸素及び鉄を含有するチタン鉱石を、炭素の存在下で塩素ガスと接触させることにより製造される。より具体的に説明すると、粒状のチタン鉱石と粒状のコークスを反応炉内に装入した状態で、炉下方から塩素ガスを吹き込み、800〜1200℃の温度範囲で流動層を形成し、反応を継続する。反応生成ガスは、反応炉の炉頂部から取り出され、移送配管を通って凝縮器に送られることにより、四塩化チタンが液状で回収される。   Titanium tetrachloride, which is a raw material for producing sponge titanium, is produced by bringing titanium ore containing titanium, oxygen and iron into contact with chlorine gas in the presence of carbon. More specifically, in a state where granular titanium ore and granular coke are charged into the reaction furnace, chlorine gas is blown from the bottom of the furnace to form a fluidized bed at a temperature range of 800 to 1200 ° C. continue. The reaction product gas is taken out from the top of the reactor and sent to a condenser through a transfer pipe, whereby titanium tetrachloride is recovered in a liquid state.

このような流動反応を用いたによる四塩化チタンの製造方法は、例えば特許文献1及び特許文献2に示されている。また、四塩化チタンの生産性を改善するために、移送配管に設けた圧力制御弁により炉内圧力制御を行うことは特許文献3に記載されている。   For example, Patent Document 1 and Patent Document 2 show a method for producing titanium tetrachloride by using such a fluid reaction. Moreover, in order to improve the productivity of titanium tetrachloride, it is described in patent document 3 that pressure control in a furnace is performed by the pressure control valve provided in the transfer piping.

特開昭49−42518号公報JP 49-42518

特開平1−188424号公報JP-A-1-188424

特開昭62−196471号公報JP-A-62-196471

ところで、流動反応炉で生じる生成ガスには、四塩化チタンの他に、塩化第一鉄、塩化第二鉄、その他の塩化物、一酸化炭素、二酸化炭素等が含まれている。生成ガス中の塩化第一鉄は融点、露点などの関係で移送配管の内面、特に入口部の内面に凝縮付着しやすく、配管閉塞を発生させる原因になる。ちなみに、塩化第一鉄の融点は672℃、生成ガスから塩化第一鉄が凝縮する温度範囲は650〜850℃である。そして、配管が閉塞した場合は、反応炉の稼働を停止して移送配管を閉塞部分で解体して、閉塞物を除去したり移送配管を交換したりする必要があった。   By the way, the product gas generated in the fluidized reaction furnace contains ferrous chloride, ferric chloride, other chlorides, carbon monoxide, carbon dioxide and the like in addition to titanium tetrachloride. Ferrous chloride in the product gas tends to condense and adhere to the inner surface of the transfer pipe, particularly the inner surface of the inlet, due to the melting point, dew point, and the like, causing the pipe to be blocked. Incidentally, the melting point of ferrous chloride is 672 ° C., and the temperature range in which ferrous chloride is condensed from the product gas is 650 to 850 ° C. And when piping was obstruct | occluded, it was necessary to stop operation | movement of a reactor and to disassemble transfer piping in the obstruction | occlusion part, to remove obstruction | occlusion, or to replace transfer piping.

しかしながら、移送配管の解体には手間がかかり、炉操業停止による生産性低下も問題になる。特に、生成ガス中の塩化第一鉄の凝集による移送配管の閉塞は、一箇所とは限らず、何箇所にも生じるので、この問題は非常に重大である。   However, the dismantling of the transfer pipe takes time, and a decrease in productivity due to the shutdown of the furnace operation also becomes a problem. In particular, the clogging of the transfer pipe due to the aggregation of ferrous chloride in the generated gas is not limited to one place, and occurs at any number of places, so this problem is very serious.

このような事情を背景として、生成ガスが反応炉から移送配管へ入る前に、液状の四塩化チタンを反応炉内に霧状に吹き込んで生成ガスと接触させることにより、その生成ガスの温度を塩化第一鉄の凝縮温度範囲(650〜850℃)より低い温度まで低下させる技術は、特許文献4に記載されている。この技術によると、移送配管に侵入する段階では、既に生成ガスの温度は塩化第一鉄の凝縮温度範囲より低い温度まで低下している。このため、移送配管においては、もはや内面に塩化第一鉄が凝集せず、これによる配管閉塞が防止されることになる。   Against this backdrop, before the product gas enters the transfer pipe from the reactor, liquid titanium tetrachloride is sprayed into the reactor to form a mist so that the temperature of the product gas is reduced. A technique for lowering the temperature to a temperature lower than the condensation temperature range (650 to 850 ° C.) of ferrous chloride is described in Patent Document 4. According to this technique, at the stage of entering the transfer pipe, the temperature of the product gas has already decreased to a temperature lower than the condensation temperature range of ferrous chloride. For this reason, in the transfer pipe, ferrous chloride no longer aggregates on the inner surface, thereby preventing the pipe from being blocked.

特開昭51−116198号公報JP 51-116198 A

また、移送配管内の閉塞物を機械的に取り除く装置は、例えば特許文献5に記載されている。特許文献5に記載された異物除去装置は、配管内の詰まりが顕著な部分へ挿入される掃除棒に、軸方向の打撃機能(ハンマー機能)及び回転機能(ドリル機能)を付与したものである。   An apparatus for mechanically removing the obstruction in the transfer pipe is described in Patent Document 5, for example. The foreign matter removing device described in Patent Document 5 is provided with an axial striking function (hammer function) and a rotating function (drilling function) on a cleaning rod inserted into a portion where clogging in a pipe is remarkable. .

特開2003−73121号公報JP 2003-73121 A

しかしながら、このような対策を採用しても、塩化第一鉄の凝縮による配管閉塞の問題を十分に解決することは困難である。   However, even if such measures are adopted, it is difficult to sufficiently solve the problem of the piping blockage due to the condensation of ferrous chloride.

反応炉内の温度は800〜1200℃に管理される。反応炉内の一部とはいえ、炉内の生成ガスを塩化第一鉄の凝縮温度範囲(650〜850℃)より低くすることは、実操業上は非常に困難である。このため、塩化第一鉄の凝縮温度範囲あるいはこれを超える高温の生成ガスが移送配管に流入し、移送配管途中で塩化第一鉄の凝縮温度範囲より低温となるため、塩化第一鉄の凝縮による移送配管の閉塞が避けられない。   The temperature in the reaction furnace is controlled at 800 to 1200 ° C. Although it is a part in the reaction furnace, it is very difficult in practice to make the generated gas in the furnace lower than the condensation temperature range of ferrous chloride (650 to 850 ° C.). For this reason, the condensed gas range of ferrous chloride or a high-temperature product gas that exceeds this temperature flows into the transfer pipe and becomes lower than the condensation temperature range of ferrous chloride in the middle of the transfer pipe. It is inevitable that the transfer pipe will be blocked by.

