JPH0717882A - Production of difluoromethane - Google Patents
Production of difluoromethaneInfo
- Publication number
- JPH0717882A JPH0717882A JP5191942A JP19194293A JPH0717882A JP H0717882 A JPH0717882 A JP H0717882A JP 5191942 A JP5191942 A JP 5191942A JP 19194293 A JP19194293 A JP 19194293A JP H0717882 A JPH0717882 A JP H0717882A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- chlorofluoromethane
- catalyst
- liquid phase
- gas phase
- 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.)
- Pending
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フロンガスの代替品と
して有用であって冷媒等としての用途が期待されている
ジフルオロメタン（以下、ＨＦＣ−３２と称する。）の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing difluoromethane (hereinafter referred to as HFC-32) which is useful as a substitute for CFC gas and is expected to be used as a refrigerant or the like.
【０００２】[0002]
【従来の技術】ＨＦＣ−３２の製造方法としては、例え
ば、ジクロロメタンのフッ素化反応（DE−1020968 、米
国特許第2749374 及び 2749375号 、米国特許第364454
5 号、米国特許第4147733 号、特開昭59−225132、2310
29及び231030号など）、クロロジフルオロメタンまたは
ジクロロジフルオロメタンの還元反応（EP−508660 Al
など）に記載された方法が知られている。As a method for producing HFC-32, for example, a fluorination reaction of dichloromethane (DE-1020968, US Pat. Nos. 2749374 and 2749375, US Pat. No. 364454).
5, U.S. Pat.No. 4,147,733, JP-A-59-225132, 2310
29 and 231030), reduction reaction of chlorodifluoromethane or dichlorodifluoromethane (EP-508660 Al
Etc.) is known.
【０００３】これらの公知のＨＦＣ−３２の製造方法に
よれば、液相フッ素化反応として、SbF3を触媒とし、ジ
クロロメタンと塩素及び過剰のフッ化水素とを、 120℃
から150℃の反応温度、40気圧から50気圧の反応圧力で
反応させている（DE−1020968 など）。また、Sb（Ｖ）
を含むSbCl3 と塩素にジクロロメタンとフッ酸を 120℃
で反応させる方法もある（米国特許第2749374 及び2749
375 号など）。According to these known methods for producing HFC-32, the liquid phase fluorination reaction is carried out by using SbF 3 as a catalyst, dichloromethane, chlorine and excess hydrogen fluoride at 120 ° C.
The reaction temperature is from 150 to 150 ° C, and the reaction pressure is from 40 to 50 atmospheres (DE-1020968 etc.). Also, Sb (V)
Dichloromethane and hydrofluoric acid in SbCl 3 and chlorine containing 120 ℃
There is also a method of reacting with (US Pat. Nos. 2749374 and 2749).
No. 375).
【０００４】また、気相フッ素化反応は、ジクロロメタ
ンとフッ酸とを酸化クロムなどの触媒を用いて 320℃か
ら 400℃の範囲で反応させたものである（特開昭59−22
5132、231029及び231030号など）。In the gas phase fluorination reaction, dichloromethane and hydrofluoric acid are reacted in the range of 320 ° C. to 400 ° C. using a catalyst such as chromium oxide (JP-A-59-22).
5132, 231029 and 231030 etc.).
【０００５】更に、還元反応として、PdまたはPd＋ VII
Ia族金属を活性炭に担持した触媒を用いた水素還元反応
を行っている（EP−508660 Al）。Further, as a reduction reaction, Pd or Pd + VII
A hydrogen reduction reaction is carried out using a catalyst in which a group Ia metal is supported on activated carbon (EP-508660 Al).
【０００６】上記した公知の液相フッ素化反応でジクロ
ロメタン（以下、ＨＣＣ−３０と称する。）よりＨＦＣ
−３２を効率よく合成するには、アンチモン（Ｖ）触媒
（SbClxFy)のｙ値を約５に、かつ反応温度を80℃以上に
する必要がある。しかし、この触媒の組成では、腐食性
が非常に強いため、反応器材質の選定が困難となってく
る。In the above-mentioned known liquid phase fluorination reaction, HFC was added to dichloromethane (hereinafter referred to as HCC-30).
In order to synthesize -32 efficiently, it is necessary to set the y value of the antimony (V) catalyst (SbClxFy) to about 5 and the reaction temperature to 80 ° C or higher. However, with this catalyst composition, the corrosiveness is so strong that it becomes difficult to select the reactor material.
