JP2003183320A - Method and apparatus for producing chlorinated polyvinyl chloride resin - Google Patents

Method and apparatus for producing chlorinated polyvinyl chloride resin

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Publication number
JP2003183320A
JP2003183320A JP2001385066A JP2001385066A JP2003183320A JP 2003183320 A JP2003183320 A JP 2003183320A JP 2001385066 A JP2001385066 A JP 2001385066A JP 2001385066 A JP2001385066 A JP 2001385066A JP 2003183320 A JP2003183320 A JP 2003183320A
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JP
Japan
Prior art keywords
gas
vinyl chloride
chloride resin
reaction
chlorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2001385066A
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Japanese (ja)
Inventor
Kenji Uejima
健二 上島
Takashi Wachi
俊 和地
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanegafuchi Chemical Industry Co Ltd
Original Assignee
Kanegafuchi Chemical Industry Co Ltd
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Application filed by Kanegafuchi Chemical Industry Co Ltd filed Critical Kanegafuchi Chemical Industry Co Ltd
Priority to JP2001385066A priority Critical patent/JP2003183320A/en
Publication of JP2003183320A publication Critical patent/JP2003183320A/en
Pending legal-status Critical Current

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  • Gas Separation By Absorption (AREA)
  • Drying Of Gases (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To separate and recycle only unreacted chlorine from the discharge gas as a reaction by product comprising hydrogen chloride and unreacted chlorine in the postchlorination reaction of a polyvinyl chloride resin in a gas/solid contact system. <P>SOLUTION: A method for producing a chlorinated vinyl chloride resin comprises reacting a polyvinyl chloride resin with chlorine in the gas/solid contact reaction system, discharging part or all of the reaction gas from the reactor, and bringing the discharge gas and water into contact with each other to obtain a dehydrochlorinated gas by allowing water to absorb the hydrogen chloride gas in the discharge gas, recirculating and introducing the dehydrochlorinated gas into the reactor to utilize it in the chlorination reaction of the polyvinyl chloride resin. An apparatus therefor is also provided. <P>COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、塩素と塩化ビニル
系樹脂とを気固接触場において反応させた場合に発生す
る排出ガスから、含有される塩化水素ガスを除去し、未
反応の塩素ガスを再利用することにより、塩素ガスを無
駄なく反応に利用しながら、洗浄、乾燥、廃液処理等の
後処理が簡便な塩素化塩化ビニル系樹脂を製造する技術
に関する。TECHNICAL FIELD The present invention is to remove unreacted chlorine gas by removing contained hydrogen chloride gas from exhaust gas generated when chlorine and vinyl chloride resin are reacted in a gas-solid contact field. The present invention relates to a technique for producing a chlorinated vinyl chloride resin which is easy to carry out after-treatments such as washing, drying, and waste liquid treatment while reusing chlorine gas for reaction without waste.

【０００２】[0002]

【従来の技術】塩化ビニル系樹脂を後塩素化して得られ
る塩素化塩化ビニル系樹脂は、優れた耐熱性、難燃性、
機械強度、電気特性を有しており、様々な産業で利用さ
れている。例えば、通常の塩化ビニル系樹脂のガラス転
移温度は８０℃程度であるが、塩素化塩化ビニル系樹脂
のガラス転移温度は、塩素含有量の増加と共に上昇し、
１２０〜１３０℃に達する。また、ビカット軟化温度も
同様に１２０℃程度の高い値を示す。この様な高い耐熱
性を有することから、塩素化塩化ビニル系樹脂は、耐熱
パイプ、耐熱継ぎ手、耐熱バルブ、耐熱シートなどに利
用されている。2. Description of the Related Art Chlorinated vinyl chloride resin obtained by post-chlorination of vinyl chloride resin has excellent heat resistance, flame retardancy,
It has mechanical strength and electrical properties and is used in various industries. For example, the glass transition temperature of a normal vinyl chloride resin is about 80 ° C., but the glass transition temperature of a chlorinated vinyl chloride resin rises as the chlorine content increases,
Reach 120-130 ° C. The Vicat softening temperature also shows a high value of about 120 ° C. Due to such high heat resistance, chlorinated vinyl chloride resins are used in heat resistant pipes, heat resistant joints, heat resistant valves, heat resistant sheets, and the like.

【０００３】塩素化塩化ビニル系樹脂の工業的な生産方
法は、塩化ビニル系単量体を重合して塩化ビニル系樹脂
を得る工程と、塩化ビニル系樹脂を後塩素化する工程の
２つの工程からなる。The industrial production method of chlorinated vinyl chloride resin has two steps: a step of polymerizing vinyl chloride monomer to obtain vinyl chloride resin and a step of post-chlorinating vinyl chloride resin. Consists of.

【０００４】従来の技術では、後段の後塩素化工程で
は、主に水懸濁塩素化法が用いられてきた。水懸濁塩素
化法は、固形分濃度が数％〜数十％である塩化ビニル系
樹脂の水懸濁液を反応器内に充填し、水懸濁液を攪拌し
ながら塩素を供給して反応を行う方法である。更に、こ
れだけでは塩素化反応が全く進行しないか、極めて遅い
ので、水懸濁液に反応促進のための光、熱、触媒などが
加えられる。水懸濁塩素化法には、粒子の攪拌や混合が
容易であること、水に溶解した低濃度の塩素を使用する
ため反応制御が容易であること、塩化ビニル系樹脂が水
により可塑化されて塩素が樹脂内部まで浸透しやすいこ
と等の様々な利点がある。この為、これまでに実用化さ
れている塩素化塩化ビニル系樹脂の製造設備の多くは水
懸濁塩素化法が採用されてきた。In the prior art, the water suspension chlorination method has been mainly used in the subsequent post-chlorination step. In the water suspension chlorination method, an aqueous suspension of vinyl chloride resin having a solid content concentration of several% to several tens% is filled in a reactor, and chlorine is supplied while stirring the aqueous suspension. It is a method of carrying out the reaction. Further, since the chlorination reaction does not proceed at all or is extremely slow only by this, light, heat, a catalyst and the like for accelerating the reaction are added to the water suspension. In the water suspension chlorination method, it is easy to stir and mix particles, the reaction control is easy because a low concentration of chlorine dissolved in water is used, and vinyl chloride resin is plasticized by water. There are various advantages such as that chlorine easily penetrates into the resin. Therefore, the water suspension chlorination method has been adopted in most of the chlorinated vinyl chloride resin production facilities that have been put to practical use.

【０００５】ところが、水懸濁塩素化法は本質的に解決
不可能な問題点を有している。塩化ビニル系樹脂と塩素
から塩素化塩化ビニル系樹脂が生成する反応では、式
（１）に示すように塩化水素が発生する。したがって、
反応中および反応終了後の塩素化塩化ビニル系樹脂は高
濃度の塩酸溶液に懸濁した状態になる。However, the water suspension chlorination method has a problem that is essentially unsolvable. In a reaction in which a chlorinated vinyl chloride resin is produced from a vinyl chloride resin and chlorine, hydrogen chloride is generated as shown in formula (1). Therefore,
During and after the reaction, the chlorinated vinyl chloride resin is suspended in a high-concentration hydrochloric acid solution.

【０００６】 （ＣＨ2−ＣＨＣl）n＋ｍＣl2→（ＣＨ２−ＣＨＣl）n-m （ＣＨＣl−ＣＨＣl ）m＋ｍＨＣl ・・・（１） 塩素化塩化ビニル系樹脂の最終的な出荷形態は粉体状態
である必要があるし、不純物となる塩化水素を除去する
必要があるので、塩素化反応後の塩素化塩化ビニル系樹
脂の水懸濁液は脱水・水洗・乾燥される必要がある。こ
の為、水懸濁塩素化法のプロセスは後処理工程に大きな
設備費が必要である上に、乾燥、水洗に伴うランニング
コストが増大する。しかも、水と塩化水素は共沸状態に
なるので、最終的には完全に乾燥状態にするまで、塩化
水素を製品から除去することは出来ない。(CH 2 -CHCl) n + mCl 2 → (CH 2 -CHCl) nm (CHCl-CHCl) m + mHCl (1) The final shipping form of the chlorinated vinyl chloride resin is a powder state. Since it is necessary to remove hydrogen chloride as an impurity, it is necessary to dehydrate, wash and dry the water suspension of the chlorinated vinyl chloride resin after the chlorination reaction. Therefore, in the process of the water suspension chlorination method, a large equipment cost is required for the post-treatment step, and the running cost associated with drying and washing increases. Moreover, since water and hydrogen chloride are in an azeotropic state, hydrogen chloride cannot be removed from the product until it is completely dried.

【０００７】また、水懸濁塩素化法では、反応終了時に
は反応溶液が１０重量％程度の高濃度の塩酸溶液にな
る。この為、水懸濁塩素化法では、反応器にはチタン系
やチタンパラジウム系の高価な耐食性金属材料を利用す
るか、グラスライニング、フッ素ライニング等の表面処
理を施した装置を利用する必要がある。更に、高濃度の
塩酸である反応溶液は前述の後処理工程に持ち込まれる
為、後処理工程にも高価な耐食材料を使用する必要があ
る。Further, in the water suspension chlorination method, the reaction solution becomes a high concentration hydrochloric acid solution of about 10% by weight at the end of the reaction. Therefore, in the water suspension chlorination method, it is necessary to use an expensive titanium-based or titanium-palladium-based corrosion-resistant metal material for the reactor, or use a device that has been subjected to surface treatment such as glass lining and fluorine lining. is there. Furthermore, since the reaction solution having a high concentration of hydrochloric acid is brought into the above-mentioned post-treatment step, it is necessary to use an expensive corrosion-resistant material also in the post-treatment step.

【０００８】この様に、水懸濁塩素化法の反応器は、そ
れ自体は比較的単純であり、制御が容易な装置である
が、後処理工程まで含めたプロセス全体を考慮すると、
設備コスト及びランニングコストに大きな負荷が掛かる
と言う欠点を有する装置であった。As described above, the reactor of the water suspension chlorination method is relatively simple in itself and easy to control, but considering the whole process including the post-treatment step,
The device has a drawback that a large load is applied to equipment cost and running cost.

【０００９】一方、この様な水懸濁塩素化法の欠点を補
う為に、塩化ビニル系樹脂の粉体粒子と塩素との気固接
触場を反応場とする気固接触塩素化法による塩素化塩化
ビニル系樹脂の合成方法も提案されている。例えば、特
開昭５９−２４７０５は、塩素中に少量の酸素を混入し
た塩素ガスと塩化ビニル系樹脂を気固接触場で反応させ
る事により、光の不在下で塩化ビニル系樹脂の塩素化を
進行させる方法である。また、特公昭６０−２３２２
は、高圧低温下で塩化ビニル系樹脂に塩素を含浸させた
後に、加熱する事により、塩化ビニル系樹脂内において
熱ラジカルを発生させ、気固接触場での反応で塩素化塩
化ビニル系樹脂を得る方法である。更に、光をラジカル
発生源として用いる方法においても、塩素化塩化ビニル
系樹脂の品質を改善するための方法は提案されている。
特公昭５４−３９８７８や特公昭５２−１５６３８で
は、流動層型反応器内の粉体層中に光源を挿入し、粉体
層を塩素ガスで流動化させることにより、塩化ビニル系
樹脂と塩素とを気固接触場において反応させる方法が記
載されている。On the other hand, in order to make up for such drawbacks of the water suspension chlorination method, chlorine by a gas-solid contact chlorination method in which a gas-solid contact field between vinyl chloride resin powder particles and chlorine is used as a reaction field. A method for synthesizing a vinyl chloride resin has also been proposed. For example, JP-A-59-24705 discloses a method for chlorinating a vinyl chloride resin in the absence of light by reacting a chlorine gas containing a small amount of oxygen in chlorine with a vinyl chloride resin in a gas-solid contact field. It is a method of proceeding. In addition, Japanese Examined Japanese Patent Sho 60-2322
Is a high-pressure, low-temperature, vinyl chloride resin impregnated with chlorine, and then heated to generate thermal radicals in the vinyl chloride resin, which reacts in a gas-solid contact field to remove the chlorinated vinyl chloride resin. Is the way to get. Further, even in the method using light as a radical generation source, a method for improving the quality of the chlorinated vinyl chloride resin has been proposed.
In Japanese Examined Patent Publication No. 54-39878 and Japanese Examined Patent Publication No. 52-15638, a light source is inserted into a powder layer in a fluidized bed reactor, and the powder layer is fluidized with chlorine gas, whereby vinyl chloride resin and chlorine are separated. There is described a method of reacting with a gas-solid contact field.

【００１０】気固接触塩素化法では、発生した塩化水素
は気体として系内から排出されるので、反応終了後に残
存する塩化水素は、粉体粒子の隙間に存在するものと粉
体粒子表面に吸着している塩化水素のみである。この様
な残存塩化水素は、系内を真空脱気するか、空気や窒素
等のガスを流通して気流洗浄することにより、容易に除
去することができる。したがって、気固接触塩素化法の
後処理工程には、水洗・脱水・乾燥などの複雑な工程を
経由せず、不純物である残留塩化水素の含有量が低い製
品を得ることができる。In the gas-solid catalytic chlorination method, the generated hydrogen chloride is discharged from the system as a gas, so that the hydrogen chloride remaining after the reaction is present in the gaps between the powder particles and on the surface of the powder particles. Only adsorbed hydrogen chloride. Such residual hydrogen chloride can be easily removed by vacuum degassing the system or by flushing with a gas such as air or nitrogen. Therefore, in the post-treatment step of the gas-solid contact chlorination method, a product having a low content of residual hydrogen chloride as an impurity can be obtained without passing through complicated steps such as water washing, dehydration and drying.

【００１１】更に、気固接触塩素化法では、通常、反応
系内に水が存在しないか、若しくは微量の水分が粉体粒
子に吸着している状態で反応を実施する。この様な無水
若しくは微水の系では、金属材料に対する塩素および塩
化水素の腐食性は弱く、反応器にはニッケル系、ステン
レス系、鉄系の比較的安価な金属材料を使用することが
できる。更には、後処理工程に持ち込まれる粉体粒子に
は、微量の塩素と塩化水素が残留しているのみであるの
で、後処理工程にも安価な金属材料を利用することがで
きる。Further, in the gas-solid catalytic chlorination method, the reaction is usually carried out in the state where water does not exist in the reaction system or a trace amount of water is adsorbed on the powder particles. In such an anhydrous or fine water system, the corrosiveness of chlorine and hydrogen chloride to the metal material is weak, and nickel-based, stainless-based, or iron-based relatively inexpensive metal materials can be used in the reactor. Furthermore, since only a trace amount of chlorine and hydrogen chloride remain in the powder particles brought into the post-treatment step, an inexpensive metal material can be used in the post-treatment step.

【００１２】以上の様に、塩化ビニル系樹脂の粉体層と
塩素を反応させる気固接触塩素化法は、設備コスト、廃
水処理、安全性の面から優れた特徴を有する。As described above, the gas-solid catalytic chlorination method in which a powder layer of a vinyl chloride resin is reacted with chlorine has excellent features in terms of equipment cost, wastewater treatment, and safety.

