JP2002102708A - Method for reactivating catalyst - Google Patents
Method for reactivating catalystInfo
- Publication number
- JP2002102708A JP2002102708A JP2000298231A JP2000298231A JP2002102708A JP 2002102708 A JP2002102708 A JP 2002102708A JP 2000298231 A JP2000298231 A JP 2000298231A JP 2000298231 A JP2000298231 A JP 2000298231A JP 2002102708 A JP2002102708 A JP 2002102708A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- antimony pentachloride
- catalyst
- reaction
- gas
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、気相でのフッ素化
反応に使用するフッ素化触媒の再活性化に関する。[0001] The present invention relates to reactivation of a fluorination catalyst used for a fluorination reaction in a gas phase.
【０００２】[0002]
【従来の技術】ハロゲン化炭化水素のフッ素化反応に使
用する触媒には、気相反応ではクロミアやアルミナを完
全または不完全にフッ素化したフッ化クロムやフッ化ア
ルミなど、またはアルミナや活性炭に担持した金属が用
いられ、液相反応では五塩化アンチモン、四塩化スズな
どが一般的に使用されている。2. Description of the Related Art Catalysts used in the fluorination reaction of halogenated hydrocarbons include chromium fluoride and aluminum fluoride, in which chromia and alumina are completely or incompletely fluorinated, or alumina and activated carbon in gas phase reactions. A supported metal is used, and in the liquid phase reaction, antimony pentachloride, tin tetrachloride, and the like are generally used.
【０００３】これらの触媒は長時間使用することで活性
の低下することがあるため、それを避けるためにしばし
ば酸素、塩素、フッ素化炭化水素などを反応系に存在さ
せることが提案されている。活性低下の原因は触媒の種
類により、また反応に供される原料化合物により異なる
が、活性金属の酸化数の変化、活性な化合物の構造の変
化、分解生成物または副生成物の堆積など各種の原因が
想定されている。[0003] Since the activity of these catalysts may be reduced by using them for a long time, it has been proposed that oxygen, chlorine, fluorinated hydrocarbons and the like are often present in the reaction system in order to avoid such activity. The cause of the decrease in activity varies depending on the type of catalyst and the starting compound used in the reaction, but various factors such as changes in the oxidation number of the active metal, changes in the structure of the active compound, deposition of decomposition products or by-products, etc. The cause is assumed.
【０００４】通常五塩化アンチモンは液相フッ素化反応
に使用され、大規模なフルオロカーボン類の製造に活用
されてきた。それらの使用条件においては五塩化アンチ
モンの活性低下は比較的少なく、特に原料と共に、ある
いは原料の一部として塩素を反応系に供給することで長
期にわたり製造を継続することができた。[0004] Antimony pentachloride is commonly used in liquid phase fluorination reactions and has been utilized in large-scale production of fluorocarbons. Under these conditions of use, the activity of antimony pentachloride decreased relatively little. In particular, by supplying chlorine to the reaction system together with the raw material or as a part of the raw material, the production could be continued for a long time.
【０００５】五塩化アンチモンを気相反応に使用する例
は少なく、特開２０００−７５９１号公報には、１−ク
ロロ−３，３，３−トリフルオロプロペンまたは１，
３，３，３−テトラフルオロプロペンを五塩化アンチモ
ン担持活性炭触媒を用いてフッ化水素で気相フッ素化し
て１，１，１，３，３−ペンタフルオロプロパンを製造
する方法が開示されている。[0005] There are few examples of using antimony pentachloride in a gas phase reaction, and JP-A-2000-7591 discloses that 1-chloro-3,3,3-trifluoropropene or 1,1 is used.
A method for producing 1,1,1,3,3-pentafluoropropane by vapor-phase fluorination of 3,3,3-tetrafluoropropene with hydrogen fluoride using an antimony pentachloride-supported activated carbon catalyst is disclosed. .
【０００６】さらに、ＵＳＰ５８９５８２５明細書に
は、１−クロロ−３，３，３−トリフルオロプロペンを
酸化クロム触媒を用いてフッ化水素で気相フッ素化し、
ついで得られた１，３，３，３−テトラフルオロプロペ
ンを五塩化アンチモン担持活性炭触媒を用いてフッ化水
素で気相フッ素化して１，１，１，３，３−ペンタフル
オロプロパンとする方法が開示されている。Further, US Pat. No. 5,895,825 discloses that 1-chloro-3,3,3-trifluoropropene is vapor-phase fluorinated with hydrogen fluoride using a chromium oxide catalyst.
Then, a method of vapor-phase fluorinating the obtained 1,3,3,3-tetrafluoropropene with hydrogen fluoride using an antimony pentachloride-supported activated carbon catalyst to obtain 1,1,1,3,3-pentafluoropropane. Is disclosed.
【０００７】[0007]
【発明が解決しようとする課題】前記特開２０００−７
５９１号公報とＵＳＰ５８９５８２５明細書に記載され
た五塩化アンチモン担持活性炭触媒を用いる１，１，
１，３，３−ペンタフルオロプロパンの製造方法は原料
が容易に得られることに加えて、生成物の選択率が極め
て高いという特徴を有する工業的に有利な方法である。SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 2000-7
US Pat. No. 5,591,825 and US Pat. No. 5,895,825, which use an activated carbon catalyst supported on antimony pentachloride.
The method for producing 1,3,3-pentafluoropropane is an industrially advantageous method characterized in that the raw materials are easily obtained and the selectivity of the product is extremely high.