塩化第一鉄の凝縮付着が顕著な移送配管の入口部分に、付着物を機械的に除去するドリル、ハンマーなどの異物除去装置を設置すれば、塩化第一鉄の凝縮付着が顕著な場所で移送配管を解体せずに付着物を除去することが可能になり、一定の効果が得られる。しかし、先にも述べたが、生成ガス中の塩化第一鉄の凝縮は、一箇所とは限らず、何箇所にも生じる。そして、移送配管は長く、曲がりも多いことから、異物除去装置を何箇所にも設置しなければ、根本解決には至らず、経済的な負担が甚大となる。   If a foreign substance removal device such as a drill or hammer that mechanically removes deposits is installed at the entrance of the transfer pipe where ferrous chloride condenses, the ferrous chloride condenses and adheres. The deposits can be removed without disassembling the transfer pipe, and a certain effect can be obtained. However, as described above, the condensation of ferrous chloride in the product gas is not limited to one place, but occurs in many places. And since transfer piping is long and there are many bends, if a foreign material removal apparatus is not installed in many places, it will not lead to a fundamental solution, but an economical burden will become great.

移送配管における塩化第一鉄の凝縮付着による問題は、移送配管の閉塞、配管解体に伴う炉操業の停止、及びこれに伴う生産性の低下だけではない。四塩化チタンの生産速度を大きく変更できないことも大きな問題である。   Problems caused by condensation of ferrous chloride in the transfer pipe are not only due to blockage of the transfer pipe, stoppage of the furnace operation accompanying the dismantling of the pipe, and reduction in productivity accompanying this. Another major problem is that the production rate of titanium tetrachloride cannot be changed greatly.

即ち、流動反応では、空塔線速度Vを一定範囲内に維持することが重要である(特許文献1参照)。空塔線速度Vは流動反応での重要ファクターの一つであり、流動反応炉が空と仮定した場合、炉内温度により膨脹したガスが、炉内の横断面を上昇する平均速度を表す。つまり、この空塔線速度Vは、流動反応炉内を1秒あたりに上昇するガスの体積E(m3 /sec)/流動反応炉の横断面積B(m2 )であり、流入ガス速度A(例えばmol/sec)、流動反応炉内の横断面積B、炉内温度C、炉内圧力Dの関数となる。即ち、EはA、C及びDで計算されることにより、Vは数式1のようにA、B、C、Dの関数として一義的に算出される。 That is, in the flow reaction, it is important to maintain the superficial linear velocity V within a certain range (see Patent Document 1). The superficial linear velocity V is one of the important factors in the flow reaction. When the flow reaction furnace is assumed to be empty, it represents an average speed at which the gas expanded by the furnace temperature rises in the cross section in the furnace. That is, this superficial linear velocity V is the volume E (m 3 / sec) of gas rising per second in the flow reactor and the cross-sectional area B (m 2 ) of the fluid reactor, and the inflow gas velocity A (For example, mol / sec), which is a function of the cross sectional area B, the furnace temperature C, and the furnace pressure D in the flow reactor. That is, E is calculated by A, C, and D, and V is uniquely calculated as a function of A, B, C, and D as in Equation 1.

Figure 2008137890
Figure 2008137890

流動反応では、この空塔線速度Vを下げ過ぎると安定した流動状態の維持が困難になり、逆にこれを上げすぎると未反応の原料粒子が排気と共に流出し始め、何れの場合も反応効率が著しく低下する。このため、流動反応では、空塔線速度Vを一定範囲内に維持することが重要となる。そして、この制約のために、これまでは四塩化チタンの生産速度を大きく変更することができなかった。即ち、生産速度の調節のためには、投入原料ガス量(流入ガス速度Aに対応)の変更が必要である。ところが、前述した配管閉塞の原因となる塩化第一鉄等の凝集付着のため、配管に設けた圧力制御弁が早期に使用不能となり、圧力制御弁による炉内圧力Dの意図的な制御が困難となる。炉内圧力Dの意図的な制御が困難で、これを放置せざるを得ないとなると、空塔線速度一定の制約下では流入ガス速度Aの調節代は極めて限られたものになる(数式1参照)。   In the flow reaction, if the superficial linear velocity V is lowered too much, it becomes difficult to maintain a stable flow state. Conversely, if it is raised too much, unreacted raw material particles begin to flow out together with the exhaust, and in either case, the reaction efficiency Is significantly reduced. For this reason, in the flow reaction, it is important to maintain the superficial linear velocity V within a certain range. Due to this limitation, the production rate of titanium tetrachloride could not be changed greatly until now. That is, in order to adjust the production rate, it is necessary to change the amount of the input raw material gas (corresponding to the inflow gas rate A). However, because of the agglomeration and adhesion of ferrous chloride and the like that cause the above-mentioned pipe blockage, the pressure control valve provided in the pipe becomes unusable at an early stage, and it is difficult to intentionally control the furnace pressure D by the pressure control valve. It becomes. If it is difficult to intentionally control the furnace pressure D and it must be left unattended, the allowance for adjusting the inflow gas velocity A is extremely limited under the constraint of a constant superficial line velocity (formula 1).

なお、四塩化チタンの生産速度を大きく変えようとした場合は、空塔線速度を変更するしかなく、反応効率の低下が問題になる。炉内圧力Dが制御されないことによる不可避的な圧力変動に対しては、以前より空気を投入するなどして空塔線速度Vの維持を図っているが、コークスが燃焼することによる生産性の低下等が問題になっていた。   In addition, when it is going to change the production rate of titanium tetrachloride largely, there is no choice but to change the superficial linear velocity, and the reduction of reaction efficiency becomes a problem. For unavoidable pressure fluctuations due to the fact that the pressure D in the furnace is not controlled, the superficial linear velocity V has been maintained by, for example, introducing air, but the productivity of coke burning is reduced. Decrease etc. became a problem.

