JPH11246447A - Purification of tetrafluoroethylene - Google Patents
Purification of tetrafluoroethyleneInfo
- Publication number
- JPH11246447A JPH11246447A JP4540098A JP4540098A JPH11246447A JP H11246447 A JPH11246447 A JP H11246447A JP 4540098 A JP4540098 A JP 4540098A JP 4540098 A JP4540098 A JP 4540098A JP H11246447 A JPH11246447 A JP H11246447A
- Authority
- JP
- Japan
- Prior art keywords
- tetrafluoroethylene
- polymerization inhibitor
- allophane
- contact
- ppm
- 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.)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、含フッ素ポリマ
ー、詳しくは耐熱性、耐薬品性等の優れたフッ素樹脂、
含フッ素エラストマー製造用のモノマーとして有用なテ
トラフルオロエチレンの精製方法に関する。TECHNICAL FIELD The present invention relates to a fluorine-containing polymer, specifically, a fluororesin having excellent heat resistance and chemical resistance.
The present invention relates to a method for purifying tetrafluoroethylene useful as a monomer for producing a fluorine-containing elastomer.
【０００２】[0002]
【従来の技術】テトラフルオロエチレンは、極めて有用
な単量体であり、単独重合、共重合により耐熱性，耐薬
品性等が格段に優れた含フッ素ポリマーを与え、これら
含フッ素ポリマーはその特性を生かし、産業上、種々の
用途に利用されている。2. Description of the Related Art Tetrafluoroethylene is a very useful monomer, and gives a fluoropolymer having remarkably excellent heat resistance and chemical resistance by homopolymerization and copolymerization. Utilizing this, it is used for various purposes in industry.
【０００３】通常、テトラフルオロエチレンの製造は、
工業的には６００℃以上の温度下でクロロジフルオロメ
タンを熱分解する方法が一般的である。上記した熱分解
により生成する熱分解物中には、原料のクロロジフルオ
ロメタン、目的物であるテトラフルオロエチレンの他
に、多種類のフッ化炭化水素を含んでいるため、上記熱
分解物から蒸留精製により、目的とする高純度のテトラ
フルオロエチレンを得ている。[0003] Usually, the production of tetrafluoroethylene is
Industrially, a method of thermally decomposing chlorodifluoromethane at a temperature of 600 ° C. or higher is generally used. Since the pyrolyzate generated by the above-mentioned pyrolysis contains various kinds of fluorinated hydrocarbons in addition to chlorodifluoromethane as a raw material and tetrafluoroethylene as a target, distillation from the pyrolyzate is performed. Purification yields the desired high-purity tetrafluoroethylene.
【０００４】一般に、高純度のテトラフルオロエチレン
は、極めて重合し易く、特に微量の酸素を含んでいる場
合には顕著であり、時には爆発的に重合することが知ら
れている。このため、従来より、テトラフルオロエチレ
ンを保存する際は、ピネン、リモネン、カンフェン、シ
メン、テルピネン等のテルピノイドに代表される重合禁
止剤を１００〜１００００ｐｐｍ程度添加することが行
なわれている（米国特許第２７３７５３３号公報）。In general, high-purity tetrafluoroethylene is extremely easy to polymerize, particularly when it contains a trace amount of oxygen, and is known to sometimes polymerize explosively. For this reason, conventionally, when storing tetrafluoroethylene, a polymerization inhibitor represented by a terpinoid such as pinene, limonene, camphene, cymene, terpinene or the like is added in an amount of about 100 to 10,000 ppm (US Pat. No. 2737533).
【０００５】逆に、上記したように重合禁止剤により安
定化されたテトラフルオロエチレンを重合に用いる場
合、重合禁止剤を除去する必要がある。Conversely, when tetrafluoroethylene stabilized by a polymerization inhibitor as described above is used for polymerization, it is necessary to remove the polymerization inhibitor.