【０００８】しかしながら、これらの反応により飽和化
合物である１，１，１，３，３−ペンタフルオロプロパ
ンの選択率を上げる為には比較的低温度で行うのが好適
であるが、そのような条件では触媒の活性低下は避けら
れず、本発明者らは塩素の添加によっても触媒寿命の長
期化を十分に図ることはできないことを見いだした。However, in order to increase the selectivity of 1,1,1,3,3-pentafluoropropane which is a saturated compound by these reactions, it is preferable to conduct the reaction at a relatively low temperature. Under the conditions, the activity of the catalyst is inevitably reduced, and the present inventors have found that the addition of chlorine cannot sufficiently extend the life of the catalyst.
【０００９】液相法で用いた五塩化アンチモンの再活性
化は均一の液体状態で塩素添加により行うことができる
ことが知られているが、気相反応に用いる固体の五塩化
アンチモン担持活性炭の再活性化については何ら文献に
記載されていない。It is known that the reactivation of antimony pentachloride used in the liquid phase method can be carried out by adding chlorine in a uniform liquid state. No activation is described in the literature.
【００１０】[0010]
【問題点を解決するための具体的手段】本発明者らは、
五塩化アンチモン担持活性炭触媒を再活性化して初期の
触媒活性を再現する方法について検討を進めたところ、
意外にも１５０℃以上の高温度において塩素と接触させ
ることで五塩化アンチモンの揮散もなく活性が再現する
ことを見いだし、本発明に至った。[Specific means for solving the problem]
After examining a method to reproduce the initial catalytic activity by reactivating the activated carbon catalyst supporting antimony pentachloride,
Surprisingly, it was found that the activity was reproduced without contacting chlorine at a high temperature of 150 ° C. or higher without volatilization of antimony pentachloride, and the present invention was reached.
【００１１】すなわち、本発明は、ハロゲン化炭化水素
をフッ化水素でフッ素化してフッ素原子数の多いフッ素
含有ハロゲン化炭化水素とする際に使用することで活性
の低下した五塩化アンチモン担持活性炭触媒を再活性化
する方法であって、活性の低下した五塩化アンチモン担
持活性炭触媒を１５０℃以上において塩素ガスと接触さ
せることからなる再活性化方法である。That is, the present invention provides an activated carbon catalyst supported on antimony pentachloride having reduced activity by using it when fluorinating a halogenated hydrocarbon with hydrogen fluoride to obtain a fluorine-containing halogenated hydrocarbon having a large number of fluorine atoms. And reacting the activated carbon catalyst having reduced activity with antimony pentachloride at 150 ° C. or higher with chlorine gas.
【００１２】本発明にかかる五塩化アンチモン担持活性
炭触媒は、ハロゲン化炭化水素をフッ化水素で気相フッ
素化してフッ素原子数の多いフッ素含有ハロゲン化炭化
水素を製造する際に使用した結果、活性の低下を来した
五塩化アンチモン担持活性炭触媒である。その様な反応
は、３０℃〜１５０℃程度の比較的低温での気相フッ素
化反応であって、フッ化水素でのハロゲン交換によるフ
ッ素化および／またはフッ化水素の二重結合への付加に
よる反応が挙げられる。The activated carbon catalyst supporting antimony pentachloride according to the present invention is used when producing a fluorine-containing halogenated hydrocarbon having a large number of fluorine atoms by vapor-phase fluorination of a halogenated hydrocarbon with hydrogen fluoride. This is an activated carbon catalyst supported on antimony pentachloride, which has a reduced water content. Such a reaction is a gas-phase fluorination reaction at a relatively low temperature of about 30 ° C. to 150 ° C., in which fluorination by halogen exchange with hydrogen fluoride and / or addition of hydrogen fluoride to a double bond are performed. Reaction.
【００１３】この様な反応としては、例えば、１−クロ
ロ−３，３，３−トリフルオロプロペンまたは１，３，
３，３−テトラフルオロプロペンを３０〜１５０℃、ま
たは３０〜１３０℃程度の温度でフッ化水素によりフッ
素化して気相で１，１，１，３，３−ペンタフルオロプ
ロパンを製造する反応、１、１−ジクロロ−１−フルオ
ロエタンまたは１−クロロ−１，１−ジフルオロエタン
を３０〜１５０℃、または３０〜１３０℃程度の温度で
フッ化水素により気相で１，１，１−トリフルオロエタ
ンを製造する反応などが挙げられるがこれらに限られな
い。さらに、前者の反応は１，１，１，３，３−ペンタ
フルオロプロパンに少量含まれる１−クロロ−３，３，
３−トリフルオロプロペンまたは１，３，３，３−テト
ラフルオロプロペンを３０〜１５０℃、または３０〜１
３０℃程度の温度でフッ化水素により気相で処理して
１，１，１，３，３−ペンタフルオロプロパンの純度を
向上させる処理であってもよい。Such reactions include, for example, 1-chloro-3,3,3-trifluoropropene or 1,3,3
A reaction of fluorinating 3,3-tetrafluoropropene with hydrogen fluoride at a temperature of about 30 to 150 ° C. or about 30 to 130 ° C. to produce 1,1,1,3,3-pentafluoropropane in a gas phase; 1,1-Dichloro-1-fluoroethane or 1-chloro-1,1-difluoroethane is vapor-phased with hydrogen fluoride at a temperature of about 30 to 150 ° C. or about 30 to 130 ° C. in 1,1,1-trifluoro phase using hydrogen fluoride. Examples include, but are not limited to, reactions that produce ethane. Furthermore, the former reaction is based on 1-chloro-3,3,3 contained in a small amount in 1,1,1,3,3-pentafluoropropane.
3-trifluoropropene or 1,3,3,3-tetrafluoropropene at 30 to 150 ° C. or 30 to 1
A process for improving the purity of 1,1,1,3,3-pentafluoropropane by performing a process in a gas phase with hydrogen fluoride at a temperature of about 30 ° C.
