JPS6148486B2 - - Google Patents
Info
- Publication number
- JPS6148486B2 JPS6148486B2 JP11744077A JP11744077A JPS6148486B2 JP S6148486 B2 JPS6148486 B2 JP S6148486B2 JP 11744077 A JP11744077 A JP 11744077A JP 11744077 A JP11744077 A JP 11744077A JP S6148486 B2 JPS6148486 B2 JP S6148486B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- activated carbon
- chloride monomer
- adsorption tower
- boiling point
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 94
- 238000001179 sorption measurement Methods 0.000 claims description 61
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 36
- 238000009835 boiling Methods 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 26
- 230000001186 cumulative effect Effects 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 21
- 238000001816 cooling Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 238000010793 Steam injection (oil industry) Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は塩化ビニルモノマーとこれより高い沸
点をもつ高沸点成分とを含有するガス中より塩化
ビニルモノマーを分離し回収する方法に関する。
活性炭を充填した吸着塔に、空気又は不活性ガ
ス中に含有する成分を吸着後、吸着された成分を
水蒸気、空気あるいは不活性ガス等を吹き込む
か、吸着塔を減圧する方法等により脱離して回収
することは既によく知られている。
一方塩化ビニルモノマーの製造工場から排出さ
れるガス中には製造原料である塩化エチレンが未
反応のまま塩化ビニルモノマーと同時に含まれ
る。また塩化ビニル系樹脂の製造工場から排出さ
れるガス中には塩化ビニルモノマーと共重合する
成分、例えば酢酸ビニル、アクリロニトリル等が
未反応のまま塩化ビニルモノマーと同時に含有さ
れる。このようにして排出される混合ガスは系外
に廃棄して焼却する方法があるが、この方法は経
済的に不利であるばかりでなく燃焼廃ガスによる
環境汚染の問題があり、工場の全体的な経済性か
ら塩化ビニルモノマーを回収し再利用を図ること
がもとより望ましい。この点から前記混合ガス中
から塩化ビニルモノマーを分離回収するに際し
て、活性炭による吸着・脱離によつて回収するこ
とは当然に考えられることである。
しかし従来は塩化ビニルモノマーと塩化エチレ
ン、酢酸ビニル、アクリロニトリル等の高沸点成
分とを含有するガス中より、活性炭を使用して塩
化ビニルモノマーを分離し回収する方法は採用さ
れていない。これは塩化ビニルモノマーと前記高
沸点成分とはそれぞれ活性炭に対する被吸着能が
異なるために相互に吸着を妨害し合い活性炭の吸
着能を低下させることに起因している。
本発明は塩化ビニルモノマーとこれより高い沸
点をもつ高沸点成分とを含有するガス中より活性
炭を使用して塩化ビニルモノマーを分離回収する
ものであつて、本発明者等が塩化ビニルモノマー
と前記高沸点成分との活性炭に対する吸着特性を
探究した結果、前記高沸点成分をほぼ完全に吸着
し塩化ビニルモノマーは極く微量しか吸着しない
活性炭と塩化ビニルモノマーを効率よく吸着する
活性炭との組み合せを見い出し本発明に到達した
ものである。
本発明において、両活性炭の特性は単位重量当
りの累積細孔容積によつて決定づけられるが、相
対的関係から言えば前記高沸点成分を吸着すべき
第１吸着塔に充填される活性炭（以下活性炭Ａと
略称）の累積細孔容積が塩化ビニルモノマーを吸
着すべき第２吸着塔に充填される活性炭（以下活
性炭Ｂと略称）のそれよりも小さいことが必要で
ある。
活性炭の累積細孔容積は一定の重量単位当りに
占める所定半径以下の細孔の容積値を累積したも
のをいう。このような累積細孔容積の測定には各
種の方法があるが、メタノール吸着法による細孔
半径15Åまでの累積細孔容積は活性炭Ａの場合
0.25〜0.30c.c./ｇ、活性炭Ｂの場合0.35c.c./ｇ以上
であつて活性炭Ａのそれよりも大きいことが望ま
しい。
本発明は前記のごとき活性炭Ａを充填した第１
吸着塔と前記のごとき活性炭Ｂを充填した第２吸
着塔に塩化ビニルモノマーと前記高沸点成分とを
含有するガスを順次導入して、活性炭Ａに前記高
沸点成分を、活性炭Ｂに塩化ビニルモノマーをそ
れぞれ吸着せしめ、活性炭Ｂより塩化ビニルモノ
マーを脱着し回収することができる。
以下添付図に基づいて本発明の一例について説
明すると、１および２は活性炭Ａを充填した第１
吸着塔、３および４は活性炭Ｂを充填した第２吸
着塔であり、第１吸着塔１と第２吸着塔３との系
列、第１吸着塔２と第２吸着塔４との系列は直列
に接続されている。５および６は冷却コンデンサ
ー、７，８はドレンセパレーターである。
塩化ビニルモノマーとこれより高い沸点をもつ
高沸点成分を含有する空気または不活性ガス（以
下混合ガスと略称する）をまず第１吸着塔１に導
入する。高沸点成分は塩化ビニルモノマー、ポリ
塩化ビニル、塩化ビニルを構成単位とするコポリ
マーの製造工程で塩化ビニルモノマーとともに排
出ガス中に含有され、塩化ビニルモノマーより高
い沸点をもつ成分であつて、塩化エチレン、酢酸
ビニル、アクリロニトリルなどである。不活性ガ
スは工業的実施の観点から窒素ガスが最も望まし
い。
第１吸着塔１に導入された混合ガス中の前記高
沸点成分は活性炭Ａに吸着され、他の含有成分は
極く微量しか活性炭Ａに吸着されない。次いで高
沸点成分がほぼ完全に吸着除去された混合ガスは
第２吸着塔３に導入され、塩化ビニルモノマーの
大部分が活性炭Ｂに吸着される。
混合ガスの導入による吸着時間は第１吸着塔１
から排出されるガス中の高沸点成分の濃度を測定
して決定する。第１吸着塔１における高沸点成分
の吸着が飽和状態に達したら、直ちに混合ガスの
導入を第１吸着塔２と第２吸着塔４の系列に切り
換える。第１吸着塔２と第２吸着塔４における吸
着処理を行う間に第１吸着塔１と第２吸着塔３系
列の脱離処理を行うと同時に活性炭の再生を行
う。脱離処理法は、吸着塔内に水蒸気を吹込む方
法、吸着塔内を減圧にする方法、吸着塔内に充填
された活性炭を加熱する方法等がいずも採用でき