【０００７】また、気相反応では、反応器が大きくな
り、かつ反応温度を高くする必要があるため、コスト及
び副生成物の問題が生ずる。さらに、反応の性質上、反
応器の大きさに比例してＨＦＣ−３２を得ることが困難
である。Further, in the gas phase reaction, the reactor becomes large and it is necessary to raise the reaction temperature, which causes problems of cost and by-products. Furthermore, due to the nature of the reaction, it is difficult to obtain HFC-32 in proportion to the size of the reactor.
【０００８】更に、クロロジフルオロメタンの還元反応
では、クロロジフルオロメタンは還元されにくく、か
つ、転化率を上げるために反応温度を高くすると、選択
率の低下を招く。ジクロロジフルオロメタンでは、それ
自身が規制フロンであるため、近い将来に生産されなく
なるという欠点を持つ。Further, in the reduction reaction of chlorodifluoromethane, chlorodifluoromethane is not easily reduced, and if the reaction temperature is raised to increase the conversion rate, the selectivity is lowered. Dichlorodifluoromethane has a drawback that it will not be produced in the near future because it is a regulated CFC itself.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、触媒
による腐食性を低下させ、反応温度等の反応条件を緩和
でき、コスト、収率の面で有利なＨＦＣ−３２の製造方
法を提供することにある。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a method for producing HFC-32, which is capable of reducing corrosiveness by a catalyst, relaxing reaction conditions such as reaction temperature, and advantageous in terms of cost and yield. To do.
【００１０】[0010]
【課題を解決するための手段】本発明者は、上記の問題
を解決するために、まず、アンチモン（Ｖ）触媒（SbCl
xFy)のｙ値を低く（３以下）した状態でＨＣＣ−３０を
反応させ（以下、第１工程と称する。）、このときに生
じたクロロフルオロメタン（以下、ＨＣＦＣ−３１と称
する。）をさらにフッ素化反応させて（以下、第２工程
と称する。）、ＨＦＣ−３２を得る方法を見出した。In order to solve the above-mentioned problems, the present inventor firstly conducted an antimony (V) catalyst (SbCl 2
HCC-30 was reacted with the y value of xFy) kept low (3 or less) (hereinafter referred to as the first step), and chlorofluoromethane (hereinafter referred to as HCFC-31) generated at this time was reacted. Further, a method for obtaining HFC-32 by performing a fluorination reaction (hereinafter referred to as the second step) was found.
【００１１】即ち、本発明は、ジクロロメタン（ＨＣＣ
−３０）をSbClxFy(但し、ｘ＋ｙ＝５、１≦ｙ≦３であ
る。）で表されるアンチモン触媒の存在下にフッ化水素
と液相で反応させてクロロフルオロメタン（ＨＣＦＣ−
３１）を得る第１工程と；次いで、反応生成物中のＨＣ
ＦＣ−３１を単独で液相又は気相で触媒と接触させるこ
と、又は、反応生成物中のＨＣＦＣ−３１をフッ化水素
と気相で触媒の存在下に接触させることによって、ジフ
ルオロメタン（ＨＦＣ−３２）を得る第２工程と；から
なるＨＦＣ−３２の製造方法に係るものである。That is, the present invention relates to dichloromethane (HCC
-30) is reacted with hydrogen fluoride in the liquid phase in the presence of an antimony catalyst represented by SbClxFy (where x + y = 5, 1 ≦ y ≦ 3) to obtain chlorofluoromethane (HCFC-
31) in the first step; and then HC in the reaction product
By contacting FC-31 alone with a catalyst in a liquid phase or a gas phase, or by contacting HCFC-31 in a reaction product with hydrogen fluoride in a gas phase in the presence of a catalyst, difluoromethane (HFC And a second step of obtaining -32).
【００１２】本発明の方法によれば、ＨＦＣ−３２の製
造プロセスを主として上記の第１工程及び第２工程の２
段階に分け、第１工程（液相フッ素化反応）を腐食性の
弱い条件で、即ち、上記アンチモン触媒のフッ素の割合
を１≦ｙ≦３と小さくして行うことを特徴としている。
これによって、反応器材質の制約を軽減し、その材質選
定が容易となり、従って既存の反応器を使用することが
できる。According to the method of the present invention, the manufacturing process of HFC-32 is mainly performed by the above-mentioned first step and second step.
It is characterized in that the first step (liquid phase fluorination reaction) is performed under weakly corrosive conditions, that is, the proportion of fluorine in the antimony catalyst is set as small as 1 ≦ y ≦ 3.
This alleviates the restrictions on the material of the reactor and facilitates the selection of the material, so that the existing reactor can be used.
