JP2000256232A - Purification method of vinyl chloride - Google Patents
Purification method of vinyl chlorideInfo
- Publication number
- JP2000256232A JP2000256232A JP11064622A JP6462299A JP2000256232A JP 2000256232 A JP2000256232 A JP 2000256232A JP 11064622 A JP11064622 A JP 11064622A JP 6462299 A JP6462299 A JP 6462299A JP 2000256232 A JP2000256232 A JP 2000256232A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- alkali metal
- metal hydroxide
- water
- acetylene
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【課題】 微量塩化水素及び水分を含有する塩化ビニル
を固体のアルカリ金属水酸化物と接触させて精製する際
に、アセチレンの発生を抑制した精製法を提供する。
【解決手段】 塩化ビニルを固体のアルカリ金属水酸化
物で処理して、塩化ビニル中の塩化水素、水を除去する
際、塩化ビニルと固体アルカリ金属水酸化物を、３５℃
以下の温度で接触させること、或いは塩化ビニルを、固
体アルカリ金属水酸化物の充填層に通液して塩化ビニル
中の塩化水素、水を除去する方法に於いて、該充填層へ
通液される塩化ビニル中の水の累積量が、固体アルカリ
金属水酸化物１ｇ当たり、０．２０ｇ以下の時点で、充
填層中のアルカリ金属水酸化物を交換することを特徴と
する塩化ビニルの精製方法。PROBLEM TO BE SOLVED: To provide a purification method which suppresses generation of acetylene when purifying vinyl chloride containing trace amounts of hydrogen chloride and water with a solid alkali metal hydroxide for purification. SOLUTION: When vinyl chloride is treated with a solid alkali metal hydroxide to remove hydrogen chloride and water in the vinyl chloride, the vinyl chloride and the solid alkali metal hydroxide are treated at 35 ° C.
In the method of contacting vinyl chloride at the following temperature or by passing vinyl chloride through a packed layer of solid alkali metal hydroxide to remove hydrogen chloride and water in vinyl chloride, Wherein the alkali metal hydroxide in the packed bed is replaced when the cumulative amount of water in the vinyl chloride is 0.20 g or less per 1 g of solid alkali metal hydroxide. .
Description
【０００１】[0001]
【発明の属する技術分野】本発明は塩化ビニルの精製方
法に関する。詳しくは、工業的に製造された塩化ビニル
中に存在する微量の塩化水素及び水を除去する方法に関
する。[0001] The present invention relates to a method for purifying vinyl chloride. More specifically, the present invention relates to a method for removing trace amounts of hydrogen chloride and water present in industrially produced vinyl chloride.
【０００２】[0002]
【従来の技術】工業的に使用されている塩化ビニルは、
一般に、１，２−ジクロルエタンの熱分解により製造さ
れている。熱分解で得られた粗塩化ビニルは、塩化水
素、未反応の１，２−ジクロルエタン等を分別蒸留によ
り分離し、精製される。しかし、この様に精製された塩
化ビニル中にはなお、微量の塩化水素、水が含まれてお
り、容器の腐食や、かかる塩化ビニルから得られた重合
体の付着の原因となっている。そのため、アルカリ金属
水酸化物を水溶液として或いは固体状で塩化ビニルと接
触させて、塩化水素及び水を除する方法が知られている
（特開昭５７−２０９２３４号）。2. Description of the Related Art Vinyl chloride used industrially is:
Generally, it is produced by thermal decomposition of 1,2-dichloroethane. Crude vinyl chloride obtained by thermal decomposition is purified by separating hydrogen chloride, unreacted 1,2-dichloroethane and the like by fractional distillation. However, the thus-purified vinyl chloride still contains trace amounts of hydrogen chloride and water, causing corrosion of the container and adhesion of a polymer obtained from the vinyl chloride. Therefore, a method is known in which an alkali metal hydroxide is brought into contact with vinyl chloride in the form of an aqueous solution or in a solid state to remove hydrogen chloride and water (JP-A-57-209234).