本発明の目的は、移送配管における塩化第一鉄の凝縮による閉塞を確実に且つ経済的に防止できる四塩化チタン製造装置を提供することにある。   The objective of this invention is providing the titanium tetrachloride manufacturing apparatus which can prevent reliably and economically obstruction | occlusion by condensation of ferrous chloride in a transfer piping.

塩化第一鉄の凝縮付着による配管閉塞の問題を解決するために、本発明者は、異物除去装置の設置数を極力少なく(例えば1つに)しても、閉塞防止効果が十分に得られる方法について検討した。その結果、移送配管における塩化第一鉄の凝縮を意図的に一箇所で集中して発生させ、その一箇所に異物除去装置を設置すれば、配管全体の閉塞を防止でき、その結果、配管の解体に伴う炉操業の停止、及びこれに伴う生産性の低下を回避できることが判明した。また、凝縮発生箇所の下流側に設けた圧力制御弁により炉内圧力を長期にわたって精度よく安定的に制御できるようになり、その結果として投入原料ガス量を変更したときの空塔線速度の変動を抑制でき、これにより四塩化チタンの生産速度を大幅に変更できるようになることが明らかになった。   In order to solve the problem of piping blockage due to condensation of ferrous chloride, the present inventor can obtain a sufficient blockage preventing effect even if the number of foreign matter removing devices is reduced as much as possible (for example, one). The method was examined. As a result, if the condensation of ferrous chloride in the transfer pipe is intentionally concentrated in one place and a foreign substance removal device is installed in that place, the entire pipe can be prevented from being blocked. It has been found that it is possible to avoid the shutdown of the furnace operation associated with the dismantling and the resulting decrease in productivity. In addition, the pressure control valve provided on the downstream side of the condensation generation point enables the furnace pressure to be accurately and stably controlled over a long period of time. As a result, fluctuations in the superficial line speed when the amount of input raw material gas is changed It has become clear that the production rate of titanium tetrachloride can be significantly changed.

本発明の四塩化チタン製造装置は、かかる知見に基づいて開発されたものであり、流動層反応により四塩化チタンを製造する反応炉と、移送配管を通して反応炉から送られる生成ガスを液化させる凝縮器と、650℃以上の生成ガスが流通する前記移送配管途中に設けられ、その生成ガスを強制冷却する冷却手段と、冷却手段による強制ガス冷却によって前記移送配管内面に凝縮し付着した塩化第一鉄を機械的に除去するべく、冷却手段と共に前記移送配管途中に設けられた除去手段とを具備している。   The titanium tetrachloride production apparatus of the present invention was developed on the basis of such knowledge, and is a reactor for producing titanium tetrachloride by a fluidized bed reaction, and a condensation for liquefying a product gas sent from the reaction furnace through a transfer pipe. A cooling means for forcibly cooling the generated gas, and a first chloride chloride condensed and adhered to the inner surface of the transfer pipe by forced gas cooling by the cooling means. In order to mechanically remove iron, a removing means provided in the middle of the transfer pipe is provided together with a cooling means.

ここにおける除去手段は、軸方向に進退駆動される掃除棒の軸回りの回転により凝縮付着物を除去するもの、軸方向に進退駆動される掃除棒の軸方向の振動による打撃により凝縮付着物を除去するもの、或いは軸方向に進退駆動される掃除棒の軸回りの回転及び軸方向の振動による打撃により凝縮付着物を除去するものの何れかである。   The removing means here removes the condensed deposits by rotating around the axis of the cleaning rod driven forward and backward in the axial direction, and removes the condensed deposits by striking due to the vibration in the axial direction of the cleaning rod driven forward and backward in the axial direction. Either the one to be removed or the one to remove the condensed deposits by the rotation of the cleaning rod driven forward and backward in the axial direction and the impact by the vibration in the axial direction.

本発明の四塩化チタン製造装置においては、移送配管途中の冷却手段により生成ガスが強制冷却されることにより、生成ガス中の塩化第一鉄が結露し、配管内面に付着堆積する。このため、冷却部の上流側にも下流側にも塩化第一鉄の凝縮による付着は実質的に生じず、冷却部にのみ凝縮付着が生じる。   In the titanium tetrachloride production apparatus of the present invention, when the product gas is forcibly cooled by the cooling means in the middle of the transfer pipe, ferrous chloride in the product gas is condensed and deposited on the inner surface of the pipe. For this reason, adhesion due to condensation of ferrous chloride does not substantially occur on either the upstream side or the downstream side of the cooling section, and condensation deposition occurs only on the cooling section.

即ち、本発明の四塩化チタン製造装置においては、移送配管途中の一箇所に意図的に凝縮を集中発生させる。これにより、一箇所の冷却部に除去手段を設けるだけで、配管全体における閉塞を確実に且つ経済的に防止できる。   That is, in the titanium tetrachloride production apparatus of the present invention, condensation is intentionally generated in one place in the middle of the transfer pipe. Thereby, the clogging in the whole piping can be reliably and economically prevented only by providing the removing means at one cooling section.

生成ガスの強制冷却については、生成ガスから塩化第一鉄が凝縮する温度範囲(650〜850℃)より高い850℃超の生成ガスが流通する箇所で、その生成ガスを上記の凝縮温度範囲より低い650℃未満に強制冷却するのが、上流及び下流での凝縮を完全防止できる点から特に好ましいが、冷却前が850℃以下で冷却後が650℃以上の冷却条件でも塩化第一鉄の積極的な凝縮が可能であり、その結果として上流及び下流での凝縮が抑制される。つまり、塩化第一鉄の凝縮温度範囲内でもガス温度が急激に下がる場所をつくれば積極的な凝縮が可能であり、その前後では凝縮が抑制されるということである。従って、基本的な冷却条件としては、650℃以上の生成ガスが流通する箇所で、その生成ガスを強制冷却するものとした。本発明の強制冷却手段と除去手段を共に設置する場所は、移送配管の入り口部が望ましい。なぜなら、除去された凝縮付着物が反応炉内に落下し、その処理が簡単になるからである。   For forced cooling of the product gas, at a location where the product gas exceeding 850 ° C., which is higher than the temperature range (650 to 850 ° C.) where ferrous chloride is condensed from the product gas, flows from the above condensation temperature range. Although forced cooling to a temperature lower than 650 ° C. is particularly preferable from the viewpoint of completely preventing upstream and downstream condensation, ferrous chloride is actively used even under cooling conditions of 850 ° C. or lower before cooling and 650 ° C. or higher after cooling. Condensation is possible, and as a result, upstream and downstream condensation is suppressed. In other words, if a place where the gas temperature falls rapidly even within the condensation temperature range of ferrous chloride, positive condensation is possible, and condensation is suppressed before and after that. Accordingly, the basic cooling condition is that the generated gas is forcibly cooled at a location where the generated gas at 650 ° C. or higher flows. The place where both the forced cooling means and the removing means of the present invention are installed is preferably the entrance of the transfer pipe. This is because the condensed deposits that have been removed fall into the reaction furnace and the processing becomes simple.