【００１３】しかしながら、気固接触反応法において
は、反応の進行に伴い、塩素が消費され、同モル数即ち
同体積の塩化水素が生成する為、反応ガス中の塩素が塩
化水素により希釈されてゆくと言う問題がある。目的と
する塩素含有量の塩素化塩化ビニル系樹脂目を得るため
に必要な塩素を全て反応器内に充填しておけば良いので
はあるが、例えば通常の塩素化塩化ビニル系樹脂製品で
ある塩素含有量６８重量％の樹脂を得る為には、原料の
塩化ビニル系樹脂１トン当たり１８０ｍ3の塩素ガスが
必要であり、巨大な反応器や高圧反応器を要し、現実的
ではない。実用的な方法としては、反応器にガスの出入
り口を設け、塩素ガスを流通させることにより、反応生
成物である塩化水素を反応器外部に搬出する塩素流通法
がある。特公昭５４−３９８７８や特公昭５２−１５６
３８は、塩素流通法を利用している。However, in the gas-solid contact reaction method, chlorine is consumed with the progress of the reaction and hydrogen chloride having the same number of moles, that is, the same volume, is produced, so that chlorine in the reaction gas is diluted with hydrogen chloride. There is a problem of going. Although it is only necessary to fill all the chlorine necessary to obtain the desired chlorine content of the chlorinated vinyl chloride resin in the reactor, for example, a normal chlorinated vinyl chloride resin product. In order to obtain a resin having a chlorine content of 68% by weight, 180 m 3 of chlorine gas is needed per ton of vinyl chloride resin as a raw material, which requires a huge reactor and a high-pressure reactor, which is not realistic. As a practical method, there is a chlorine flow method in which a reactor is provided with a gas inlet / outlet and chlorine gas is circulated so that hydrogen chloride, which is a reaction product, is carried out of the reactor. JP-B-54-39878 and JP-B-52-156
38 uses the chlorine distribution method.

【００１４】塩素流通法では、反応生成物である塩化水
素と未反応塩素が混合した状態で、排出ガスとして反応
器外に搬出されてしまうため、未反応の塩素ガスが無駄
に廃棄されてしまう。特開昭５７−９８５０７では、未
反応の塩素を含む排出ガスを他のプロセスで利用するか
循環利用することが記載されているが、具体的手法につ
いては一切記述がない。特公昭５２−１５６３８では、
反応器を複数段設け、塩化水素と未反応塩素の混合ガス
である排出ガスを別の反応器内で反応させ、未反応塩素
ガスを再利用する方法が記載されている。しかし、この
様な方法においても、塩素を完全に再利用することは困
難であるし、排出ガスを導入する反応器内では塩素濃度
が低くなり、反応速度が低下する。液体塩素と窒素の混
合雰囲気において塩化ビニル系樹脂を塩素化する技術が
開示されている特表昭５７−５０１１８４では、塩素、
塩化水素、窒素の混合ガスである排出ガスから低温コン
デンサーを用いて塩素を凝縮分離した後、塩化水素と窒
素を分離し、窒素と液体塩素を反応に再利用する技術が
実施例として記載されている。しかし、この技術は、気
固接触場で反応を行う本発明とは技術思想が異なる上
に、塩素の凝縮温度（−３４．１℃）以下に低下させる
為の冷凍機が必須である為に設備コストが高く、窒素と
塩化水素を分離する技術については全く記載されていな
い。In the chlorine flow method, the reaction product hydrogen chloride and unreacted chlorine are mixed and carried out of the reactor as exhaust gas, so that unreacted chlorine gas is wasted. . Japanese Patent Application Laid-Open No. 57-98507 describes that the exhaust gas containing unreacted chlorine is used in another process or recycled, but no specific method is described. In Japanese Examined Patent Publication No. 52-15638,
A method in which a plurality of reactors are provided, exhaust gas which is a mixed gas of hydrogen chloride and unreacted chlorine is reacted in another reactor, and the unreacted chlorine gas is reused is described. However, even with such a method, it is difficult to completely reuse chlorine, and the chlorine concentration becomes low in the reactor into which the exhaust gas is introduced, so that the reaction rate decreases. In Japanese Patent Publication No. 57-501184, which discloses a technique for chlorinating vinyl chloride resin in a mixed atmosphere of liquid chlorine and nitrogen, chlorine,
A technique of condensing and separating chlorine from an exhaust gas which is a mixed gas of hydrogen chloride and nitrogen using a low temperature condenser, then separating hydrogen chloride and nitrogen, and reusing nitrogen and liquid chlorine in a reaction is described as an example. There is. However, this technique has a technical concept different from that of the present invention in which the reaction is performed in a gas-solid contact field, and in addition, a refrigerator for lowering the condensation temperature of chlorine (−34.1 ° C.) or lower is essential. The equipment cost is high, and the technology for separating nitrogen and hydrogen chloride is not described at all.

【００１５】[0015]

【発明が解決しようとする課題】本発明の目的は、後処
理の簡便性と設備コスト性に優れた気固接触反応法にお
いて、未反応の塩素ガスを循環利用し、塩素の利用率を
向上させる方法および装置を提供することにある。An object of the present invention is to improve the utilization rate of chlorine by circulating and utilizing unreacted chlorine gas in the gas-solid contact reaction method which is excellent in the convenience of post-treatment and the facility cost. It is to provide a method and an apparatus.

【００１６】[0016]

【課題を解決するための手段】本発明者は、塩化ビニル
系樹脂と塩素を気固接触場で反応させる方法において、
工業的に実用可能な未反応塩素ガスと塩化水素ガスの分
離法を研究した。その結果、未反応塩素ガスと塩化水素
ガスの混合ガスである排出ガスを水と接触させることに
より、排出ガスから塩化水素のみを除去し、得られた未
反応塩素ガスを再度、塩素化反応に循環利用できること
を見い出し、本発明を完成した。Means for Solving the Problems In the method of reacting a vinyl chloride resin with chlorine in a gas-solid contact field,
A method for separating unreacted chlorine gas and hydrogen chloride gas, which is industrially practical, was studied. As a result, by contacting the exhaust gas, which is a mixed gas of unreacted chlorine gas and hydrogen chloride gas, with water, only hydrogen chloride is removed from the exhaust gas, and the resulting unreacted chlorine gas is subjected to the chlorination reaction again. The present invention has been completed by finding that it can be recycled.

【００１７】即ち、本発明は、（１）塩化ビニル系樹脂
を後塩素化反応させて塩素化塩化ビニル系樹脂を製造す
る方法において、塩化ビニル系樹脂と塩素とを気固接触
反応場で反応させ、反応ガスの一部又は全部を反応器の
外部に排出し、排出ガスと水とを接触させることによ
り、排出ガス中の塩化水素ガスを水に吸収させて脱塩化
水素ガスを得た後に、脱塩化水素ガスを反応器内に環
流、導入し、塩化ビニル系樹脂の塩素化反応に利用する
ことを特徴とする塩素化塩化ビニル系樹脂の製造方法
（請求項１）、（２）脱塩化水素ガスと接触させる水
が、循環水及び／又は貯水である請求項１に記載の塩素
化塩化ビニル系樹脂の製造方法（請求項２）、（３）脱
塩化水素ガスと接触させる水が、零℃を越え、４０℃以
下の範囲の温度の水である請求項１及び２に記載の塩素
化塩化ビニル系樹脂の製造方法（請求項３）、（４）脱
塩化水素ガスを脱水した後に、再び反応器に導入し、塩
化ビニル系樹脂の塩素化反応に利用する請求項１、２お
よび３に記載の塩素化塩化ビニル系樹脂の製造方法（請
求項４）、（５）脱塩化水素ガスを５℃以下、零下１０
１℃以上の範囲の温度に冷却した後に、脱水ガスとして
再び反応器に導入し、塩化ビニル系樹脂の塩素化反応に
利用する請求項４に記載の塩素化塩化ビニル系樹脂の製
造方法（請求項５）、（６）脱塩化水素ガスを零下１３
℃以下、零下１０１℃以上の範囲の温度に冷却した後
に、脱水ガスとして再び反応器に導入し、塩化ビニル系
樹脂の塩素化反応に利用する請求項４に記載の塩素化塩
化ビニル系樹脂の製造方法（請求項６）、（７）脱塩化
水素ガスを零下３６℃以下、零下１０１℃以上の範囲の
温度に冷却して液化し、液化した塩素を再び気化させた
後に、脱水ガスとして再び反応器に導入し、塩化ビニル
系樹脂の塩素化反応に利用する請求項４に記載の塩素化
塩化ビニル系樹脂の製造方法（請求項７）、（８）脱塩
化水素ガスを硫酸、塩化カルシウム、ゼオライト、モレ
キュラーシーブス、五酸化二燐から選択される少なくと
も１種と接触させた後に、脱水ガスとして再び反応器に
導入し、塩化ビニル系樹脂の塩素化反応に利用する請求
項４に記載の塩素化塩化ビニル系樹脂の製造方法（請求
項８）、（９）脱塩化水素ガスを５℃以下に冷却し、冷
却と同時に又は冷却後に硫酸、塩化カルシウム、ゼオラ
イト、モレキュラーシーブス、五酸化二燐から選択され
る少なくとも１種と接触させた後に、脱水ガスとして再
び反応器に導入し、塩化ビニル系樹脂の塩素化反応に利
用する請求項４に記載の塩素化塩化ビニル系樹脂の製造
方法（請求項９）、（１０）脱水ガスの含水量が５０重
量ｐｐｍ以下である請求項７〜９に記載の塩素化塩化ビ
ニル系樹脂の製造方法（１０）、（１１）水に吸収され
た塩化水素と等量のモル数の塩素を、脱塩化水素ガス又
は脱水ガスと共に反応器内に供給する請求項１〜１０に
記載の塩素化塩化ビニル系樹脂の製造方法（請求項１
１）、（１２）反応器、脱塩化水素器、脱水器から成る
装置を密閉型装置とし、密閉型装置内部の圧力を一定に
保つ為に必要な塩素を、密閉型装置内部に供給する請求
項１〜１１に記載の塩素化塩化ビニル系樹脂の製造方法
（請求項１２）、（１３）塩素化反応の反応促進の為に
光を使用する、請求項１〜１２に記載の塩素化塩化ビニ
ル系樹脂の製造方法（請求項１３）、（１４）反応促進
の為の光の光源が、低圧水銀灯、高圧水銀灯、超高圧水
銀灯、メタルハライドランプから選択される少なくとも
一種である請求項１３に記載の塩素化塩化ビニル系樹脂
の製造方法（請求項１４）、（１５）塩化ビニル系樹脂
粉体と塩素ガスを気固接触反応場で反応させる反応器、
該反応器から反応ガスを排出する排出ガス管、該排出管
に接続された脱塩化水素器、および該脱塩化水素器から
の塩素ガスを含む脱塩化水素ガスを反応器に環流するた
めの導入ガス管を備えてなる塩化ビニル系樹脂を後塩素
化反応させて塩素化塩化ビニル系樹脂を製造する装置
（請求項１５）、（１６）脱塩化水素器が反応ガスと水
を接触させ、反応ガス中の塩化水素ガスを水に吸収させ
る装置である請求項１５記載の装置（請求項１６）、
（１７）脱塩化水素ガスと接触させる水が、零℃を越
え、４０℃以下の範囲の温度の水である請求項１５及び
１６に記載の装置（請求項１７）、（１８）脱塩化水素
ガスを脱水した後に、反応器に導入する請求項１５、１
６および１７に記載の装置（請求項１８）、（１９）脱
塩化水素ガスを５℃以下、零下１０１℃以上の範囲の温
度に冷却した後に、脱水ガスとして再び反応器に導入
し、塩化ビニル系樹脂の塩素化反応に利用する請求項１
８に記載の装置（請求項１９）、（２０）脱塩化水素ガ
スを零下１３℃以下、零下１０１℃以上の範囲の温度に
冷却した後に、脱水ガスとして再び反応器に導入し、塩
化ビニル系樹脂の塩素化反応に利用する請求項１８に記
載の装置（請求項２０）、（２１）脱塩化水素ガスを零
下３６℃以下、零下１０１℃以上の範囲の温度に冷却し
て液化し、液化した塩素を再び気化させた後に、脱水ガ
スとして再び反応器に導入し、塩化ビニル系樹脂の塩素
化反応に利用する請求項１８に記載の装置（請求項２
１）、（２２）脱塩化水素ガスを硫酸、塩化カルシウ
ム、ゼオライト、モレキュラーシーブス、五酸化二燐か
ら選択される少なくとも１種と接触させた後に、脱水ガ
スとして再び反応器に導入し、塩化ビニル系樹脂の塩素
化反応に利用する請求項１８に記載の装置（請求項２
２）、（２３）脱塩化水素ガスを５℃以下に冷却し、冷
却と同時に又は冷却後に硫酸、塩化カルシウム、ゼオラ
イト、モレキュラーシーブス、五酸化二燐から選択され
る少なくとも１種と接触させた後に、脱水ガスとして再
び反応器に導入し、塩化ビニル系樹脂の塩素化反応に利
用する請求項１８に記載の装置（請求項２３）、（２
４）脱水ガスの含水量が５０重量ｐｐｍ以下である請求
項２１〜２３に記載の装置（請求項２４）、（２５）水
に吸収された塩化水素と等量のモル数の塩素を、脱塩化
水素ガス又は脱水ガスと共に反応器内に供給する請求項
１５〜２４に記載の装置（請求項２５）、（２６）反応
器、塩化水素吸収器、脱水器から成る装置を密閉型装置
とし、密閉型装置内部の圧力を一定に保つ為に必要な塩
素を、密閉型装置内部に供給する請求項１５〜２４に記
載の装置（請求項２６）、（２７）塩素化反応の反応促
進の為に光を使用する、請求項１５〜２６に記載の装置
（請求項２７）、および（２８）反応促進の為の光の光
源が、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタル
ハライドランプから選択される少なくとも一種である請
求項２７に記載の装置（請求項２８）、に関する。That is, according to the present invention, (1) in a method for producing a chlorinated vinyl chloride resin by post-chlorinating a vinyl chloride resin, the vinyl chloride resin and chlorine are reacted in a gas-solid contact reaction field. Then, a part or all of the reaction gas is discharged to the outside of the reactor, and the exhaust gas and water are brought into contact with each other to absorb the hydrogen chloride gas in the exhaust gas into the water to obtain dehydrochlorination gas. A method for producing a chlorinated vinyl chloride resin, characterized in that dehydrochlorination gas is refluxed and introduced into the reactor and used for the chlorination reaction of the vinyl chloride resin (Claim 1), (2) The water contacted with the hydrogen chloride gas is circulating water and / or stored water. The method for producing a chlorinated vinyl chloride resin according to claim 1 (claim 2), (3) the water contacted with the dehydrochlorinated gas is , Water at a temperature in the range above 0 ° C and below 40 ° C Method for producing chlorinated vinyl chloride resin according to claim 1 or claim 2 (claim 3), (4) Dehydrochlorination gas is dehydrated, and then introduced into the reactor again to chlorinate vinyl chloride resin. The method for producing a chlorinated vinyl chloride resin according to any one of claims 1, 2 and 3 (claim 4), wherein (5) dehydrochlorination gas is at 5 ° C or less and below zero 10
The method for producing a chlorinated vinyl chloride-based resin according to claim 4, wherein after cooling to a temperature in the range of 1 ° C. or higher, the dehydrated gas is introduced again into the reactor and used for the chlorination reaction of the vinyl chloride-based resin. Item 5), (6) Dehydrochlorination gas below zero 13
5. The chlorinated vinyl chloride resin according to claim 4, which is cooled to a temperature in the range of not more than 0 ° C. and below 101 ° C. below zero and then introduced again into the reactor as a dehydration gas for use in the chlorination reaction of the vinyl chloride resin. Manufacturing method (Claim 6), (7) Dehydrochlorination gas is liquefied by cooling to a temperature in the range of 36 ° C. below zero and 101 ° C. below zero, and liquefied chlorine is vaporized again, and then again used as dehydrated gas. The method for producing a chlorinated vinyl chloride resin according to claim 4, which is introduced into a reactor and used for a chlorination reaction of the vinyl chloride resin (claim 7), (8) dehydrochlorination gas is sulfuric acid, calcium chloride. 5. The method according to claim 4, which is brought into contact with at least one selected from zeolite, molecular sieves and diphosphorus pentoxide, and then introduced into the reactor again as dehydration gas to be used for the chlorination reaction of vinyl chloride resin. Chlorination Method for producing vinyl chloride resin (Claim 8), (9) Cooling dehydrochlorination gas to 5 ° C. or lower, and selecting from sulfuric acid, calcium chloride, zeolite, molecular sieves, and diphosphorus pentoxide simultaneously with or after cooling. The method for producing a chlorinated vinyl chloride resin according to claim 4, wherein the dehydrated gas is introduced into the reactor again and used in the chlorination reaction of the vinyl chloride resin after being brought into contact with at least one of the above-mentioned compounds (claim 5). 9), (10) The method for producing a chlorinated vinyl chloride resin according to claims 7 to 9, wherein the dehydrated gas has a water content of 50 ppm by weight or less, and (11) hydrogen chloride absorbed in water. The method for producing a chlorinated vinyl chloride resin according to any one of claims 1 to 10, wherein an equal number of moles of chlorine is supplied into the reactor together with dehydrochlorination gas or dehydration gas (claim 1
1), (12) A device comprising a reactor, a dehydrochlorination device, and a dehydrator is a closed type device, and chlorine required for maintaining a constant pressure inside the closed type device is supplied into the closed type device. The method for producing a chlorinated vinyl chloride resin according to any one of Items 1 to 11 (Claim 12), and (13) the use of light to accelerate the reaction of the chlorination reaction. The method for producing a vinyl resin (Claim 13), (14) The light source for accelerating the reaction is at least one selected from a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp. (15) A reactor for reacting vinyl chloride resin powder and chlorine gas in a gas-solid contact reaction field,
An exhaust gas pipe for discharging a reaction gas from the reactor, a dehydrochlorination device connected to the exhaust pipe, and an introduction for refluxing the dehydrochlorination gas containing chlorine gas from the dehydrochlorination device to the reactor. An apparatus for producing a chlorinated vinyl chloride resin by subjecting a vinyl chloride resin having a gas pipe to a post-chlorination reaction (claim 15), (16) a dehydrochlorination device brings the reaction gas and water into contact, The device according to claim 15 (claim 16), which is a device for absorbing hydrogen chloride gas in the gas into water.
(17) The apparatus according to claims 15 and 16 (claim 17), wherein the water contacted with the dehydrochlorination gas has a temperature in the range of more than 0 ° C and 40 ° C or less, (18) dehydrochlorination. 16. Dehydrating the gas and then introducing it into the reactor.
The apparatus according to claims 6 and 17 (claim 18), (19) After cooling the dehydrochlorination gas to a temperature in the range of 5 ° C or lower and 101 ° C or lower below zero, it is introduced again into the reactor as dehydrated gas to obtain vinyl chloride. Use for chlorination reaction of resin
8. The apparatus according to claim 8 (claim 19), (20) after cooling the dehydrochlorination gas to a temperature in the range of 13 ° C. below zero and 101 ° C. below zero, it is again introduced into the reactor as dehydration gas, and a vinyl chloride system is used. The apparatus according to claim 18 (claim 20) for use in a chlorination reaction of a resin, (21) dehydrochlorination gas is liquefied by being cooled to a temperature in the range of 36 ° C below zero or 101 ° C below zero. The apparatus according to claim 18, wherein after the vaporized chlorine is vaporized again, it is introduced again into the reactor as a dehydration gas and used for the chlorination reaction of the vinyl chloride resin (claim 2).
1) and (22) After dehydrochlorination gas is contacted with at least one selected from sulfuric acid, calcium chloride, zeolite, molecular sieves and diphosphorus pentoxide, it is introduced into the reactor again as dehydration gas, and vinyl chloride is added. The apparatus according to claim 18 used for a chlorination reaction of a resin (claim 2
2), (23) cooling the dehydrochlorination gas to 5 ° C. or lower, and after contacting with at least one selected from sulfuric acid, calcium chloride, zeolite, molecular sieves and diphosphorus pentoxide simultaneously with or after cooling The apparatus according to claim 18 (claim 23), (2), which is introduced into the reactor again as dehydration gas and used for the chlorination reaction of the vinyl chloride resin.
4) The apparatus according to any one of claims 21 to 23 (claim 24), wherein the water content of the dehydrated gas is 50 ppm by weight or less, and (25) dehydrogenating chlorine in an amount equal to that of hydrogen chloride absorbed in water. An apparatus comprising a device (claim 25), (26) reactor, a hydrogen chloride absorber, and a dehydrator according to any one of claims 15 to 24, which is supplied together with hydrogen chloride gas or dehydration gas into a closed type device, The apparatus (claim 26) according to any one of claims 15 to 24, wherein chlorine required for keeping the pressure inside the closed apparatus constant is supplied to the inside of the closed apparatus, and (27) for accelerating the reaction of the chlorination reaction. The light source for accelerating the reaction is selected from a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp. 28. At least one of Location (claim 28) relates.