るが、図面のフローシートでは水蒸気吹込み方法
を例示している。
このようにして両系列の吸着塔において、塩化
ビニルモノマーと高沸点成分との吸着・脱離を交
互に行うことができる。水蒸気吹き込みによつ
て、第１吸着塔１，２に充填された活性炭Ａより
脱離した高沸点成分を水蒸気と共に冷却コンデン
サー５で冷却し、ドレンセパレター７で凝縮水と
分離回収し、第２吸着塔３，４に充填された活性
炭Ｂより脱離した塩化ビニルモノマーを水蒸気と
共に冷却コンデンサー６で冷却してドレンセパレ
ター８で凝縮水と分離し回収する。
本発明によれば、第１吸着塔で高沸点成分をほ
ぼ完全に吸着して第２吸着塔に導入させないよう
にしているので、第２吸着塔において回収せんと
する塩化ビニルモノマーの吸着能を阻害すること
なく、しかもほぼ塩化ビニルモノマーのみ吸着さ
れるために塩化ビニルモノマーの分離回収が極め
て効率的に行なえる。
次に本発明の効果を具体的数値例をもつて明ら
かにする。
実施例 １
表−１に示す混合ガスを、メタノール吸着法に
よる細孔半径15Åまでの累積細孔容積が0.29c.c./
ｇの活性炭を13ｇ充填した第１吸着塔と前記累積
細孔容積0.36c.c./ｇの活性炭を12ｇ充填した第２
吸着塔とに順次導入した後、吸着された各成分を
脱離回収したところ、次の通りであつた。
The present invention relates to a method for separating and recovering vinyl chloride monomer from a gas containing vinyl chloride monomer and high-boiling components having a higher boiling point. After adsorbing components contained in air or inert gas into an adsorption tower filled with activated carbon, the adsorbed components are desorbed by blowing water vapor, air, inert gas, etc., or by reducing the pressure in the adsorption tower. Retrieval is already well known. On the other hand, the gas discharged from a vinyl chloride monomer manufacturing plant contains unreacted ethylene chloride, which is a manufacturing raw material, at the same time as the vinyl chloride monomer. In addition, components that copolymerize with vinyl chloride monomers, such as vinyl acetate, acrylonitrile, etc., are contained unreacted at the same time as vinyl chloride monomers in the gas discharged from a vinyl chloride resin manufacturing plant. There is a method of disposing of the mixed gas discharged in this way outside the system and incinerating it, but this method is not only economically disadvantageous, but also has the problem of environmental pollution due to combustion waste gas, and the overall It is desirable to recover and reuse vinyl chloride monomers from the viewpoint of economic efficiency. From this point of view, when separating and recovering the vinyl chloride monomer from the mixed gas, it is naturally conceivable that the vinyl chloride monomer be recovered by adsorption and desorption using activated carbon. However, conventional methods have not been adopted to separate and recover vinyl chloride monomer using activated carbon from a gas containing vinyl chloride monomer and high-boiling components such as ethylene chloride, vinyl acetate, and acrylonitrile. This is because the vinyl chloride monomer and the above-mentioned high-boiling point components have different adsorption abilities to activated carbon, and therefore they interfere with each other's adsorption and reduce the adsorption ability of activated carbon. The present invention uses activated carbon to separate and recover vinyl chloride monomer from a gas containing vinyl chloride monomer and a high-boiling component having a higher boiling point. As a result of exploring the adsorption characteristics of activated carbon with high boiling point components, we discovered a combination of activated carbon that almost completely adsorbs the high boiling point components and only a trace amount of vinyl chloride monomer, and activated carbon that efficiently