前記冷却手段は、移送配管内に液体四塩化チタンを噴霧する噴霧器が構造が簡単で好ましい。前記除去手段としては、軸回りの回転により結露付着物を除去するドリルや、軸方向の打撃により結露付着物を除去するハンマーなどを使用できるが、なかでもハンマーが除去効率、構造等の点から好ましい。   The cooling means is preferably a sprayer that sprays liquid titanium tetrachloride in the transfer pipe because of its simple structure. As the removing means, a drill that removes condensation deposits by rotating around the shaft, a hammer that removes condensation deposits by hitting in the axial direction, and the like can be used. preferable.

本発明の四塩化チタン製造装置を使用することにより、炉内圧力を長期にわたって精度よく安定的に制御できるようになる結果、流動層反応により四塩化チタンを製造する際に、反応炉へ投入する原料ガス量を変更すると共に、この投入原料ガス量の変更に伴う空塔線速度の変動を所定範囲内に収めるべく、反応炉内の圧力を制御することにより、四塩化チタンの生産速度を変更することができ、より具体的には、投入原料ガス量を増加させたときに炉内圧力を上昇させ、投入原料ガス量を減少させたときに炉内圧力を低下させることにより、空塔線速度を所定の範囲内に維持することができる。   By using the titanium tetrachloride production apparatus of the present invention, the furnace pressure can be controlled accurately and stably over a long period of time. As a result, when producing titanium tetrachloride by a fluidized bed reaction, the reactor is charged into the reaction furnace. In addition to changing the amount of raw material gas, the production rate of titanium tetrachloride is changed by controlling the pressure in the reactor so that fluctuations in the superficial line speed associated with this change in the amount of raw material gas can be kept within the specified range. More specifically, by increasing the furnace pressure when the input raw material gas amount is increased and decreasing the furnace pressure when the input raw material gas amount is decreased, The speed can be maintained within a predetermined range.

炉内圧力を制御するためには、配管途中に設けた圧力制御弁を用いるのが一般的である。この圧力制御弁は、安定な動作のために、前記冷却手段及び除去手段より下流側に設けることが推奨される。   In order to control the pressure in the furnace, a pressure control valve provided in the middle of the piping is generally used. This pressure control valve is recommended to be provided downstream of the cooling means and the removing means for stable operation.

投入原料ガス量の変更に伴う空塔線速度の変動範囲は、好ましくは0.05〜0.4m/secであり、より好ましくは0.08〜0.3m/sec、特に好ましくは0.1〜0.2m/secである。即ち、酸化チタン粉末(粒状チタン鉱石)から四塩化チタンを製造する一般的な工程で用いる原料粒径の場合、この範囲より空塔線速度を下げると安定した流動状態の維持が困難になり、逆に空塔線速度を上げすぎると未反応の原料粒子が排気と共に流出し始める。   The fluctuation range of the superficial linear velocity accompanying the change of the input raw material gas amount is preferably 0.05 to 0.4 m / sec, more preferably 0.08 to 0.3 m / sec, and particularly preferably 0.1. ~ 0.2 m / sec. That is, in the case of the raw material particle size used in a general process for producing titanium tetrachloride from titanium oxide powder (granular titanium ore), it becomes difficult to maintain a stable fluid state if the superficial linear velocity is lowered from this range, Conversely, if the superficial linear velocity is increased too much, unreacted raw material particles begin to flow out with the exhaust.

望ましい炉内圧力範囲は0.05〜0.29MPaであり、より望ましくは0.13〜0.29MPaである。炉内圧力を広範囲に制御できるとはいえ、余りに低すぎると空塔線速度を所定範囲内に維持しても流動状態が安定しにくくなり、高すぎる場合は反応炉の安全が懸念される。   A desirable furnace pressure range is 0.05 to 0.29 MPa, and more desirably 0.13 to 0.29 MPa. Although the pressure in the furnace can be controlled over a wide range, if it is too low, the flow state becomes difficult to stabilize even if the superficial linear velocity is maintained within a predetermined range, and if it is too high, the safety of the reactor is concerned.

本発明の四塩化チタン製造装置は、反応炉から凝縮器へ生成ガスを移送する移送配管の途中で生成ガスを強制的に冷却して意図的かつ集中的に凝縮を発生させ、その凝縮付着物を機械的に除去することにより、移送配管における塩化第一鉄の凝縮による閉塞を経済性よく確実に防止できる。   The titanium tetrachloride production apparatus of the present invention forcibly cools the product gas in the middle of the transfer pipe for transferring the product gas from the reactor to the condenser, intentionally and intensively generates the condensed deposits. By mechanically removing the clogging, the blockage due to the condensation of ferrous chloride in the transfer pipe can be reliably prevented with good economic efficiency.

その結果、炉内圧力を長期にわたって精度よく安定的に制御でき、反応炉へ投入する原料ガス量を変更すると共に、この投入原料ガス量の変更に伴う空塔線速度の変動を所定範囲内に収めるべく、反応炉内の圧力を制御することにより、反応炉での四塩化チタンの生産効率を低下させずに、その四塩化チタンの生産速度を大きく変更することができる。   As a result, the furnace pressure can be controlled accurately and stably over a long period of time, the amount of raw material gas charged into the reactor is changed, and fluctuations in the superficial line speed caused by this change in the amount of raw material gas are within a predetermined range. In order to accommodate it, by controlling the pressure in the reaction furnace, the production rate of titanium tetrachloride can be greatly changed without reducing the production efficiency of titanium tetrachloride in the reaction furnace.

以下に本発明の実施形態を図面に基づいて説明する。図1は本発明の一実施形態を示す四塩化チタン製造装置の主要部の構成図である。   Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a configuration diagram of a main part of a titanium tetrachloride production apparatus showing an embodiment of the present invention.