【００１３】また、第２工程での反応、つまりＨＣＦＣ
−３１のフッ素化反応をフッ化水素（ＨＦ）を用いて気
相で行う場合は、ＨＣＣ−３０とＨＦを気相中のみで反
応させ、ＨＦＣ−３２を生成させる場合に比べて、より
緩和された反応条件（例えば、より低い反応温度）を採
用できる。結果として触媒寿命を長く保てるとともに、
気相反応器を小さくすることができ、副生成物も減少さ
せることができる。The reaction in the second step, that is, HCFC
When the fluorination reaction of −31 is carried out in the gas phase using hydrogen fluoride (HF), it is more relaxed than the case where HCC-30 and HF are reacted only in the gas phase to produce HFC-32. The reaction conditions described (eg, lower reaction temperature) can be employed. As a result, the catalyst life can be maintained for a long time,
The gas phase reactor can be made smaller and byproducts can be reduced.
【００１４】さらに、第２工程でのＨＣＦＣ−３１のフ
ッ素化反応は、ＨＦの非存在下で（即ち、ＨＣＦＣ−３
１単独で）気相又は液相で反応させてＨＦＣ−３２を得
ることができるので、プロセス上や、触媒寿命、反応器
材質、反応条件の点で有利となる。Further, the fluorination reaction of HCFC-31 in the second step is conducted in the absence of HF (that is, HCFC-3).
Since HFC-32 can be obtained by reacting in a gas phase or a liquid phase (alone 1), it is advantageous in terms of process, catalyst life, reactor material, and reaction conditions.
【００１５】本発明の方法に基づくＨＦＣ−３２の製造
工程の一例を示すと、図１に示す通りである。An example of the manufacturing process of HFC-32 based on the method of the present invention is shown in FIG.
【００１６】本発明によるＨＣＣ−３０のフッ素化反応
の１例として、次のようなプロセスが挙げられる。An example of the fluorination reaction of HCC-30 according to the present invention is the following process.
【００１７】第１工程の反応器内にアンチモン触媒を調
製してＨＣＣ−３０とＨＦを連続的に仕込み、反応出口
より生成ガスを抜き出す。この際、未反応ＨＣＣ−３０
の反応器からの放出を防止するために、反応圧力を調節
すること又は出口側に蒸留塔を設けること、或いはその
両方を行うことがよい。An antimony catalyst is prepared in the reactor of the first step, HCC-30 and HF are continuously charged, and the produced gas is extracted from the reaction outlet. At this time, unreacted HCC-30
It is advisable to adjust the reaction pressure or to provide a distillation column at the outlet side, or both, in order to prevent the release of the above-mentioned from the reactor.
【００１８】第１工程の出口ガス（主として、ＨＦＣ−
３２、ＨＣＦＣ−３１及びHCl からなる。）から蒸留塔
でＨＦＣ−３２とHCl を分離することが望ましい。この
時、残りのガスはそのまま第１工程に戻して反応させて
もよいが、本発明では、残りのガス（主としてＨＣＦＣ
−３１とＨＦ）からＨＣＦＣ−３１を分離し、第２工程
で、ＨＣＦＣ−３１を気相または液相で触媒の存在下に
不均化反応させてＨＦＣ−３２を生成させるか、或いは
ＨＦ量を調整して気相でＨＣＦＣ−３１をフッ素化反応
させてＨＦＣ−３２を生成させることが特徴的である。
生成されたＨＦＣ−３２は分離する。The outlet gas of the first step (mainly HFC-
32, HCFC-31 and HCl. It is desirable to separate HFC-32 and HCl from a) in a distillation column. At this time, the remaining gas may be directly returned to the first step for reaction, but in the present invention, the remaining gas (mainly HCFC
-31 and HF) to separate HCFC-31, and in the second step, HCFC-31 is disproportionated in the gas or liquid phase in the presence of a catalyst to produce HFC-32, or the amount of HF is increased. Is adjusted to cause fluorination reaction of HCFC-31 in the gas phase to generate HFC-32.
The generated HFC-32 is separated.
【００１９】そして、上記の不均化反応で生成したＨＣ
Ｃ−３０は第１工程に、未反応のＨＣＦＣ−３１は第１
工程又は第２工程に戻せばよい。また、後者の場合（Ｈ
ＣＦＣ−３１のＨＦによる気相フッ素化）も同様であ
る。The HC produced in the above disproportionation reaction
C-30 is in the first step, unreacted HCFC-31 is in the first step
It may be returned to the process or the second process. In the latter case (H
The same applies to the vapor phase fluorination of CFC-31 with HF).