【００１４】活性の低下した五塩化アンチモン担持活性
炭触媒において五塩化アンチモンがどの様な形態に変化
しているかは明確ではないが、３価アンチモンの塩素フ
ッ素化物または５価もしくは３価のアンチモン含酸素塩
素化フッ素化物となっているものと推定される。It is not clear what form antimony pentachloride has changed in the activated carbon catalyst supporting antimony pentachloride with reduced activity, but it is not clear whether chlorofluoride of trivalent antimony or oxygen containing pentavalent or trivalent antimony is contained. It is presumed to be chlorinated fluorinated products.
【００１５】本発明の方法は、気相において所定の温度
で塩素を活性の低下した五塩化アンチモン担持活性炭触
媒に接触させることで行う。温度は１５０℃以上であ
り、１５０〜２５０℃程度が好ましく、１６０〜２２０
℃程度がより好ましい。１５０℃未満では五塩化アンチ
モン担持活性炭触媒の活性化は起こり難く、２５０℃を
超えると五塩化アンチモンの揮散や還元が起こることが
あり避けるのが望ましい。The process of the present invention is carried out by contacting chlorine at a predetermined temperature in a gas phase with an activated carbon catalyst having reduced activity on antimony pentachloride. The temperature is 150 ° C. or higher, preferably about 150 to 250 ° C., and 160 to 220 ° C.
C. is more preferable. If the temperature is lower than 150 ° C, activation of the antimony pentachloride-supported activated carbon catalyst is unlikely to occur.
【００１６】塩素ガスは、単独で使用してもよく不活性
ガス（例えば、窒素、アルゴン）と共に使用してもよ
い。また、フッ素化剤として作用するフッ素化炭化水
素、フッ化水素等と共に使用してもよい。あるいは、反
応温度が一致する場合には、他のハロゲン化炭化水素の
フッ素化反応等の類似の反応を行いながら塩素を共存さ
せることで再活性化の処理を行うこともできる。再活性
化した五塩化アンチモン担持活性炭触媒を使用するに
は、１５０℃以上において塩素ガス接触させ、次いでフ
ッ化水素ガスを接触させる等の方法を適用して予め反応
温度以上の温度でフッ化水素と接触させておくのが好ま
しい。The chlorine gas may be used alone or with an inert gas (eg, nitrogen, argon). Further, it may be used together with a fluorinated hydrocarbon, hydrogen fluoride or the like acting as a fluorinating agent. Alternatively, when the reaction temperatures are the same, a reactivation treatment can be performed by coexisting chlorine while performing a similar reaction such as a fluorination reaction of another halogenated hydrocarbon. To use the reactivated antimony pentachloride-supported activated carbon catalyst, a method such as contacting with chlorine gas at 150 ° C. or higher and then contacting hydrogen fluoride gas is applied in advance at a temperature not lower than the reaction temperature. It is preferable to keep in contact with.
【００１７】塩素ガスの使用量は、活性低下の程度およ
び活性低下の原因にもよるが、アンチモン１モルに対し
０．０１モル程度以上であって１０００モル程度以下を
使用し、１００モル以下が好ましく、１０モル程度以下
がより好ましい。０．０１モル程度でも接触方法によっ
ては十分な効果を生じることもある。塩素ガスの接触方
法としては、加熱装置を備えた容器に五塩化アンチモン
担持活性炭触媒を充填して均一に接触するように塩素ガ
スを流通させればよい。容器は反応容器をそのまま使用
するのが便利である。塩素の供給速度は任意であるが、
１〜３００秒程度の接触時間とすればよい。The amount of chlorine gas used depends on the degree of activity decrease and the cause of the activity decrease. The amount of chlorine gas is about 0.01 mol or more and about 1000 mol or less per mol of antimony, and 100 mol or less is used. It is more preferably about 10 mol or less. Even if it is about 0.01 mol, a sufficient effect may be produced depending on the contact method. As a method for contacting chlorine gas, a container equipped with a heating device may be filled with an antimony pentachloride-supported activated carbon catalyst and the chlorine gas may be circulated so as to make uniform contact. It is convenient to use the reaction vessel as it is. The supply rate of chlorine is optional,
The contact time may be about 1 to 300 seconds.
【００１８】処理形式は固定床、流動床等いずれであっ
てもよい。反応器は、耐熱性と塩素、フッ化水素、塩化
水素等に対する耐食性を有する材質で作られればよく、
鉄、ステンレス鋼、ハステロイ、モネル、白金などが好
ましい。また、これらの金属でライニングされた材料で
作ることもできる。The treatment type may be a fixed bed, a fluidized bed or the like. The reactor may be made of a material having heat resistance and corrosion resistance to chlorine, hydrogen fluoride, hydrogen chloride, etc.
Iron, stainless steel, Hastelloy, Monel, platinum and the like are preferred. It can also be made of materials lined with these metals.
【００１９】本発明の再活性化方法の操作圧力は常圧
（１気圧付近）でよいが、加圧下であってもよい。０〜
２．０ＭＰａ（ゲージ圧）がより好ましく、実際上は０
〜１．０ＭＰａ（ゲージ圧）程度で行うのが好ましい。The operating pressure of the reactivation method of the present invention may be normal pressure (around 1 atm), or may be pressurized. 0 to
2.0 MPa (gauge pressure) is more preferable, and in practice, 0 MPa
It is preferably performed at about 1.0 MPa (gauge pressure).