【００１８】[0018]

【発明の実施の形態】本発明で用いる塩化ビニル系樹脂
は、塩化ビニル系樹脂が樹脂の内部まで均一に塩素化さ
せ反応効率を高める観点などから、粉体状であることが
好ましい。本発明で言う粉体とは、前述の様に気相中に
おいて単独に移動可能な粒子の集合体であり、各粒子の
粒径の目安としては、およそ１０μｍ以上２０００μｍ
以下（平均粒径が５０〜５００μｍ）の範囲にある。本
発明では、気相中において単独で移動可能な粒子の一つ
一つを粉体粒子、粉体粒子の集合体を粉体層と呼び区別
する。BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin used in the present invention is preferably in powder form from the viewpoint of uniformly chlorinating the vinyl chloride resin to the inside of the resin to enhance reaction efficiency. The powder referred to in the present invention is an aggregate of particles that can move independently in the gas phase as described above, and the standard of the particle size of each particle is about 10 μm to 2000 μm.
It is in the following range (average particle size is 50 to 500 μm). In the present invention, each of the particles that can move independently in the gas phase is called a powder particle, and an aggregate of powder particles is called a powder layer to distinguish them.

【００１９】粉体粒子の粒径分布は、粉体の流動性を高
める観点、および反応を均一に進行させると言う観点か
ら、均一であることが好ましいことから本発明における
塩化ビニル系樹脂の粉体層は、５０μｍ以上、５００μ
ｍ以下の粒子径が主体となる粉体粒子（平均粒径が１０
０〜３００μｍ）の集合体であることが好ましい。個々
の粉体粒子は、塩化ビニル系樹脂の連続相からなってい
ても良いし、より小さな一次粒子の集合体であっても良
い。Since the particle size distribution of the powder particles is preferably uniform from the viewpoint of improving the fluidity of the powder and the viewpoint of allowing the reaction to proceed uniformly, the powder of the vinyl chloride resin in the present invention is preferable. Body layer is 50μm or more, 500μ
Powder particles mainly having a particle size of m or less (average particle size is 10
It is preferably an aggregate of 0 to 300 μm). Each powder particle may be composed of a continuous phase of vinyl chloride resin, or may be an aggregate of smaller primary particles.

【００２０】塩化ビニル系樹脂の製造方法は、懸濁重合
法、塊状重合法、気相重合法、乳化重合法等の様々な方
法があるが、本発明で用いる塩化ビニル系樹脂はいずれ
の方法で得られたものでも使用できる。また、塩化ビニ
ルと反応可能な、例えば酢酸ビニル等の不飽和炭化水素
化合物との共重合体を用いても良い。重合反応後に得ら
れた塩化ビニル系樹脂が水懸濁液で有れば、乾燥して粉
体とする。塊状であれば粉砕等の操作が必要である。し
かし、塊状重合で得られる塩化ビニル系樹脂は、粉砕工
程に困難がある。気相重合による塩化ビニル系樹脂は通
常、入手が難しい。また、乳化重合法で得られる塩化ビ
ニル系樹脂は乳化剤が多量に混入している。これらのこ
とから、本発明に用いられる塩化ビニル系樹脂として
は、懸濁重合法で得られるものが好ましい。There are various methods for producing the vinyl chloride resin, such as suspension polymerization method, bulk polymerization method, gas phase polymerization method and emulsion polymerization method. Any method can be used for the vinyl chloride resin used in the present invention. You can also use the one obtained in. Further, a copolymer with an unsaturated hydrocarbon compound such as vinyl acetate which can react with vinyl chloride may be used. If the vinyl chloride resin obtained after the polymerization reaction is an aqueous suspension, it is dried to give a powder. If it is a lump, operations such as crushing are necessary. However, the vinyl chloride resin obtained by bulk polymerization has a difficulty in the pulverization process. Vinyl chloride resins obtained by gas phase polymerization are usually difficult to obtain. Further, the vinyl chloride resin obtained by the emulsion polymerization method contains a large amount of emulsifier. From these things, as the vinyl chloride resin used in the present invention, those obtained by the suspension polymerization method are preferable.

【００２１】本発明では、塩化ビニル系樹脂が流動可能
な粉体層であれば、水分が含まれていても使用できる
が、含水量が多すぎると、反応により発生する塩化水素
が樹脂中から除去し難くなる。したがって、粉体層中の
含水量が５重量％未満であることが好ましい。なお、静
電気による粉体粒子の凝集や容器への付着を防止するた
めに、塩化ビニル系樹脂の粉体に意図的に５重量％未満
の水分を含ませることは可能である。In the present invention, a vinyl chloride resin can be used even if it contains water as long as it is a powder layer in which the resin can flow, but if the water content is too high, hydrogen chloride generated by the reaction will be generated from the resin. It becomes difficult to remove. Therefore, the water content in the powder layer is preferably less than 5% by weight. It is possible to intentionally add less than 5% by weight of water to the vinyl chloride resin powder in order to prevent the powder particles from aggregating and adhering to the container due to static electricity.

【００２２】懸濁重合法や乳化重合法により塩化ビニル
系樹脂を合成した場合には、塩化ビニル系樹脂の微粒子
が水に分散した状態であるので、乾燥するだけで粉体粒
子を得られる。しかし、この場合、粉体粒子表面にスキ
ン層と呼ばれる連続層が形成され、塩素ガスの内部への
浸透を阻害し、反応速度が遅くなったり、反応率が粉体
粒子の半径方向に不均一になる場合がある。したがっ
て、本発明で用いる塩化ビニル系樹脂の粉体粒子は、塩
素化反応前に予め粉砕し、スキン層を破壊して用いるこ
とも有効である。When the vinyl chloride resin is synthesized by the suspension polymerization method or the emulsion polymerization method, the fine particles of the vinyl chloride resin are in a state of being dispersed in water, so that the powder particles can be obtained only by drying. However, in this case, a continuous layer called a skin layer is formed on the surface of the powder particles, which impedes the penetration of chlorine gas into the interior, slows the reaction rate, and the reaction rate is uneven in the radial direction of the powder particles. May be. Therefore, it is also effective to pulverize the powder particles of the vinyl chloride resin used in the present invention in advance before the chlorination reaction and destroy the skin layer before use.

【００２３】本発明で用いる塩素は、一般に工業的に用
いられている塩素であれば、特に制限はない。但し、塩
素中に酸素が含まれると、得られる塩素化塩化ビニル系
樹脂の熱安定性や成型時、着色の原因になることから、
塩素中に含まれる酸素濃度は１００重量ｐｐｍ以下であ
ることが好ましく、２０重量ｐｐｍ以下であることが更
に好ましい。また、塩素中に水分が含まれると、反応に
より発生する塩化水素が樹脂中から除去し難くなった
り、装置の腐食を引き起こすことがあるので、塩素ガス
中の含水量は５００重量ｐｐｍ以下であることが好まし
く、５０重量ｐｐｍ以下で有ることが更に好ましい。ま
た、反応速度や反応温度を調節するために、塩素を窒素
やアルゴン等の不活性ガスで希釈しても良い。この場合
においても、希釈後のガス中の酸素濃度は１００ｐｐｍ
以下であることが好ましく、２０ｐｐｍ以下であること
が更に好ましい。また、希釈後のガス中の含水量は５０
０重量ｐｐｍ以下であることが好ましく、５０重量ｐｐ
ｍ以下で有ることが最も好ましい。The chlorine used in the present invention is not particularly limited, as long as it is generally used industrially. However, if oxygen is contained in chlorine, it will cause coloration during thermal stability and molding of the obtained chlorinated vinyl chloride resin,
The concentration of oxygen contained in chlorine is preferably 100 ppm by weight or less, and more preferably 20 ppm by weight or less. In addition, when water is contained in chlorine, hydrogen chloride generated by the reaction may be difficult to remove from the resin or may cause corrosion of the apparatus, so the water content in chlorine gas is 500 ppm by weight or less. It is preferable that the content is 50 ppm by weight or less. Further, chlorine may be diluted with an inert gas such as nitrogen or argon in order to control the reaction rate and reaction temperature. Even in this case, the oxygen concentration in the diluted gas is 100 ppm.
It is preferably below, and more preferably below 20 ppm. The water content in the diluted gas is 50.
It is preferably 0 ppm by weight or less, and 50 ppm by weight
Most preferably, it is m or less.

【００２４】本発明で使用する装置の例を図１に示し、
それぞれ部分におけるガスの組成と定義を説明する。ボ
ンベや容器から新規に反応器に供給される塩素ガス（及
び不活性ガス）については、供給ガス（１）と呼ぶ。反
応器から排出された直後の未反応の塩素ガス、塩化水素
ガス、（及び不活性ガス）からなる混合ガスを、排出ガ
ス（２）と呼ぶ。排出ガスを水と接触させ、塩化水素を
除去した後の塩素ガス（及び不活性ガス）を、脱塩化水
素ガス（３）と呼び、更に脱塩化水素ガスに含まれる水
分を除去した後の塩素ガス（及び不活性ガス）を、脱水
ガス（４）と呼ぶ。反応器に再び導入する脱水ガス、若
しくは脱水ガスと供給ガスの混合ガスを、導入ガス
（５）と呼ぶ。An example of the apparatus used in the present invention is shown in FIG.
The composition and definition of the gas in each part will be explained. The chlorine gas (and inert gas) newly supplied to the reactor from the cylinder or container is referred to as the supply gas (1). A mixed gas composed of unreacted chlorine gas, hydrogen chloride gas (and an inert gas) immediately after being discharged from the reactor is referred to as an exhaust gas (2). The chlorine gas (and inert gas) after removing the hydrogen chloride by contacting the exhaust gas with water is called dehydrochlorination gas (3), and the chlorine after removing the water contained in the dehydrochlorination gas The gas (and the inert gas) is called the dehydration gas (4). The dehydrated gas that is reintroduced into the reactor or a mixed gas of the dehydrated gas and the feed gas is referred to as an introduced gas (5).