【００２０】第１工程のアンチモン触媒（SbClxFy)は、
少なくともｘ＋ｙ＝５の組成の触媒（５価のアンチモ
ン）を含み、１≦ｙ≦３とする。この触媒の調製方法と
しては、SbCl5 とＨＦ又はSbCl5 とSbF5を反応させて
も、SbF3とCl2 を反応させてもよい。The antimony catalyst (SbClxFy) used in the first step is
It contains at least a catalyst (pentavalent antimony) having a composition of x + y = 5, and 1 ≦ y ≦ 3. As a method for preparing this catalyst, SbCl 5 and HF, SbCl 5 and SbF 5 or SbF 3 and Cl 2 may be reacted.
【００２１】第１工程での反応温度は、40から150 ℃、
好ましくは60から120 ℃で行うのがよい。また、反応圧
力は２から80kG、好ましくは３から20kGで行うのがよ
い。反応温度、圧力は、ＨＣＣ−３０から少なくともＨ
ＣＦＣ−３１が生成するものであればよいが、この反応
条件でＨＦＣ−３２が生成しても何ら支障はない。The reaction temperature in the first step is 40 to 150 ° C.,
It is preferably carried out at 60 to 120 ° C. The reaction pressure is 2 to 80 kG, preferably 3 to 20 kG. The reaction temperature and pressure are at least H from HCC-30.
As long as CFC-31 is produced, there is no problem even if HFC-32 is produced under this reaction condition.
【００２２】次に、第１工程から得られたＨＣＦＣ−３
１及びＨＦ（ＨＦは外部から添加してもよい。）もしく
はＨＣＦＣ−３１単独を第２工程において触媒を用いて
気相反応させる。ＨＣＦＣ−３１とＨＦを反応させた場
合は、副生物のうち少なくともＨＣＣ−３０は液相フッ
素化反応（第１工程）に戻し、未反応のＨＣＦＣ−３１
は再び気相反応を行わせる。ＨＣＦＣ−３１単独で反応
する場合は、気相又は液相でＨＣＣ−３０とＨＦＣ−３
２に不均化させ、ＨＦＣ−３２を得る。この時に副生す
るＨＣＣ−３０は液相フッ素化反応（第１工程）に戻せ
ばよい。Next, HCFC-3 obtained from the first step
1 and HF (HF may be added from the outside) or HCFC-31 alone is subjected to a gas phase reaction in the second step using a catalyst. When HCFC-31 and HF are reacted, at least HCC-30 among the byproducts is returned to the liquid phase fluorination reaction (first step), and unreacted HCFC-31
Causes the gas phase reaction to occur again. When reacting with HCFC-31 alone, HCC-30 and HFC-3 in gas phase or liquid phase
Disproportionate to 2 to give HFC-32. The HCC-30 produced as a by-product at this time may be returned to the liquid phase fluorination reaction (first step).
【００２３】ＨＣＦＣ−３１の気相反応は、ＨＣＣ−３
０のそれと比べて反応温度を下げることができるため、
触媒寿命を長くし、副生成物を減少させることができ
る。The gas phase reaction of HCFC-31 is HCC-3.
Since the reaction temperature can be lowered compared to that of 0,
The catalyst life can be extended and byproducts can be reduced.
【００２４】この気相反応に使用する触媒は、表面積が
好ましくは 170m2／ｇ以上、 300m2／ｇ以下である酸化
クロム、クロムオキシフルオライド、酸化アルミニウ
ム、アルミニウムフルオライド及び塩化フッ化アルミニ
ウム（AlClxFy)から選ばれた少なくとも１種、もしくは
それを担体に担持したものを用いればよい。The catalyst used in this gas phase reaction preferably has a surface area of 170 m 2 / g or more and 300 m 2 / g or less of chromium oxide, chromium oxyfluoride, aluminum oxide, aluminum fluoride and aluminum chlorofluoride ( At least one selected from AlClxFy), or one obtained by supporting it on a carrier may be used.
【００２５】第２工程のＨＣＦＣ−３１単独の反応を液
相で行う場合、使用する触媒は、上記以外にも、AlC
l3 、ZrCl4 、TiCl4 などの金属塩化物系のルイス酸
や、それらのCl原子の一部をＦ原子に置換した化合物な
どの少なくとも１種、或いはそれを担体に担持したもの
が使用できる。その時の反応温度は10℃から100 ℃が好
ましい。When the reaction of HCFC-31 alone in the second step is carried out in the liquid phase, the catalyst to be used is AlC
At least one kind of metal chloride-based Lewis acid such as l 3 , ZrCl 4 , and TiCl 4 or a compound in which a part of Cl atoms thereof is replaced with F atoms, or a substance having it supported on a carrier can be used. . The reaction temperature at that time is preferably 10 ° C to 100 ° C.