【００２０】本明細書において「五塩化アンチモン担持
活性炭」の「五塩化アンチモン」はＳｂＣｌxＦ5-x（ｘ
は０から５の整数）で表されるアンチモン化合物を意味
する。すなわち、五塩化アンチモンは触媒として活性な
状態ではＳｂＣｌxＦ5-x（ｘは２から４の整数）で表さ
れる塩素化フッ素化アンチモンの状態であると考えられ
るからである。したがって、触媒調製に用いる際には、
必ずしも五塩化アンチモンである必要はなく五塩化アン
チモン、三塩化二フッ化アンチモン、五フッ化アンチモ
ンなどが使用でき、さらには、三塩化アンチモン、三フ
ッ化アンチモンなども活性炭に担持した後に塩素などの
酸化剤で５価アンチモンとすることで使用できる。ま
た、塩素の代わりに臭素を含む化合物であっても同様に
使用可能である。In the present specification, “antimony pentachloride” of “antimony pentachloride-supported activated carbon” is SbCl x F 5-x (x
Represents an antimony compound represented by the following formula: That is, antimony pentachloride is considered to be in a chlorinated antimony fluorinated state represented by SbCl x F 5-x (x is an integer of 2 to 4) in a state active as a catalyst. Therefore, when used for catalyst preparation,
It is not always necessary to use antimony pentachloride, and antimony pentachloride, antimony trichloride, antimony pentafluoride and the like can be used. It can be used by converting pentavalent antimony with an oxidizing agent. Further, a compound containing bromine instead of chlorine can also be used.
【００２１】調製方法としては特に限定されず五塩化ア
ンチモンが活性炭に付着しておればよい。常温付近で液
体である五塩化アンチモンの場合、後に述べるような塩
基性物質、酸または熱水による処理や脱水処理の前処理
を必要に応じて施した活性炭にそのまま滴下、スプレ
ー、浸漬等の方法で直接付着させることができる。ま
た、常温で液体または固体の化合物である場合には、化
合物を溶媒に溶解した溶液へ活性炭を浸漬し含浸させる
か、スプレーなどの方法で活性炭に付着させる。次い
で、このようにして得られたアンチモン化合物の付着し
た活性炭を加熱または／および減圧して乾燥した後、ア
ンチモンの付着した活性炭を加熱下においてフッ化水
素、塩素等と接触させることで触媒は調製される。五塩
化アンチモンを担持した場合、１００℃以上で１当量以
上の塩素により処理することが触媒の活性化に望まし
い。The preparation method is not particularly limited as long as antimony pentachloride adheres to the activated carbon. In the case of antimony pentachloride, which is a liquid at around normal temperature, a method such as dripping, spraying, dipping, etc., on activated carbon that has been subjected to a treatment with a basic substance, an acid or hot water as described below, or a pretreatment for dehydration treatment as necessary Can be directly attached. When the compound is a liquid or solid compound at room temperature, it is impregnated by immersing activated carbon in a solution of the compound in a solvent, or attached to the activated carbon by a method such as spraying. Next, the activated carbon to which the antimony compound thus obtained is attached is heated or / and dried under reduced pressure, and then the activated carbon to which antimony is attached is brought into contact with hydrogen fluoride, chlorine or the like under heating to prepare a catalyst. Is done. In the case where antimony pentachloride is supported, it is desirable to treat the catalyst with one or more equivalents of chlorine at 100 ° C. or more for activation of the catalyst.
【００２２】アンチモン化合物を溶解して触媒調製に使
用する際の溶媒としてはアンチモン化合物を溶解でき、
その際アンチモン化合物を分解しない溶媒であればよ
い。具体的には、塩化メチレン、クロロホルム、テトラ
クロロエチレン、テトラクロロエタンなどの塩素系溶
剤、１，１−ジクロロ−１−フルオロエタン３，３−ジ
クロロ−１，１，２，２，３−ペンタフルオロプロパ
ン、１，３−ビス（トリフルオロメチル）ベンゼン、ト
リフルオロメチルベンゼンなどのフッ素系溶剤、および
３−クロロ−１，１，１，３−テトラフルオロプロパ
ン、３，３−ジクロロ−１，１，１−トリフルオロプロ
パンなどのフッ素化プロパンなどが挙げられる。これら
の溶媒を使用する際または溶媒を用いない場合でも水な
どのハロゲン化物と反応性を有する物質を溶媒および処
理系から除去し、実質的に水の不存在下において担持さ
せるのが好ましい。When the antimony compound is dissolved and used for preparing the catalyst, the solvent can dissolve the antimony compound.
At that time, any solvent that does not decompose the antimony compound may be used. Specifically, chlorinated solvents such as methylene chloride, chloroform, tetrachloroethylene and tetrachloroethane, 1,1-dichloro-1-fluoroethane 3,3-dichloro-1,1,2,2,3-pentafluoropropane, Fluorinated solvents such as 1,3-bis (trifluoromethyl) benzene and trifluoromethylbenzene, and 3-chloro-1,1,1,3-tetrafluoropropane and 3,3-dichloro-1,1,1 -Fluorinated propane such as trifluoropropane. When these solvents are used or when no solvent is used, it is preferable to remove a substance having reactivity with a halide such as water from the solvent and the treatment system, and carry the substance substantially in the absence of water.
【００２３】本発明に使用する触媒調製に用いるアンチ
モン化合物の担持量は活性炭１００重量部に対し０．１
〜５００重量部であり、好ましくは１〜２５０重量部で
ある。また、アンチモン化合物に他の金属を併せて使用
することで触媒活性を調節することも好ましい。その場
合、アンチモン化合物（特に五塩化アンチモン）を主成
分として、他のニオブ化合物（特に五塩化ニオブ）また
はタンタル化合物（特に五塩化タンタル）、スズ、チタ
ン、ニオブ、タンタル、モリブテンのハロゲン化物を組
み合わせるのが好ましい。副成分金属／アンチモン化合
物の原子比は、副成分金属を含まない場合でもよいので
５０／５０〜０／１００とすることができ、３０／７０
〜０／１００が好ましい。The supported amount of the antimony compound used for preparing the catalyst used in the present invention is 0.1 to 100 parts by weight of activated carbon.
