JPS5940808B2 - Method for recovering vinyl chloride monomer - Google Patents
Method for recovering vinyl chloride monomerInfo
- Publication number
- JPS5940808B2 JPS5940808B2 JP50007307A JP730775A JPS5940808B2 JP S5940808 B2 JPS5940808 B2 JP S5940808B2 JP 50007307 A JP50007307 A JP 50007307A JP 730775 A JP730775 A JP 730775A JP S5940808 B2 JPS5940808 B2 JP S5940808B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- packed column
- vcm
- adsorbent
- primary
- 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.)
- Expired
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は低沸点成分を含む塩化ビニルモノマーから塩化
ビニルモノマー（以下ＶＣＭという）を通常ＶＣＭを重
合するさい、重合がある程度進行した時点で重合反応を
止め、未反応ＶＣＭを回収し、これを加圧液化して再使
用するか、又は蒸留等の手段を用いてＶＣＭを精製し再
使用する。DETAILED DESCRIPTION OF THE INVENTION The present invention involves the polymerization of vinyl chloride monomer (hereinafter referred to as VCM) from vinyl chloride monomers containing low-boiling components, by stopping the polymerization reaction when the polymerization has progressed to a certain extent, and removing unreacted VCM. The VCM is collected, liquefied under pressure and reused, or VCM is purified by means such as distillation and reused.
重合原料であるＶＣＭ中にはその製造過程で微量のエチ
レン、プロピレン、アセチレンおよびメチルクロライド
などの低沸点成分が含まれる。又、塩化ビニル重合中に
ＶＣＭとエチレン、プロピレン等が共重合し、これらが
未反応ＶＣＭ中に混在する。さらに、例えば懸濁重合反
応に使用する水中には少量ながら酸素ガスなどが溶存し
ており、これらが未反応ＶＣＭ中に混在する。したがつ
て、これらＶＣＭを再使用した場合、混在物が重合反応
を阻害するのみならず、重合した塩化ビニル重合体の品
質にも悪影響を及ぼす。前記した低沸点成分を除去する
には、これらが混在蓄積したＶＣＭを系外に廃棄して焼
却するか、又は蒸留によつてＶＣＭと分離する方法があ
る。VCM, which is a raw material for polymerization, contains trace amounts of low-boiling components such as ethylene, propylene, acetylene, and methyl chloride during its manufacturing process. Further, during vinyl chloride polymerization, VCM is copolymerized with ethylene, propylene, etc., and these copolymerize in unreacted VCM. Furthermore, for example, a small amount of oxygen gas is dissolved in the water used in the suspension polymerization reaction, and these gases are mixed in the unreacted VCM. Therefore, when these VCMs are reused, the inclusions not only inhibit the polymerization reaction but also adversely affect the quality of the polymerized vinyl chloride polymer. In order to remove the above-mentioned low boiling point components, there is a method of disposing of the VCM in which these components have been mixed and accumulated outside the system and incinerating it, or separating it from the VCM by distillation.