【０００６】重合禁止剤を除去する方法として、従来
は、重合に供する前に、濃硫酸により重合禁止剤を吸収
させる方法が採用されていた。しかしながら、吸収能率
が低下した廃硫酸処理の問題があり、また、重合禁止剤
により安定化された気体状のテトラフルオロエチレンを
液体の濃硫酸で処理するため、吸収効率の向上の問題、
さらに、テトラフルオロエチレンに含まれる硫酸ミスト
の除去等の装置面で問題を有していた。[0006] As a method of removing the polymerization inhibitor, a method of absorbing the polymerization inhibitor with concentrated sulfuric acid before using it for polymerization has conventionally been adopted. However, there is a problem of waste sulfuric acid treatment with reduced absorption efficiency, and a problem of improving absorption efficiency because gaseous tetrafluoroethylene stabilized by a polymerization inhibitor is treated with liquid concentrated sulfuric acid.
Further, there is a problem in terms of equipment such as removal of sulfuric acid mist contained in tetrafluoroethylene.
【０００７】また、一般に気体中の有機物の除去には、
ゼオライト等の吸着剤に接触させる方法が採用されてい
るが、上記したテトラフルオロエチレンの場合、ゼオラ
イトと接触させると、重合禁止剤のみならずテトラフル
オロエチレンも吸着され、その吸着熱によりテトラフル
オロエチレンの重合が開始し、発生する重合熱により吸
着を継続させることが困難となったり、さらに生じた重
合体が発生する重合熱により分解・炭化して、ゼオライ
トの吸着能率が低下したりする等の問題点があった。[0007] In general, for removing organic substances in a gas,
Although a method of contacting with an adsorbent such as zeolite is employed, in the case of the above-mentioned tetrafluoroethylene, when it is brought into contact with zeolite, not only the polymerization inhibitor but also tetrafluoroethylene is adsorbed, and the heat of adsorption causes the tetrafluoroethylene to be adsorbed. Of the polymerization starts, it becomes difficult to continue the adsorption due to the generated heat of polymerization, and further, the generated polymer is decomposed and carbonized by the generated heat of polymerization, and the adsorption efficiency of zeolite is reduced. There was a problem.
【０００８】上記現象を防止するために吸着層内に冷却
用の配管を多数配列するような装置面での工夫も考えら
れるが、装置面だけで問題点を解決することは困難であ
った。In order to prevent the above-mentioned phenomenon, it is conceivable to devise a device in which a large number of cooling pipes are arranged in the adsorption layer. However, it has been difficult to solve the problem only by using the device.
【０００９】本発明者らは、すでに、上記問題を解決す
るための方法として、クロロフルオロ炭化水素に接触さ
せたゼオライトと、重合禁止剤を含むテトラフルオロエ
チレンとを接触させる方法を提案している（特開平３−
２２３２１９号公報）。The present inventors have already proposed, as a method for solving the above problem, a method of contacting zeolite which has been brought into contact with chlorofluorohydrocarbon and tetrafluoroethylene containing a polymerization inhibitor. (Japanese Unexamined Patent Publication No.
223219).
【００１０】該方法を使用することにより重合禁止剤を
含むテトラフルオロエチレンから、安全に重合禁止剤を
除去できる。しかしながら、前もって、クロロフルオロ
炭化水素とゼオライトの接触工程が必要であり、操作が
煩雑であった。By using this method, a polymerization inhibitor can be safely removed from tetrafluoroethylene containing a polymerization inhibitor. However, a contact step between the chlorofluorohydrocarbon and the zeolite was required beforehand, and the operation was complicated.
【００１１】[0011]
【発明が解決しようとする課題】以上の観点から、重合
禁止剤を含むテトラフルオロエチレンから重合禁止剤を
効率的に除去できる安全且つ簡便な方法の開発が強く求
められていた。In view of the above, there has been a strong demand for the development of a safe and simple method capable of efficiently removing a polymerization inhibitor from tetrafluoroethylene containing a polymerization inhibitor.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、テトラフ
ルオロエチレンに含まれる重合禁止剤を重合反応の直前
に安全且つ簡便に除去することができる、工業的に有用
な方法を見出すべく鋭意検討を重ねた。Means for Solving the Problems The present inventors have been keen to find an industrially useful method capable of safely and simply removing a polymerization inhibitor contained in tetrafluoroethylene immediately before a polymerization reaction. The examination was repeated.