【００２６】第２工程の気相反応温度は、 100℃から35
0 ℃で、好ましくは 120℃から250℃で行うのがよい。
反応圧力は０kGから10kGで行うのがよい。また、ＨＦ／
ＨＣＦＣ−３１比は０から20がよく、より好ましくは０
から８である。The gas phase reaction temperature in the second step is from 100 ° C to 35 ° C.
It may be carried out at 0 ° C, preferably 120 ° C to 250 ° C.
The reaction pressure is preferably 0 kG to 10 kG. Also, HF /
The HCFC-31 ratio is preferably 0 to 20, more preferably 0.
To 8.
【００２７】[0027]
【発明の作用効果】本発明の方法によれば、ＨＦＣ−３
２の製造に際し、ＨＣＣ−３０とフッ酸との反応を第１
工程（液相フッ素化反応）において腐食性の弱い条件で
（即ち、Sb(V)ClxFy触媒のフッ素の割合を１≦ｙ≦３と
小さくして）行うので、反応器材質の制約を軽減し、そ
の材質選定が容易となり、従って既存の反応器を使用す
ることができる。According to the method of the present invention, HFC-3 is used.
In the production of 2, the first reaction of HCC-30 and hydrofluoric acid
Since the process (liquid phase fluorination reaction) is performed under conditions with weak corrosiveness (that is, the fluorine content of the Sb (V) ClxFy catalyst is reduced to 1 ≦ y ≦ 3), the restrictions on the reactor material are reduced. , The material can be easily selected, and thus the existing reactor can be used.
【００２８】また、第１工程で得られるＨＣＦＣ−３１
のフッ素化反応を第２工程においてＨＦを用いて気相で
行うので、ＨＣＣ−３０の気相中のみでのフッ素化と比
べて、より緩和された反応条件（例えば、より低い反応
温度）を採用でき、結果として触媒寿命を長く保てると
ともに、気相反応器を小さくすることができ、副生成物
も減少させることができる。Also, HCFC-31 obtained in the first step
Since the fluorination reaction of is carried out in the gas phase using HF in the second step, more relaxed reaction conditions (for example, lower reaction temperature) are used as compared with the fluorination of HCC-30 only in the gas phase. As a result, the catalyst life can be maintained for a long time, the gas phase reactor can be downsized, and by-products can be reduced.
【００２９】さらに、第２工程でのＨＣＦＣ−３１のフ
ッ素化反応は、HFの非存在下で（即ち、ＨＣＦＣ−３１
単独で）気相又は液相で行えるので、プロセス上や、触
媒寿命、反応器材質、反応条件の点で有利にＨＦＣ−３
２を得ることができる。Furthermore, the fluorination reaction of HCFC-31 in the second step is carried out in the absence of HF (that is, HCFC-31).
Since it can be performed (independently) in a gas phase or a liquid phase, it is advantageous in terms of process, catalyst life, reactor material, and reaction conditions.
2 can be obtained.
【００３０】[0030]
【実施例】以下、本発明の実施例について更に詳細に説
明するが、以下の実施例は本発明を限定するものではな
く、その技術的思想に基いて種々に変形可能である。EXAMPLES Examples of the present invention will be described in more detail below, but the following examples do not limit the present invention and can be variously modified based on the technical idea thereof.
【００３１】実施例１ 蒸留塔付きの 500mlハステロイ製オートクレーブにSbCl
5 598ｇ（２mol)とフッ酸 120ｇ（６mol)を仕込み、80
℃に加熱して、SbCl2F3 を生成し、発生するHCl を系外
に抜き出した。 Example 1 SbCl was added to a 500 ml Hastelloy autoclave equipped with a distillation column.
Charge 5 598 g (2 mol) and hydrofluoric acid 120 g (6 mol)
The mixture was heated to ℃, SbCl 2 F 3 was produced, and generated HCl was extracted out of the system.
【００３２】そこに、ＨＣＣ−３０ 0.65ｇ／min (7.6
mmol／min)及びフッ酸 0.3ｇ／min(15.2mmol／min)をポ
ンプで仕込んでいった。反応圧力を10kGに保ちながら、
系内のガスを徐々に抜き出し、そのうちＨＦＣ−３２と
HCl を分離した。There, HCC-30 0.65 g / min (7.6
(mmol / min) and hydrofluoric acid 0.3 g / min (15.2 mmol / min) were charged by a pump. While keeping the reaction pressure at 10 kG,
The gas in the system was gradually withdrawn, and HFC-32 and
HCl was separated.