adsorbs vinyl chloride monomer. This has led to the present invention. In the present invention, the characteristics of both activated carbons are determined by the cumulative pore volume per unit weight, but from a relative relationship, the activated carbon (hereinafter referred to as activated carbon It is necessary that the cumulative pore volume of the activated carbon (hereinafter abbreviated as activated carbon B) packed into the second adsorption tower to adsorb the vinyl chloride monomer (abbreviated as activated carbon B) is smaller than that of the activated carbon (hereinafter abbreviated as activated carbon B). The cumulative pore volume of activated carbon is the cumulative volume of pores with a predetermined radius or less that occupy a certain weight unit. There are various methods for measuring cumulative pore volume, but the cumulative pore volume up to a pore radius of 15 Å by methanol adsorption method is for activated carbon A.
0.25 to 0.30 cc/g, preferably 0.35 cc/g or more for activated carbon B and greater than that for activated carbon A. The present invention provides a first
A gas containing vinyl chloride monomer and the high boiling point component is sequentially introduced into an adsorption tower and a second adsorption tower filled with activated carbon B as described above. The vinyl chloride monomer can be desorbed and recovered from the activated carbon B. An example of the present invention will be described below based on the attached drawings. 1 and 2 are first cylinders filled with activated carbon A.
Adsorption towers 3 and 4 are second adsorption towers filled with activated carbon B, and the series of the first adsorption tower 1 and the second adsorption tower 3 and the series of the first adsorption tower 2 and the second adsorption tower 4 are connected in series. It is connected to the. 5 and 6 are cooling condensers, and 7 and 8 are drain separators. Air or an inert gas (hereinafter referred to as mixed gas) containing a vinyl chloride monomer and a high-boiling component having a higher boiling point is first introduced into the first adsorption tower 1. The high boiling point component is contained in the exhaust gas together with the vinyl chloride monomer in the manufacturing process of vinyl chloride monomer, polyvinyl chloride, and copolymers with vinyl chloride as constituent units, and is a component that has a higher boiling point than the vinyl chloride monomer. , vinyl acetate, acrylonitrile, etc. The most desirable inert gas is nitrogen gas from the viewpoint of industrial implementation. The high boiling point components in the mixed gas introduced into the first adsorption tower 1 are adsorbed on the activated carbon A, and only very small amounts of other components are adsorbed on the activated carbon A. Next, the mixed gas from which the high-boiling components have been almost completely adsorbed and removed is introduced into the second adsorption tower 3, where most of the vinyl chloride monomer is adsorbed onto the activated carbon B. The adsorption time due to the introduction of the mixed gas is the first adsorption tower 1.