【００２５】本発明における反応ガスの収支について説
明する。気固接触反応においては、式（１）に示すよう
に１分子の塩素ガスと塩化ビニル系樹脂が反応し、１分
子の塩化水素ガスが発生する。反応前のガス組成は塩素
ガス単独、若しくは塩素ガスと不活性ガスの混合ガスで
あり、反応後のガス組成は塩素ガスと塩化水素ガスの混
合ガス、若しくは塩素ガス、塩化水素ガス、不活性ガス
の混合ガスである。反応の前後では気相部の圧および体
積は変化しない為、反応器を密閉型にしてしまうと、反
応器を巨大にするか、高圧反応器を利用する必要があ
り、現実的ではない。反応器をガス流通式にして新しい
塩素ガス反応器内に供給し、同時に塩化水素を反応器外
に排出すれば、内圧を上げることなく、反応に必要な塩
素を連続的に供給することが可能であるが、未反応の塩
素も一緒に排出されてしまい、塩素の利用効率が低下し
てしまう。ガス流通量を極めて低量に設定すれば、塩素
の利用率を向上させることは可能であるが、反応器内部
の塩素濃度が低下して塩素化塩化ビニル系樹脂の生成速
度が遅くなる。また、反応器内部の塩素濃度が低下する
と、脱塩化水素反応等の副反応が進行する割合が増加す
るため、得られる塩素化塩化ビニル系樹脂の品質が低下
する。そこで、反応器から排出されるガスから塩化水素
のみを除去し、塩素濃度を高めたガスを再び反応に利用
すれば、反応速度と品質を保つために必要な塩素を供給
しながら、塩素の利用効率を高めることができる。The balance of the reaction gas in the present invention will be described. In the gas-solid contact reaction, one molecule of chlorine gas reacts with the vinyl chloride resin as shown in formula (1) to generate one molecule of hydrogen chloride gas. The gas composition before the reaction is chlorine gas alone or a mixed gas of chlorine gas and an inert gas, and the gas composition after the reaction is a mixed gas of chlorine gas and hydrogen chloride gas, or chlorine gas, hydrogen chloride gas, an inert gas. It is a mixed gas of. Since the pressure and volume of the gas phase part do not change before and after the reaction, if the reactor is sealed, it is necessary to make the reactor huge or use a high pressure reactor, which is not realistic. If the reactor is made into a gas flow type and supplied into a new chlorine gas reactor, and at the same time hydrogen chloride is discharged to the outside of the reactor, chlorine required for the reaction can be continuously supplied without increasing the internal pressure. However, unreacted chlorine is also discharged together with the chlorine, resulting in a decrease in chlorine utilization efficiency. If the gas flow rate is set to be extremely low, it is possible to improve the utilization rate of chlorine, but the chlorine concentration inside the reactor will decrease and the production rate of chlorinated vinyl chloride resin will slow down. Further, when the chlorine concentration inside the reactor decreases, the rate of advancing side reactions such as dehydrochlorination reaction increases, so the quality of the obtained chlorinated vinyl chloride resin decreases. Therefore, if only hydrogen chloride is removed from the gas discharged from the reactor and the gas with an increased chlorine concentration is used again in the reaction, the chlorine can be used while supplying the chlorine required to maintain the reaction rate and quality. The efficiency can be increased.

【００２６】塩素と塩化水素の分離方法について説明す
る。本発明では、塩素と塩化水素の水への溶解度が大き
く異なる性質を利用して塩素と塩化水素とを分離する。
理化学事典（岩波書店）によれば、水１００ｇに対する
溶解量は、塩素は０．６４１ｇ（２５℃）のみである
が、塩化水素は７１．９ｇ（２０℃）にのぼる。塩素の
溶解度は、塩化水素が共存すると更に低下することも知
られている。したがって、反応器からの排出ガスを水と
接触させることにより、排出ガス中の塩化水素を水に溶
解させて除去することができる。この時、塩素や希釈用
の不活性ガスは水に殆ど溶解しないため、排出ガスから
塩化水素のみをほぼ完全に除去した脱塩化水素ガスを得
ることができる。A method of separating chlorine and hydrogen chloride will be described. In the present invention, chlorine and hydrogen chloride are separated by utilizing the property that the solubilities of chlorine and hydrogen chloride in water are greatly different.
According to the Physics and Chemistry Encyclopedia (Iwanami Shoten), the amount of dissolved chlorine in 100 g of water is only 0.641 g (25 ° C.), but the amount of hydrogen chloride is 71.9 g (20 ° C.). It is also known that the solubility of chlorine is further reduced when hydrogen chloride coexists. Therefore, by bringing the exhaust gas from the reactor into contact with water, hydrogen chloride in the exhaust gas can be dissolved in water and removed. At this time, since chlorine and an inert gas for dilution are hardly dissolved in water, it is possible to obtain a dehydrochlorinated gas in which only hydrogen chloride is almost completely removed from the exhaust gas.

【００２７】排出ガスと水を接触させる方法および装置
は、公知の技術を使用することができ、特に制限はな
い。一般的な装置としては、スクラバーや気泡塔を使用
すると良い。スクラバーを使用する場合には、複数の水
滴を降らせた空間中に排出ガスを通過させても良いし、
スクラバー内に設置した充填物に水を注ぎながら充填物
の空間に排出ガスを通過させると接触効率を高めること
ができて良い。脱塩化水素に使用する水は、塩化水素吸
収後は塩酸になるが、塩化水素濃度が飽和状態の塩酸に
なるまで水を使用することが出来る。したがって、スク
ラバーを使用する場合には、スクラバー底部から回収さ
れた塩酸を上部汲み上げ再度、脱塩化水素の為に循環水
として使用することが好ましいが、水を循環することは
必須ではなく、一度だけ接触させて使用してもかまわな
い。気泡塔を使用する場合には塔内の貯水が飽和状態の
塩酸になるまで使用することができる。但し、塩酸を飽
和状態まで使用すると、塩化水素の吸収能力が低下する
恐れもあるので、塩酸濃度を３５重量％以下にすること
が好ましく、２０重量％以下にすることが更に好まし
い。水資源の節約と言う観点からは、脱塩化水素装置に
使用する水は、塩酸が望みの濃度に達するまで、循環再
利用することが好ましい。この様にして生成した塩酸中
には僅かな塩素が溶解しているが、空気や窒素でバブリ
ングする等の方法で塩素を除去することができ、塩酸と
して他のプロセスやその他工業用に使用することができ
る。As the method and apparatus for contacting the exhaust gas with water, known techniques can be used and there is no particular limitation. A scrubber or bubble column may be used as a general device. When using a scrubber, the exhaust gas may pass through the space where multiple drops of water have fallen,
The contact efficiency may be improved by passing the exhaust gas through the space of the packing while pouring water into the packing installed in the scrubber. The water used for dehydrochlorination becomes hydrochloric acid after absorbing hydrogen chloride, but water can be used until the hydrochloric acid concentration becomes saturated hydrochloric acid. Therefore, when using a scrubber, it is preferable to pump up the hydrochloric acid recovered from the bottom of the scrubber and use it again as circulating water for dehydrochlorination, but it is not essential to circulate the water, and only once. It does not matter if they are used in contact with each other. When a bubble column is used, it can be used until the stored water in the column becomes saturated hydrochloric acid. However, when hydrochloric acid is used up to a saturated state, the absorption capacity of hydrogen chloride may decrease, so the concentration of hydrochloric acid is preferably 35% by weight or less, more preferably 20% by weight or less. From the viewpoint of saving water resources, it is preferable that the water used in the dehydrochlorination apparatus be recycled and reused until the hydrochloric acid reaches a desired concentration. Although a small amount of chlorine is dissolved in the hydrochloric acid generated in this way, it can be removed by bubbling with air or nitrogen, and used as hydrochloric acid for other processes or for other industrial uses. be able to.

【００２８】排出ガスと接触させる水の温度について説
明する。排出ガスと接触させる水の温度は、低温である
程、塩化水素の溶解度は高くなり、効率良く塩化水素を
吸収することができる。排出ガスと接触させる水の温度
が、４０℃以下であると飽和塩酸の濃度を３５重量％以
上（工業的に利用される濃塩酸濃度）にすることがで
き、好ましい。また、排出ガスと接触させる水の温度が
低いほど、脱塩化水素ガスに含有される水分が低下して
ガスの腐食性が低下するし、後段の脱水器への能力負荷
が減少する。例えば、５℃、１５、℃、４０℃の水の平
衡水蒸気圧は、それぞれ６．２ｍｍＨｇ 、１２．８ｍ
ｍＨｇ 、５５．３ｍｍＨｇであり、含水量に換算する
と２０６８重量ｐｐｍ、４２７０重量ｐｐｍ 、１８４
６７重量ｐｐｍとなる。ガスの腐食性の観点からは、排
出ガスと接触させる水の温度は、含水量が５０００ｐｐ
ｍ程度になる１５℃以下であることがより好ましく、２
０００ｐｐｍ程度になる５℃以下であることが最も好ま
しい。The temperature of the water brought into contact with the exhaust gas will be described. The lower the temperature of the water brought into contact with the exhaust gas, the higher the solubility of hydrogen chloride, and the more efficient the absorption of hydrogen chloride. When the temperature of the water contacted with the exhaust gas is 40 ° C. or lower, the concentration of saturated hydrochloric acid can be 35% by weight or more (concentrated hydrochloric acid concentration used industrially), which is preferable. Further, the lower the temperature of the water to be brought into contact with the exhaust gas, the lower the water content in the dehydrochlorination gas, the lower the corrosiveness of the gas, and the lower the capacity load on the dehydrator in the subsequent stage. For example, the equilibrium water vapor pressures of water at 5 ° C, 15, ° C, and 40 ° C are 6.2 mmHg and 12.8 m, respectively.
mHg 2, 55.3 mmHg, and converted into water content, 2068 ppm by weight, 4270 ppm by weight, 184
It becomes 67 weight ppm. From the viewpoint of the corrosiveness of gas, the temperature of the water contacted with the exhaust gas has a water content of 5000 pp.
It is more preferable that the temperature is 15 ° C. or lower, which is about m
Most preferably, the temperature is 5 ° C or lower, which is about 000 ppm.

【００２９】塩化水素が水に溶解する際には、水和熱が
発生する為、排出ガスと接触させる循環水や貯水を冷却
装置で除熱しながら、所定の温度に調整すると良い。Since hydration heat is generated when hydrogen chloride is dissolved in water, it is advisable to adjust the temperature to a predetermined temperature while removing the circulating water and stored water that come into contact with the exhaust gas with a cooling device.

【００３０】脱塩化水素ガス中の水の存在は、塩化ビニ
ル系樹脂の塩素化反応に対しては悪影響を及ぼさない
が、反応終了後の塩素化塩化ビニル系樹脂に吸着した塩
酸の除去を困難にする。また、水を含有する脱塩化水素
ガスを反応器に導入する場合には、反応器や配管に高価
な耐腐食材料を使用する必要がある。耐腐食材料として
は、チタン、チタン−パラジウム合金、ニッケル系合
金、グラスライニング、ゴムライニング、テフロン（登
録商標）ライニング、ＰＶＣライニング等の材料が上げ
られる。The presence of water in the dehydrochlorinated gas has no adverse effect on the chlorination reaction of the vinyl chloride resin, but it is difficult to remove the hydrochloric acid adsorbed on the chlorinated vinyl chloride resin after the reaction is completed. To Further, when introducing dehydrochlorination gas containing water into the reactor, it is necessary to use an expensive corrosion-resistant material for the reactor and piping. Examples of the corrosion resistant material include titanium, titanium-palladium alloy, nickel alloy, glass lining, rubber lining, Teflon (registered trademark) lining, PVC lining and the like.

【００３１】後処理における塩化水素除去の容易化と装
置の腐食性に関する観点から、排出ガスと水を接触させ
て得た脱塩化水素ガスは、脱水してから反応器に導入す
ることが好ましい。具体的には、脱水ガス中の含水量を
５００ｐｐｍ以下にすると金属の腐食性を低下させるこ
とが出来る為に好ましく、５０ｐｐｍ以下にすると殆ど
の金属材料が長期に渡り腐食しない為、最も好ましい。From the viewpoint of facilitating the removal of hydrogen chloride in the post-treatment and the corrosiveness of the apparatus, it is preferable that the dehydrochlorinated gas obtained by contacting the exhaust gas with water is dehydrated and then introduced into the reactor. Specifically, if the water content in the dehydrated gas is 500 ppm or less, the corrosiveness of the metal can be lowered, and if it is 50 ppm or less, most metal materials do not corrode for a long period of time, and it is most preferable.

【００３２】本発明で用いる脱水器は、従来工業的に用
いられる技術が使用でき、特に制限はない。工業的上、
一般的に、好ましい脱水方法として、冷却脱水法と脱水
剤を用いる方法がある。冷却脱水法は、脱塩化水素塩素
ガスを冷却して水蒸気圧を低下させ、水を凝縮させる方
法である。反応器や配管に耐腐食材料を用いる場合に
は、塩素化塩化ビニル系樹脂の表面への水の結露を防止
できれば良いので、５℃以下に冷却することが好まし
い。冷却脱水法では、望む含水量から水蒸気圧を逆算す
れば、脱水に必要な冷却温度を決定することが出来る。
例えば、含水量を５００ｐｐｍまで低下させようとすれ
ば、零下１３℃以下に冷却する必要があるし、５０ｐｐ
ｍまで低下させようとすれば、零下３６℃以下に冷却す
る必要がある。但し、零下１０１℃未満まで冷却する
と、塩素が固化してしまう為、冷却温度は零下１０１℃
以上である必要がある。The dehydrator used in the present invention can use the technology conventionally used in the industry and is not particularly limited. Industrially,
Generally, a preferable dehydration method includes a cooling dehydration method and a method using a dehydrating agent. The cooling dehydration method is a method of cooling dehydrochlorinated chlorine gas to reduce the water vapor pressure and condensing water. When a corrosion-resistant material is used for the reactor and the pipe, it is preferable to cool it to 5 ° C. or lower because it is enough to prevent the dew condensation of water on the surface of the chlorinated vinyl chloride resin. In the cooling dehydration method, the cooling temperature required for dehydration can be determined by back-calculating the water vapor pressure from the desired water content.
For example, if the water content is to be reduced to 500 ppm, it is necessary to cool it to 13 ° C. or below, and 50 pp.
If the temperature is to be reduced to m, it is necessary to cool the temperature to 36 ° C. or below. However, when cooling to below 101 ° C below zero, chlorine solidifies, so the cooling temperature is 101 ° C below zero.
It must be above.

【００３３】脱水剤を用いる場合には、塩素と反応しな
い脱水剤を用いる必要がある。例としては、硫酸、塩化
カルシウム、ゼオライト、モレキュラーシーブス、五酸
化二燐が上げられる。これらの脱水剤の内、硫酸は液体
である為、大量の取り扱いが容易であり、工業的に用い
る場合に好ましい。濃硫酸は強力な脱水剤であり、塩素
ガスの含水量を５０ｐｐｍ以下にすることができるが、
脱水が進むにつれて硫酸が水で希釈されて行き、脱水能
力が低下する。９０重量％以上の濃度の硫酸と平衡状態
にある塩素の含水量は５０重量ｐｐｍ以下であるので、
脱水ガスは最終的に９０重量％以上の濃度の硫酸と接触
させることが好ましい。When using a dehydrating agent, it is necessary to use a dehydrating agent that does not react with chlorine. Examples include sulfuric acid, calcium chloride, zeolites, molecular sieves, diphosphorus pentoxide. Of these dehydrating agents, sulfuric acid is a liquid, and therefore it is easy to handle a large amount and is preferable for industrial use. Concentrated sulfuric acid is a strong dehydrating agent and can reduce the water content of chlorine gas to 50 ppm or less.
As the dehydration progresses, the sulfuric acid is diluted with water, and the dehydration ability decreases. Since the water content of chlorine in equilibrium with sulfuric acid having a concentration of 90% by weight or more is 50 ppm by weight or less,
It is preferable that the dehydration gas is finally brought into contact with sulfuric acid having a concentration of 90% by weight or more.

【００３４】本発明における、より効果的な脱水方法
は、冷却脱水法と脱水剤法を併用する方法である。冷却
脱水法のみで、十分な脱水をするためには上述のように
極低温まで塩素を冷却する必要があり、設備費が増大す
る。したがって、冷却脱水法で脱塩化水素ガスから一部
の水を除去し、脱水剤で再度脱水することもできる。こ
の場合、冷却装置の能力を低く抑える観点から、冷却脱
水法での冷却温度を例えば、５℃以下に設定すると良
い。A more effective dehydration method in the present invention is a method in which a cooling dehydration method and a dehydrating agent method are used in combination. In order to perform sufficient dehydration only by the cooling dehydration method, it is necessary to cool chlorine to an extremely low temperature as described above, which increases equipment costs. Therefore, it is also possible to remove a part of water from the dehydrochlorination gas by the cooling dehydration method and perform dehydration again with the dehydrating agent. In this case, from the viewpoint of suppressing the capacity of the cooling device to be low, the cooling temperature in the cooling dehydration method may be set to, for example, 5 ° C. or lower.