【０００３】しかしながら、アルカリ金属水酸化物の水
溶液と接触させる方法は、塩化水素は有効に除去できる
が、処理後の塩化ビニルを乾燥する必要があり、装置及
び操作が煩雑となる欠点がある。又、固体のアルカリ金
属水酸化物を用いる方法は、塩化ビニルとアルカリ金属
水酸化物が接触することによりアセチレンを発生させる
という問題点がある。アセチレンが混入すると塩化ビニ
ルの重合度を低下させ、或いは生成したポリ塩化ビニル
の熱安定性を低下させる原因となる。アセチレン生成を
避ける方法として、特開昭５７−２０９３４号では、ア
ルカリ金属水酸化物の代わりにアルカリ土類金属水酸化
物の使用を提案している。しかしてアルカリ土類金属水
酸化物では必ずしも効果が十分ではなく、又価格が高い
という欠点がある。[0003] However, the method of bringing into contact with an aqueous solution of an alkali metal hydroxide can effectively remove hydrogen chloride, but requires drying the treated vinyl chloride, and has a drawback in that the apparatus and operation are complicated. Further, the method using a solid alkali metal hydroxide has a problem that acetylene is generated by contact between vinyl chloride and the alkali metal hydroxide. When acetylene is mixed in, the degree of polymerization of vinyl chloride is reduced or the thermal stability of the produced polyvinyl chloride is reduced. As a method for avoiding the generation of acetylene, Japanese Patent Application Laid-Open No. 57-20934 proposes to use an alkaline earth metal hydroxide instead of an alkali metal hydroxide. However, alkaline earth metal hydroxides are not always effective enough and have the disadvantage of high price.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、かかる事情
に鑑み成されたものであって、固体のアルカリ金属水酸
化物を使用して、アセチレンを発生させることなく、微
量の塩化水素、水を含有する塩化ビニルを精製する工業
的有利な方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and uses a solid alkali metal hydroxide to generate a small amount of hydrogen chloride and water without generating acetylene. It is an object of the present invention to provide an industrially advantageous method for purifying vinyl chloride containing a.
【０００５】[0005]
【課題を解決するための手段】本発明者等は上記目的を
達成するため、鋭意検討を重ね、塩化ビニルと固体のア
ルカリ金属水酸化物を接触させる際の条件を制御するこ
とにより、アセチレンの生成を抑制し得ることを知り本
発明に到達した。即ち本発明は、塩化ビニルを固体のア
ルカリ金属水酸化物で処理して、塩化ビニル中の塩化水
素、水を除去する際、塩化ビニルと固体アルカリ金属水
酸化物を、３５℃以下の温度で接触させること、或いは
塩化ビニルを、固体アルカリ金属水酸化物の充填層に通
液して塩化ビニル中の塩化水素、水を除去する方法に於
いて、該充填層へ通液される塩化ビニル中の水の累積量
が、固体アルカリ金属水酸化物１ｇ当たり、０．２０ｇ
以下の時点で、充填層中のアルカリ金属水酸化物を交換
することを特徴とする塩化ビニルの精製方法に存する。Means for Solving the Problems To achieve the above object, the present inventors have conducted intensive studies and controlled the conditions under which vinyl chloride and solid alkali metal hydroxide were brought into contact with each other, whereby acetylene conversion was achieved. The inventors have found that generation can be suppressed, and arrived at the present invention. That is, in the present invention, when treating vinyl chloride with a solid alkali metal hydroxide to remove hydrogen chloride and water in the vinyl chloride, the vinyl chloride and the solid alkali metal hydroxide are treated at a temperature of 35 ° C. or lower. Contacting or passing vinyl chloride through a packed layer of solid alkali metal hydroxide to remove hydrogen chloride and water in the vinyl chloride. Is 0.20 g per 1 g of solid alkali metal hydroxide.
The present invention resides in a method for purifying vinyl chloride, which comprises exchanging an alkali metal hydroxide in a packed bed at the following points.