【００３３】残りのガスからＨＦを分離して、ＨＣＦＣ
−３１を80cc／min の割合で、酸化クロム８ｇを充填し
て 150℃に加熱した20Ａハステロイ反応器に流通した。
この反応器の出口ガスとして、下記の成分を得た。ＨＦ
Ｃ−３２の収率は比較的良好であった。HF is separated from the remaining gas to produce HCFC
-31 was flowed at a rate of 80 cc / min into a 20A Hastelloy reactor filled with 8 g of chromium oxide and heated to 150 ° C.
The following components were obtained as the outlet gas of this reactor. HF
The yield of C-32 was relatively good.
【００３４】ＨＣＣ−３０ 35.6cc／min ＨＣＦＣ−３１ 8.8cc／min ＨＦＣ−３２ 35.6cc／minHCC-30 35.6cc / min HCFC-31 8.8cc / min HFC-32 35.6cc / min
【００３５】実施例２ 実施例１と同様に液相反応（第１工程）を行い、反応圧
力を10kGに保ちながら系内のガスを徐々に抜き出し、そ
のうちＨＦＣ−３２と塩酸を分離した。残りのガスであ
るＨＣＦＣ−３１とＨＦをそれぞれ 100cc／min 、 300
cc／min の割合に調整し、酸化クロム５ｇを充填して 2
10℃に加熱した20Ａハステロイ反応器に流通した。この
反応器の出口ガスとして、下記の成分を得た。ＨＦＣ−
３２の収率はかなり向上した。 Example 2 A liquid phase reaction (first step) was carried out in the same manner as in Example 1, and the gas in the system was gradually extracted while maintaining the reaction pressure at 10 kG, and HFC-32 and hydrochloric acid were separated from the gas. The remaining gases, HCFC-31 and HF, are 100cc / min and 300, respectively.
Adjust to cc / min and fill with 5g of chromium oxide. 2
It was passed through a 20A Hastelloy reactor heated to 10 ° C. The following components were obtained as the outlet gas of this reactor. HFC-
The yield of 32 was improved considerably.
【００３６】ＨＣＣ−３０ 6.9cc／min ＨＣＦＣ−３１ 12.0cc／min ＨＦＣ−３２ 81.1cc／minHCC-30 6.9cc / min HCFC-31 12.0cc / min HFC-32 81.1cc / min
【００３７】実施例３ 蒸留塔付きの 500mlハステロイ製オートクレーブにSbCl
5 598ｇ（２mol)とフッ酸 120ｇ（６mol)を仕込み、80
℃に加熱して発生するHCl を系外に抜き出し、SbCl2F3
組成の触媒を生成させた。 Example 3 SbCl was added to a 500 ml Hastelloy autoclave equipped with a distillation column.
Charge 5 598 g (2 mol) and hydrofluoric acid 120 g (6 mol)
HCl generated by heating to ℃ is extracted to the outside of the system, and SbCl 2 F 3
A catalyst of composition was produced.
【００３８】そこに、ＨＣＣ−３０ 0.65ｇ／min (7.6
mmol／min)及びフッ酸 0.3ｇ／min(15.2mmol／min)をポ
ンプで仕込んでいった。反応圧力を10kGに保ちながら、
系内のガスを徐々に抜き出し、そのうちＨＦＣ−３２と
塩酸を分離した。HCC-30 0.65 g / min (7.6
(mmol / min) and hydrofluoric acid 0.3 g / min (15.2 mmol / min) were charged by a pump. While keeping the reaction pressure at 10 kG,
The gas in the system was gradually extracted, and HFC-32 and hydrochloric acid were separated from it.
【００３９】残りのガスからＨＦを分離して、凝縮させ
たＨＣＦＣ−３１ 50ｇ（0.73mol)を、200ml オートク
レーブに塩化フッ化アルミニウム 2.5ｇとともに仕込
み、室温で10時間攪拌した。反応生成物として下記の成
分を得た。この例でも、ＨＦＣ−３２の収率は比較的良
好であった。HF was separated from the remaining gas, and 50 g (0.73 mol) of condensed HCFC-31 was charged into a 200 ml autoclave together with 2.5 g of aluminum fluoride chloride and stirred at room temperature for 10 hours. The following components were obtained as reaction products. Also in this example, the yield of HFC-32 was relatively good.