【００１３】そして、種々の吸着剤に関し検討を重ねた
結果、直径数オングストロームの均一な細孔を利用する
ことにより選択的な吸着性を有するゼオライトとは異な
り、ゼオライトのように細孔径は制御されておらず、ま
た数十オングストロームと大きな細孔を有するという性
質を利用して専ら酸等の極性物質の吸着剤として広く使
われているアロフェンが、前述したテルペン化合物のよ
うな極性の低い物質を、選択的に、かつ大量に吸着除去
でき、さらには殆ど発熱も発生しないという、全く予期
し得なかった知見を得た。As a result of repeated investigations on various adsorbents, unlike zeolites having selective adsorptivity by utilizing uniform pores having a diameter of several angstroms, the pore diameter is controlled like zeolite. Allophane, which is widely used exclusively as an adsorbent for polar substances such as acids, utilizing its property of having large pores of several tens of angstroms, has a low polarity substance such as the aforementioned terpene compound. A completely unexpected finding was obtained that it could be selectively and adsorbed and removed in large quantities, and furthermore, hardly generated heat.
【００１４】そして、その知見をもとに、効率的にテト
ラフルオロエチレン中の重合禁止剤を吸着除去する方法
を見出し、本発明を完成するに至った。Based on the knowledge, a method for efficiently adsorbing and removing the polymerization inhibitor in tetrafluoroethylene was found, and the present invention was completed.
【００１５】即ち本発明は、アロフェンと、重合禁止剤
を含むテトラフルオロエチレンとを接触させ、重合禁止
剤を除去することを特徴とするテトラフルオロエチレン
の精製方法である。That is, the present invention is a method for purifying tetrafluoroethylene, which comprises contacting allophane with tetrafluoroethylene containing a polymerization inhibitor to remove the polymerization inhibitor.
【００１６】[0016]
【発明の実施の形態】アロフェンは、組成式ｎＳｉＯ2
・Ａｌ2Ｏ3・ｍＨ2Ｏで表されるアルミニウムの含水ケ
イ酸塩である非晶質の粘土鉱物であり、本発明では、公
知のものが何ら制限なく用いることが出来る。上記アロ
フェンの組成式においてｎは１．０〜２．０のものが好
ましい。BEST MODE FOR CARRYING OUT THE INVENTION Allophane has the composition formula nSiO 2
· Al 2 O 3 · mH is amorphous clay mineral is aluminum hydrous silicate represented by 2 O, in the present invention may be known ones used without any limitation. In the above allophane composition formula, n is preferably from 1.0 to 2.0.
【００１７】本発明において、アロフェンの形状は、特
に制限なく、粉末状、顆粒状、粒状あるいはペレット状
に成形したものを用いることができる。具体的な形状
は、重合禁止剤を含むテトラフルオロエチレンとの接触
方法によって適宜決定すれば良く、例えば、充填塔方式
で接触させる場合には、平均粒子径が２０ｍｍより小さ
い顆粒またはペレット状のものを用いれば良く、平均粒
子径０．３〜１０ｍｍの顆粒またはペレット状のものが
より好適である。In the present invention, the shape of allophane is not particularly limited, and allophane can be used in the form of powder, granule, granule or pellet. The specific shape may be appropriately determined depending on the method of contact with tetrafluoroethylene containing a polymerization inhibitor. For example, in the case of contacting with a packed tower method, granules or pellets having an average particle diameter smaller than 20 mm And granules or pellets having an average particle diameter of 0.3 to 10 mm are more preferable.
【００１８】本発明において重合禁止剤は、テトラフル
オロエチレンの重合を防止するために使用される化合物
であれば何ら制限されず、好適には、テルペン化合物が
用いられる。上記テルペン化合物を具体的に例示すれ
ば、リモネン、ピネン、カンフェン、シメン、テルピネ
ン等のテンペン炭化水素；シトロネロール、チルピネオ
ール、ボルネオール等のテルペンアルコール；テルペン
アルデヒド；テルペンケトン等のモノテルペノイド：セ
スキテルペノイド：ジテルペノイド等のテルペノイドが
挙げられる。In the present invention, the polymerization inhibitor is not particularly limited as long as it is a compound used for preventing the polymerization of tetrafluoroethylene, and a terpene compound is preferably used. Specific examples of the terpene compound include tenpen hydrocarbons such as limonene, pinene, camphene, cymene, and terpinene; terpene alcohols such as citronellol, tilpineol, and borneol; terpene aldehydes; monoterpenoids such as terpene ketones; And the like.