【０００６】本発明者等は、塩化ビニルと固体のアルカ
リ金属水酸化物を接触させる際、アセチレンが生成する
条件に付き検討をしたところ、接触温度及び、又はアル
カリ金属水酸化物の湿潤状態が大きく、関係しているこ
とを見出した。即ち、通常、工業的に製造される塩化ビ
ニルは、１，２−ジクロルエタンを塩化ビニルと塩化水
素に熱分解し、塩化水素を分離後、未反応１，２−ジク
ロルエタン等の高沸物を蒸留分離し、蒸留塔留出物を熱
交換器により冷却して精製された塩化ビニルを液状で回
収する。熱交換器は、通常、再冷塔で冷却された再冷水
を用いて冷却されることから、４０〜５０℃程度までし
か塩化ビニルを冷却出来ない。従って、従来は、４０〜
５０℃の温度で塩化ビニルと固体のアルカリ金属水酸化
物との接触が行われており、アセチレンが発生してい
た。しかして本発明者等は、接触時の塩化ビニルの温度
を３５℃以下にするとアセチレンの生成を抑制すること
が出来ることを見出した。The present inventors have studied the conditions under which acetylene is formed when vinyl chloride is brought into contact with a solid alkali metal hydroxide, and found that the contact temperature and / or the wet state of the alkali metal hydroxide were reduced. I found that it was big and related. That is, normally, industrially produced vinyl chloride is obtained by thermally decomposing 1,2-dichloroethane into vinyl chloride and hydrogen chloride, separating hydrogen chloride, and distilling unreacted 1,2-dichloroethane and other high-boiling substances. Separation, the distillation column distillate is cooled by a heat exchanger, and the purified vinyl chloride is recovered in a liquid state. Since the heat exchanger is usually cooled using re-cooled water cooled in a re-cooling tower, it can only cool vinyl chloride up to about 40 to 50 ° C. Therefore, conventionally, 40 to
The contact between vinyl chloride and the solid alkali metal hydroxide was performed at a temperature of 50 ° C., and acetylene was generated. Thus, the present inventors have found that the production of acetylene can be suppressed by setting the temperature of vinyl chloride at the time of contact to 35 ° C. or lower.
【０００７】又、固体アルカリ金属水酸化物の湿潤状態
もアセチレン発生速度に大きく影響し、湿潤した状態で
塩化ビニルと接触した場合、アセチレンを発生させる速
度が高いことが判明した。しかして、塩化ビニルをアル
カリ金属水酸化物の水溶液に接触させてもアセチレンは
発生しない。この理由は次の通りと推定される。固体の
アルカリ金属水酸化物を水に溶解すると、アルカリ金属
イオンとヒドロキシイオンに電離するが、水素結合によ
り、ヒドロキシイオンに水が結合する。更に多量の水
が、この周囲を取り囲み、塩化ビニルとの反応に寄与す
るヒドロキシイオンの量を低下させるため、アセチレン
は発生しない。一方、固体のアルカリ金属水酸化物は、
乾燥状態では結晶構造を保っている。このため、結晶の
外側の水酸基（ヒドロキシイオン）は、周囲をアルカリ
金属原子に取り囲まれ、一面しか塩化ビニルとの反応に
寄与しない。従って、乾燥状態のアルカリ金属水酸化物
の場合は、アセチレン生成速度が遅く、実質的にアセチ
レンの発生がない。It has also been found that the wet state of the solid alkali metal hydroxide greatly affects the acetylene generation rate, and that the acetylene generation rate is high when the wet state contacts vinyl chloride. Thus, acetylene is not generated even when vinyl chloride is brought into contact with an aqueous solution of an alkali metal hydroxide. The reason is presumed to be as follows. When a solid alkali metal hydroxide is dissolved in water, it is ionized into an alkali metal ion and a hydroxy ion, but water is bonded to the hydroxy ion by hydrogen bonding. Acetylene is not generated because more water surrounds the periphery and reduces the amount of hydroxy ions that contribute to the reaction with vinyl chloride. On the other hand, solid alkali metal hydroxides
The crystal structure is maintained in the dry state. For this reason, the hydroxyl groups (hydroxy ions) outside the crystal are surrounded by alkali metal atoms, and only one side contributes to the reaction with vinyl chloride. Therefore, in the case of the alkali metal hydroxide in a dry state, the acetylene generation rate is low and substantially no acetylene is generated.