本実施形態の四塩化チタン製造装置は、流動反応炉10を備えている。この反応炉10は、粒状のチタン鉱石と粒状のコークスを塩化炉内に装入した状態で、炉下方から塩素ガスを吹き込み、800〜1200℃の温度範囲で流動層を形成することにより、四塩化チタンを生成する。生成ガスには、四塩化チタンの他に、塩化第一鉄、塩化第二鉄、その他の塩化物、一酸化炭素、二酸化炭素等が含まれている。この生成ガスは、反応炉10の炉頂部から移送配管20を通して四塩化チタン回収部である凝縮器へ送られる。   The titanium tetrachloride production apparatus according to the present embodiment includes a flow reaction furnace 10. This reactor 10 is obtained by injecting chlorine gas from the bottom of the furnace with granular titanium ore and granular coke charged into the chlorination furnace to form a fluidized bed in a temperature range of 800 to 1200 ° C. Titanium chloride is produced. In addition to titanium tetrachloride, the product gas contains ferrous chloride, ferric chloride, other chlorides, carbon monoxide, carbon dioxide, and the like. This product gas is sent from the top of the reactor 10 through the transfer pipe 20 to a condenser which is a titanium tetrachloride recovery unit.

移送配管20は、反応炉10の炉頂部に設けられた導入部21と、導入部21から側方へ延出した配管本体22とからなり、反応炉10の真上で直角に湾曲している。   The transfer pipe 20 includes an introduction part 21 provided at the top of the reactor 10 and a pipe body 22 extending laterally from the introduction part 21, and is bent at a right angle directly above the reaction furnace 10. .

移送配管20における閉塞防止装置30として、移送配管20の導入部21に冷却手段である噴霧器31と、除去手段である掃除棒32とが設けられている。噴霧器31は、導入部21内に液体四塩化チタンを霧状にして注入することにより、反応炉10から導入部21に流入する生成ガスを、導入部21内で塩化第一鉄の露点範囲より低温の650℃未満に冷却し、650℃以上の生成ガスが導入部21から流出するのを阻止する。   As the blockage preventing device 30 in the transfer pipe 20, a sprayer 31 as a cooling means and a cleaning rod 32 as a removing means are provided in the introduction portion 21 of the transfer pipe 20. The sprayer 31 injects the liquid titanium tetrachloride into the introduction part 21 in the form of a mist, so that the generated gas flowing from the reaction furnace 10 into the introduction part 21 is introduced into the introduction part 21 from the dew point range of ferrous chloride. The temperature is cooled to a temperature lower than 650 ° C., and the product gas having a temperature of 650 ° C. or higher is prevented from flowing out from the introduction portion 21.

掃除棒32は、反応炉10の出口の真上に鉛直に配置された回転機能を有するハンマーであり、使用されないときは、移送配管20の導入部21から上方へ鉛直に延出した管状の収納部33内に収容される。この掃除棒32は、ヘッド部32aとこれを支持する軸部32bとからなり、駆動部としての第1駆動部34及び第2駆動部35により駆動される。第1駆動部34は、掃除棒32に軸方向の衝撃のための振動と、軸回りの回転とを付与する。第2駆動部35は、掃除棒32を第1駆動部34と共に軸方向に進退駆動して、ヘッド部32aを収納部33内から少なくとも移送配管20の入口部を通過して反応炉10の出口まで下降させると共に、その出口から収納部33内へ上昇させる。   The cleaning rod 32 is a hammer having a rotating function that is vertically disposed right above the outlet of the reaction furnace 10. When not used, the cleaning rod 32 is a tubular storage that extends vertically from the introduction portion 21 of the transfer pipe 20. It is accommodated in the part 33. The cleaning bar 32 includes a head portion 32a and a shaft portion 32b that supports the head portion 32a, and is driven by a first drive portion 34 and a second drive portion 35 as drive portions. The first drive unit 34 imparts vibration for the impact in the axial direction and rotation around the axis to the cleaning rod 32. The second drive unit 35 drives the cleaning rod 32 forward and backward in the axial direction together with the first drive unit 34, and passes the head unit 32 a from the inside of the storage unit 33 through at least the inlet part of the transfer pipe 20 to the outlet of the reactor 10. To the storage portion 33 from the outlet.

収納部33の上部には、掃除棒32の軸部外面をシールするシール部36が設けられている。このシール部36により、収納部33内が炉外から気密に隔離される。一方、収納部33の下部には、開閉弁としてのボールバルブ37が取り付けられている。ボールバルブ37により、収納部33内が炉内に対して開放可能に閉止される。   A seal portion 36 that seals the outer surface of the shaft portion of the cleaning rod 32 is provided on the upper portion of the storage portion 33. The seal portion 36 hermetically isolates the inside of the storage portion 33 from the outside of the furnace. On the other hand, a ball valve 37 as an on-off valve is attached to the lower portion of the storage portion 33. The inside of the storage part 33 is closed by the ball valve 37 so as to be openable to the inside of the furnace.

移送配管20の配管本体22には、反応炉10内の圧力を制御するために圧力制御弁40が設けられている。圧力制御弁40は、塩化第一鉄の凝集付着の影響を回避するために閉塞防止装置30の下流側に配置されており、反応炉10内の圧力を目標値に制御するために、反応炉10内に設けられた圧力計41aの出力信号に基づいて操作される。圧力計41aは、導入部21内の閉塞状況を監視するために、配管本体22の入口近傍(圧力制御弁40の上流側)に設けた圧力計41bと組み合わされている。   A pressure control valve 40 is provided in the pipe body 22 of the transfer pipe 20 in order to control the pressure in the reaction furnace 10. The pressure control valve 40 is disposed on the downstream side of the clogging prevention device 30 in order to avoid the influence of ferrous chloride agglomeration and adhesion, and in order to control the pressure in the reaction furnace 10 to a target value, the reaction furnace 10 is operated based on the output signal of the pressure gauge 41a provided in the inside. The pressure gauge 41 a is combined with a pressure gauge 41 b provided in the vicinity of the inlet of the pipe body 22 (upstream of the pressure control valve 40) in order to monitor the blockage state in the introduction part 21.

また、生成ガスの冷却温度を管理するために、導入部21のガス出口近傍には、ガス温度計50が設けられている。   Further, a gas thermometer 50 is provided in the vicinity of the gas outlet of the introduction unit 21 in order to manage the cooling temperature of the product gas.