【００３５】本発明における反応器への塩素ガスの供給
方法について説明する。本発明においては、反応器内に
供給する塩素の状態は、気体でも液体でも良いし、上述
の様に不活性ガスで希釈した状態でも良い。但し、液体
塩素が直接塩化ビニル系樹脂に接触すると、塩化ビニル
系樹脂の表面構造及び内部構造が変化してしまう為、液
体塩素が反応器内で気化するより以前に塩化ビニル系樹
脂と接触しない工夫をする必要がある。例えば、工業的
に市販されている高圧ボンベに封入した液体塩素を使用
する場合には、液体塩素ボンベから取り出した液体塩素
を別の容器中で気化させた後に反応器に供給すれば良
い。液体塩素を反応器内に供給する場合には、液体塩素
ボンベから取り出した液体塩素を、反応器内で気化させ
れば良い。反応器内で塩素を気化させる方法は、気化熱
が反応熱を奪い反応器内の温度上昇を緩和する効果が有
り好ましい。The method of supplying chlorine gas to the reactor in the present invention will be described. In the present invention, the state of chlorine supplied into the reactor may be a gas or a liquid, or may be a state diluted with an inert gas as described above. However, if liquid chlorine comes into direct contact with vinyl chloride resin, the surface structure and internal structure of vinyl chloride resin will change, so liquid chlorine will not contact vinyl chloride resin before it vaporizes in the reactor. It is necessary to devise. For example, when liquid chlorine enclosed in a commercially available high-pressure cylinder is used, liquid chlorine taken out from the liquid chlorine cylinder may be vaporized in another container and then supplied to the reactor. When supplying liquid chlorine into the reactor, liquid chlorine taken out from the liquid chlorine cylinder may be vaporized in the reactor. The method of vaporizing chlorine in the reactor is preferable because it has the effect that the heat of vaporization removes the heat of reaction and moderates the temperature rise in the reactor.

【００３６】供給ガスの供給位置は、反応器、脱塩化水
素器、脱水器からなる装置全体の何れの場所でも良い。
脱塩化水素器や脱水器の負荷を低減すると言う観点か
ら、特に理由がなければ、脱水器の出口以降の位置から
脱水ガスと混合して反応器内に導入ガスとして導入して
も良いし、好ましくは、脱水ガスとは別に供給ガスを直
接反応器に供給するのがよい。The supply position of the supply gas may be any place in the entire apparatus including the reactor, the dehydrochlorination unit and the dehydrator.
From the viewpoint of reducing the load on the dehydrochlorination unit or dehydrator, unless otherwise specified, it may be mixed with dehydration gas from a position after the outlet of the dehydrator and introduced as an introduction gas into the reactor, Preferably, the feed gas may be directly fed to the reactor separately from the dehydration gas.

【００３７】本発明では、未反応の塩素ガスが循環再利
用される為、反応器、脱塩化水素器、脱水器からなる全
装置を密閉系にすることが出来る。反応前には、全装置
の系内に塩素ガス（及び、不活性ガス）置換するまで塩
素ガスを供給し、反応開始後は、反応に利用された塩素
と等モル量の塩素を供給ガスとして供給すれば、塩素濃
度が一定の条件で反応を継続することが出来る。全装置
が密閉系の場合には、脱塩化水素器において塩化水素が
水に吸収されると内圧が低下する為、密閉系の全装置の
内圧を測定し、内圧が一定値になる様に塩素ガスを含む
供給ガスを供給すれば良い。In the present invention, since unreacted chlorine gas is circulated and reused, the whole system including the reactor, the dehydrochlorination unit and the dehydrator can be closed system. Before the reaction, chlorine gas is supplied to the system of all equipment until it is replaced with chlorine gas (and an inert gas), and after the reaction is started, the same amount of chlorine as the chlorine used in the reaction is used as the supply gas. If supplied, the reaction can be continued under the condition that the chlorine concentration is constant. If all equipment is a closed system, the internal pressure will decrease when hydrogen chloride is absorbed by water in the dehydrochlorination equipment.Therefore, measure the internal pressure of all equipment in a closed system and make sure that the internal pressure is constant. Supply gas containing gas may be supplied.

【００３８】本発明で用いる塩素化反応の装置は塩素と
塩化ビニル系樹脂を気固接触場で反応させるものであれ
ば公知の方法、装置が使用しうる。塩化ビニル系樹脂が
樹脂の内部まで均一に塩素化させると言う観点、および
反応効率を高める観点からは、粉体状の塩化ビニル系樹
脂を流動化させながら塩素ガスと接触させる方法を用い
ることが好ましい。塩素化反応を推進するためには、塩
素ラジカルを発生させる必要がある。塩素ラジカルを発
生させる方法としては、触媒によりラジカルを発生させ
る方法、１００℃以上の熱の作用により塩素ラジカルを
発生させる方法、光のエネルギーによりラジカル発生さ
せる方法、およびこれらの方法を併用する方法があげら
れる。反応制御の簡便さ、樹脂を熱劣化から保護すると
いう観点から、光ラジカル発生を利用することが好まし
い。As the chlorination reaction apparatus used in the present invention, known methods and apparatuses can be used as long as chlorine and vinyl chloride resin are reacted in a gas-solid contact field. From the viewpoint of uniformly chlorinating the vinyl chloride resin to the inside of the resin, and from the viewpoint of increasing the reaction efficiency, it is possible to use a method in which the powdery vinyl chloride resin is brought into contact with chlorine gas while being fluidized. preferable. In order to promote the chlorination reaction, it is necessary to generate chlorine radicals. As a method of generating a chlorine radical, there are a method of generating a radical by a catalyst, a method of generating a chlorine radical by the action of heat of 100 ° C. or higher, a method of generating a radical by light energy, and a method of using these methods in combination. can give. From the viewpoint of easy reaction control and protection of the resin from thermal deterioration, it is preferable to utilize photoradical generation.

【００３９】本発明で用いる粉体層の流動方法について
説明する。本発明で言う流動状態とは、粉体粒子が連続
的、又は断続的に、且つ継続的に運動若しくは移動して
いる状態の全てを指している。したがって、粉体層中に
気体を流通して粒子を運動させる流動層を用いての流動
状態のみに限定されるものではない。本発明での流動化
方法は、従来用いられる粉体の反応器にある方法を使用
しても良いし、混合装置、攪拌装置、燃焼装置、乾燥装
置、粉砕装置、造粒装置等に利用される方法を応用して
も良い。具体的には、水平円筒型、Ｖ型、二重円錐型、
揺動回転型の様な容器回転型装置や、単軸リボン型、複
軸パドル型、回転鋤形、二軸遊星攪拌型、円錐スクリュ
ー型等の様な機械攪拌型の装置を使用すると良い。これ
らの装置の具体的な形状については、化学工学便覧（化
学工学会編、改訂六版、８７６頁）に記載されている。The flow method of the powder layer used in the present invention will be described. The fluidized state in the present invention refers to all the states in which the powder particles continuously or intermittently and continuously move or move. Therefore, the fluidized bed is not limited to the fluidized state in which the gas is circulated in the powder bed to move the particles. The fluidization method in the present invention may use the method in a conventionally used powder reactor, or may be used in a mixing device, a stirring device, a combustion device, a drying device, a pulverizing device, a granulating device, or the like. You may apply the method. Specifically, horizontal cylinder type, V type, double cone type,
It is preferable to use a container rotation type device such as an oscillating rotation type, or a mechanical stirring type device such as a single-axis ribbon type, a multi-axis paddle type, a rotary plow type, a twin-axis planetary stirring type, and a conical screw type. The specific shapes of these devices are described in the Chemical Engineering Handbook (edited by the Society of Chemical Engineering, 6th revised edition, page 876).

【００４０】本発明で用いる光源の種類について説明す
る。本発明での光の役割は、塩素を励起して塩素ラジカ
ルを発生させ、塩化ビニル系樹脂への塩素付加反応を促
進させることにある。塩素は、可視域から紫外線までの
幅広い波長にエネルギー吸収帯域を有するので、本発明
では太陽光、人工光の様々な光源を使用することができ
る。塩素は波長が３２０〜３６０ｎｍの紫外線に対して
最も強い吸収帯を有するので、この波長範囲を多く含む
光源を用いることが好ましい。具体的には、低圧水銀
灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ
等の紫外線を多く放出する光源が上げられる。光源の保
護、冷却などの目的に応じて、光源を透明のカバーで覆
う事もできる。この場合、透明カバーの材質は、石英、
ＰＹＲＥＸ（登録商標）、硬質ガラス、軟質ガラス管等
を使用することが出来るが、塩素化反応に効果的な紫外
線領域の波長を有効に利用する為には、石英若しくはＰ
ＹＲＥＸ（登録商標）を用いることが好ましく、石英を
用いることが最も好ましいThe types of light sources used in the present invention will be described. The role of light in the present invention is to excite chlorine to generate chlorine radicals and accelerate the chlorine addition reaction to the vinyl chloride resin. Since chlorine has an energy absorption band in a wide wavelength range from the visible range to the ultraviolet ray, various light sources such as sunlight and artificial light can be used in the present invention. Since chlorine has the strongest absorption band for ultraviolet rays having a wavelength of 320 to 360 nm, it is preferable to use a light source including a large number of this wavelength range. Specifically, a light source that emits a large amount of ultraviolet rays, such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp can be used. The light source can be covered with a transparent cover depending on the purpose of protecting the light source, cooling or the like. In this case, the material of the transparent cover is quartz,
PYREX (registered trademark), hard glass, soft glass tube or the like can be used, but in order to effectively use the wavelength in the ultraviolet region effective for the chlorination reaction, quartz or P
It is preferable to use YREX (registered trademark), and it is most preferable to use quartz.

【００４１】[0041]

【実施例】次に本発明の方法の実施例をあげて具体的に
説明する。但し、本実施例は本発明を限定するものでは
ない。EXAMPLES Next, examples of the method of the present invention will be specifically described. However, the present embodiment does not limit the present invention.

【００４２】（実施例１）図２に実施例に使用した塩素
化反応装置を示す。(Example 1) FIG. 2 shows a chlorination reaction apparatus used in Examples.

【００４３】反応器（容量が１５００ｍｌのＰＹＲＥＸ
（登録商標）製ナス型フラスコ）には、塩化ビニル系樹
脂Ａの粉体を充填し、温浴に浸して回転させながら粉体
層の温度を調節する。粉体層の温度は、粉体層内に差し
込んだ熱電対で測定できる。ガス循環・排気切換バルブ
には三方コックを用い、反応装置系内を窒素や塩素でガ
ス置換する場合には排気側に、反応装置系内を密閉して
塩素を循環利用する場合には循環側に切り替えることが
できる。塩素を循環利用する場合には、塩素ボンベに取
り付けられた圧力調整機を通して塩素が供給され、反応
系内の圧力が一定に保たれる。また、塩素が反応装置系
外に排出される場合には、排出ガスは排ガス処理装置へ
と導入される。脱塩化水素器（容量が１０００ｍｌのＰ
ＹＲＥＸ（登録商標）製容器）には、水が充填されてお
り、排出ガスは水中に吹き込まれて塩化水素が吸収され
る。脱塩化水素器の底部にはコックが付いており、任意
の時間に塩化水素を吸収した水をサンプリング吸収液の
一部を分取して得た塩酸の中和滴定値から塩化水素発生
量および塩素化塩化ビニル系樹脂の塩素含有量を継続的
に算出しすることが出来る。脱水器（容量が５００ｍｌ
のＰＹＲＥＸ（登録商標）製容器）は、氷温槽で０〜５
℃程度に冷却されており、必要に応じ、硫酸やモレキュ
ラーシーブス等の脱水剤を充填する。反応装置系内のガ
スを循環する場合には、循環ポンプを用い、図２の矢印
の方向にガスを循環させながら流量調整バルブを開閉し
て所定流量のガスを循環させる。Reactor (PYREX with a capacity of 1500 ml
(Registered trademark) eggplant-shaped flask) is filled with powder of vinyl chloride resin A, and the temperature of the powder layer is adjusted by immersing in a warm bath and rotating. The temperature of the powder layer can be measured with a thermocouple inserted in the powder layer. A three-way cock is used for the gas circulation / exhaust switching valve, and is used on the exhaust side when the inside of the reactor system is replaced with nitrogen or chlorine, and on the circulation side when the inside of the reactor system is closed and chlorine is circulated. Can be switched to. When chlorine is circulated and used, chlorine is supplied through a pressure regulator attached to a chlorine cylinder to keep the pressure in the reaction system constant. When chlorine is discharged to the outside of the reactor system, the exhaust gas is introduced into the exhaust gas treatment device. Dehydrochlorinator (P with a capacity of 1000 ml
A container made of yrex (registered trademark) is filled with water, and the exhaust gas is blown into the water to absorb hydrogen chloride. A cock is attached to the bottom of the dehydrochlorination unit, and the amount of generated hydrogen chloride and the amount of generated hydrogen chloride can be determined from the neutralization titration value of hydrochloric acid obtained by fractionating a portion of the sampling absorption liquid from water that has absorbed hydrogen chloride at any time. It is possible to continuously calculate the chlorine content of the chlorinated vinyl chloride resin. Dehydrator (500ml capacity
PYREX (registered trademark) container) is 0-5 in an ice bath.
It is cooled to about ℃, and if necessary, it is filled with a dehydrating agent such as sulfuric acid or molecular sieves. When circulating the gas in the reactor system, a circulation pump is used to circulate the gas in the direction of the arrow in FIG.

【００４４】後塩素化反応に利用する塩化ビニル系樹脂
は以下の方法で作製した。攪拌翼を装備したステンレス
製オ−トクレ−ブに、イオン交換水４００部、平均分子
量２００万のポリエチレンオキサイドを０．００５重量
部、ヒドロキシプロピルメチルセルロースを０．０４重
量部、濃度７０％のジ−２−エチルヘキシルパ−オキシ
ジカ−ボネ−トのイソパラフィン溶液０．０５重量部を
仕込み、オ−トクレ−ブ内を真空脱気した後、塩化ビニ
ル系単量体１００重量部を仕込んだ。その後、攪拌下で
懸濁重合を行い、重合度が約１０００である塩化ビニル
系樹脂を得た。塩化ビニル系樹脂の懸濁液を脱水、乾燥
し、粉体状の塩化ビニル系樹脂を得た。これを塩化ビニ
ル系樹脂Ａ（嵩比重：０．５ｇ／ｃｍ3、平均粒子径：
２２０μ）とした。The vinyl chloride resin used in the post-chlorination reaction was prepared by the following method. In a stainless steel autoclave equipped with a stirring blade, 400 parts of ion-exchanged water, 0.005 part by weight of polyethylene oxide having an average molecular weight of 2,000,000, 0.04 part by weight of hydroxypropylmethylcellulose, and a dilute having a concentration of 70% were used. 0.05 parts by weight of an isoparaffin solution of 2-ethylhexyl peroxydicarbonate was charged, the interior of the autoclave was deaerated under vacuum, and then 100 parts by weight of a vinyl chloride monomer was charged. Then, suspension polymerization was performed under stirring to obtain a vinyl chloride resin having a degree of polymerization of about 1000. The suspension of vinyl chloride resin was dehydrated and dried to obtain a powdery vinyl chloride resin. Vinyl chloride resin A (bulk specific gravity: 0.5 g / cm 3 , average particle size:
220 μ).