しかし、焼却する方法は経済的にも不利であるばかりで
なく燃焼部ガスは環境汚染の源となるなど好ましくない
。又、蒸留によつて分離する方法は例えば比較的多く混
在するメチルクロライドなどはＶＣＭと比揮発度がかな
り近いため高性能の精留が必要である。本発明者等は、
前述の低沸点成分を含むＶＣＭからＶＣＭを効果的に分
離回収する方法を研究した結果、固体吸着剤に対する各
混合成分の吸着能の差を利用することにより効果的に目
的を達することを見出した。すなわち本発明は低沸点成
分を含む塩化ビニルモノマーを固体吸着剤を充填したｌ
次充填塔に導入し該吸着剤にＶＣＭを吸着させ、該吸着
剤がＶＣＭで破過される前に前記ＶＣＭの導入を止め不
活性ガスをキャリアガスとして導入してｌ次充填塔に直
列に連結し、かつ１次充填塔より少ない断面積の２次充
填塔にさらに導入して低沸点成分をガスクロマト的に展
開分離して除去し、吸着剤からＶＣＭを回収する方法お
よびその装置を要旨とするものである。本発明で用いる
１次、２次充填塔に用いる固体吸着剤は合成ゼオライト
、活性アルミナ、活性炭などがあるが、ＶＣＭを吸着し
かつＶＣＭと低沸点成分例えばメチルクロライドとの吸
着能において差の大きい活性炭を用いることにより、特
に好ましい結果を得た。活性炭はその活性炭を製造する
さいの原料により性能が異なるが、本発明に用いる活性
炭は特に制限されるものではない。次に本発明の一実施
態様である活性炭を用いた、窒素ガス、メチルクロライ
ド、ＶＣＭの混合物の分離について図面により順次説明
する。However, the method of incineration is not only economically disadvantageous but also undesirable as the combustion gas becomes a source of environmental pollution. In addition, when separating by distillation, for example, methyl chloride, which is present in a relatively large amount, has a specific volatility quite close to that of VCM, so high-performance rectification is required. The inventors,
As a result of research into a method for effectively separating and recovering VCM from VCM containing low-boiling components mentioned above, it was discovered that the objective could be effectively achieved by utilizing the difference in adsorption capacity of each mixed component to a solid adsorbent. . That is, the present invention is a method for preparing a lubricant containing a vinyl chloride monomer containing a low-boiling point component and filled with a solid adsorbent.
Next, the adsorbent is introduced into the packed column to adsorb VCM, and before the adsorbent is broken through the VCM, the introduction of the VCM is stopped, and an inert gas is introduced as a carrier gas, and the VCM is connected in series to the first packed column. Summary of a method and apparatus for recovering VCM from an adsorbent by connecting it and further introducing it into a secondary packed column having a smaller cross-sectional area than the primary packed column, developing and separating low-boiling components using gas chromatography, and recovering VCM from the adsorbent. That is. The solid adsorbents used in the primary and secondary packed columns used in the present invention include synthetic zeolite, activated alumina, and activated carbon, but they adsorb VCM and have a large difference in adsorption ability between VCM and low-boiling components such as methyl chloride. Particularly favorable results were obtained by using activated carbon. The performance of activated carbon varies depending on the raw material used to manufacture the activated carbon, but the activated carbon used in the present invention is not particularly limited. Next, separation of a mixture of nitrogen gas, methyl chloride, and VCM using activated carbon, which is an embodiment of the present invention, will be explained in sequence with reference to the drawings.
固体吸着剤（活性炭）を充填した１次充填塔に不活性ガ
ス（窒素ガス）、ＶＣＭ以外の低沸点成分（メチルクロ
ライド）およびＶＣＭの混合物を原料ガス導入口２より
好ましくは常温で導入すると、まず窒素ガスが流出し、
次いで濃縮されたメチルクロライドが流出する。When a mixture of an inert gas (nitrogen gas), a low-boiling component other than VCM (methyl chloride), and VCM is introduced into a primary packed column filled with a solid adsorbent (activated carbon) through the raw gas inlet 2, preferably at room temperature, First, nitrogen gas flows out,
The concentrated methyl chloride then flows out.
ここで更に原料ガスの導入を続けると流出物中のメチル
クロライド濃度が減少し、ついには原料ガスと同じ組成
のガスが流出する。したがつて、吸着剤がＶＣＭによつ
て破過される前に、好ましくはＣＭによる破過点が充填
層の１／２〜２／３の点に達した時（１次充填塔中に設
置した温度計３で検知する）原料ガスの流入を止め、次
いで窒素ガスなどの不活性ガスをキヤリアガスとしてガ
ス入口８より充填層に流して２次充填塔４に導入する。
このように不活性ガスを導入すると、吸着剤層に残存す
るメチルクロライドなどの低沸点成分は、ガスクロマト
的に展開され、効率良く、ＶＣＭと分離できる。２次充
填塔は、１次充填塔で大部分ＶＣＭは吸着されるので、
又経済的な面から１次充填塔に比較して塔断面積は１／
５〜１／２０、塔長は１／２〜２が好ましい。If the raw material gas is further introduced here, the methyl chloride concentration in the effluent decreases, and finally a gas having the same composition as the raw material gas flows out. Therefore, before the adsorbent is broken through by VCM, preferably when the breakthrough point by CM reaches 1/2 to 2/3 of the packed bed (installed in the primary packed column). The flow of the raw material gas (detected with a thermometer 3) is stopped, and then an inert gas such as nitrogen gas is passed through the gas inlet 8 into the packed bed as a carrier gas and introduced into the secondary packed tower 4.