次に、本実施形態の四塩化チタン製造装置の機能、並びにこれを用いた四塩化チタン製造方法について説明する。   Next, the function of the titanium tetrachloride manufacturing apparatus of this embodiment and the titanium tetrachloride manufacturing method using the same will be described.

通常の操業では、掃除棒32は上昇し、そのヘッド部32aは収納部33内に収容される。また、ボールバルブ37が閉じられ、収納部33内が反応炉10内及び移送配管20内から隔絶される。反応炉10で生じる生成ガスは、炉内では800〜1200℃である。この生成ガスは、移送配管20の導入部21から配管本体22を経て四塩化チタン回収部である凝縮器へ送られるが、導入部21内で噴霧器31から噴出される霧状の液体四塩化チタンにより、生成ガス中の塩化第一鉄の凝縮温度範囲(650〜850℃)より低温(650℃未満)に強制的に冷却される。このため、生成ガス中の塩化第一鉄は、実質全量が導入部21の内面に凝縮し付着堆積する。   In a normal operation, the cleaning rod 32 is raised and the head portion 32 a is accommodated in the accommodating portion 33. Further, the ball valve 37 is closed, and the inside of the storage part 33 is isolated from the inside of the reaction furnace 10 and the inside of the transfer pipe 20. The product gas generated in the reaction furnace 10 is 800 to 1200 ° C. in the furnace. This generated gas is sent from the introduction part 21 of the transfer pipe 20 through the pipe main body 22 to the condenser which is the titanium tetrachloride recovery part, and the mist-like liquid titanium tetrachloride ejected from the sprayer 31 in the introduction part 21. Thus, the ferrous chloride in the product gas is forcibly cooled to a lower temperature (below 650 ° C.) than the condensation temperature range (650 to 850 ° C.). For this reason, the ferrous chloride in the product gas is condensed and deposited on the inner surface of the introduction portion 21 in a substantial amount.

これにより、移送配管20の配管本体22内に塩化第1鉄が侵入する事態が回避される。一方、移送配管20の導入部21内では、操業の継続に伴って付着物60が増えていく。付着物60が増えると、ここにおける圧力損失ΔPが増大する。この圧力損失ΔPは、圧力計41a,41bの計測値をPa,Pbとすると(Pa−Pb)にて求まる。圧力損失ΔPから導入部21内の付着物60による閉塞状況を監視し、問題となるレベルまで閉塞が進むと、付着物60の除去操作が行われる。   Thereby, the situation where ferrous chloride penetrate | invades in the piping main body 22 of the transfer piping 20 is avoided. On the other hand, in the introduction part 21 of the transfer pipe 20, the deposits 60 increase as the operation continues. When the deposit 60 increases, the pressure loss ΔP here increases. This pressure loss ΔP is obtained by (Pa−Pb), where Pa and Pb are measured values of the pressure gauges 41a and 41b. The clogging state due to the deposit 60 in the introduction portion 21 is monitored from the pressure loss ΔP, and when the blockage proceeds to a problematic level, the deposit 60 is removed.

付着物60の除去操作では、まずボールバルブ37が開放される。次いで、掃除棒32が衝撃付与のための振動、及び回転を行いながら下降する。これにより、付着物60が掃除棒32のヘッド部32aで簡単に破壊除去される。除去された付着物60は、反応炉10内に落下し、系外への排除を必要としない。付着物60の破壊除去が終わると、ヘッド部32aが収納部33内に侵入するまで、掃除棒32が上昇する。最後に、ボールバルブ37が閉じ、元の状態に戻る。   In the operation of removing the deposit 60, the ball valve 37 is first opened. Next, the cleaning rod 32 descends while performing vibration and rotation for applying an impact. Thereby, the deposit 60 is easily broken and removed by the head portion 32a of the cleaning rod 32. The removed deposit 60 falls into the reaction furnace 10 and does not need to be excluded from the system. After the destructive removal of the deposit 60 is completed, the cleaning stick 32 is raised until the head portion 32a enters the storage portion 33. Finally, the ball valve 37 closes and returns to the original state.

かくして、移送配管20の途中一箇所(ここでは導入部21)に1つの閉塞防止装置30を設けるだけで、移送配管20の全体における塩化第一鉄の凝集付着による閉塞が防止される。また、閉塞防止装置30の下流側に設けられた圧力制御弁40では塩化第一鉄の凝集付着が防止されることにより、その安定な動作が保証される。これにより、高精度な炉内圧力管理が可能になり、その結果として四塩化チタンの広範囲の生産速度変更が可能になる。   Thus, the blockage due to the agglomeration of ferrous chloride in the entire transfer pipe 20 can be prevented only by providing one blockage prevention device 30 at one place in the transfer pipe 20 (here, the introduction portion 21). In addition, the pressure control valve 40 provided on the downstream side of the blockage preventing device 30 prevents the ferrous chloride from aggregating and adhering, thereby ensuring its stable operation. As a result, the furnace pressure can be managed with high accuracy, and as a result, the production rate of titanium tetrachloride can be changed over a wide range.

即ち、四塩化チタンの生産速度を上げる場合は、反応炉10に投入する原料ガス(塩素ガス)の投入量を増大させる。これを放置すると、数式1中の流入ガス速度Aが増大し、空塔線速度Vが増大する。そこで、空塔線速度Vの増大を阻止するべく、圧力制御弁40を操作して炉内圧力Dを高める。これにより、空塔線速度Vの変動範囲を微小に抑制しながら、四塩化チタンの生産速度を大きく増大させることができる。四塩化チタンの生産速度を下げる場合は、反応炉10に投入する原料ガス(塩素ガス)の投入量を低減させると共に、これに伴う空塔線速度Vの低下を阻止するべく、圧力制御弁40を操作して炉内圧力Dを低下させる。これにより、空塔線速度Vの変動範囲を微小に抑制しながら、四塩化チタンの生産速度を大きく低下させることができる。   That is, when increasing the production rate of titanium tetrachloride, the input amount of the raw material gas (chlorine gas) input to the reaction furnace 10 is increased. If this is left as it is, the inflow gas velocity A in Equation 1 increases and the superficial line velocity V increases. Therefore, in order to prevent an increase in the superficial linear velocity V, the pressure control valve 40 is operated to increase the furnace pressure D. As a result, the production rate of titanium tetrachloride can be greatly increased while minutely suppressing the fluctuation range of the superficial linear velocity V. In order to reduce the production rate of titanium tetrachloride, the pressure control valve 40 is used in order to reduce the input amount of the raw material gas (chlorine gas) input to the reactor 10 and to prevent the decrease in the superficial line speed V accompanying this. Is operated to lower the furnace pressure D. As a result, the production rate of titanium tetrachloride can be greatly reduced while minutely suppressing the fluctuation range of the superficial linear velocity V.