To 500 parts by weight, preferably 1 to 250 parts by weight. It is also preferable to adjust the catalytic activity by using another metal in combination with the antimony compound. In that case, an antimony compound (especially antimony pentachloride) is used as a main component, and another niobium compound (especially niobium pentachloride) or a tantalum compound (especially tantalum pentachloride) is combined with a halide of tin, titanium, niobium, tantalum, or molybdenum. Is preferred. The atomic ratio of the subcomponent metal / antimony compound may be 50/50 to 0/100 because the subcomponent metal may not be contained, and 30/70.
~ 0/100 is preferred.
【００２４】本発明の再活性化方法で担体として用いる
活性炭は、木材、木炭、椰子殻炭、パーム核炭、素灰等
を原料とする植物系、泥炭、亜炭、褐炭、瀝青炭、無煙
炭等を原料とする石炭系、石油残滓、オイルカーボン等
を原料とする石油系または炭化ポリ塩化ビニリデン等の
合成樹脂系がある。これら市販の活性炭から選択し使用
することができ、例えば、瀝青炭から製造された活性炭
（東洋カルゴン製ＢＰＬ粒状活性炭）、椰子殻炭（武田
薬品工業製粒状白鷺ＧＸ、Ｇ２Ｘ、ＳＸ、ＣＸ、ＸＲ
Ｃ、東洋カルゴン製ＰＣＢ）等が挙げられるが、これら
に限定されない。形状、大きさも通常粒状で用いられる
が、球状、繊維状、粉体状、ハニカム状等反応器に適合
すれば通常の知識範囲の中で使用することができる。The activated carbon used as a carrier in the reactivation method of the present invention may be selected from plant materials, peat, lignite, lignite, bituminous coal, anthracite, etc. which are made from wood, charcoal, coconut husk charcoal, palm kernel charcoal, ash and the like. There are petroleum-based materials such as coal-based materials, petroleum residues, and oil carbon as raw materials, and synthetic resin-based materials such as polyvinylidene chloride. The activated carbon can be selected from these commercially available activated carbons. For example, activated carbon produced from bituminous coal (BPL granular activated carbon manufactured by Toyo Calgon), coconut shell charcoal (Granulated Shirasagi GX, G2X, SX, CX, XR manufactured by Takeda Pharmaceutical Co., Ltd.)
C, PCBs manufactured by Toyo Calgon, and the like, but are not limited thereto. The shape and size are also usually used in the form of granules, but they can be used within the ordinary knowledge range as long as they are suitable for a spherical, fibrous, powdery, or honeycomb reactor.
【００２５】本発明において使用する活性炭は比表面積
の大きな活性炭が好ましい。活性炭の比表面積ならびに
細孔容積は、市販品の規格の範囲で十分であるが、それ
ぞれ４００ｍ2／ｇより大きく、０．１ｃｍ3／ｇより大
きいことが望ましい。またそれぞれ８００〜３０００ｍ
2／ｇ、０．２〜１．０ｃｍ3／ｇであればよい。さらに
活性炭を担体に用いる場合、水酸化アンモニウム、水酸
化ナトリウム、水酸化カリウム等の塩基性水溶液に常温
付近で１０時間程度またはそれ以上の時間浸漬するか、
活性炭を触媒担体に使用する際に慣用的に行われる硝
酸、塩酸、フッ酸等の酸による前処理を施し、予め担体
表面の活性化ならびに灰分の除去を行うことが望まし
い。The activated carbon used in the present invention is preferably an activated carbon having a large specific surface area. The specific surface area and the pore volume of the activated carbon are within the range of the specifications of commercial products, but are preferably larger than 400 m 2 / g and larger than 0.1 cm 3 / g, respectively. In addition, each 800-3000m
2 / g and 0.2 to 1.0 cm 3 / g may be used. Furthermore, when using activated carbon as a carrier, ammonium hydroxide, sodium hydroxide, or immersed in a basic aqueous solution such as potassium hydroxide at about room temperature for about 10 hours or more,
It is desirable to perform a pretreatment with an acid such as nitric acid, hydrochloric acid, hydrofluoric acid, etc., which is conventionally performed when using activated carbon as a catalyst carrier, to activate the carrier surface and remove ash in advance.
【００２６】また、本発明にかかる触媒ではいずれの方
法により前処理される場合も、アンチモン化合物を担持
処理する際に加水分解等により劣化しないように前もっ
て加熱したり、減圧等することで水分除去を可及的に行
うのが望ましい。When the catalyst according to the present invention is pretreated by any method, water is removed by heating or reducing the pressure in advance so that the catalyst does not deteriorate due to hydrolysis or the like when the antimony compound is supported. It is desirable to perform as much as possible.
【００２７】何れの方法で調製した触媒も、使用の前に
予めフッ化水素などのフッ素化剤および／または塩素と
接触させておき、反応中の触媒の組成変化、短寿命化、
異常反応などを防止することが有効である。Before use, the catalyst prepared by any of the methods is brought into contact with a fluorinating agent such as hydrogen fluoride and / or chlorine to change the composition of the catalyst during the reaction, shorten the life of the catalyst,
It is effective to prevent abnormal reactions and the like.
【００２８】以下に、実施例をもって本発明をより詳細
に説明するが、これらの実施態様に限られるものではな
い。実施例において有機物組成の「％」はガスクロマト
グラムの「面積％」である。Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto. In Examples, “%” of the organic composition is “area%” of the gas chromatogram.
【００２９】[0029]
【実施例】［調製例１］１リットルガラス製フラスコ
に、表面積１２００ｍ2／ｇ、細孔径１８オングストロ
ームの粒状椰子殻炭（武田薬品工業製粒状白鷺Ｇ２Ｘ、
４〜６メッシュ）１リットルを入れ１３０〜１５０℃に
加温した後真空ポンプにより水分を除去した。水分の留
出が認められなくなった時点でフラスコ内に窒素を導入
して常圧とした。EXAMPLES [Preparation Example 1] Granular coconut shell charcoal having a surface area of 1200 m 2 / g and a pore size of 18 Å (granular Shirasagi G2X manufactured by Takeda Pharmaceutical Co., Ltd.) was placed in a 1-liter glass flask.