【００１９】アロフェンと重合禁止剤を含むテトラフル
オロエチレンとの接触方法は、特に制限されないが、通
常、工業的に採用されている充填塔方式が好適に採用さ
れる。The method of contacting allophane with tetrafluoroethylene containing a polymerization inhibitor is not particularly limited, but usually, a packed column system which is industrially employed is suitably employed.
【００２０】上記した充填塔方式を採用した場合の各種
条件、たとえば、アロフェンの充填段、充填塔内での接
触時間等は、テトラフルオロエチレン中に含まれる重合
禁止剤の濃度によって適宜決定すればよい。例えば、テ
トラフルオロエチレン中に含まれる重合禁止剤の濃度が
５００ｐｐｍ程度の場合、空間速度を１〜２０ｍｉｎ-1
で接触させると、容積比で充填層容積の１万〜１０万倍
の重合禁止剤を含むテトラフルオロエチレンから、重合
禁止剤濃度が０．１ｐｐｍ以下まで重合禁止剤を除去す
ることができる。また、接触時の温度は、特に限定され
ず、常温下でも本発明の効果は十分に発揮されるが、冷
却下の方が吸着量が増えるため好ましい。ただし、冷却
のため装置が複雑となるので、接触時の温度は、その目
的に応じて適宜決定すればよい。接触時の圧力は、特に
制限されず、たとえば、常圧〜２０ｋｇ／ｃｍ2−Ｇで
おこなえばよい。Various conditions when the above-mentioned packed tower system is employed, for example, the stage of packing allophane, the contact time in the packed tower, and the like can be determined appropriately according to the concentration of the polymerization inhibitor contained in tetrafluoroethylene. Good. For example, when the concentration of the polymerization inhibitor contained in tetrafluoroethylene is about 500 ppm, the space velocity is 1 to 20 min -1.
, It is possible to remove the polymerization inhibitor from tetrafluoroethylene containing a polymerization inhibitor having a volume ratio of 10,000 to 100,000 times the volume of the packed bed to a polymerization inhibitor concentration of 0.1 ppm or less. Further, the temperature at the time of contact is not particularly limited, and the effect of the present invention can be sufficiently exerted even at room temperature, but cooling is preferred because the amount of adsorption increases. However, since the device becomes complicated for cooling, the temperature at the time of contact may be appropriately determined according to the purpose. The pressure at the time of contact is not particularly limited, and may be, for example, normal pressure to 20 kg / cm 2 -G.
【００２１】飽和吸着後のアロフェンは、たとえば、１
５０〜１６０℃、２時間ほど加熱することにより再生す
ることができる。また、アロフェンは、重合禁止剤の吸
着除去能力が非常に大きいため、特に再生ぜずに廃棄し
てもよい。Allophane after saturation adsorption is, for example, 1
It can be regenerated by heating at 50 to 160 ° C. for about 2 hours. Further, allophane may be discarded without being particularly regenerated because the ability to adsorb and remove the polymerization inhibitor is very large.
【００２２】また、上記したように、本発明は、アロフ
ェンがテルペン化合物を選択的に吸着除去できるという
知見に基づいたものであり、テトラフルオロエチレンの
精製のみならず、テルペン化合物を含む物質からテルペ
ン化合物を除去する方法にも適用できる。Further, as described above, the present invention is based on the finding that allophane can selectively adsorb and remove terpene compounds, and not only purifies tetrafluoroethylene but also removes terpene compounds from substances containing terpene compounds. The present invention can also be applied to a method for removing a compound.