When an inert gas is introduced in this manner, low-boiling components such as methyl chloride remaining in the adsorbent layer are developed gas chromatographically and can be efficiently separated from VCM. In the secondary packed tower, most of the VCM is adsorbed in the primary packed tower, so
Also, from an economic point of view, the cross-sectional area of the column is 1/1 compared to that of a primary packed column.
5 to 1/20, and the column length is preferably 1/2 to 2.
吸着したＣＭを吸着剤から回収するには、ＶＣＭを吸着
した吸着剤をＣＭが離脱しない程度の減圧下におき、残
存するキャリアガスを除去し、吸着剤充填層を減圧下に
外部から加熱するか又は加熱した不活性ガスを流通させ
ることによりＶＣＭを回収することが出来る。To recover adsorbed CM from the adsorbent, the adsorbent that has adsorbed VCM is placed under reduced pressure to the extent that CM does not separate, the remaining carrier gas is removed, and the adsorbent packed bed is externally heated under reduced pressure. Alternatively, VCM can be recovered by flowing heated inert gas.
しかしより好ましい方法は、加熱水蒸気を水蒸気導入口
５を通して充填層に流通させ、充填層を加熱する方法で
ある。回収したＶＣＭは必要とあれば水と分離し再使用
する。ＶＣＭを除却回収した吸着剤は乾燥し再度使用に
供する。ＶＣＭに混合する低沸点ガスがエチレン、プロ
ピレン等の場合でも前述の方法で分離出来る。However, a more preferred method is to flow heated steam through the steam inlet 5 to the packed bed to heat the packed bed. The recovered VCM is separated from water and reused if necessary. The adsorbent that has removed and recovered VCM is dried and used again. Even if the low boiling point gas mixed with VCM is ethylene, propylene, etc., it can be separated by the method described above.
本発明の方法は効率よく低沸点成分を含むＶＣＭからＶ
ＣＭを分離回収することができる。The method of the present invention efficiently converts VCM containing low boiling point components into VCM.
CM can be separated and recovered.
次に本発明を実施例で詳述する。実施例 １
直径２，５ｃ７ｎ長さ２５ｃＴｒＬのガラス製カラムに
活性炭（コーワＣＧ−４１０Ａ）を５０ｇｒ充填し（１
次充填塔）、これに直径１ＣＴＬ長さ１５ＣＴＬのガラ
ス製カラムに活性素５ｇｒを充填して（２次充填塔）直
列に接続し、窒素３５．８％、メチルクロライド０．５
２％、ＶＣＭ６３．６８％からなる原料ガスを常圧で、
吸着熱は自然放熱させて、０．５１／分の流速で通し、
１次充填塔の出口側に装着した温度計で吸着熱を測定し
、１次充填塔におけるＶＣＭの破過点を検知し、破過直
後原料ガスを止め、次いで窒素ガスを０．５．ｅ／分の
流速で導入して２次充填塔に通した。Next, the present invention will be explained in detail with reference to Examples. Example 1 A glass column with a diameter of 2.5c7n and a length of 25cTrL was filled with 50g of activated carbon (Kowa CG-410A) (1
Next, a glass column with a diameter of 1 CTL and a length of 15 CTL was packed with 5 gr of active elements (secondary packed column) and connected in series with 35.8% nitrogen and 0.5 methyl chloride.