One liter of the solution (4 to 6 mesh) was heated to 130 to 150 ° C., and then water was removed by a vacuum pump. When the distillation of water was stopped, nitrogen was introduced into the flask to adjust the pressure to normal pressure.
【００３０】［調製例２］１リットルガラス製フラスコ
に、表面積１２００ｍ2／ｇ、細孔径１８オングストロ
ームの粒状椰子殻炭（武田薬品工業製粒状白鷺Ｇ２Ｘ、
４〜６メッシュ）１リットルを入れ１３０〜１５０℃に
加温した後真空ポンプにより水分を除去した。水分の留
出が認められなくなった時点でフラスコ内に窒素を導入
して常圧とし、５００ｇの五塩化アンチモンを滴下ロー
トにて１時間にわたり攪拌しながら活性炭層に導入し
た。五塩化アンチモンを含浸した活性炭は約１時間、１
５０℃に保持して熟成した。[Preparation Example 2] Granular coconut shell charcoal having a surface area of 1200 m 2 / g and a pore size of 18 Å (granular Shirasagi G2X manufactured by Takeda Pharmaceutical Co., Ltd.) was placed in a 1-liter glass flask.
One liter of the solution (4 to 6 mesh) was heated to 130 to 150 ° C., and then water was removed by a vacuum pump. When the distillation of water was no longer observed, nitrogen was introduced into the flask to normal pressure, and 500 g of antimony pentachloride was introduced into the activated carbon layer while stirring with a dropping funnel for 1 hour. Activated carbon impregnated with antimony pentachloride should be
Aged at 50 ° C.
【００３１】〔実施例１〕電気炉を備えた円筒形反応管
（ＳＵＳ３１６Ｌ製、直径４．０ｃｍ、長さ３０ｃｍ）
に調製例２で調製した触媒を２５０ミリリットル充填
し、約２５ミリリットル／分の流量で窒素ガスを流しな
がら反応管の温度を１００℃に上げ、その後窒素ガスを
停止しフッ化水素を約０．２ｇ／分の速度で供給しなが
ら１００℃で６時間保った。次に反応管の温度を８０℃
に下げ反応準備を完了した。[Example 1] A cylindrical reaction tube equipped with an electric furnace (SUS316L, diameter 4.0 cm, length 30 cm)
Was charged with 250 ml of the catalyst prepared in Preparation Example 2, and the temperature of the reaction tube was raised to 100 ° C. while flowing nitrogen gas at a flow rate of about 25 ml / min. It was kept at 100 ° C. for 6 hours while feeding at a rate of 2 g / min. Next, the temperature of the reaction tube was set to 80 ° C.
And the reaction preparation was completed.
【００３２】フッ化水素０．３２ｇ／分、塩素１．３ｍ
ｇ／分の供給量で反応管入り口から供給し、その直後に
１−クロロ−３，３，３−トリフルオロプロペン（トラ
ンス体／シス体のモル比は９／１）を予め気化させて
０．２６ｇ／分の速度で反応管入り口に供給を開始し
た。0.32 g / min of hydrogen fluoride, 1.3 m of chlorine
g / min at the inlet of the reaction tube, and immediately thereafter, 1-chloro-3,3,3-trifluoropropene (trans / cis-form molar ratio: 9/1) was previously vaporized to 0 Feeding was started at a rate of .26 g / min at the inlet of the reaction tube.
【００３３】そのまま反応を続け、反応開始２時間後に
は反応は安定したので、その後４時間にわたって反応管
から流出する生成ガスを水中に吹き込み塩化水素やフッ
化水素の酸性ガスを除去した後、ドライアイス−アセト
ン−トラップで有機物を捕集した。捕集した有機物の重
量は６１．１ｇでありこれをガスクロマトグラフィーで
分析したところ、１，１，１，３，３−ペンタフルオロ
プロパン９８．９％、１−クロロ−３，３，３−トリフ
ルオロプロペン０．３％、１，３，３，３−テトラフル
オロプロペン０．１％であった。The reaction was continued as it was, and the reaction was stabilized 2 hours after the start of the reaction. Thereafter, the product gas flowing out of the reaction tube was blown into water for 4 hours to remove the acid gas such as hydrogen chloride and hydrogen fluoride. Organics were collected with an ice-acetone-trap. The weight of the collected organic matter was 61.1 g, which was analyzed by gas chromatography to find that 98.9% of 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3- It was 0.3% of trifluoropropene and 0.1% of 1,3,3,3-tetrafluoropropene.
【００３４】さらに反応を継続して１００時間後に反応
管出口ガスをサンプリングし、塩化水素を含む酸性ガス
を除去後ガスクロマトグラフィで分析したところ、１，
１，１，３，３−ペンタフルオロプロパン９６．５％、
１−クロロ−３，３，３−トリフルオロプロペン１．３
％であった。Further, after 100 hours of continuing the reaction, the gas at the outlet of the reaction tube was sampled, and the acidic gas containing hydrogen chloride was removed.
96.5% of 1,1,3,3-pentafluoropropane,
1-chloro-3,3,3-trifluoropropene 1.3
%Met.
【００３５】そこで、原料の１−クロロ−３，３，３−
トリフルオロプロペンとフッ化水素の供給を停止し、代
わりに窒素ガス２０ｍｌ／分と塩素ガス１０ｍｌ／分の
供給を開始し、反応管の温度を１８０℃に上昇させ、そ
のまま１２時間にわたり処理を継続した。Therefore, the raw material 1-chloro-3,3,3-
The supply of trifluoropropene and hydrogen fluoride was stopped, and instead, the supply of nitrogen gas 20 ml / min and the supply of chlorine gas 10 ml / min were started, the temperature of the reaction tube was raised to 180 ° C., and the treatment was continued for 12 hours. did.