Determine by measuring the concentration of high boiling point components in the gas discharged from the When the adsorption of high-boiling components in the first adsorption tower 1 reaches a saturated state, the introduction of the mixed gas is immediately switched to the series of the first adsorption tower 2 and the second adsorption tower 4. While the adsorption treatment is performed in the first adsorption tower 2 and the second adsorption tower 4, the desorption treatment is performed on the first adsorption tower 1 and the second adsorption tower 3 series, and at the same time, the activated carbon is regenerated. As desorption treatment methods, methods such as blowing steam into the adsorption tower, reducing the pressure inside the adsorption tower, and heating the activated carbon packed in the adsorption tower can be adopted, but the flow sheet shown in the drawings shows that The steam injection method is illustrated. In this way, adsorption and desorption of the vinyl chloride monomer and high-boiling components can be performed alternately in both series of adsorption towers. The high boiling point components desorbed from the activated carbon A filled in the first adsorption towers 1 and 2 by steam injection are cooled together with the steam in the cooling condenser 5, separated and recovered from the condensed water in the drain separator 7, and then The vinyl chloride monomer desorbed from the activated carbon B packed in the adsorption towers 3 and 4 is cooled together with water vapor in a cooling condenser 6, separated from condensed water in a drain separator 8, and recovered. According to the present invention, the first adsorption tower almost completely adsorbs high-boiling components and prevents them from being introduced into the second adsorption tower, so the adsorption capacity of the vinyl chloride monomer to be recovered in the second adsorption tower is reduced. Since almost only the vinyl chloride monomer is adsorbed without any hindrance, the vinyl chloride monomer can be separated and recovered very efficiently. Next, the effects of the present invention will be explained using specific numerical examples. Example 1 The mixed gas shown in Table 1 was obtained by the methanol adsorption method until the cumulative pore volume up to a pore radius of 15 Å was 0.29 cc/
The first adsorption tower was filled with 13g of activated carbon with a cumulative pore volume of 0.36cc/g, and the second adsorption tower was filled with 12g of activated carbon with a cumulative pore volume of 0.36cc/g.
After sequential introduction into an adsorption tower, each adsorbed component was desorbed and recovered, and the results were as follows.
【表】
実施例 ２
表−２に示す混合ガスを、メタノール吸着法に
よる細孔半径15Åまでの累積細孔容積が0.27c.c./
ｇの活性炭を13ｇ充填した第１吸着塔と前記累積
細孔容積が0.37c.c./ｇの活性炭を12ｇ充填した第
２吸着塔とに順次導入した後、吸着された各成分
を脱離回収したとこは次の通りであつた。[Table] Example 2 The mixed gas shown in Table 2 was measured using the methanol adsorption method until the cumulative pore volume up to a pore radius of 15 Å was 0.27 cc/
The mixture was sequentially introduced into a first adsorption tower filled with 13 g of activated carbon with a cumulative pore volume of 0.37 cc/g and a second adsorption tower filled with 12 g of activated carbon with a cumulative pore volume of 0.37 cc/g, and each adsorbed component was desorbed and recovered. was as follows.
【表】
実施例 ３
表−３に示す混合ガスを、メタノール吸着法に
よる細孔半径15Åまでの累積細孔容積が0.29c.c./
ｇの活性炭を13ｇ充填した第１吸着塔と前記累積
細孔容積が0.37c.c./ｇの活性炭を12ｇ充填した第
２吸着塔とに順次導入した後、吸着された各成分
を脱離回収したところ次の通りであつた。[Table] Example 3 The mixed gas shown in Table 3 was measured by the methanol adsorption method until the cumulative pore volume up to a pore radius of 15 Å was 0.29 cc/
After sequentially introducing 13 g of activated carbon into the first adsorption tower filled with 13 g of activated carbon and the second adsorption tower filled with 12 g of activated carbon with a cumulative pore volume of 0.37 cc/g, each adsorbed component was desorbed and recovered. It was as follows.