【００２３】[0023]
【発明の効果】本発明の方法によれば、テトラフルオロ
エチレン中の重合禁止剤、特にテルペン化合物を従来の
方法に較べ簡単な方法で十分に除去できる。According to the method of the present invention, a polymerization inhibitor, particularly a terpene compound, in tetrafluoroethylene can be sufficiently removed by a simpler method than the conventional method.
【００２４】したがって、本発明により精製されたテト
ラフルオロエチレンからは、重合禁止剤を全く含まない
テトラフルオロエチレンから得られる重合体と耐熱性、
機械的物性は全く変わることはない重合体を得ることが
できる。Therefore, from the tetrafluoroethylene purified according to the present invention, a polymer obtained from tetrafluoroethylene containing no polymerization inhibitor and heat resistance,
A polymer whose mechanical properties do not change at all can be obtained.
【００２５】[0025]
【実施例】本発明を更に具体的に説明するため、以下に
実施例を挙げて説明するが、本発明はこれらの実施例に
限定されるものではない。EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
【００２６】実施例１ ＳｉＯ2とＡｌ2Ｏ3のモル比が1：１．１５のアロフェン
（商品名セカードＫ−３；粒子径５．８ｍｍの成形品、
品川化成株式会社製）１．１ｌを内径５ｃｍ、長さ６０
ｃｍのステンレス製の円筒状容器に充填し、吸着塔とし
た。Example 1 Allophane having a molar ratio of SiO 2 and Al 2 O 3 of 1: 1.15 (trade name: Cecard K-3; molded product having a particle diameter of 5.8 mm;
(Shinagawa Chemical Co., Ltd.) 1.1 liters with inner diameter 5cm, length 60
cm of a stainless steel cylindrical container to form an adsorption tower.
【００２７】次いで、テトラフルオロエチレン（純度９
９．９９％以上）のボンベからテトラフルオロエチレン
を、リモネンが入った容器の底部に導入することによ
り、容器上部からリモネンを含んだテトラフルオロエチ
レンが排出するようにした。Next, tetrafluoroethylene (purity 9
By introducing tetrafluoroethylene into the bottom of the container containing limonene from a cylinder (at least 9.99%), tetrafluoroethylene containing limonene was discharged from the top of the container.
【００２８】そして、リモネン容器上部と吸着塔上部を
パイプでつなぎ、吸着塔底部よりテトラフルオロエチレ
ンを排出できるようにして吸着実験を行った。Then, the upper part of the limonene container and the upper part of the adsorption tower were connected by a pipe, and an adsorption experiment was conducted so that tetrafluoroethylene could be discharged from the bottom of the adsorption tower.
【００２９】常温、空間速度４．６ｍｉｎ-1で、リモネ
ンを含むテトラフルオロエチレンを、最初、吸着塔内の
圧力が大気圧となるように流し、その後４ｋｇ／ｃｍ2
−Ｇの圧力で流したところ、吸着塔上部でのテトラフル
オロエチレン中のリモネン濃度は４８０ｐｐｍであり、
吸着塔下部から排出されるテトラフルオロエチレン中の
リモネン濃度は０．１ｐｐｍ以下であった。At room temperature and a space velocity of 4.6 min -1 , tetrafluoroethylene containing limonene is first flowed so that the pressure in the adsorption tower becomes atmospheric pressure, and then 4 kg / cm 2.
When flowing at a pressure of -G, the limonene concentration in tetrafluoroethylene at the top of the adsorption tower was 480 ppm,
The limonene concentration in tetrafluoroethylene discharged from the lower part of the adsorption tower was 0.1 ppm or less.
【００３０】また、処理能力を求めるため、吸着実験を
連続して行ったところ、用いたアロフェンの容積の３万
倍のリモネンを含んだテトラフルオロエチレンを流した
ところで、テトラフルオロエチレン中のリモネン濃度が
急激に増加し、３ｐｐｍとなった。In order to determine the processing capacity, adsorption experiments were performed continuously. When tetrafluoroethylene containing limonene having a volume of 30,000 times the volume of allophane used was flown, the limonene concentration in tetrafluoroethylene was determined. Rapidly increased to 3 ppm.
