JPS6127375B2 - - Google Patents
Info
- Publication number
- JPS6127375B2 JPS6127375B2 JP52036302A JP3630277A JPS6127375B2 JP S6127375 B2 JPS6127375 B2 JP S6127375B2 JP 52036302 A JP52036302 A JP 52036302A JP 3630277 A JP3630277 A JP 3630277A JP S6127375 B2 JPS6127375 B2 JP S6127375B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- reaction
- fluoride
- catalyst
- chlorofluorohydrocarbons
- 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
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000006462 rearrangement reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000006276 transfer reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical class F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- UGCSPKPEHQEOSR-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1,2-difluoroethane Chemical compound FC(Cl)(Cl)C(F)(Cl)Cl UGCSPKPEHQEOSR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- -1 CCl 3 F Chemical class 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005935 Sulfuryl fluoride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- LSJNBGSOIVSBBR-UHFFFAOYSA-N thionyl fluoride Chemical compound FS(F)=O LSJNBGSOIVSBBR-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は異性化された水素含有クロロフルオロ
炭化水素の製法、さらに詳しくは、水素含有クロ
ロフルオロ炭化水素を触媒の存在下に転移反応に
付して、溶媒、冷媒、エアゾル噴射剤、他の有用
な化合物の中間体として有用な、より改良された
性質を示す異性化された水素含有クロロフルオロ
炭化水素の製法に関する。
従来、水素を含有しないクロロフルオロ炭化水
素（以下、非含水素フロンという）では、塩化ア
ルミニウムを触媒として転移反応を行なうことに
より異性化されたクロロフルオロ炭化水素を得て
いた。しかしながら、水素含有クロロフルオロ炭
化水素（以下、含水素フロンという）にあつて
は、前記塩化アルミニウムに接触させても転移反
応は生起せず、塩化水素が脱離する分解反応が生
起して目的とする異性体がほとんど生じない。例
えば、CHClFCClF2室温で塩化アルミニウムに
接触させても瞬時に反応するがCHCl2CF3はほと
んど生じない。
本発明の目的は、含水素フロンから異性化され
た含水素フロンを好収率で得ることである。
本発明によれば、前記目的は、含水素フロンを
触媒AlClxFyOzに接触せしめて転位することによ
り異性化された含水素フロンとすることにより達
成することができる。これにより、前記含水素フ
ロンを分解することなく転移反応を円滑に進行せ
しめ、目的とする異性体を好収率で得ることがで
きる。
本発明において用いられる前記触媒は、反応の
進行につれて、その活性が低下しやすい。例え
ば、
CHClFCClF2→CHCl2CF3
では、最初はほとんど100％の転化率で反応が進
行するが、２時間後には、全く進行しなくなる。
しかして、本発明の他の態様の目的は、触媒活
性の低下を生ぜしめることなく、前述の転移反応
を行なうことである。
この目的は、前記本発明において、水素を含ま
ないクロロ炭化水素またはクロロフルオロ炭化水
素、すなわちパークロロ炭化水素またはパークロ
ロフルオロ炭化水素を含水素フロンに添加するこ
とにより達成することができる。これにより、相
当長時間にわたり触媒活性を持続することができ
る。例えば、
CHClFClF2→CHCl2CF3
では、10時間でも20時間でも活性が持続する。
本発明において使用される触媒は、
AlClxFyOz、但しｘ＋ｙ＋ｚ＝３、０＜ｘ＜３、
０＜ｙ＜３、０≦ｚ＜３／２、の式を有する塩素
化弗素化アルミニウムまたは塩素弗素化アルミナ
である。
具体的な重量組成は、全重量に対して塩素が０
％より多く、通常0.1％より多く５％以下、弗素
や５％以上で64％以下、酸素が０％以上で67％以
下、好ましくは、塩素が0.2〜2.0％、弗素が８〜
60％である。
本発明において使用される触媒は、公知物質で
あるが、その製法を挙げるとつぎのものがある。
塩素化弗素化アルミニウムは、塩化アルミニウ
ムに弗化水素、弗酸、炭素数４以下の好ましくは
炭素数２以下のフルオロ炭化水素またはクロロフ
ルオロ炭化水素例えばCCl3F、CCl2FCCl2F、
CCl2FCClF2を作用させて製造することができ
る。その際、パーフルオロ炭化水素の場合、クロ
ロ炭化水素、クロロフルオロ炭化水素を共存させ
てもよく、クロロフルオロ炭化水素の場合、クロ
ロ炭化水素を共存させてもよい。温度条件は、０
℃乃至塩化アルミニウムの昇華点、好ましくは、
作用物質の沸点以下の高温である。具体的には０
℃〜100℃である。塩素化弗素化アルミナは、活
性化アルミナに100〜600℃でクロロフルオロ炭化
水素をまたはフルオロ炭化水素とクロロ炭化水素
例えばCCl4もしくはクロロフルオロ炭化水素例
えばCCl3F、CCl2FCCl2F、CCl2FCClF2とを作
用させて製造することができる。または、20〜
450℃で弗化水素、300〜500℃で弗化硫黄
（SF4、SF6など）、弗化スルフリル、弗化チオニ