【００４５】図２に示した反応器に塩化ビニル系樹脂Ａ
の粉体を１８７．７３ｇ＝３ｍｏｌを充填した。ガス循
環・排気切換バルブを排気状態に設定し、反応器を６０
℃の温浴に浸して回転させながら、反応容器の空間部分
に２００ｍｌ／分の流量で窒素ガスを６０分間流通し、
更に２００ｍｌ／分の流量で塩素ガスを３０分間流通し
た。Vinyl chloride resin A was added to the reactor shown in FIG.
187.73 g = 3 mol of the above powder was charged. Set the gas circulation / exhaust switching valve to the exhaust state and set the reactor to 60
Nitrogen gas was passed through the space of the reaction vessel at a flow rate of 200 ml / min for 60 minutes while being immersed in a warm bath at ℃ and rotated,
Further, chlorine gas was circulated for 30 minutes at a flow rate of 200 ml / min.

【００４６】ガス循環・排気切換バルブを循環状態に設
定して反応装置内を密閉状態にし、反応装置内部の圧力
が０．０２ＭＰａに達するまで圧力調整弁を通して塩素
を充填した。圧力調整弁は、反応装置内の圧力が０．０
２ＭＰａ以下に低下すると塩素ボンベから塩素を供給す
る様に設定された。その後、循環ポンプを作動させ、反
応器に導入されるガス量が６００ｍｌ／分になるように
流量調節バルブを調節した。１０分間程度ガスの循環状
態を継続した後、粉体層上面から３５ｃｍ離した位置に
設置した４００Ｗの高圧水銀灯を用いて、粉体層表面に
紫外線を照射した。水銀灯を点灯させると反応が開始
し、塩化水素と塩素の混合ガスが発生する。脱塩化水素
器から排出されたガスは脱水器に導入された。脱水器は
氷温浴で０℃に冷却されているのみで、内部には脱水剤
を充填しなかった。The gas circulation / exhaust switching valve was set to a circulating state to make the inside of the reaction apparatus hermetically closed, and chlorine was filled through the pressure control valve until the pressure inside the reaction apparatus reached 0.02 MPa. The pressure control valve has a pressure of 0.0 in the reactor.
It was set to supply chlorine from a chlorine cylinder when the pressure dropped to 2 MPa or less. Then, the circulation pump was operated, and the flow rate control valve was adjusted so that the amount of gas introduced into the reactor was 600 ml / min. After continuing the gas circulation state for about 10 minutes, the powder layer surface was irradiated with ultraviolet rays using a 400 W high pressure mercury lamp installed at a position 35 cm away from the upper surface of the powder layer. When the mercury lamp is turned on, the reaction starts and a mixed gas of hydrogen chloride and chlorine is generated. The gas discharged from the dehydrochlorination unit was introduced into the dehydrator. The dehydrator was only cooled to 0 ° C. in an ice bath, and the inside was not filled with a dehydrating agent.

【００４７】粉体層中に熱電対を挿入し、粉体層の温度
を測定したところ、水銀灯の点灯後から反応が開始して
反応熱が発生するので、１０分後には粉体層の温度が約
８０℃に達した。反応時間が１３０分経過した時点で水
銀灯を消灯し、反応を終了させた。When a thermocouple was inserted into the powder layer and the temperature of the powder layer was measured, the reaction started after the mercury lamp was turned on and reaction heat was generated. Reached about 80 ° C. When the reaction time of 130 minutes had passed, the mercury lamp was turned off to terminate the reaction.

【００４８】反応終了後は、反応容器の温度を６０℃に
保ちながら、反応容器内に６００ｍｌ／分の流量で窒素
ガスを流通して残留する塩素および塩化水素を洗浄除去
した。窒素置換を１００分間継続したものをサンプル１
とした。After the completion of the reaction, while keeping the temperature of the reaction vessel at 60 ° C., nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to remove residual chlorine and hydrogen chloride by washing. Sample 1 after continuous nitrogen replacement for 100 minutes
And

【００４９】反応に使用された塩素量およびサンプル１
の塩素含有量は、脱塩化水素器内に吸収された塩化水素
を中和滴定して算出された。即ち、式（１）より、塩化
ビニル系樹脂の塩素化反応においては塩素が１ｍｏｌが
消費されると、塩化水素が１ｍｏｌ生成するので、発生
した塩化水素量が分かれば、塩素化された塩化ビニル系
樹脂の量が計算できる。また、原料の塩化ビニル系樹脂
の塩素含有量を５６．８重量％とし、発生した塩化水素
と同量のモル数の塩素と塩化ビニル系樹脂中の水素とが
置換したものと仮定して塩素化塩化ビニル系樹脂の塩素
含有量を算出できる。その結果、反応に使用された塩素
量は、１．５１ｍｏｌであり、塩素含有量は、６６．２
重量％と計算された。また、反応前後の塩素ボンベの重
量変化から供給した塩素の総量を計算すると、１．６２
ｍｏｌであった。従って、実施例１での塩素の利用率
（反応開始後）は、９３．２％であることが判明した。
反応以外に消費された塩素は、脱塩化水素器中の水に溶
解した塩素および反応容器からの漏洩した塩素と推定さ
れる。Amount of chlorine used in the reaction and sample 1
The chlorine content of was calculated by neutralization titration of hydrogen chloride absorbed in the dehydrochlorination unit. That is, from the formula (1), when 1 mol of chlorine is consumed in the chlorination reaction of the vinyl chloride resin, 1 mol of hydrogen chloride is produced. Therefore, if the amount of hydrogen chloride produced is known, the chlorinated vinyl chloride is obtained. The amount of system resin can be calculated. Also, assuming that the chlorine content of the vinyl chloride resin as a raw material is 56.8% by weight, and assuming that the same number of moles of chlorine as the generated hydrogen chloride are replaced with hydrogen in the vinyl chloride resin, The chlorine content of the modified vinyl chloride resin can be calculated. As a result, the amount of chlorine used in the reaction was 1.51 mol, and the chlorine content was 66.2.
Calculated as weight percent. In addition, the total amount of chlorine supplied was calculated to be 1.62 from the weight change of the chlorine cylinder before and after the reaction.
It was mol. Therefore, it was found that the utilization rate of chlorine (after the start of the reaction) in Example 1 was 93.2%.
The chlorine consumed except for the reaction is presumed to be chlorine dissolved in water in the dehydrochlorination unit and chlorine leaked from the reaction vessel.

【００５０】（実施例２）図２に示す反応装置を用い、
実施例１で用いたものと同じ塩化ビニル系樹脂Ａの塩素
化反応を実施した。反応器に塩化ビニル系樹脂Ａの粉体
を３７５ｇ＝６ｍｏｌを充填した。ガス循環・排気切換
バルブを排気状態に設定し、反応容器を６０℃の温浴に
浸して回転させながら、反応容器の空間部分に２００ｍ
ｌ／分の流量で窒素ガスを６０分間流通し、更に塩素ガ
スを６００ｍｌ／分の流量で１０分間、２００ｍｌ／分
の流量で２０分間流通した。Example 2 Using the reaction apparatus shown in FIG.
The same chlorination reaction of vinyl chloride resin A as that used in Example 1 was carried out. The reactor was filled with 375 g = 6 mol of powder of vinyl chloride resin A. With the gas circulation / exhaust switching valve set to the exhaust state, the reaction vessel was immersed in a 60 ° C hot bath and rotated, and the space inside the reaction vessel was set to 200 m.
Nitrogen gas was circulated for 60 minutes at a flow rate of 1 / min, chlorine gas was further circulated for 10 minutes at a flow rate of 600 ml / min, and for 20 minutes at a flow rate of 200 ml / min.

【００５１】ガス循環・排気切換バルブを循環状態に設
定して反応装置内を密閉状態にし、反応装置内部の圧力
が０．０２ＭＰａに達するまで圧力調整弁を通して塩素
を充填した。圧力調整弁は、反応装置内の圧力が０．０
２ＭＰａ以下に低下すると塩素ボンベから塩素を供給す
る様に設定された。その後、循環ポンプを作動させ、反
応器に導入されるガス量が１０００ｍｌ／分になるよう
に流量調節バルブを調節した。１０分間程度ガスの循環
状態を継続した後、粉体層上面から３５ｃｍ離した位置
に設置した４００Ｗの高圧水銀灯を用いて、粉体層表面
に紫外線を照射した。水銀灯を点灯させると反応が開始
し、塩化水素と塩素の混合ガスが発生する。脱塩化水素
器から排出されたガスは脱水器に導入された。脱水器は
氷温浴で０℃に冷却されており、底部にはモレキュラー
シーブスが充填されている。The gas circulation / exhaust switching valve was set to a circulating state to make the inside of the reaction apparatus hermetically closed, and chlorine was filled through the pressure control valve until the pressure inside the reaction apparatus reached 0.02 MPa. The pressure control valve has a pressure of 0.0 in the reactor.
It was set to supply chlorine from a chlorine cylinder when the pressure dropped to 2 MPa or less. Then, the circulation pump was operated, and the flow rate control valve was adjusted so that the amount of gas introduced into the reactor was 1000 ml / min. After continuing the gas circulation state for about 10 minutes, the powder layer surface was irradiated with ultraviolet rays using a 400 W high pressure mercury lamp installed at a position 35 cm away from the upper surface of the powder layer. When the mercury lamp is turned on, the reaction starts and a mixed gas of hydrogen chloride and chlorine is generated. The gas discharged from the dehydrochlorination unit was introduced into the dehydrator. The dehydrator is cooled to 0 ° C. in an ice bath and the bottom is filled with molecular sieves.

【００５２】粉体層中に熱電対を挿入し、粉体層の温度
を測定したところ、水銀灯の点灯後から反応が開始して
反応熱が発生するので、１０分後には粉体層の温度が約
８０℃に達した。反応時間が２００分経過した時点で水
銀灯を消灯し、反応を終了させた。When a thermocouple was inserted into the powder layer and the temperature of the powder layer was measured, the reaction started after the mercury lamp was turned on and reaction heat was generated. Reached about 80 ° C. When the reaction time reached 200 minutes, the mercury lamp was turned off to terminate the reaction.

【００５３】反応終了後は、反応容器の温度を６０℃に
保ちながら、反応容器内に６００ｍｌ／分の流量で窒素
ガスを流通して残留する塩素および塩化水素を洗浄除去
した。窒素置換を１００分間継続したものをサンプル２
とした。After completion of the reaction, while maintaining the temperature of the reaction vessel at 60 ° C., nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to wash and remove residual chlorine and hydrogen chloride. Sample 2 after 100 minutes of nitrogen substitution
And

【００５４】反応に利用された塩素量とサンプル２の塩
素含有量を実施例１と同様の方法で算出した。その結
果、反応に利用された塩素は２．８６ｍｏｌであり、サ
ンプル２の塩素含有量は、６６．４重量％と計算され
た。また、反応前後の塩素ボンベの重量変化から供給し
た塩素の総量を計算すると、３．０７ｍｏｌであった。
従って、実施例２での塩素の利用率は、９３．２％であ
ることが判明した。The amount of chlorine used in the reaction and the chlorine content of Sample 2 were calculated in the same manner as in Example 1. As a result, the amount of chlorine used for the reaction was 2.86 mol, and the chlorine content of Sample 2 was calculated to be 66.4% by weight. Further, the total amount of chlorine supplied was calculated from the weight change of the chlorine cylinder before and after the reaction, and was 3.07 mol.
Therefore, it was found that the chlorine utilization rate in Example 2 was 93.2%.

【００５５】（実施例３）図２に示す反応装置を用い、
実施例１で用いたものと同じ塩化ビニル系樹脂Ａの塩素
化反応を実施した。反応器に塩化ビニル系樹脂Ａの粉体
を１８７．４７ｇ＝３ｍｏｌを充填した。ガス循環・排
気切換バルブを排気状態に設定し、反応容器を７０℃の
温浴に浸して回転させながら、反応容器の空間部分に２
００ｍｌ／分の流量で窒素ガスを６０分間流通し、更に
塩素ガスを６００ｍｌ／分の流量で１０分間、２００ｍ
ｌ／分の流量で２０分間流通した。(Example 3) Using the reaction apparatus shown in FIG.
The same chlorination reaction of vinyl chloride resin A as that used in Example 1 was carried out. The reactor was filled with 187.47 g = 3 mol of powder of vinyl chloride resin A. Set the gas circulation / exhaust switching valve to the exhaust state, immerse the reaction vessel in a 70 ° C hot bath and rotate it, and place 2 in the space of the reaction vessel.
Nitrogen gas is flown for 60 minutes at a flow rate of 00 ml / min, and chlorine gas is flown for 10 minutes at a flow rate of 600 ml / min for 200 minutes.
Flowed at a flow rate of 1 / min for 20 minutes.

【００５６】ガス循環・排気切換バルブを循環状態に設
定して反応装置内を密閉状態にし、反応装置内部の圧力
が０．０２ＭＰａに達するまで圧力調整弁を通して塩素
を充填した。圧力調整弁は、反応装置内の圧力が０．０
２ＭＰａ以下に低下すると塩素ボンベから塩素を供給す
る様に設定された。その後、循環ポンプを作動させ、反
応器に導入されるガス量が６００ｍｌ／分になるように
流量調節バルブを調節した。１０分間程度ガスの循環状
態を継続した後、粉体層上面から３５ｃｍ離した位置に
設置した４００Ｗの高圧水銀灯を用いて、粉体層表面に
紫外線を照射した。水銀灯を点灯させると反応が開始
し、塩化水素と塩素の混合ガスが発生する。脱塩化水素
器から排出されたガスは脱水器に導入された。脱水器は
氷温浴で０℃に冷却されており、脱水剤として９８％の
濃硫酸が充填されている。The gas circulation / exhaust switching valve was set to a circulating state to make the inside of the reaction apparatus hermetically closed, and chlorine was filled through the pressure control valve until the pressure inside the reaction apparatus reached 0.02 MPa. The pressure control valve has a pressure of 0.0 in the reactor.
It was set to supply chlorine from a chlorine cylinder when the pressure dropped to 2 MPa or less. Then, the circulation pump was operated, and the flow rate control valve was adjusted so that the amount of gas introduced into the reactor was 600 ml / min. After continuing the gas circulation state for about 10 minutes, the powder layer surface was irradiated with ultraviolet rays using a 400 W high pressure mercury lamp installed at a position 35 cm away from the upper surface of the powder layer. When the mercury lamp is turned on, the reaction starts and a mixed gas of hydrogen chloride and chlorine is generated. The gas discharged from the dehydrochlorination unit was introduced into the dehydrator. The dehydrator is cooled to 0 ° C. in an ice bath and is filled with 98% concentrated sulfuric acid as a dehydrating agent.

【００５７】粉体層中に熱電対を挿入し、粉体層の温度
を測定したところ、水銀灯の点灯後から反応が開始して
反応熱が発生するので、１０分後には粉体層の温度が約
９０℃に達した。反応時間が１１０分経過した時点で水
銀灯を消灯し、反応を終了させた。A thermocouple was inserted into the powder layer and the temperature of the powder layer was measured. The reaction started after the mercury lamp was turned on to generate reaction heat. Reached about 90 ° C. When the reaction time reached 110 minutes, the mercury lamp was turned off to terminate the reaction.