【００３１】また、吸着塔内にテトラフルオロエチレン
を流し始めた時も、吸着塔はほとんど温度上昇が観測さ
れず、その後も温度上昇もなく吸着実験を継続できた。When the flow of tetrafluoroethylene was started to flow into the adsorption tower, almost no temperature rise was observed in the adsorption tower, and the adsorption experiment could be continued without a temperature increase thereafter.
【００３２】実施例２ アロフェンとして、０．５〜３ｍｍの粒子径を有する顆
粒（商品名セカードＫＷ、品川化成株式会社製）を用
い、リモネンの代りにピネンを用い、３ｋｇ／ｃｍ2−
Ｇの圧力下、空間速度７．６ｍｉｎ-1の流速で処理を行
った以外は、実施例１と同様にして吸着実験を行なっ
た。Example 2 Granules having a particle size of 0.5 to 3 mm (trade name: Cecard KW, manufactured by Shinagawa Kasei Co., Ltd.) were used as allophane, and pinene was used instead of limonene, and 3 kg / cm 2 −
An adsorption experiment was performed in the same manner as in Example 1 except that the treatment was performed at a flow rate of 7.6 min -1 under the pressure of G.
【００３３】その結果、吸着塔入口でのテトラフルオロ
エチレン中のピネン濃度は５５０ｐｐｍであったが、吸
着塔出口でのテトラフルオロエチレン中のピネン濃度
は、０．１ｐｐｍ以下であった。As a result, the pinene concentration in tetrafluoroethylene at the inlet of the adsorption tower was 550 ppm, but the pinene concentration in tetrafluoroethylene at the outlet of the adsorption tower was 0.1 ppm or less.
【００３４】ピネンを含むテトラフルオロエチレンにつ
いて、吸着実験を連続しておこなったところ、アロフェ
ン容積の１０万倍のピネンを含むテトラフルオロエチレ
ンから、ピネンの吸着除去をおこなうことができた。ま
た、吸着塔内の温度上昇も認められなかった。Adsorption experiments were continuously performed on tetrafluoroethylene containing pinene. As a result, adsorption and removal of pinene could be performed from tetrafluoroethylene containing 100,000 times the volume of allophane. In addition, no temperature increase in the adsorption tower was observed.
【００３５】実施例３ リモネンの代わりにシメンを用い、空間速度３．０ｍｉ
ｎ-1の流速で処理した以外は、実施例１同様に吸着実験
をおこなった。Example 3 A space velocity of 3.0 mi was obtained by using cymene instead of limonene.
An adsorption experiment was performed in the same manner as in Example 1 except that the treatment was performed at a flow rate of n -1 .
【００３６】その結果、テトラフルオロエチレン中のシ
メン濃度は吸着塔入口で約４００ｐｐｍ、吸着塔出口で
は０．２ｐｐｍであり、用いたアロフェンの４．５万倍
のシメンを含むテトラフルオロエチレンから、シメンの
吸着除去をおこなうことができた。As a result, the concentration of cymene in the tetrafluoroethylene was about 400 ppm at the entrance of the adsorption tower and 0.2 ppm at the exit of the adsorption tower. Was able to be removed by adsorption.
【００３７】実施例４ 粒子径８．６ｍｍのアロフェン成形品（商品名セカード
Ｋ−１、品川化成株式会社製）と粒子径５．８ｍｍのア
ロフェン（商品名セカードＫ−１、品川化成株式会社
製）の１：１の混合物を用いた以外は、実施例１と同様
にリモネンの吸着実験をおこなった。Example 4 Allophane molded product having a particle size of 8.6 mm (trade name: Cecard K-1, manufactured by Shinagawa Kasei Co., Ltd.) and an allophane having a particle size of 5.8 mm (trade name: Cecard K-1, manufactured by Shinagawa Kasei Co., Ltd.) The limonene adsorption experiment was performed in the same manner as in Example 1 except that a 1: 1 mixture of (1) was used.