ル、20〜450℃で弗化アンモニウム（酸性弗化ア
ンモニウム、中性弗化アンモニウムなど）の無機
弗化物を作用させた後、クロロフルオロ炭化水素
またはクロロ炭化水素を作用させることにより製
造することができる。
本発明において、出発物質となる水素含有クロ
ロフルオロ炭化水素は、炭素数２、水素数１また
は２を有し、その他は、塩素または弗素で置換さ
れた脂肪族炭化水素である。例を挙げれば、
CHClFCCl2F、CHClFCClF2、CHClFCHClFで
ある。これらはつぎの転移反応をする。
CHClFCCl2F→CHCl2CClF2
CHClFCClF2→CHCl2CF3
CHClFCHClF→CHCl2CHF2
転移反応の温度および圧力は、出発物質および
目的物質が気体であるように選べばよく、最高温
度は約300℃である。液体が触媒に生ずると活性
が低下するので好ましくなく、約300℃より高い
温度では出発物質が分解するからである。接触時
間は、温度、圧力および出発物質の種類に依存す
る。通常0.02分〜２分である。酸素または空気の
共存は、炭素数の析出による触媒の活性の低下を
防止するため有効である。共存量は、出発物質に
対し、酸素0.1モル％〜300モル％、好ましくは、
１モル％〜50モル％である。
本発明の一実施態様におけるパークロロ炭化水
素またはパークロロフルオロ炭化水素は、炭素数
１〜３好ましくは１〜２の飽和脂肪族炭化水素の
水素全部が塩素または弗素によつて置換されたも
のである。転移反応条件下、つぎに示す添加量に
よる添加体の分圧において、気体で存在するもの
が好ましい。特に好ましいものを例示すると四塩
化炭素、トリクロロフルオロメタン、１・１・２
−トリクロロ−１・２・２−トリフルオロエタ
ン、１・１・１−トリクロロ−２・２・２−トリ
フルオロエタン、１・１・２・２−テトラクロロ
−１・２−ジフルオロエタン、１・１・１・２−
テトラクロロ−２・２−ジフルオロエタンであ
る。添加量は、出発物質１モルに対し少くとも
0.01モル必要である。添加量の上限は特にない
が、工業的に目的物質を得る点から考慮して３モ
ル以下とするのが好ましい。
また、パークロロフルオロ炭化水素を含水素フ
ロンとともに活性化アルミナ床または塩化アルミ
ニウム床を100℃以上でかなり長時間通ずるとき
は、前述した組成の塩素化弗素化アルミナまたは
塩素化弗素化アルミニウムが生成する。したがつ
て、そのときは、あたかも活性化アルミナまたは
塩化アルミニウムが本発明に係る転移反応を触媒
するかの如く挙動する。しかしこのときは、本発
明に係る触媒が生成したことによるものである。
以下、実施例で本発明を説明する。実施例にお
いて、異性体の確認は、赤外線分光分析およびマ
ススペクトル分析により行なつた。
比較例 １
活性アルミナ（水沢化学製ネオビードＣ−４、
４mmφ）を１・１・２−トリクロロ−１・２・２
−トリフルオロエタンで処理して得た塩素化フツ
素化アルミナ（重量組成：Al 49.8％、Cl 0.5
％、F9.5％、O40.2％）50c.c.をガラス製反応管
（直径24mm、長さ1000mm）に充填して、100℃に保
つた。窒素（200c.c.／分）およびCHClFCClF2
（60c.c.／分）を前記反応管の上部から反応管に導
入し、大気圧下に100℃で反応させ、反応管から
排出されたガスをガスクロマトグラフにより分析
した。結果はつぎの表のとおりであつた。
The present invention relates to a method for producing isomerized hydrogen-containing chlorofluorohydrocarbons, and more particularly, to subjecting hydrogen-containing chlorofluorohydrocarbons to a rearrangement reaction in the presence of a catalyst to produce solvents, refrigerants, aerosol propellants, and other useful materials. The present invention relates to a process for producing isomerized hydrogen-containing chlorofluorohydrocarbons which exhibit improved properties and are useful as intermediates for chemical compounds. Conventionally, for chlorofluorohydrocarbons that do not contain hydrogen (hereinafter referred to as hydrogen-free fluorocarbons), isomerized chlorofluorohydrocarbons have been obtained by carrying out a transfer reaction using aluminum chloride as a catalyst. However, in the case of hydrogen-containing chlorofluorohydrocarbons (hereinafter referred to as hydrogen-containing fluorocarbons), no transfer reaction occurs even when they are brought into contact with the aluminum chloride, and a decomposition reaction in which hydrogen chloride is eliminated occurs, resulting in the target being not reached. Very few isomers are produced. For example, when CHClFCClF 2 is brought into contact with aluminum chloride at room temperature, it reacts instantly, but hardly any CHCl 2 CF 3 is produced. An object of the present invention is to obtain