【００４０】ＨＣＣ−３０ 29.5ｇ ＨＣＦＣ−３１ 2.5ｇ ＨＦＣ−３２ 18ｇHCC-30 29.5 g HCFC-31 2.5 g HFC-32 18 g
【図１】本発明の方法に基づくＨＦＣ−３２（ジフルオ
ロメタン）の製造工程の一例を示すフロー図である。FIG. 1 is a flow chart showing an example of a manufacturing process of HFC-32 (difluoromethane) based on the method of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０７Ｂ 61/00 ３００ Ｃ０９Ｋ 5/04 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location // C07B 61/00 300 C09K 5/04
Claims (10)
＝５、１≦ｙ≦３である。）で表されるアンチモン触媒
の存在下にフッ化水素と液相で反応させてクロロフルオ
ロメタンを得る第１工程と；次いで、反応生成物中のク
ロロフルオロメタンを単独で液相又は気相で触媒と接触
させること、又は、反応生成物中のクロロフルオロメタ
ンをフッ化水素と気相で触媒の存在下に接触させること
によって、ジフルオロメタンを得る第２工程と；からな
るジフルオロメタンの製造方法。1. Dichloromethane is added to SbClxFy (provided that x + y
= 5, 1 ≦ y ≦ 3. A first step of reacting with hydrogen fluoride in a liquid phase in the presence of an antimony catalyst represented by to obtain chlorofluoromethane; and then, chlorofluoromethane in the reaction product alone in a liquid phase or in a gas phase. A second step of obtaining difluoromethane by contacting it with a catalyst or by contacting chlorofluoromethane in the reaction product with hydrogen fluoride in the gas phase in the presence of a catalyst; .
とフッ化水素との接触における触媒が、酸化クロム、ク
ロムオキシフルオライド、酸化アルミニウム、アルミニ
ウムフルオライド及び塩化フッ化アルミニウムから選ば
れた少なくとも１種、或いはそれを担体に担持したもの
からなっている、請求項１に記載した製造方法。2. The catalyst in the contact between chlorofluoromethane and hydrogen fluoride in the second step is at least one selected from chromium oxide, chromium oxyfluoride, aluminum oxide, aluminum fluoride and aluminum chlorofluoride, Alternatively, the production method according to claim 1, which comprises the carrier supported on the carrier.
の気相反応においてフッ化水素とクロロフルオロメタン
との比がモル比で（０〜20）：１である、請求項１又は
２に記載した製造方法。3. The production according to claim 1, wherein the molar ratio of hydrogen fluoride to chlorofluoromethane in the gas phase reaction of chlorofluoromethane in the second step is (0-20): 1. Method.
のうち少なくともクロロフルオロメタン、ジフルオロメ
タン及び塩酸を抜き出し、これらのうちジフルオロメタ
ンと塩酸を分離し、クロロフルオロメタンを気相または
液相でフッ素化する、請求項１〜３のいずれか１項に記
載した製造方法。4. At least chlorofluoromethane, difluoromethane and hydrochloric acid are withdrawn from the reaction product from the liquid phase reactor in the first step, and difluoromethane and hydrochloric acid are separated from these to obtain chlorofluoromethane in a gas phase or The manufacturing method according to claim 1, wherein the fluorination is performed in a liquid phase.
スに含まれるフッ化水素を除去若しくは同伴したまま、
さらにフッ化水素を外部から加えて第２工程でクロロフ
ルオロメタンを気相でフッ素化する、請求項１〜４のい
ずれか１項に記載した製造方法。5. The hydrogen fluoride contained in the gas withdrawn from the liquid-phase reactor in the first step is removed or entrained,
Further, hydrogen fluoride is added from the outside to fluorinate chlorofluoromethane in the gas phase in the second step, the production method according to claim 1.
応生成物のうち、ジフルオロメタンを分離し、クロロフ
ルオロメタンを第１工程又は第２工程の気相又は液相反
応器に、ジクロロメタンを第１工程の液相反応器に戻
す、請求項１〜５のいずれか１項に記載した製造方法。6. Of the reaction products from the gas phase or liquid phase reactor of the second step, difluoromethane is separated and chlorofluoromethane is fed to the gas phase or liquid phase reactor of the first step or the second step. The method according to any one of claims 1 to 5, wherein dichloromethane is returned to the liquid phase reactor in the first step.