【００３８】その結果、吸着塔入口でのテトラフルオロ
エチレン中のリモネン濃度は５００ｐｐｍであり、吸着
塔下部から排出されるテトラフルオロエチレン中のリモ
ネン濃度は０．１ｐｐｍ以下であり、用いたアロフェン
の２．５万倍のリモネンを含むテトラフルオロエチレン
から、リモネンの吸着除去をおこなうことができた。As a result, the limonene concentration in tetrafluoroethylene at the inlet of the adsorption tower was 500 ppm, the limonene concentration in tetrafluoroethylene discharged from the lower part of the adsorption tower was 0.1 ppm or less, and 2 ppm of allophane used Limonene was adsorbed and removed from tetrafluoroethylene containing 50,000 times of limonene.
【００３９】比較例１ 実施例１においてアロフェンのかわりにモレキュラーシ
ーブス１３Ｘ（キシダ化学株式会社製、１／１６ペレッ
ト）を用いた以外は、実施例１と同様にして吸着実験を
行った。Comparative Example 1 An adsorption experiment was performed in the same manner as in Example 1, except that Molecular Sieves 13X (manufactured by Kishida Chemical Co., Ltd., 1/16 pellet) was used instead of allophane.
【００４０】リモネンを含むテトラフルオロエチレン
を、大気圧下、空間速度１．５ｍｉｎ-1の流速で流した
ところ、すぐに吸着塔内の温度が急激に上昇したため、
吸着実験を停止した。その後、吸着塔内を開け、モレキ
ュラーシーブを取り出したところ、局部的にモレキュラ
ーシーブのペレットが黒色の塊となっていた。この黒色
の塊をフッ酸で溶解し、残った少量の残さを分析したと
ころ、テトラフルオロエチレンの重合体であった。急激
に上昇した吸着熱によりテトラフルオロエチレンの重合
が進み、さらに蓄熱によりポリテトラフルオロエチレン
の分解・炭化が進んだものと推定される。When tetrafluoroethylene containing limonene was flowed under atmospheric pressure at a flow rate of 1.5 min -1 , the temperature in the adsorption tower immediately rose sharply.
The adsorption experiment was stopped. Thereafter, the inside of the adsorption tower was opened, and the molecular sieve was taken out. As a result, the molecular sieve pellets were locally formed into a black mass. This black lump was dissolved with hydrofluoric acid, and a small amount of the remaining residue was analyzed. As a result, it was found to be a polymer of tetrafluoroethylene. It is presumed that the polymerization of tetrafluoroethylene proceeded due to the rapidly rising heat of adsorption, and the decomposition and carbonization of polytetrafluoroethylene proceeded due to the heat storage.
【００４１】参考例 本発明の精製を行ったテトラフルオロエチレンと、重合
禁止剤を含まないテトラフルオロエチレンとを用いて重
合実験を行った。２５０ｍｌの攪拌機を備えたステンレ
ス製の耐圧容器にパーフルオロヘプタン１１０ｍｌ、Ｃ
Ｆ2＝ＣＦＯＣＦ2ＣＦ2ＣＦ3、５ｇを加えた。次に耐圧
容器内の脱酸素を行うため、内容物を冷却固化し、その
後脱気するという操作を３回繰返した。その後、重合開
始剤として（ＣＦ3ＣＦ2ＣＦ2ＣＯ2）2を０．４ｇ加
え、さらにテトラフルオロエチレンを３ｋｇ／ｃｍ2−
Ｇの圧力で圧入し、１８℃で４時間重合を行った。Reference Example A polymerization experiment was performed using the purified tetrafluoroethylene of the present invention and tetrafluoroethylene containing no polymerization inhibitor. In a stainless steel pressure vessel equipped with a 250 ml stirrer, 110 ml of perfluoroheptane, C
F 2 = CFOCF 2 CF 2 CF 3 , 5 g was added. Next, in order to deoxygenate the inside of the pressure vessel, the operation of cooling and solidifying the contents and then degassing was repeated three times. Thereafter, 0.4 g of (CF 3 CF 2 CF 2 CO 2 ) 2 was added as a polymerization initiator, and tetrafluoroethylene was further added at 3 kg / cm 2 −
G was injected under pressure and polymerization was carried out at 18 ° C. for 4 hours.