こうして四塩化チタン生産速度の大幅な変更が可能になり、同時に空塔線速度Vの変動抑制による生産効率の低下が防止される。また、空気の投入が不要になることからも生産効率の低下が防止される。   In this way, the production rate of titanium tetrachloride can be significantly changed, and at the same time, a decrease in production efficiency due to suppression of fluctuations in the superficial line velocity V is prevented. In addition, since the introduction of air is not necessary, a decrease in production efficiency is prevented.

空塔線速度Vの変動範囲を0.1〜0.2m/secに抑制する場合について、図1の四塩化チタン製造装置を用いて従来法と本発明法の比較を行う。従来法では炉内圧力放置で投入原料ガス量を変更するが、生産速度の変動幅は「最大生産速度/最小生産速度」の比率で表して約2であった。炉内圧力は絶対圧で0.24MPa(相対圧で1.4気圧)を中心に推移した。これに対し、本発明法では投入原料ガス量の変更に伴い炉内圧力を例えば絶対圧で0.13〜0.29MPa(相対圧で0.3〜1.9気圧)の範囲で制御することにより、生産速度の変動幅は前記比率で4.5となり、炉内圧力の制御幅が絶対圧で0.15〜0.25MPa(相対圧で0.5〜1.5気圧)の場合は、生産速度の変動幅は前記比率で4となり、いずれの場合も生産速度の大幅な変更が可能になる。   In the case where the fluctuation range of the superficial linear velocity V is suppressed to 0.1 to 0.2 m / sec, the conventional method and the method of the present invention are compared using the titanium tetrachloride production apparatus of FIG. In the conventional method, the amount of input raw material gas is changed by leaving the pressure in the furnace, but the fluctuation range of the production rate is about 2 expressed as a ratio of “maximum production rate / minimum production rate”. The pressure inside the furnace changed around 0.24 MPa in absolute pressure (1.4 atm in relative pressure). On the other hand, in the method of the present invention, the pressure in the furnace is controlled in the range of, for example, 0.13 to 0.29 MPa (relative pressure: 0.3 to 1.9 atmospheres) as the pressure of the raw material gas is changed. Thus, the fluctuation range of the production rate is 4.5 in the above ratio, and when the control width of the furnace pressure is 0.15 to 0.25 MPa in absolute pressure (0.5 to 1.5 atm in relative pressure), The fluctuation range of the production speed is 4 in the above ratio, and in any case, the production speed can be significantly changed.

同一反応炉で四塩化チタンの生産速度を大きく変更できることのメリットは以下のとおりである。従来は生産量を減少させたければ、現状の反応炉を停止して代わりに小型の反応炉を可動させなければならない。逆に生産量を増加させたければ、別の反応炉を追加操業させなければならない。このため、規模が異なる複数の反応炉を用意する必要があった。しかるに、同一反応炉で四塩化チタンの生産速度を大きく変更できれば、複数炉も炉の切り替えも不要になる。同一反応炉で四塩化チタンの生産速度を大きく変更できることの経済的メリットは多大である。   The merit of being able to greatly change the production rate of titanium tetrachloride in the same reactor is as follows. Conventionally, if it is desired to reduce the production volume, the current reactor must be stopped and a small reactor must be moved instead. Conversely, if it is desired to increase production, another reactor must be operated additionally. For this reason, it was necessary to prepare a plurality of reactors of different scales. However, if the production rate of titanium tetrachloride can be greatly changed in the same reaction furnace, it is not necessary to switch between multiple furnaces or furnaces. The economic merit of being able to greatly change the production rate of titanium tetrachloride in the same reactor is great.

なお、上記実施形態では、閉塞防止装置30は、移送配管20の入口部である導入部21に設けたが、その下流側でもよい。但し、移送配管20の入口部から離れると、閉塞防止装置30までの間に生成ガスが冷え、生成ガス中の塩化第一鉄が結露する危険性が生じる。移送配管20の入口部ではこの危険がなく、入口部から離れたとしても、生成ガス温度が塩化第一鉄の凝縮温度範囲(650〜850℃)の下限(650℃)より低温になるまでの間に閉塞防止装置30を設ける必要があり、望ましくは塩化第一鉄の凝縮温度範囲(650〜850℃)の上限(850℃)より高温の領域に設ける。   In addition, in the said embodiment, although the obstruction | occlusion prevention apparatus 30 was provided in the introducing | transducing part 21 which is an inlet_port | entrance part of the transfer piping 20, the downstream may be sufficient. However, if it leaves | separates from the inlet_port | entrance part of the transfer piping 20, produced gas will cool between the blockage | prevention prevention apparatuses 30, and the danger that ferrous chloride in produced gas will condense arises. There is no such danger at the inlet of the transfer pipe 20, and even if it is away from the inlet, the generated gas temperature is lower than the lower limit (650 ° C.) of the ferrous chloride condensation temperature range (650 to 850 ° C.). It is necessary to provide the clogging prevention device 30 between them. Desirably, it is provided in a region higher than the upper limit (850 ° C.) of the ferrous chloride condensation temperature range (650 to 850 ° C.).

本発明の一実施形態を示す四塩化チタン製造装置の主要部の構成図である。It is a block diagram of the principal part of the titanium tetrachloride manufacturing apparatus which shows one Embodiment of this invention.