ら 150℃であり、第２工程の気相反応の反応温度が 100
℃から 350℃である、請求項１〜６のいずれか１項に記
載した製造方法。7. The reaction temperature of the liquid phase reaction of the first step is 40 to 150 ° C., and the reaction temperature of the gas phase reaction of the second step is 100.
The manufacturing method according to any one of claims 1 to 6, wherein the temperature is from 350C to 350C.
ら80kGであり、第２工程の気相反応の反応圧力が０kGか
ら10kGである、請求項１〜７のいずれか１項に記載した
製造方法。8. The reaction pressure of the liquid phase reaction of the first step is 2 kG to 80 kG, and the reaction pressure of the gas phase reaction of the second step is 0 kG to 10 kG. The described manufacturing method.
ロロフルオロメタンを触媒の存在下に単独で反応させ、
ジフルオロメタンを製造する、請求項４〜８のいずれか
１項に記載した製造方法。9. The chlorofluoromethane withdrawn from the liquid phase reactor of the first step is reacted alone in the presence of a catalyst,
The manufacturing method according to claim 4, wherein difluoromethane is manufactured.
m2／ｇ以下である酸化クロム、クロムオキシフルオライ
ド、酸化アルミニウム、アルミニウムフルオライド、塩
化フッ化アルミニウム、金属塩化物系のルイス酸及びこ
のルイス酸の塩素原子の一部をフッ素原子に置換した化
合物から選ばれた少なくとも１種、或いはそれを担体に
担持したものからなっている、請求項９に記載した製造
方法。10. The catalyst has a surface area of 170 m 2 / g or more, 300
Chromium oxide, chromium oxyfluoride, aluminum oxide, aluminum fluoride, aluminum fluoride chloride, metal chloride-based Lewis acid having a m 2 / g or less and a part of chlorine atoms of this Lewis acid are replaced with fluorine atoms. The production method according to claim 9, comprising at least one selected from the compounds, or one obtained by supporting it on a carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5191942A JPH0717882A (en) | 1993-07-05 | 1993-07-05 | Production of difluoromethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5191942A JPH0717882A (en) | 1993-07-05 | 1993-07-05 | Production of difluoromethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0717882A true JPH0717882A (en) | 1995-01-20 |
Family
ID=16283025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5191942A Pending JPH0717882A (en) | 1993-07-05 | 1993-07-05 | Production of difluoromethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717882A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995015937A1 (en) * | 1993-12-09 | 1995-06-15 | Daikin Industries, Ltd. | Process for producing difluoromethane and 1,1,1,2-tetrafluoroethane |
| WO1995035271A1 (en) * | 1994-06-20 | 1995-12-28 | Daikin Industries, Ltd. | Process for producing difluoromethane |
| WO1996001241A1 (en) * | 1994-07-01 | 1996-01-18 | Daikin Industries, Ltd. | Process for producing difluoromethane |
| EP1542949A1 (en) * | 2002-07-10 | 2005-06-22 | Srf Limited | A process for the production of difluoromethane |
| JPWO2005026090A1 (en) * | 2003-09-10 | 2006-11-16 | 昭和電工株式会社 | Production method of hydrofluorocarbon, its product and its use |
-
1993
- 1993-07-05 JP JP5191942A patent/JPH0717882A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995015937A1 (en) * | 1993-12-09 | 1995-06-15 | Daikin Industries, Ltd. | Process for producing difluoromethane and 1,1,1,2-tetrafluoroethane |
| US5849963A (en) * | 1993-12-09 | 1998-12-15 | Daikin Industries, Ltd. | Method for producing difluoromethane and 1,1,1,2-tetrafluoroethane |
| WO1995035271A1 (en) * | 1994-06-20 | 1995-12-28 | Daikin Industries, Ltd. | Process for producing difluoromethane |
| AU697434B2 (en) * | 1994-06-20 | 1998-10-08 | Daikin Industries, Ltd. | Process for the preparation of difluoromethane |
| WO1996001241A1 (en) * | 1994-07-01 | 1996-01-18 | Daikin Industries, Ltd. | Process for producing difluoromethane |
| US6407296B1 (en) | 1994-07-01 | 2002-06-18 | Daikin Industries Ltd. | Process for producing difluoromethane |
| EP1542949A1 (en) * | 2002-07-10 | 2005-06-22 | Srf Limited | A process for the production of difluoromethane |
| EP1542949A4 (en) * | 2002-07-10 | 2006-05-17 | Srf Ltd | A process for the production of difluoromethane |
| JPWO2005026090A1 (en) * | 2003-09-10 | 2006-11-16 | 昭和電工株式会社 | Production method of hydrofluorocarbon, its product and its use |
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