【００４２】この実験を、実施例１の精製を行ったテト
ラフルオロエチレン及び重合禁止剤を含まないテトラフ
ルオロエチレンについて行った。結果を表１に示した。This experiment was carried out on the purified tetrafluoroethylene of Example 1 and tetrafluoroethylene containing no polymerization inhibitor. The results are shown in Table 1.
【００４３】[0043]
【表１】 [Table 1]
Claims (2)
ルオロエチレンとを接触させることを特徴とするテトラ
フルオロエチレンの精製方法。1. A method for purifying tetrafluoroethylene, which comprises contacting allophane with tetrafluoroethylene containing a polymerization inhibitor.
とを接触させることを特徴とするテルペン化合物の除去
方法。2. A method for removing a terpene compound, which comprises contacting allophane with a substance containing a terpene compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4540098A JPH11246447A (en) | 1998-02-26 | 1998-02-26 | Purification of tetrafluoroethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4540098A JPH11246447A (en) | 1998-02-26 | 1998-02-26 | Purification of tetrafluoroethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11246447A true JPH11246447A (en) | 1999-09-14 |
Family
ID=12718216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4540098A Withdrawn JPH11246447A (en) | 1998-02-26 | 1998-02-26 | Purification of tetrafluoroethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11246447A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001098384A3 (en) * | 2000-06-19 | 2002-06-20 | Mitsui Du Pont Fluorchemical | Process for manufacture of a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether) |
| WO2009130986A1 (en) | 2008-04-25 | 2009-10-29 | 旭硝子株式会社 | Method for purifying tetrafluoroethylene |
| WO2014203354A1 (en) | 2013-06-19 | 2014-12-24 | 三菱電機株式会社 | Refrigeration cycle device |
| WO2014203355A1 (en) | 2013-06-19 | 2014-12-24 | 三菱電機株式会社 | Refrigeration cycle device |
| US9347446B2 (en) | 2013-04-17 | 2016-05-24 | Mitsubishi Electric Corporation | Refrigerant compressor including a polymerization inhibitor contained therein |
| US9915465B2 (en) | 2014-04-10 | 2018-03-13 | Mitsubishi Electric Corporation | Heat pump compressor including liquid crystal polymer insulating material |
-
1998
- 1998-02-26 JP JP4540098A patent/JPH11246447A/en not_active Withdrawn
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001098384A3 (en) * | 2000-06-19 | 2002-06-20 | Mitsui Du Pont Fluorchemical | Process for manufacture of a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether) |
| US6586546B2 (en) | 2000-06-19 | 2003-07-01 | Dupont-Mitsui Fluorochemicals Co. Ltd. | Process for manufacture of a copolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether) |
| WO2009130986A1 (en) | 2008-04-25 | 2009-10-29 | 旭硝子株式会社 | Method for purifying tetrafluoroethylene |
| EP2269969A1 (en) * | 2008-04-25 | 2011-01-05 | Asahi Glass Company, Limited | Method for purifying tetrafluoroethylene |
| CN102015594A (en) * | 2008-04-25 | 2011-04-13 | 旭硝子株式会社 | Method for purifying tetrafluoroethylene |
| US8247626B2 (en) | 2008-04-25 | 2012-08-21 | Asahi Glass Company, Limited | Method for purifying tetrafluoroethylene |
| EP2269969A4 (en) * | 2008-04-25 | 2014-04-30 | Asahi Glass Co Ltd | Method for purifying tetrafluoroethylene |
| JP5531952B2 (en) * | 2008-04-25 | 2014-06-25 | 旭硝子株式会社 | Method for purifying tetrafluoroethylene |
| US9347446B2 (en) | 2013-04-17 | 2016-05-24 | Mitsubishi Electric Corporation | Refrigerant compressor including a polymerization inhibitor contained therein |
| WO2014203354A1 (en) | 2013-06-19 | 2014-12-24 | 三菱電機株式会社 | Refrigeration cycle device |
| WO2014203355A1 (en) | 2013-06-19 | 2014-12-24 | 三菱電機株式会社 | Refrigeration cycle device |
| US9915465B2 (en) | 2014-04-10 | 2018-03-13 | Mitsubishi Electric Corporation | Heat pump compressor including liquid crystal polymer insulating material |
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