【０００８】一方、湿潤したアルカリ金属水酸化物は、
水分により一部のアルカリ金属水酸化物が解離しヒドロ
キシイオンを生成するが、このイオンは更に水素結合に
より水と結合することはない。このため、固体或いは水
溶液状態のアルカリ金属水酸化物に比べ、反応に寄与す
るヒドロキシイオンが多量に存在し、アセチレン生成速
度が速くなるものと考えられる。On the other hand, the wetted alkali metal hydroxide is
Moisture dissociates some alkali metal hydroxides to form hydroxy ions, which are not further bonded to water by hydrogen bonding. Therefore, it is considered that a large amount of hydroxy ions contributing to the reaction is present and the acetylene generation rate is higher than that of the alkali metal hydroxide in a solid or aqueous solution state.
【０００９】[0009]
【発明の実施の形態】上述の如く、工業的に製造される
塩化ビニルは、１，２−ジクロルエタンを塩化ビニルと
塩化水素に熱分解し、塩化水素を分離後、未反応１，２
−ジクロルエタン等の高沸物を蒸留分離し、蒸留塔留出
物を熱交換器により冷却して精製された塩化ビニルを液
状で回収する。かかる塩化ビニルは、通常、温度が４０
〜５０℃程度である。それ故、本発明に従って３５℃以
下の温度で、塩化ビニルをアルカリ金属水酸化物と接触
させるためには、高沸蒸留塔から得られる塩化ビニル
を、更に、冷却する必要がある。冷却方法はどの様な方
法であっても構わない。例えば、吸収冷凍機もしくはア
ンモニア冷凍機等で冷却した冷媒を用いて温度４０〜５
０℃程度の塩化ビニルと熱交換して、３５℃以下に冷却
する。或いは、塩化ビニルの蒸留精製時に、吸収冷凍機
もしくはアンモニア冷凍機等で冷却した冷媒を用いて熱
交換して、３５℃以下に冷却された塩化ビニルを得る等
の方法がある。塩化ビニルと固体のアルカリ金属水酸化
物との接触温度は、３５℃以下、好ましくは２５℃以
下、更に好ましくは０〜２５℃である。DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, industrially produced vinyl chloride is obtained by thermally decomposing 1,2-dichloroethane into vinyl chloride and hydrogen chloride, separating hydrogen chloride and then reacting unreacted 1,2.
-Distilling off high boiling substances such as dichloroethane and cooling the distillate of the distillation column with a heat exchanger to recover purified vinyl chloride in a liquid state. Such vinyl chlorides are typically used at temperatures of 40
~ 50 ° C. Therefore, in order to contact vinyl chloride with an alkali metal hydroxide at a temperature of 35 ° C. or less according to the present invention, the vinyl chloride obtained from the high boiling distillation column needs to be further cooled. The cooling method may be any method. For example, using a refrigerant cooled by an absorption refrigerator or an ammonia refrigerator, etc.
Heat exchange with vinyl chloride at about 0 ° C. and cool to 35 ° C. or less. Alternatively, there is a method in which heat is exchanged with a refrigerant cooled by an absorption refrigerator or an ammonia refrigerator or the like during the distillation purification of vinyl chloride to obtain vinyl chloride cooled to 35 ° C. or lower. The contact temperature between vinyl chloride and the solid alkali metal hydroxide is 35 ° C or lower, preferably 25 ° C or lower, more preferably 0 to 25 ° C.