2%, VCM63.68% at normal pressure,
The heat of adsorption is allowed to radiate naturally and passed through at a flow rate of 0.51/min.
The heat of adsorption is measured with a thermometer attached to the outlet side of the primary packed column, the breakthrough point of VCM in the primary packed column is detected, and immediately after the breakthrough point, the raw material gas is stopped, and then the nitrogen gas is injected at 0.5. It was introduced at a flow rate of e/min and passed through a secondary packed column.
２次充填塔の出口におけるガス組成を分析した。The gas composition at the outlet of the secondary packed column was analyzed.
結果を表１に示した。実施例 ２直径１．５？長さ１０
ＣＴ！Ｌのカラムに活性炭５ｇｒを充填して２次充填塔
として用いた以外は実施例１と同様に試験した。The results are shown in Table 1. Example 2 Diameter 1.5? length 10
CT! The test was carried out in the same manner as in Example 1, except that the L column was filled with 5 grams of activated carbon and used as a secondary packed column.
結果を表２に示した。実施例 ３直径１．０ＣＴＩＬ長
さ７．５ＣＴＬのカラムに活性炭２，５７ｒを充填し、
２次充填塔として用いた以外は実施例１と同様に試験し
た。The results are shown in Table 2. Example 3 A column with a diameter of 1.0CTIL and a length of 7.5CTL was filled with 2.57r of activated carbon.
The test was carried out in the same manner as in Example 1 except that it was used as a secondary packed column.
結果を表３に示した。比較例 １実施例１で用いた１次
充填塔のみを用い、実施例１と同様に試験した。The results are shown in Table 3. Comparative Example 1 A test was conducted in the same manner as in Example 1 using only the primary packed column used in Example 1.
結果を表４に示した。実施例 ４実施例１において窒素
ガスを導入して低沸成分を除去後充填塔内温度を５０℃
とし、１７０〜１９０℃に加熱した水蒸気を導入した。The results are shown in Table 4. Example 4 In Example 1, after introducing nitrogen gas and removing low-boiling components, the temperature inside the packed column was set to 50°C.
Steam heated to 170-190°C was introduced.
塔を通過した水蒸気は冷却し水分を疑縮させＶＣＭと分
離しＶＣＭは回収した。この操作を繰返して試験した。
結果を表５に示した。The steam that passed through the tower was cooled to cause moisture to condense and separate from VCM, which was recovered. This operation was repeated for testing.
The results are shown in Table 5.
第１図は本発明の一実施態様に用いる装置の経路図であ
る。
第１図中１は１次充填塔、２は原料ガス導入口、３は温
度計、４は２次充填塔、５は水蒸気導入口、６は冷却器
、７は分離器、８はキヤリヤーガス導入口を示す。FIG. 1 is a route diagram of an apparatus used in one embodiment of the present invention. In Figure 1, 1 is the primary packed tower, 2 is the feed gas inlet, 3 is the thermometer, 4 is the secondary packed tower, 5 is the steam inlet, 6 is the cooler, 7 is the separator, and 8 is the carrier gas inlet. Show mouth.