【００５８】反応終了後は、反応容器の温度を６０℃に
保ちながら、反応容器内に６００ｍｌ／分の流量で窒素
ガスを流通して残留する塩素および塩化水素を洗浄除去
した。窒素置換を１００分間継続したものをサンプル３
とした。After completion of the reaction, while maintaining the temperature of the reaction vessel at 60 ° C., nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to remove residual chlorine and hydrogen chloride by washing. Sample 3 after 100 minutes of nitrogen substitution
And

【００５９】反応に利用された塩素量とサンプル３の塩
素含有量を実施例１と同様の方法で算出した。その結
果、反応に利用された塩素は１．４５ｍｏｌであり、サ
ンプル３の塩素含有量は、６５．９重量％と計算され
た。また、反応前後の塩素ボンベの重量変化から供給し
た塩素の総量を計算すると、１．５３ｍｏｌであった。
従って、実施例３での塩素の利用率は、９４．８％であ
ることが判明した。The amount of chlorine used in the reaction and the chlorine content of Sample 3 were calculated by the same method as in Example 1. As a result, the amount of chlorine used for the reaction was 1.45 mol, and the chlorine content of Sample 3 was calculated to be 65.9% by weight. Further, the total amount of chlorine supplied was calculated from the weight change of the chlorine cylinder before and after the reaction, and was 1.53 mol.
Therefore, it was found that the chlorine utilization rate in Example 3 was 94.8%.

【００６０】（比較例１）図２に示す反応装置を用い、
実施例１で用いたものと同じ塩化ビニル系樹脂Ａの塩素
化反応を実施した。反応器に塩化ビニル系樹脂Ａの粉体
を１８７．７３ｇ＝３ｍｏｌを充填した。ガス循環・排
気切換バルブを排気状態に設定し、反応容器を６０℃の
温浴に浸して回転させながら、反応容器の空間部分に２
００ｍｌ／分の流量で窒素ガスを６０分間流通し、更に
塩素ガスを２００ｍｌ／分の流量で３０分間流通した。(Comparative Example 1) Using the reactor shown in FIG.
The same chlorination reaction of vinyl chloride resin A as that used in Example 1 was carried out. The reactor was filled with 187.73 g = 3 mol of powder of vinyl chloride resin A. Set the gas circulation / exhaust switching valve to the exhaust state, immerse the reaction vessel in a 60 ° C warm bath and rotate it, and place 2 in the space of the reaction vessel.
Nitrogen gas was passed for 60 minutes at a flow rate of 00 ml / min, and chlorine gas was passed for 30 minutes at a flow rate of 200 ml / min.

【００６１】ガス量が６００ｍｌ／分になるように流量
調節バルブを調節した後、粉体層上面から３５ｃｍ離し
た位置に設置した４００Ｗの高圧水銀灯を用いて、粉体
層表面に紫外線を照射した。水銀灯を点灯させると反応
が開始し、ガス排出口から排出された塩素と塩化水素の
混合ガスが脱塩化水素器に導入される。脱塩化水素器か
ら排出されたガスを脱水器を通過し、排ガス処理設備に
排出した。After adjusting the flow rate control valve so that the gas amount was 600 ml / min, the powder layer surface was irradiated with ultraviolet rays using a 400 W high pressure mercury lamp installed at a position 35 cm away from the upper surface of the powder layer. . The reaction starts when the mercury lamp is turned on, and the mixed gas of chlorine and hydrogen chloride discharged from the gas discharge port is introduced into the dehydrochlorination unit. The gas discharged from the dehydrochlorination unit passed through the dehydrator and was discharged to the exhaust gas treatment facility.

【００６２】粉体層中に熱電対を挿入し、粉体層の温度
を測定したところ、水銀灯の点灯後から反応が開始して
反応熱が発生するので、１０分後には粉体層の温度が約
８０℃に達した。反応時間が１５０分経過した時点で水
銀灯を消灯し、反応を終了させた。When a thermocouple was inserted into the powder layer and the temperature of the powder layer was measured, the reaction started after the mercury lamp was turned on and reaction heat was generated. Reached about 80 ° C. When the reaction time of 150 minutes had passed, the mercury lamp was turned off to terminate the reaction.

【００６３】反応終了後は、反応容器の温度を６０℃に
保ちながら、反応容器内に６００ｍｌ／分の流量で窒素
ガスを流通して残留する塩素および塩化水素を洗浄除去
した。窒素置換を１００分間継続したものを比較サンプ
ル１とした。After completion of the reaction, while maintaining the temperature of the reaction vessel at 60 ° C., nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to remove residual chlorine and hydrogen chloride by washing. Comparative sample 1 was obtained by continuing nitrogen substitution for 100 minutes.

【００６４】反応に利用された塩素量と比較サンプル１
の塩素含有量を実施例１と同様の方法で算出した。その
結果、反応に利用された塩素は１．６１ｍｏｌであり、
比較サンプル１の塩素含有量は、６６．７重量％と計算
された。また、反応前後の塩素ボンベの重量変化から供
給した塩素の総量を計算すると、４．０２ｍｏｌであっ
た。従って、比較例１での塩素の利用率は、４０．０％
であることが判明した。Comparison sample 1 with the amount of chlorine used in the reaction
The chlorine content of was calculated in the same manner as in Example 1. As a result, the amount of chlorine used for the reaction was 1.61 mol,
The chlorine content of Comparative Sample 1 was calculated to be 66.7% by weight. The total amount of chlorine supplied was calculated from the change in the weight of the chlorine cylinder before and after the reaction, and was 4.02 mol. Therefore, the utilization rate of chlorine in Comparative Example 1 was 40.0%.
It turned out to be

【００６５】（比較例２）図２に示す反応装置を用い、
実施例１で用いたものと同じ塩化ビニル系樹脂Ａの塩素
化反応を実施した。反応器に塩化ビニル系樹脂Ａの粉体
を３７５．２７ｇ＝６ｍｏｌを充填した。ガス循環・排
気切換バルブを排気状態に設定し、反応容器を６０℃の
温浴に浸して回転させながら、反応容器の空間部分に２
００ｍｌ／分の流量で窒素ガスを３０分間流通し、更に
塩素ガスを２００ｍｌ／分の流量で３０分間流通した。
更に、ガス量が１０００ｍｌ／分になるように流量調節
バルブを調節した後、粉体層上面から３５ｃｍ離した位
置に設置した４００Ｗの高圧水銀灯を用いて、粉体層表
面に紫外線を照射した。水銀灯を点灯させると反応が開
始し、ガス排出口から排出された塩素と塩化水素の混合
ガスが脱塩化水素器に導入される。脱塩化水素器から排
出されたガスを脱水器を通過し、排ガス処理設備に排出
した。Comparative Example 2 Using the reaction apparatus shown in FIG.
The same chlorination reaction of vinyl chloride resin A as that used in Example 1 was carried out. The reactor was charged with 375.27 g = 6 mol of powder of vinyl chloride resin A. Set the gas circulation / exhaust switching valve to the exhaust state, immerse the reaction vessel in a 60 ° C warm bath and rotate it, and place 2 in the space of the reaction vessel.
Nitrogen gas was passed at a flow rate of 00 ml / min for 30 minutes, and chlorine gas was passed at a flow rate of 200 ml / min for 30 minutes.
Furthermore, after adjusting the flow rate control valve so that the gas amount was 1000 ml / min, the powder layer surface was irradiated with ultraviolet rays using a 400 W high pressure mercury lamp installed at a position 35 cm away from the upper surface of the powder layer. The reaction starts when the mercury lamp is turned on, and the mixed gas of chlorine and hydrogen chloride discharged from the gas discharge port is introduced into the dehydrochlorination unit. The gas discharged from the dehydrochlorination unit passed through the dehydrator and was discharged to the exhaust gas treatment facility.

【００６６】粉体層中に熱電対を挿入し、粉体層の温度
を測定したところ、水銀灯の点灯後から反応が開始して
反応熱が発生するので、１０分後には粉体層の温度が約
８０℃に達した。反応時間が１８０分経過した時点で水
銀灯を消灯し、反応を終了させた。When a thermocouple was inserted into the powder layer and the temperature of the powder layer was measured, the reaction started after the mercury lamp was turned on and reaction heat was generated. Reached about 80 ° C. When the reaction time of 180 minutes had passed, the mercury lamp was turned off to terminate the reaction.

【００６７】反応終了後は、反応容器の温度を６０℃に
保ちながら、反応容器内に６００ｍｌ／分の流量で窒素
ガスを流通して残留する塩素および塩化水素を洗浄除去
した。窒素置換を１００分間継続したものを比較サンプ
ル２とした。After the completion of the reaction, while maintaining the temperature of the reaction vessel at 60 ° C., nitrogen gas was passed through the reaction vessel at a flow rate of 600 ml / min to remove residual chlorine and hydrogen chloride by washing. Comparative sample 2 was obtained by continuing nitrogen substitution for 100 minutes.

【００６８】反応に利用された塩素量と比較サンプル１
の塩素含有量を実施例１と同様の方法で算出した。その
結果、反応に利用された塩素は２．７２ｍｏｌであり、
比較サンプル２の塩素含有量は、６５．４重量％と計算
された。また、反応前後の塩素ボンベの重量変化から供
給した塩素の総量を計算すると、９．７１ｍｏｌであっ
た。従って、比較例２での塩素の利用率は、２８．０％
であることが判明した。Amount of chlorine used for reaction and comparative sample 1
The chlorine content of was calculated in the same manner as in Example 1. As a result, the amount of chlorine used in the reaction was 2.72 mol,
The chlorine content of Comparative Sample 2 was calculated to be 65.4% by weight. Further, the total amount of chlorine supplied was calculated from the change in the weight of the chlorine cylinder before and after the reaction, and was found to be 9.71 mol. Therefore, the utilization rate of chlorine in Comparative Example 2 was 28.0%.
It turned out to be

【００６９】表１に実施例１〜３およぼ比較例１〜２の
結果をまとめる。表１の結果より、本発明の方法を用い
て塩素を再利用した実施例１〜３は、塩素利用率が９０
％以上であることがわかる。これに対して、塩素の再利
用を行わない比較例１〜２の塩素の利用率は３０〜４０
％程度の低い水準であることがわかる。Table 1 summarizes the results of Examples 1 to 3 and Comparative Examples 1 and 2. From the results of Table 1, in Examples 1 to 3 in which chlorine was reused by using the method of the present invention, the chlorine utilization rate was 90.
It turns out that it is more than%. On the other hand, the chlorine utilization rate of Comparative Examples 1 and 2 in which chlorine is not reused is 30 to 40.
It can be seen that the level is as low as about%.

【００７０】[0070]

【表１】 [Table 1]

【００７１】[0071]

【発明の効果】本発明により、塩化ビニル系樹脂を後塩
素化反応させて塩素化塩化ビニル系樹脂を製造する気固
接触反応法において、その後処理の簡便性と設備コスト
性を生かし、かつ未反応の塩素ガスを循環利用して、塩
素の利用率を向上させることにより、気固接触反応法を
工業的に有利に実施することができる。According to the present invention, in a gas-solid contact reaction method for producing a chlorinated vinyl chloride resin by subjecting a vinyl chloride resin to a post-chlorination reaction, the simplicity of the post-treatment and the cost of equipment can be utilized, and The gas-solid contact reaction method can be industrially advantageously carried out by recycling chlorine gas in the reaction to improve the utilization rate of chlorine.

【図面の簡単な説明】[Brief description of drawings]

【図１】塩素を再利用する装置の模式図である。FIG. 1 is a schematic view of an apparatus for recycling chlorine.

【図２】脱塩化水素器に貯水を使用し、脱水器に氷温冷
却とモレキュラーシーブス若しくは濃硫酸を用いた装置
の図である。FIG. 2 is a diagram of an apparatus in which water storage is used for a dehydrochlorination unit and ice cooling and molecular sieves or concentrated sulfuric acid are used for a dehydrator.

【符号の説明】[Explanation of symbols]

１ 供給ガス ２ 排出ガス ３ 脱塩化水素ガス ４ 脱水ガス ５ 導入ガス ６ 塩素供給源 ７ 反応器 ８ 脱塩化水素器 ９ 脱水機 １０ ガス循環ポンプ １１ 反応器 １２ ＰＶＣ樹脂 １３ 温浴 １４ 光源 １５ 脱塩化水素器 １６ 水 １７ 脱水器 １８ 氷温浴 １９ モレキュラーシーブス若しくは濃硫酸 ２０ ガス流量計 ２１ 圧力調整機 ２２ 塩素ボンベ ２３ ガス循環・排気切換バルブ ２４ 循環流量調節バルブ ２５ 流量調節バルブ 1 supply gas 2 exhaust gas 3 Dehydrochlorination gas 4 dehydration gas 5 Introduced gas 6 Chlorine supply source 7 reactor 8 Dehydrochlorination equipment 9 dehydrator 10 gas circulation pump 11 reactor 12 PVC resin 13 hot bath 14 Light source 15 Dehydrochlorination equipment 16 water 17 dehydrator 18 ice bath 19 Molecular sieves or concentrated sulfuric acid 20 gas flow meter 21 Pressure regulator 22 Chlorine cylinder 23 Gas circulation / exhaust switching valve 24 Circulation flow control valve 25 Flow control valve

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 19/12 Ｂ０１Ｊ 19/12 Ｃ Ｃ０８Ｆ 14/06 Ｃ０８Ｆ 14/06 Ｆターム(参考） 4D020 AA10 BA23 BC06 CB01 CB08 CD03 DA03 DB02 DB06 4D052 AA02 BA00 CE00 GA04 GB02 GB03 HA03 HA09 HA12 HA41 HB01 4G075 AA32 BA02 BD13 BD14 BD27 CA03 CA33 CA54 DA01 EA06 EB01 EB09 EB31 FB02 FB06 FB12 FB13 4J100 AC03P CA01 CA31 HA21 HB04 HE01 HE22 HF01 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B01J 19/12 B01J 19/12 C C08F 14/06 C08F 14/06 F term (reference) 4D020 AA10 BA23 BC06 CB01 CB08 CD03 DA03 DB02 DB06 4D052 AA02 BA00 CE00 GA04 GB02 GB03 HA03 HA09 HA12 HA41 HB01 4G075 AA32 BA02 BD13 BD14 BD27 CA03 CA33 CA54 DA01 EA06 EB01 EB09 EB31 FB02 FB06 FB12 FB13 4J100 AC22 H04 CA01 HE31 HA31

Claims (28)