【００１０】本発明方法に使用される固体のアルカリ金
属水酸化物としては、水酸化カリウム、水酸化ナトリウ
ム等が挙げられ、好ましくは水酸化ナトリウムである。
これらのアルカリ金属水酸化物は、粒状、ペレット状等
如何なる形状であってもよく、また、シリカ或いはアル
ミナ等の多孔性物質に担持して用いても良い。アルカリ
金属水酸化物と塩化ビニルとの接触方法は、回分式、又
は流通式による連続法の何れでも良い。工業的な精製法
の具体例は、アルカリ金属水酸化物の充填層に塩化ビニ
ルを流通させて接触する方法である。この方法における
塩化ビニルの流量、接触時間等の接触条件は、塩化ビニ
ル中の塩化水素及び水の量に応じて適宜決められるが、
通常単位充填物当たりの塩化ビニルの流量は、０．１〜
１０００ １／Ｈｒ．望ましくは１〜５０ １／Ｈｒ．
である。The solid alkali metal hydroxide used in the method of the present invention includes potassium hydroxide, sodium hydroxide and the like, and is preferably sodium hydroxide.
These alkali metal hydroxides may be in any shape such as granules or pellets, or may be used by being supported on a porous substance such as silica or alumina. The method of contacting the alkali metal hydroxide with vinyl chloride may be either a batch method or a continuous method using a flow method. A specific example of an industrial refining method is a method in which vinyl chloride is passed through a packed bed of an alkali metal hydroxide to make contact therewith. The contact conditions such as the flow rate of vinyl chloride and the contact time in this method are appropriately determined according to the amounts of hydrogen chloride and water in the vinyl chloride.
Usually, the flow rate of vinyl chloride per unit charge is 0.1 to
1000 1 / Hr. Desirably, 1 to 50 1 / Hr.
It is.
【００１１】本出願の他の発明は、水分量が管理された
アルカリ金属水酸化物の充填層に塩化ビニルを流通させ
て接触させる方法である。即ち、上述の如く、アルカリ
金属水酸化物の湿潤状態はアセチレンの発生に大きく関
係する。従って本発明方法によれば、固体のアルカリ金
属水酸化物の充填層に塩化ビニルを流通接触させて精製
する方法に於いて、充填層中の固体アルカリ金属水酸化
物１ｇ当たりの水の累積通液量が、０．２０ｇ以下、好
ましくは０．１５ｇ以下、更に好ましくは０．０１〜
０．１ｇの範囲で充填層のアルカリ金属水酸化物を交換
することが必要である。水の累積通液量は、通液する塩
化ビニルに含まれる水分濃度と塩化ビニルの累積通液量
の積を、アルカリ金属水酸化物の充填量で割った値であ
る。なお塩化ビニル中の水分測定は、ＪＩＳ Ｋ ００
６８により実施し、１ｐｐｍ（重量）の単位まで測定す
る。Another invention of the present application is a method in which vinyl chloride is allowed to flow through and contact a packed layer of an alkali metal hydroxide whose moisture content is controlled. That is, as described above, the wet state of the alkali metal hydroxide is greatly related to the generation of acetylene. Therefore, according to the method of the present invention, in a method of purifying vinyl chloride by flowing and contacting the packed bed of solid alkali metal hydroxide, the accumulated flow of water per 1 g of solid alkali metal hydroxide in the packed bed is improved. The liquid amount is 0.20 g or less, preferably 0.15 g or less, more preferably 0.01 to
It is necessary to exchange the alkali metal hydroxide in the packed bed in the range of 0.1 g. The cumulative flow rate of water is a value obtained by dividing the product of the concentration of water contained in the flowing vinyl chloride and the cumulative flow rate of vinyl chloride by the filling amount of the alkali metal hydroxide. The water content in vinyl chloride was measured according to JIS K 00
68 and measured to the nearest 1 ppm (weight).
【００１２】この様に、水分量が管理された充填層によ
り塩化ビニルを精製する場合も、接触温度は３５℃以下
であることが好ましく、更に好ましくは２５℃以下、特
に好ましくは０〜２５℃である。以上詳述した本発明方
法によれば、実質的にアセチレンを発生させることな
く、塩化ビニルを精製することができる。As described above, even when purifying vinyl chloride using a packed bed in which the amount of water is controlled, the contact temperature is preferably 35 ° C. or lower, more preferably 25 ° C. or lower, and particularly preferably 0 to 25 ° C. It is. According to the method of the present invention described in detail above, vinyl chloride can be purified substantially without generating acetylene.