符号の説明Explanation of symbols

10 塩化炉
20 移送配管
30 閉塞防止装置
31 噴霧器(冷却手段)
32 掃除棒(除去手段)
40 圧力制御弁
41a,41b 圧力計
50 温度計
60 付着物
DESCRIPTION OF SYMBOLS 10 Chlorination furnace 20 Transfer piping 30 Blocking prevention apparatus 31 Sprayer (cooling means)
32 Cleaning stick (removal means)
40 Pressure control valve 41a, 41b Pressure gauge 50 Thermometer 60 Deposit

Claims (6)

流動層反応により四塩化チタンを製造する反応炉と、移送配管を通して反応炉から送られる生成ガスを液化させる凝縮器と、650℃以上の生成ガスが流通する前記移送配管途中に設けられ、その生成ガスを強制冷却する冷却手段と、冷却手段による強制ガス冷却によって前記移送配管内面に凝縮し付着した塩化第一鉄を機械的に除去するべく、冷却手段と共に前記移送配管途中に設けられた除去手段とを具備しており、前記除去手段は、軸方向に進退駆動される掃除棒の軸方向の振動による打撃により凝縮付着物を除去することを特徴とする四塩化チタン製造装置。   A reaction furnace for producing titanium tetrachloride by a fluidized bed reaction, a condenser for liquefying a product gas sent from the reaction furnace through a transfer pipe, and the transfer pipe in which the product gas of 650 ° C. or higher circulates is produced. A cooling means for forcibly cooling the gas, and a removing means provided in the middle of the transfer pipe together with the cooling means for mechanically removing ferrous chloride condensed and adhered to the inner surface of the transfer pipe by the forced gas cooling by the cooling means And the removing means removes the condensed deposits by striking due to the vibration in the axial direction of the cleaning rod driven forward and backward in the axial direction. 流動層反応により四塩化チタンを製造する反応炉と、移送配管を通して反応炉から送られる生成ガスを液化させる凝縮器と、650℃以上の生成ガスが流通する前記移送配管途中に設けられ、その生成ガスを強制冷却する冷却手段と、冷却手段による強制ガス冷却によって前記移送配管内面に凝縮し付着した塩化第一鉄を機械的に除去するべく、冷却手段と共に前記移送配管途中に設けられた除去手段とを具備しており、前記除去手段は、軸方向に進退駆動される掃除棒の軸回りの回転により凝縮付着物を除去することを特徴とする四塩化チタン製造装置。   A reaction furnace for producing titanium tetrachloride by a fluidized bed reaction, a condenser for liquefying a product gas sent from the reaction furnace through a transfer pipe, and the transfer pipe in which the product gas of 650 ° C. or higher circulates is produced. A cooling means for forcibly cooling the gas, and a removing means provided in the middle of the transfer pipe together with the cooling means for mechanically removing ferrous chloride condensed and adhered to the inner surface of the transfer pipe by the forced gas cooling by the cooling means And the removing means removes the condensed deposits by rotating around the axis of a cleaning rod driven to move back and forth in the axial direction. 流動層反応により四塩化チタンを製造する反応炉と、移送配管を通して反応炉から送られる生成ガスを液化させる凝縮器と、650℃以上の生成ガスが流通する前記移送配管途中に設けられ、その生成ガスを強制冷却する冷却手段と、冷却手段による強制ガス冷却によって前記移送配管内面に凝縮し付着した塩化第一鉄を機械的に除去するべく、冷却手段と共に前記移送配管途中に設けられた除去手段とを具備しており、前記除去手段は、軸方向に進退駆動される掃除棒の軸回りの回転及び軸方向の振動による打撃により凝縮付着物を除去することを特徴とする四塩化チタン製造装置。   A reaction furnace for producing titanium tetrachloride by a fluidized bed reaction, a condenser for liquefying a product gas sent from the reaction furnace through a transfer pipe, and the transfer pipe in which the product gas of 650 ° C. or higher circulates is produced. A cooling means for forcibly cooling the gas, and a removing means provided in the middle of the transfer pipe together with the cooling means for mechanically removing ferrous chloride condensed and adhered to the inner surface of the transfer pipe by the forced gas cooling by the cooling means And the removal means removes the condensed deposit by the rotation of the cleaning rod driven forward and backward in the axial direction and the impact caused by the vibration in the axial direction. . 前記冷却手段は、850℃超の生成ガスが流通する配管途中に設けられ、その生成ガスを650℃未満に強制冷却する請求項1、2又は3に記載の四塩化チタン製造装置。   The said cooling means is a titanium tetrachloride manufacturing apparatus of Claim 1, 2 or 3 provided in the middle of piping through which the product gas over 850 degreeC distribute | circulates, and forcibly cooling the produced gas to less than 650 degreeC. 前記冷却手段は、前記移送配管内に液体四塩化チタンを噴霧する噴霧器である請求項1、2又は3に記載の四塩化チタン製造装置。   The titanium tetrachloride production apparatus according to claim 1, 2, or 3, wherein the cooling means is a sprayer that sprays liquid titanium tetrachloride into the transfer pipe. 前記移送配管途中に設けられた冷却手段及び除去手段より下流側に、炉内圧力制御用の圧力制御弁を具備する請求項1、2又は3に記載の四塩化チタン製造装置。   The titanium tetrachloride production apparatus according to claim 1, 2 or 3, further comprising a pressure control valve for controlling the pressure in the furnace downstream of the cooling means and the removing means provided in the transfer pipe.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4942518A (en) * 1972-08-31 1974-04-22
JPS51116198A (en) * 1975-04-04 1976-10-13 Nippon Mining Co Ltd Method for production of titanium tetrachloride
JPS5217393A (en) * 1975-07-04 1977-02-09 Laporte Industries Ltd Shenkachitan no kaishu hoho
JPS62196471A (en) * 1986-02-21 1987-08-29 Osaka Titanium Seizo Kk Rotating type pressure regulating valve
JPH04144917A (en) * 1990-10-01 1992-05-19 Ishihara Sangyo Kaisha Ltd Cleaning of distribution plate nozzle
JP2001062416A (en) * 1999-08-31 2001-03-13 Toho Titanium Co Ltd Clogging removing device for sponge titanium production
JP2001227738A (en) * 2000-02-16 2001-08-24 Takuma Co Ltd Cleaning device for duct

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4942518A (en) * 1972-08-31 1974-04-22
JPS51116198A (en) * 1975-04-04 1976-10-13 Nippon Mining Co Ltd Method for production of titanium tetrachloride
JPS5217393A (en) * 1975-07-04 1977-02-09 Laporte Industries Ltd Shenkachitan no kaishu hoho
JPS62196471A (en) * 1986-02-21 1987-08-29 Osaka Titanium Seizo Kk Rotating type pressure regulating valve
JPH04144917A (en) * 1990-10-01 1992-05-19 Ishihara Sangyo Kaisha Ltd Cleaning of distribution plate nozzle
JP2001062416A (en) * 1999-08-31 2001-03-13 Toho Titanium Co Ltd Clogging removing device for sponge titanium production
JP2001227738A (en) * 2000-02-16 2001-08-24 Takuma Co Ltd Cleaning device for duct

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