【特許請求の範囲】[Claims] 【請求項１】 塩化ビニル系樹脂を後塩素化反応させて
塩素化塩化ビニル系樹脂を製造する方法において、塩化
ビニル系樹脂と塩素とを気固接触反応場で反応させ、反
応ガスの一部又は全部を反応器の外部に排出し、排出ガ
スと水とを接触させることにより、排出ガス中の塩化水
素ガスを水に吸収させて脱塩化水素ガスを得た後に、該
脱塩化水素ガスを反応器内に環流、導入し、塩化ビニル
系樹脂の塩素化反応に利用することを特徴とする塩素化
塩化ビニル系樹脂の製造方法。1. A method for producing a chlorinated vinyl chloride resin by subjecting a vinyl chloride resin to a post-chlorination reaction, wherein the vinyl chloride resin and chlorine are reacted in a gas-solid contact reaction field, and a part of the reaction gas is reacted. Alternatively, the hydrogen chloride gas in the exhaust gas is absorbed into water by contacting the exhaust gas with water to obtain dehydrochlorinated gas, and then the dehydrochlorinated gas is removed. A method for producing a chlorinated vinyl chloride resin, which comprises refluxing and introducing it into a reactor and utilizing it for a chlorination reaction of a vinyl chloride resin. 【請求項２】 脱塩化水素ガスと接触させる水が、循環
水及び／又は貯水である請求項１に記載の塩素化塩化ビ
ニル系樹脂の製造方法。2. The method for producing a chlorinated vinyl chloride resin according to claim 1, wherein the water brought into contact with the dehydrochlorination gas is circulating water and / or stored water. 【請求項３】 脱塩化水素ガスと接触させる水が、零℃
を越え、４０℃以下の範囲の温度の水である請求項１及
び２に記載の塩素化塩化ビニル系樹脂の製造方法。3. The water contacted with the dehydrochlorination gas has a temperature of 0 ° C.
The method for producing a chlorinated vinyl chloride resin according to claim 1 or 2, wherein the temperature of the water is above 40 ° C and below 40 ° C. 【請求項４】 脱塩化水素ガスを脱水した後に、再び反
応器に導入し、塩化ビニル系樹脂の塩素化反応に利用す
る請求項１、２および３に記載の塩素化塩化ビニル系樹
脂の製造方法。4. The production of a chlorinated vinyl chloride resin according to claim 1, 2 or 3, wherein the dehydrochlorinated gas is dehydrated and then introduced into the reactor again to be used for the chlorination reaction of the vinyl chloride resin. Method. 【請求項５】 脱塩化水素ガスを５℃以下、零下１０１
℃以上の範囲の温度に冷却した後に、脱水ガスとして再
び反応器に導入し、塩化ビニル系樹脂の塩素化反応に利
用する請求項４に記載の塩素化塩化ビニル系樹脂の製造
方法。5. Dehydrochlorination gas is kept at 5 ° C. or below at a temperature below zero 101
The method for producing a chlorinated vinyl chloride resin according to claim 4, which is cooled to a temperature in the range of 0 ° C. or higher and then introduced again into the reactor as a dehydration gas and used for the chlorination reaction of the vinyl chloride resin. 【請求項６】 脱塩化水素ガスを零下１３℃以下、零下
１０１℃以上の範囲の温度に冷却した後に、脱水ガスと
して再び反応器に導入し、塩化ビニル系樹脂の塩素化反
応に利用する請求項４に記載の塩素化塩化ビニル系樹脂
の製造方法。6. A method in which dehydrochlorination gas is cooled to a temperature in the range of 13 ° C. below zero and 101 ° C. below zero, and then introduced into the reactor again as dehydration gas for use in the chlorination reaction of vinyl chloride resin. Item 5. A method for producing a chlorinated vinyl chloride resin according to Item 4. 【請求項７】 脱塩化水素ガスを零下３６℃以下、零下
１０１℃以上の範囲の温度に冷却して液化し、液化した
塩素を再び気化させた後に、脱水ガスとして再び反応器
に導入し、塩化ビニル系樹脂の塩素化反応に利用する請
求項４に記載の塩素化塩化ビニル系樹脂の製造方法。7. The dehydrochlorination gas is liquefied by cooling to a temperature in the range of 36 ° C. below zero and 101 ° C. below zero, liquefied chlorine is vaporized again, and then introduced into the reactor again as dehydrated gas, The method for producing a chlorinated vinyl chloride resin according to claim 4, which is used for a chlorination reaction of a vinyl chloride resin. 【請求項８】 脱塩化水素ガスを硫酸、塩化カルシウ
ム、ゼオライト、モレキュラーシーブス、五酸化二燐か
ら選択される少なくとも１種と接触させた後に、脱水ガ
スとして再び反応器に導入し、塩化ビニル系樹脂の塩素
化反応に利用する請求項４に記載の塩素化塩化ビニル系
樹脂の製造方法。8. The dehydrochlorination gas is brought into contact with at least one selected from sulfuric acid, calcium chloride, zeolite, molecular sieves and diphosphorus pentoxide, and then introduced into the reactor again as dehydrated gas to obtain a vinyl chloride system. The method for producing a chlorinated vinyl chloride resin according to claim 4, which is used for a chlorination reaction of a resin. 【請求項９】 脱塩化水素ガスを５℃以下に冷却し、冷
却と同時に又は冷却後に硫酸、塩化カルシウム、ゼオラ
イト、モレキュラーシーブス、五酸化二燐から選択され
る少なくとも１種と接触させた後に、脱水ガスとして再
び反応器に導入し、塩化ビニル系樹脂の塩素化反応に利
用する請求項４に記載の塩素化塩化ビニル系樹脂の製造
方法。9. Dehydrochlorination gas is cooled to 5 ° C. or lower, and at the same time as or after cooling, contacting with at least one selected from sulfuric acid, calcium chloride, zeolite, molecular sieves and diphosphorus pentoxide, The method for producing a chlorinated vinyl chloride resin according to claim 4, wherein the dehydrated gas is reintroduced into the reactor and used for the chlorination reaction of the vinyl chloride resin. 【請求項１０】 脱水ガスの含水量が５０重量ｐｐｍ以
下である請求項７〜９に記載の塩素化塩化ビニル系樹脂
の製造方法。10. The method for producing a chlorinated vinyl chloride resin according to claim 7, wherein the dehydrated gas has a water content of 50 ppm by weight or less. 【請求項１１】 水に吸収された塩化水素と等量のモル
数の塩素を、脱塩化水素ガス又は脱水ガスと共に反応器
内に供給する請求項１〜１０に記載の塩素化塩化ビニル
系樹脂の製造方法。11. The chlorinated vinyl chloride resin according to claim 1, wherein chlorine in an amount equivalent to that of hydrogen chloride absorbed in water is supplied into the reactor together with dehydrochlorination gas or dehydration gas. Manufacturing method. 【請求項１２】 反応器、脱塩化水素器、脱水器から成
る装置を密閉型装置とし、密閉型装置内部の圧力を一定
に保つ為に必要な塩素を、密閉型装置内部に供給する請
求項１〜１１に記載の塩素化塩化ビニル系樹脂の製造方
法。12. A closed type device comprising a reactor, a dehydrochlorination device, and a dehydrator, and chlorine required for maintaining a constant pressure inside the closed type device is supplied into the closed type device. The method for producing a chlorinated vinyl chloride resin according to any one of 1 to 11. 【請求項１３】 塩素化反応の反応促進の為に光を使用
する、請求項１〜１２に記載の塩素化塩化ビニル系樹脂
の製造方法。13. The method for producing a chlorinated vinyl chloride resin according to claim 1, wherein light is used to accelerate the reaction of the chlorination reaction. 【請求項１４】 反応促進の為の光の光源が、低圧水銀
灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ
から選択される少なくとも一種である請求項１３に記載
の塩素化塩化ビニル系樹脂の製造方法。14. The method for producing a chlorinated vinyl chloride resin according to claim 13, wherein the light source for accelerating the reaction is at least one selected from a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp and a metal halide lamp. . 【請求項１５】 塩化ビニル系樹脂粉体と塩素ガスを気
固接触反応場で反応させる反応器、該反応器から反応ガ
スを排出する排出ガス管、該排出管に接続された脱塩化
水素器、および該脱塩化水素器からの塩素ガスを含む脱
塩化水素ガスを反応器に環流するための導入ガス管を備
えてなる塩化ビニル系樹脂を後塩素化反応させて塩素化
塩化ビニル系樹脂を製造する装置。15. A reactor for reacting vinyl chloride resin powder and chlorine gas in a gas-solid contact reaction field, an exhaust gas pipe for exhausting a reaction gas from the reactor, and a dehydrochlorination device connected to the exhaust pipe. , And a chlorinated vinyl chloride resin by post-chlorinating a vinyl chloride resin having an introduction gas pipe for circulating dehydrochlorination gas containing chlorine gas from the dehydrochlorination unit to the reactor. Equipment to manufacture. 【請求項１６】 脱塩化水素器が反応ガスと水を接触さ
せ、反応ガス中の塩化水素ガスを水に吸収させる装置で
ある請求項１５記載の装置。16. The apparatus according to claim 15, wherein the dehydrochlorination unit is an apparatus for bringing the reaction gas and water into contact with each other and allowing the hydrogen chloride gas in the reaction gas to be absorbed by water. 【請求項１７】 脱塩化水素ガスと接触させる水が、零
℃を越え、４０℃以下の範囲の温度の水である請求項１
５及び１６に記載の装置。17. The water contacted with the dehydrochlorination gas is water having a temperature in the range of more than 0 ° C. and 40 ° C. or less.
The device according to 5 and 16. 【請求項１８】 脱塩化水素ガスを脱水した後に、反応
器に導入する請求項１５、１６および１７に記載の装
置。18. The apparatus according to claim 15, 16 or 17, wherein the dehydrochlorinated gas is dehydrated and then introduced into the reactor. 【請求項１９】 脱塩化水素ガスを５℃以下、零下１０
１℃以上の範囲の温度に冷却した後に、脱水ガスとして
再び反応器に導入し、塩化ビニル系樹脂の塩素化反応に
利用する請求項１８に記載の装置。19. Dehydrochlorination gas is kept at 5 ° C. or lower at a temperature below zero.
The apparatus according to claim 18, wherein after cooling to a temperature in the range of 1 ° C or higher, it is introduced into the reactor again as dehydrated gas and used for the chlorination reaction of the vinyl chloride resin. 【請求項２０】 脱塩化水素ガスを零下１３℃以下、零
下１０１℃以上の範囲の温度に冷却した後に、脱水ガス
として再び反応器に導入し、塩化ビニル系樹脂の塩素化
反応に利用する請求項１８に記載の装置。20. After cooling the dehydrochlorinated gas to a temperature in the range of 13 ° C. below zero and 101 ° C. or more below zero, it is introduced into the reactor again as dehydration gas and used for the chlorination reaction of vinyl chloride resin. Item 19. The device according to item 18. 【請求項２１】 脱塩化水素ガスを零下３６℃以下、零
下１０１℃以上の範囲の温度に冷却して液化し、液化し
た塩素を再び気化させた後に、脱水ガスとして再び反応
器に導入し、塩化ビニル系樹脂の塩素化反応に利用する
請求項１８に記載の装置。21. Dehydrochlorination gas is liquefied by cooling to a temperature in the range of 36 ° C. below zero and 101 ° C. below zero, and after liquefied chlorine is vaporized again, it is introduced again into the reactor as dehydrated gas, The apparatus according to claim 18, which is used for a chlorination reaction of vinyl chloride resin. 【請求項２２】 脱塩化水素ガスを硫酸、塩化カルシウ
ム、ゼオライト、モレキュラーシーブス、五酸化二燐か
ら選択される少なくとも１種と接触させた後に、脱水ガ
スとして再び反応器に導入し、塩化ビニル系樹脂の塩素
化反応に利用する請求項１８に記載の装置。22. The dehydrochlorination gas is contacted with at least one selected from sulfuric acid, calcium chloride, zeolite, molecular sieves and diphosphorus pentoxide, and then introduced into the reactor again as dehydrated gas to obtain a vinyl chloride system. The apparatus according to claim 18, which is used for a chlorination reaction of a resin. 【請求項２３】 脱塩化水素ガスを５℃以下に冷却し、
冷却と同時に又は冷却後に硫酸、塩化カルシウム、ゼオ
ライト、モレキュラーシーブス、五酸化二燐から選択さ
れる少なくとも１種と接触させた後に、脱水ガスとして
再び反応器に導入し、塩化ビニル系樹脂の塩素化反応に
利用する請求項１８に記載の装置。23. Cooling the dehydrochlorinated gas to 5 ° C. or lower,
Simultaneously with or after cooling, it is contacted with at least one selected from sulfuric acid, calcium chloride, zeolite, molecular sieves and diphosphorus pentoxide, and then introduced into the reactor again as dehydration gas to chlorinate the vinyl chloride resin. The device according to claim 18, which is used for a reaction. 【請求項２４】 脱水ガスの含水量が５０重量ｐｐｍ以
下である請求項２１〜２３に記載の装置。24. The apparatus according to claim 21, wherein the dehydrated gas has a water content of 50 ppm by weight or less. 【請求項２５】 水に吸収された塩化水素と等量のモル
数の塩素を、脱塩化水素ガス又は脱水ガスと共に反応器
内に供給する請求項１５〜２４に記載の装置。25. The apparatus according to any one of claims 15 to 24, wherein chlorine in an amount equal to that of hydrogen chloride absorbed in water is supplied into the reactor together with dehydrochlorination gas or dehydration gas. 【請求項２６】 反応器、塩化水素吸収器、脱水器から
成る装置を密閉型装置とし、密閉型装置内部の圧力を一
定に保つ為に必要な塩素を、密閉型装置内部に供給する
請求項１５〜２４に記載の装置。26. A device comprising a reactor, a hydrogen chloride absorber, and a dehydrator is a closed type device, and chlorine required for maintaining a constant pressure inside the closed type device is supplied into the closed type device. The apparatus according to 15 to 24. 【請求項２７】 塩素化反応の反応促進の為に光を使用
する、請求項１５〜２６に記載の装置。27. The apparatus according to claim 15, wherein light is used to promote the reaction of the chlorination reaction. 【請求項２８】 反応促進の為の光の光源が、低圧水銀
灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ
から選択される少なくとも一種である請求項２７に記載
の装置。28. The apparatus according to claim 27, wherein the light source for accelerating the reaction is at least one selected from a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp.
JP2001385066A 2001-12-18 2001-12-18 Method and apparatus for producing chlorinated polyvinyl chloride resin Pending JP2003183320A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006272241A (en) * 2005-03-30 2006-10-12 Kaneka Corp Separation/recovery method of paper component and polyvinylchloride component from polyvinylchloride resin-based wallpaper, and regeneratd polyvinylchloride resin
WO2014157346A1 (en) * 2013-03-29 2014-10-02 株式会社カネカ Production method and production device for chlorinated vinyl chloride-based resin
WO2017065224A1 (en) * 2015-10-15 2017-04-20 株式会社カネカ Chlorinated vinyl chloride resin production method
WO2017145864A1 (en) * 2016-02-25 2017-08-31 株式会社カネカ Method for producing chlorinated vinyl chloride resin
CN108948238A (en) * 2018-08-29 2018-12-07 江苏德邦工程有限公司 A kind of method preparing chliorinated polyvinyl chloride and its preparation facilities
CN110028604A (en) * 2019-04-24 2019-07-19 杭州新元化工技术开发有限公司 A kind of preparation method of chliorinated polyvinyl chloride
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006272241A (en) * 2005-03-30 2006-10-12 Kaneka Corp Separation/recovery method of paper component and polyvinylchloride component from polyvinylchloride resin-based wallpaper, and regeneratd polyvinylchloride resin
WO2014157346A1 (en) * 2013-03-29 2014-10-02 株式会社カネカ Production method and production device for chlorinated vinyl chloride-based resin
US9399687B2 (en) 2013-03-29 2016-07-26 Kaneka Corportion Method and apparatus for producing chlorinated vinyl chloride-based resin
JPWO2017065224A1 (en) * 2015-10-15 2018-08-02 株式会社カネカ Method for producing chlorinated vinyl chloride resin
WO2017065224A1 (en) * 2015-10-15 2017-04-20 株式会社カネカ Chlorinated vinyl chloride resin production method
CN108602911A (en) * 2016-02-25 2018-09-28 株式会社钟化 The manufacturing method of chlorinated vinyl chloride-based resin
WO2017145864A1 (en) * 2016-02-25 2017-08-31 株式会社カネカ Method for producing chlorinated vinyl chloride resin
US10590210B2 (en) 2016-02-25 2020-03-17 Kaneka Corporation Method for producing chlorinated vinyl chloride resin
CN108948238A (en) * 2018-08-29 2018-12-07 江苏德邦工程有限公司 A kind of method preparing chliorinated polyvinyl chloride and its preparation facilities
CN108948238B (en) * 2018-08-29 2023-06-30 江苏德邦工程有限公司 Method for preparing chlorinated polyvinyl chloride and preparation device thereof
CN110028604A (en) * 2019-04-24 2019-07-19 杭州新元化工技术开发有限公司 A kind of preparation method of chliorinated polyvinyl chloride
CN118022653A (en) * 2024-04-15 2024-05-14 丹阳市助剂化工厂有限公司 Chlorinated paraffin production device and production method thereof
CN118022653B (en) * 2024-04-15 2024-06-11 丹阳市助剂化工厂有限公司 Chlorinated paraffin production device and production method thereof

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