【００１３】[0013]
【実施例】以下、実施例及び比較例により本発明を更に
具体的に説明するが、本発明はその要旨を超えない限り
以下の例に制約されるものではない。なお、以下の例に
おいて、「ｐｐｍ」及び「％」は「重量ｐｐｍ」及び
「重量％」を意味する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist thereof. In the following examples, “ppm” and “%” mean “ppm by weight” and “% by weight”.
【００１４】実施例１ 水分濃度２９０ｐｐｍ、塩化水素濃度０．２ｐｐｍ、ア
セチレン濃度０．１０ｐｐｍ以下の塩化ビニル４５０ｇ
に、固体水酸化ナトリウム（東ソー社製、工業用水酸化
ナトリウム）を４０ｇ加え、オートクレーブにて２０℃
で３時間撹拌した。３時間後、オートクレーブ気相部及
び液層部のアセチレン濃度を測定し、アセチレンの量を
求めたところ、０．１０ｐｐｍ以下で、アセチレンの発
生は認められなかった。又水分量及び塩化水素はそれぞ
れ６５ｐｐｍ、０．１ｐｐｍ以下であった。Example 1 450 g of vinyl chloride having a water concentration of 290 ppm, a hydrogen chloride concentration of 0.2 ppm, and an acetylene concentration of 0.10 ppm or less
, 40 g of solid sodium hydroxide (manufactured by Tosoh Corporation, industrial sodium hydroxide) was added, and the mixture was autoclaved to 20 ° C.
For 3 hours. After 3 hours, the acetylene concentration in the gas phase part and the liquid layer part in the autoclave was measured, and the amount of acetylene was determined. The water content and hydrogen chloride were 65 ppm and 0.1 ppm, respectively.
【００１５】比較例１ オートクレーブの温度を５０℃にした以外は実施例１と
同様にして塩化ビニルを処理した。３時間後のアセチレ
ン量は０．２４ｐｐｍで、アセチレンの発生が認められ
た。又水分量及び塩化水素はそれぞれ６０ｐｐｍ、０．
１ｐｐｍ以下であった。Comparative Example 1 Vinyl chloride was treated in the same manner as in Example 1 except that the temperature of the autoclave was changed to 50 ° C. After 3 hours, the amount of acetylene was 0.24 ppm, and generation of acetylene was observed. The water content and hydrogen chloride were 60 ppm and 0.1 ppm, respectively.
It was 1 ppm or less.
【００１６】比較例２ 固体水酸化ナトリウムに水１０ｇを加えた以外は実施例
１と同様にして塩化ビニルを処理した。３時間後のアセ
チレン量は０．７９ｐｐｍで、多量のアセチレン発生が
認められた。又水分量及び塩化水素はそれぞれ１７０ｐ
ｐｍ、０．１ｐｐｍ以下であった。Comparative Example 2 Vinyl chloride was treated in the same manner as in Example 1 except that 10 g of water was added to solid sodium hydroxide. After 3 hours, the amount of acetylene was 0.79 ppm, and generation of a large amount of acetylene was observed. Water content and hydrogen chloride are each 170p
pm and 0.1 ppm or less.
【００１７】実施例２ 水の累積通液量が０．０５［ｇ−Ｈ2 Ｏ／ｇ−ＮａＯ
Ｈ］の固体水酸化ナトリウムの充填層に、水分濃度４ｐ
ｐｍ、塩化水素濃度０．２ｐｐｍ、アセチレン濃度０．
１０ｐｐｍ以下の塩化ビニルを、６ｋｇ／ｃｍ2 Ｇ、２
５℃で流通させ、０．２時間接触させた。塩化ビニルと
固体水酸化ナトリウムとの接触比率は、９ｇ／時間／ｇ
−ＮａＯＨとした。接触後の塩化ビニル液中のアセチレ
ン濃度は、０．１０ｐｐｍ以下でアセチレンの発生は認
められなかった。又、水分及び塩化水素の濃度はそれぞ
れ３ｐｐｍ、０．１ｐｐｍ以下であった。Example 2 The cumulative flow rate of water was 0.05 [g-H 2 O / g-NaO
H] in a packed bed of solid sodium hydroxide
pm, hydrogen chloride concentration 0.2 ppm, acetylene concentration 0.