【００３６】次いで、反応管の温度を下げながら窒素と
塩素の供給を停止し代わりにフッ化水素を約０．２ｇ／
分の速度で供給し、反応管の温度を１００℃で６時間保
った。Next, while lowering the temperature of the reaction tube, the supply of nitrogen and chlorine was stopped, and about 0.2 g /
Min, and the temperature of the reaction tube was maintained at 100 ° C. for 6 hours.
【００３７】その後、フッ化水素０．３２ｇ／分、塩素
１．３ｍｇ／分の供給量で反応管入り口から供給し、そ
の直後に１−クロロ−３，３，３−トリフルオロプロペ
ン（トランス体／シス体のモル比は９／１）を予め気化
させて０．２６ｇ／分の速度で反応管入り口に供給を開
始した。Thereafter, hydrogen was supplied from the inlet of the reaction tube at a supply amount of 0.32 g / min and chlorine at a supply amount of 1.3 mg / min, and immediately thereafter, 1-chloro-3,3,3-trifluoropropene (trans form) The 9/1) / mol ratio of cis-isomer was vaporized in advance, and supply to the inlet of the reaction tube was started at a rate of 0.26 g / min.
【００３８】反応開始１０時間後に反応管出口ガスをサ
ンプリングし、塩化水素を含む酸性ガスの除去後ガスク
ロマトグラフィで分析したところ、１，１，１，３，３
−ペンタフルオロプロパン９９．０％、１−クロロ−
３，３，３−トリフルオロプロペン０．１％であり、触
媒は活性であった。10 hours after the start of the reaction, the gas at the outlet of the reaction tube was sampled, and after analysis of gas chromatography after removal of the acid gas containing hydrogen chloride, 1,1,1,3,3
-Pentafluoropropane 99.0%, 1-chloro-
3,3,3-trifluoropropene was 0.1% and the catalyst was active.
【００３９】〔実施例２〕電気炉を備えた円筒形反応管
（ＳＵＳ３１６Ｌ製、直径４．０ｃｍ、長さ３０ｃｍ）
に調製例２で調製した触媒を２５０ミリリットル充填
し、約２５ミリリットル／分の流量で窒素ガスを流しな
がら反応管の温度を１００℃に上げ、その後窒素ガスを
停止しフッ化水素を約０．２ｇ／分の速度で供給しなが
ら１００℃で６時間保った。次に反応管の温度を５０℃
に下げ反応準備を完了した。Example 2 Cylindrical reaction tube equipped with an electric furnace (SUS316L, diameter 4.0 cm, length 30 cm)
Was charged with 250 ml of the catalyst prepared in Preparation Example 2, and the temperature of the reaction tube was raised to 100 ° C. while flowing nitrogen gas at a flow rate of about 25 ml / min. It was kept at 100 ° C. for 6 hours while feeding at a rate of 2 g / min. Next, raise the temperature of the reaction tube to 50 ° C.
And the reaction preparation was completed.
【００４０】フッ化水素０．３２ｇ／分の供給量で反応
管入り口から供給し、その直後に１，３，３，３−テト
ラフルオロプロペンを予め気化させて０．２３ｇ／分の
速度で反応管入り口に供給を開始した。Hydrogen fluoride was supplied from the inlet of the reaction tube at a supply rate of 0.32 g / min, and immediately thereafter, 1,3,3,3-tetrafluoropropene was vaporized in advance and reacted at a rate of 0.23 g / min. Feeding started at the tube entrance.
【００４１】そのまま反応を続け、反応開始２時間後に
は反応は安定したので、その後４時間にわたって反応管
から流出する生成ガスを水中に吹き込み塩化水素やフッ
化水素の酸性ガスを除去した後、ドライアイス−アセト
ン−トラップで有機物を捕集した。捕集した有機物の重
量は６３．１ｇでありこれをガスクロマトグラフィーで
分析したところ、１，１，１，３，３−ペンタフルオロ
プロパン９９．７％、１，３，３，３−テトラフルオロ
プロペン０．３％であった。The reaction was continued as it was, and the reaction was stabilized 2 hours after the start of the reaction. Thereafter, the product gas flowing out of the reaction tube was blown into water for 4 hours to remove the acid gas such as hydrogen chloride and hydrogen fluoride. Organics were collected with an ice-acetone-trap. The weight of the collected organic matter was 63.1 g, which was analyzed by gas chromatography to find that 99.7% of 1,1,1,3,3-pentafluoropropane and 1,3,3,3-tetrafluoro Propene was 0.3%.
【００４２】さらに反応を継続して１００時間後に反応
管出口ガスをサンプリングし、塩化水素を含む酸性ガス
の除去後ガスクロマトグラフィで分析したところ、１，
１，１，３，３−ペンタフルオロプロパン９７．４％、
１，３，３，３−テトラフルオロプロペン２．６％であ
った。Further, 100 hours after the reaction was continued, the gas at the outlet of the reaction tube was sampled and analyzed by gas chromatography after removing the acid gas containing hydrogen chloride.
97.4% of 1,1,3,3-pentafluoropropane,
1,3,3,3-tetrafluoropropene was 2.6%.
【００４３】そこで、原料の１，３，３，３−テトラフ
ルオロプロペンとフッ化水素の供給を停止し、代わりに
窒素ガス２０ｍｌ／分と塩素ガス１０ｍｌ／分の供給を
開始し、反応管の温度を２００℃に上昇させ、そのまま
２０時間にわたり処理を継続した。Therefore, the supply of the raw materials 1,3,3,3-tetrafluoropropene and hydrogen fluoride was stopped, and instead, the supply of nitrogen gas 20 ml / min and the supply of chlorine gas 10 ml / min was started, and the supply of the reaction tube was started. The temperature was raised to 200 ° C. and the treatment continued for 20 hours.