【表】
実施例 ４
第２吸着塔に充填される活性炭の累積細孔容積
が0.36c.c./ｇ、0.38c.c./ｇの活性炭をそれぞれ使用
した他は実施例１同様にして混合ガスの分離回収
を行なつたところ、いずれも実施例１同様の結果
を示した。
実施例 ５
累積細孔容積が0.29c.c./ｇの活性炭を第１吸着
塔に充填し、累積細孔容積が0.36c.c./ｇの活性炭
を第２吸着塔に充填した他は実施例２同様にして
混合ガスの分離回収を行なつたところ、実施例２
同様の結果を示した。
実施例 ６
累積細孔容積が0.29c.c./ｇの活性炭を第１吸着
塔に充填し、累積細孔容積が0.38c.c./ｇの活性炭
を充填した他は実施例２同様にして混合ガスの分
離回収を行なつたところ、実施例２同様の結果を
示した。[Table] Example 4 A mixed gas was separated and recovered in the same manner as in Example 1, except that activated carbon with a cumulative pore volume of 0.36 cc/g and 0.38 cc/g was used to fill the second adsorption tower. When carried out, the same results as in Example 1 were obtained in both cases. Example 5 The same procedure as Example 2 was carried out except that activated carbon with a cumulative pore volume of 0.29 cc/g was packed in the first adsorption tower, and activated carbon with a cumulative pore volume of 0.36 cc/g was packed in the second adsorption tower. When the mixed gas was separated and recovered, Example 2
showed similar results. Example 6 Separation and recovery of a mixed gas was carried out in the same manner as in Example 2, except that activated carbon with a cumulative pore volume of 0.29 cc/g was filled in the first adsorption tower, and activated carbon with a cumulative pore volume of 0.38 cc/g was filled. When carried out, the same results as in Example 2 were shown.
図面は本発明の一例を示すフローシートであ
る。
１，２……第１吸着塔、３，４……第２吸着
塔、５，６……冷却コンデンサー、７，８……ド
レンセパレター。
The drawing is a flow sheet showing an example of the present invention. 1, 2...First adsorption tower, 3, 4... Second adsorption tower, 5, 6... Cooling condenser, 7, 8... Drain separator.
Claims (1)
つ高沸点成分とを含有するガスを、メタノール吸
着法による細孔半径15Åまでの累積細孔容積が、
0.30c.c./ｇ以下の活性炭を充填した第１吸着塔に
導入して前記高沸点成分を吸着させ、次いで前記
累積細孔容積が、0.35c.c./ｇ以上である活性炭を
充填した第２吸着塔に導入して塩化ビニルモノマ
ーを吸着させ、然る後活性炭から塩化ビニルモノ
マーを脱着させることを特徴とする塩化ビニルモ
ノマーの回収方法。 ２ 前記高沸点成分が塩化ビニルモノマー又は塩
化ビニル系樹脂の製造工程で排出されるガス中に
塩化ビニルモノマーと同時に含有されるものであ
る特許請求の範囲第１項に記載の方法。[Claims] 1. A gas containing a vinyl chloride monomer and a high boiling point component having a higher boiling point is mixed with a gas containing a vinyl chloride monomer and a high boiling point component having a higher boiling point by methanol adsorption with a cumulative pore volume up to a pore radius of 15 Å.
The high boiling point components are introduced into a first adsorption tower filled with activated carbon of 0.30 cc/g or less to adsorb it, and then introduced into a second adsorption tower filled with activated carbon whose cumulative pore volume is 0.35 cc/g or more. 1. A method for recovering vinyl chloride monomer, which comprises introducing activated carbon to adsorb the vinyl chloride monomer, and then desorbing the vinyl chloride monomer from activated carbon. 2. The method according to claim 1, wherein the high boiling point component is contained simultaneously with the vinyl chloride monomer in the gas discharged during the manufacturing process of the vinyl chloride monomer or the vinyl chloride resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11744077A JPS5452015A (en) | 1977-09-30 | 1977-09-30 | Method of recovering vinyl chloride monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11744077A JPS5452015A (en) | 1977-09-30 | 1977-09-30 | Method of recovering vinyl chloride monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5452015A JPS5452015A (en) | 1979-04-24 |
| JPS6148486B2 true JPS6148486B2 (en) | 1986-10-24 |
Family
ID=14711695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11744077A Granted JPS5452015A (en) | 1977-09-30 | 1977-09-30 | Method of recovering vinyl chloride monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5452015A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6358389U (en) * | 1986-10-06 | 1988-04-19 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356265B (en) * | 2014-10-31 | 2017-09-15 | 陕西煤业化工技术研究院有限责任公司 | A kind of fire retardant reinforced polyvinyl-chloride active carbon with high specific surface area load nano particle composite and preparation method |
-
1977
- 1977-09-30 JP JP11744077A patent/JPS5452015A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6358389U (en) * | 1986-10-06 | 1988-04-19 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5452015A (en) | 1979-04-24 |
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