6 ppm / cm 2 G,
It was circulated at 5 ° C. and contacted for 0.2 hours. The contact ratio between vinyl chloride and solid sodium hydroxide is 9 g / hour / g
-NaOH. The acetylene concentration in the vinyl chloride solution after the contact was 0.10 ppm or less, and no generation of acetylene was observed. The concentrations of water and hydrogen chloride were 3 ppm and 0.1 ppm, respectively.
【００１８】比較例３ 流通系で、水分濃度２ｐｐｍ以下、塩化水素濃度０．２
ｐｐｍ、アセチレン濃度０．１０ｐｐｍ以下の塩化ビニ
ルを、６ｋｇ／ｃｍ2 Ｇ、４０℃で４０％水酸化ナトリ
ウム水溶液と０．３時間接触させた。塩化ビニルと水酸
化ナトリウム水溶液との流量比（重量）は１７：１とし
た。処理後の塩化ビニル中のアセチレン濃度は０．１０
ｐｐｍ以下で、アセチレンの発生は認められなかった
が、水分濃度は２００ｐｐｍに上昇した。一方塩化水素
は０．１ｐｐｍ以下であった。Comparative Example 3 In a flow system, a water concentration of 2 ppm or less and a hydrogen chloride concentration of 0.2
ppm, vinyl chloride having an acetylene concentration of 0.10 ppm or less was brought into contact with a 40% aqueous sodium hydroxide solution at 6 kg / cm 2 G and 40 ° C. for 0.3 hours. The flow ratio (weight) between vinyl chloride and the aqueous sodium hydroxide solution was 17: 1. The acetylene concentration in the treated vinyl chloride is 0.10
At below ppm, no acetylene generation was observed, but the water concentration rose to 200 ppm. On the other hand, hydrogen chloride was 0.1 ppm or less.
【００１９】比較例４ 水の累積通液量が０．２５［ｇ−Ｈ2 Ｏ／ｇ−ＮａＯ
Ｈ］の固体水酸化ナトリウムの充填層に、水分濃度２０
０ｐｐｍ、塩化水素濃度０．２ｐｐｍ、アセチレン濃度
０．１０ｐｐｍ以下の塩化ビニルを、６ｋｇ／ｃｍ2
Ｇ、４０℃で流通させ、０．２時間接触させた。塩化ビ
ニルと固体水酸化ナトリウムとの接触比率は、７ｇ／時
間／ｇ−ＮａＯＨとした。接触後の塩化ビニル液中のア
セチレン濃度は、０．１５ｐｐｍでアセチレンの発生が
認められた。又、水分及び塩化水素の濃度はそれぞれ７
０ｐｐｍ、０．１ｐｐｍ以下であった。Comparative Example 4 The cumulative flow rate of water was 0.25 [g-H 2 O / g-NaO
H] in a packed bed of solid sodium hydroxide.
0 ppm, a hydrogen chloride concentration of 0.2 ppm, and an acetylene concentration of 0.10 ppm or less, vinyl chloride of 6 kg / cm 2
G, circulated at 40 ° C. and contacted for 0.2 hours. The contact ratio between vinyl chloride and solid sodium hydroxide was 7 g / hour / g-NaOH. The acetylene concentration in the vinyl chloride solution after the contact was 0.15 ppm, and generation of acetylene was recognized. The concentration of water and hydrogen chloride is 7
0 ppm and 0.1 ppm or less.