【００４４】次いで、反応管の温度を下げながら窒素と
塩素の供給を停止し代わりにフッ化水素を約０．２ｇ／
分の速度で供給し、反応管の温度を５０℃で６時間保っ
た。Then, while lowering the temperature of the reaction tube, the supply of nitrogen and chlorine was stopped, and about 0.2 g /
The reaction tube temperature was maintained at 50 ° C. for 6 hours.
【００４５】その後、フッ化水素０．３２ｇ／分の供給
量で反応管入り口から供給し、その直後に１，３，３，
３−テトラフルオロプロペンを予め気化させて０．２３
ｇ／分の速度で反応管入り口に供給を開始した。Thereafter, hydrogen fluoride was supplied from the inlet of the reaction tube at a supply amount of 0.32 g / min.
3-tetrafluoropropene was previously vaporized to give 0.23
Feeding was started at the rate of g / min to the inlet of the reaction tube.
【００４６】反応開始１０時間後に反応管出口ガスをサ
ンプリングし、塩化水素を含む酸性ガスの除去後ガスク
ロマトグラフィで分析したところ、１，１，１，３，３
−ペンタフルオロプロパン９７．４％、１，３，３，３
−テトラフルオロプロペン２．６％であり、触媒は活性
であった。After 10 hours from the start of the reaction, the gas at the outlet of the reaction tube was sampled and analyzed by gas chromatography after removing the acidic gas containing hydrogen chloride.
97.4% pentafluoropropane, 1,3,3,3
2.6% tetrafluoropropene and the catalyst was active.
【００４７】[0047]
【発明の効果】本発明の方法は、低温度でのフッ素化反
応に使用することにより活性の低下した五塩化アンチモ
ン担持活性炭触媒を容易に再活性化できるという効果を
奏する。The method of the present invention has an effect that an activated carbon catalyst carrying antimony pentachloride having reduced activity by using it in a fluorination reaction at a low temperature can be easily reactivated.
───────────────────────────────────────────────────── 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） // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 佐久 冬彦 埼玉県川越市今福中台2805番地 セントラ ル硝子株 式会社化学研究所内 (72)発明者 日比野 泰雄 埼玉県川越市今福中台2805番地 セントラ ル硝子株 式会社化学研究所内 Ｆターム(参考） 4G069 AA10 BA08A BA08B BB08A BB08B BC26A BC26B BD12B CB25 GA07 4H006 AA02 AC30 AC55 AC84 BA13 EA02 4H039 CA51 CD20 CF10 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Fuyuhiko Saku 2805 Imafukunakadai, Kawagoe-shi, Saitama Address Central Glass Co., Ltd. Chemical Research Laboratory (72) Inventor Yasuo Hibino 2805 Imafukunakadai, Kawagoe-shi, Saitama Prefecture Central Glass Co., Ltd. Chemical Research Laboratory F-term (reference) 4G069 AA10 BA08A BA08B BB08A BB08B BC26A BC26B BD12B CB25 GA07 4H006 AA02 AC30 AC55 AC84 BA13 EA02 4H039 CA51 CD20 CF10
Claims (4)
化してフッ素原子数の多いフッ素含有ハロゲン化炭化水
素とする際に使用することで活性の低下した五塩化アン
チモン担持活性炭触媒を再活性化する方法であって、活
性の低下した五塩化アンチモン担持活性炭触媒を１５０
℃以上において塩素ガスと接触させることからなる再活
性化方法。1. An activated carbon catalyst supported on antimony pentachloride, whose activity has been reduced by using it when fluorinating a halogenated hydrocarbon with hydrogen fluoride to obtain a fluorine-containing halogenated hydrocarbon having a large number of fluorine atoms. Activated carbon catalyst with reduced activity on antimony pentachloride
A reactivation method comprising contacting with chlorine gas at a temperature of at least ℃.
炭触媒を１５０℃以上において塩素ガスとフッ化水素ガ
スとを共に接触させることからなる請求項１記載の再活
性化方法。2. The reactivation method according to claim 1, wherein the activated carbon catalyst supporting antimony pentachloride having reduced activity is brought into contact with both chlorine gas and hydrogen fluoride gas at 150 ° C. or higher.
炭触媒を１５０℃以上において塩素ガス接触させ、次い
でフッ化水素ガスを接触させることからなる請求項１記
載の再活性化方法。3. The reactivation method according to claim 1, wherein the activated carbon catalyst supporting antimony pentachloride having reduced activity is brought into contact with chlorine gas at 150 ° C. or higher, and then brought into contact with hydrogen fluoride gas.
クロロ−３，３，３−トリフルオロプロペンまたは１，
３，３，３−テトラフルオロプロペンとフッ化水素を反
応させ１，１，１，３，３−ペンタフルオロプロパンを
製造する際に使用した触媒である請求項１乃至３の何れ
かに記載の再活性化方法。4. The activated carbon catalyst supporting antimony pentachloride comprises 1-
Chloro-3,3,3-trifluoropropene or 1,
The catalyst according to any one of claims 1 to 3, wherein the catalyst is used when 3,3,3-tetrafluoropropene is reacted with hydrogen fluoride to produce 1,1,1,3,3-pentafluoropropane. Reactivation method.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008530091A (en) * | 2005-02-09 | 2008-08-07 | ハネウェル・インターナショナル・インコーポレーテッド | Process for producing 1,1,1-trifluoroethane |
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|---|---|---|---|---|
| JP2008530091A (en) * | 2005-02-09 | 2008-08-07 | ハネウェル・インターナショナル・インコーポレーテッド | Process for producing 1,1,1-trifluoroethane |
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