Claims (1)
吸着剤を充填した１次充填塔に導入し該吸着剤に塩化ビ
ニルモノマーを吸着させ、１次充填塔の吸着剤が塩化ビ
ニルモノマーで破過される以前に前記塩化ビニルモノマ
ーの導入を止め、次いで不活性ガスを１次充填塔および
、１次充填塔に直列に連結した、１次充填塔より少ない
断面積の２次充填塔に導入してメチルクロライドを展開
して分離除去し、吸着剤から塩化ビニルモノマーを回収
することを特徴とするメチルクロライドを含む塩化ビニ
ルモノマーから塩化ビニルモノマーの分離回収方法。 ２ 固体吸着剤を充填した１次充填塔とこれに直列に連
結し、かつ１次充填塔より少ない断面積の２次充填塔か
らなる低沸点成分を含む塩化ビニルモノマーから塩化ビ
ニルモノマーを分離回収する装置。[Scope of Claims] 1. A vinyl chloride monomer containing methyl chloride is introduced into a primary packed column packed with a solid adsorbent, and the vinyl chloride monomer is adsorbed onto the adsorbent, and the adsorbent in the primary packed column absorbs the vinyl chloride monomer. The introduction of the vinyl chloride monomer is stopped before the vinyl chloride monomer is broken through, and then the inert gas is introduced into the primary packed column and the secondary packed column, which is connected in series to the primary packed column and has a smaller cross-sectional area than the primary packed column. 1. A method for separating and recovering vinyl chloride monomers from vinyl chloride monomers containing methyl chloride, which comprises introducing the vinyl chloride monomer into an adsorbent, developing and separating and removing the methyl chloride, and recovering the vinyl chloride monomer from the adsorbent. 2 Separation and recovery of vinyl chloride monomers from vinyl chloride monomers containing low-boiling components, consisting of a primary packed column filled with solid adsorbent and a secondary packed column connected in series to this and having a smaller cross-sectional area than the primary packed column. device to do.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50007307A JPS5940808B2 (en) | 1975-01-16 | 1975-01-16 | Method for recovering vinyl chloride monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50007307A JPS5940808B2 (en) | 1975-01-16 | 1975-01-16 | Method for recovering vinyl chloride monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51105006A JPS51105006A (en) | 1976-09-17 |
| JPS5940808B2 true JPS5940808B2 (en) | 1984-10-03 |
Family
ID=11662342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50007307A Expired JPS5940808B2 (en) | 1975-01-16 | 1975-01-16 | Method for recovering vinyl chloride monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5940808B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017029868A1 (en) * | 2015-08-17 | 2017-02-23 | ダイキン工業株式会社 | Method for separating halogenated unsaturated carbon compound |
-
1975
- 1975-01-16 JP JP50007307A patent/JPS5940808B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51105006A (en) | 1976-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4696682A (en) | Solid adsorbent for carbon monoxide and process for separation from gas mixture | |
| KR870000765B1 (en) | Process for separating isoprene | |
| KR880002645B1 (en) | Extraction of sucrose from a mixture of sugars | |
| EP1574247A1 (en) | Hydrocarbon separation method | |
| KR101017697B1 (en) | Adsorbents for purification of C2-C3 olefins | |
| US2529289A (en) | Preparation of an intermediate fraction with solid adsorbents | |
| US4812147A (en) | Multicomponent adsorption process | |
| JP2542394B2 (en) | Hexafluoropropylene purification method | |
| US2823766A (en) | Gas removal with a carbon-water slurry | |
| AU672612B2 (en) | Process for producing hydrocarbon partial oxidation products | |
| SE452952B (en) | MULTIPLE STEP ADSORPTION PROCESS FOR SEPARATION OF ORGANIC LIQUIDS FROM WATER | |
| US6348636B1 (en) | Purification of polymeric dispersions by stripping in the presence of adsorbent materials | |
| JPS5940808B2 (en) | Method for recovering vinyl chloride monomer | |
| JPH03291245A (en) | Removal of vinylidene chloride from 1,1-dichloro-1-fluoroethane | |
| US2636574A (en) | Fluidized selective adsorption separation process | |
| JPS6020367B2 (en) | Method for separating and recovering vinyl chloride monomer | |
| JPS6126417B2 (en) | ||
| JP2011102236A (en) | Recovery of organic from process flare header | |
| US3335547A (en) | Process for the purification of ethylene oxide | |
| US5567836A (en) | Process for separation of methyltrichlorosilane from dimethyldichlorosilane | |
| JPH1067692A (en) | Selective removal of perfluoroisobutylene from halogenated hydrocarbon flow | |
| JPS6148486B2 (en) | ||
| SU1214175A1 (en) | Method of recuperation of solvents from steam and air mixtures | |
| JPS6351056B2 (en) | ||
| JPH0579754A (en) | Manufacturing method of high purity nitrogen |