【００２０】[0020]
【発明の効果】本発明方法によれば、固体のアルカリ金
属水酸化物を使用して、塩化ビニル中の微量水分及び塩
化水素を除去する際、アセチレンの発生を抑制し、高品
質の精製塩化ビニルを得ることができる。According to the method of the present invention, when a trace amount of water and hydrogen chloride in vinyl chloride are removed by using a solid alkali metal hydroxide, generation of acetylene is suppressed, and high-quality purified chloride is obtained. Vinyl can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 廣戸 健一郎 岡山県倉敷市潮通三丁目10番地 三菱化学 株式会社水島事業所内 (72)発明者 糸山 和年 岡山県倉敷市潮通三丁目10番地 三菱化学 株式会社水島事業所内 Ｆターム(参考） 4H006 AA02 AD17 BA02 BA29 BC18 BC50 BC51 EA03 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Kenichiro Hiroto 3-10-10 Shiodori, Kurashiki-shi, Okayama Prefecture Mitsubishi Chemical Corporation Mizushima Office (72) Inventor Kazutoshi Itoyama 3--10, Shiodori, Kurashiki-shi, Okayama Mitsubishi Chemical F-term in Mizushima Plant (reference) 4H006 AA02 AD17 BA02 BA29 BC18 BC50 BC51 EA03
Claims (5)
化物で処理して、塩化ビニル中の塩化水素、水を除去す
る際、塩化ビニルと固体アルカリ金属水酸化物を、３５
℃以下の温度で接触させることを特徴とする塩化ビニル
の精製方法。(1) treating vinyl chloride with a solid alkali metal hydroxide to remove hydrogen chloride and water in the vinyl chloride,
A method for purifying vinyl chloride, comprising contacting at a temperature of not more than ° C.
ウム及び、又は水酸化カリウムであることを特徴とする
請求項１記載の塩化ビニルの精製方法。2. The method for purifying vinyl chloride according to claim 1, wherein the alkali metal hydroxide is sodium hydroxide and / or potassium hydroxide.
物の充填層に通液して塩化ビニル中の塩化水素、水を除
去する方法に於いて、該充填層へ通液される塩化ビニル
中の水の累積量が、固体アルカリ金属水酸化物１ｇ当た
り、０．２０ｇ以下の時点で、充填層中のアルカリ金属
水酸化物を交換することを特徴とする塩化ビニルの精製
方法。3. A method for removing vinyl chloride and water in vinyl chloride by passing vinyl chloride through a packed layer of solid alkali metal hydroxide, wherein said vinyl chloride is passed through said packed bed. Wherein the accumulated amount of water is 0.20 g or less per 1 g of solid alkali metal hydroxide, and the alkali metal hydroxide in the packed bed is exchanged.
アルカリ金属水酸化物層へ、通液することを特徴とする
請求項３記載の塩化ビニルの精製方法。4. The method for purifying vinyl chloride according to claim 3, wherein the vinyl chloride is passed through the solid alkali metal hydroxide layer at a temperature of 35 ° C. or lower.
ウム及び、又は水酸化カリウムであることを特徴とする
請求項３又は４記載の塩化ビニルの精製方法。5. The method for purifying vinyl chloride according to claim 3, wherein the alkali metal hydroxide is sodium hydroxide and / or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06462299A JP3861497B2 (en) | 1999-03-11 | 1999-03-11 | Method for purifying vinyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06462299A JP3861497B2 (en) | 1999-03-11 | 1999-03-11 | Method for purifying vinyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000256232A true JP2000256232A (en) | 2000-09-19 |
| JP3861497B2 JP3861497B2 (en) | 2006-12-20 |
Family
ID=13263556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06462299A Expired - Fee Related JP3861497B2 (en) | 1999-03-11 | 1999-03-11 | Method for purifying vinyl chloride |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039377A (en) * | 2005-08-03 | 2007-02-15 | Tokuyama Corp | Storage method of vinyl chloride monomer |
| CN110683934A (en) * | 2019-10-25 | 2020-01-14 | 许柏文 | Method and system for purifying vinyl chloride monomer |
-
1999
- 1999-03-11 JP JP06462299A patent/JP3861497B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039377A (en) * | 2005-08-03 | 2007-02-15 | Tokuyama Corp | Storage method of vinyl chloride monomer |
| CN110683934A (en) * | 2019-10-25 | 2020-01-14 | 许柏文 | Method and system for purifying vinyl chloride monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3861497B2 (en) | 2006-12-20 |
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