hydrogen-containing fluorocarbon isomerized from hydrogen-containing fluorocarbon in good yield. According to the present invention, the above object can be achieved by isomerizing hydrogen-containing fluorocarbons by bringing the hydrogen-containing fluorocarbons into contact with a catalyst AlCl x F y O z and rearranging them. Thereby, the rearrangement reaction can proceed smoothly without decomposing the hydrogen-containing chlorofluorocarbon, and the desired isomer can be obtained in a good yield. The activity of the catalyst used in the present invention tends to decrease as the reaction progresses. For example, in the case of CHClFCClF 2 →CHCl 2 CF 3 , the reaction initially proceeds with almost 100% conversion, but after 2 hours, it stops proceeding at all. It is therefore an object of another aspect of the present invention to carry out the above-mentioned rearrangement reaction without causing a reduction in catalytic activity. This object can be achieved in the present invention by adding a chlorohydrocarbon or a chlorofluorohydrocarbon that does not contain hydrogen, that is, a perchlorohydrocarbon or a perchlorofluorohydrocarbon, to the hydrogen-containing fluorocarbon. Thereby, the catalyst activity can be maintained for a considerable period of time. For example, when CHClFClF 2 →CHCl 2 CF 3 , the activity persists for 10 or 20 hours. The catalyst used in the present invention is
AlCl x F y O z , where x+y+z=3, 0<x<3,
It is chlorinated fluorinated aluminum or chlorinated fluorinated alumina having the formula: 0<y<3, 0≦z<3/2. The specific weight composition is that chlorine is 0 based on the total weight.
%, usually more than 0.1% but not more than 5%, fluorine or more than 5% but not more than 64%, oxygen not less than 0% and not more than 67%, preferably chlorine 0.2-2.0%, fluorine 8-8%.
It is 60%. The catalyst used in the present invention is a known substance, and the method for producing it is as follows. Chlorinated aluminum fluoride is aluminum chloride, hydrogen fluoride, hydrofluoric acid, a fluorohydrocarbon or chlorofluorohydrocarbon having 4 or less carbon atoms, preferably 2 or less carbon atoms, such as CCl 3 F, CCl 2 FCCl 2 F,
It can be produced by reacting CCl 2 FCClF 2 . At this time, in the case of perfluorohydrocarbons, chlorohydrocarbons and chlorofluorohydrocarbons may be allowed to coexist, and in the case of chlorofluorohydrocarbons, chlorohydrocarbons may be allowed to coexist. The temperature condition is 0
°C to the sublimation point of aluminum chloride, preferably
The temperature is below the boiling point of the active substance. Specifically 0
℃~100℃. Chlorinated fluorinated alumina is prepared by adding chlorofluorohydrocarbons to activated alumina at 100-600℃ or fluorohydrocarbons and chlorohydrocarbons such as CCl 4 or chlorofluorohydrocarbons such as CCl 3 F, CCl 2 FCCl 2 F, CCl 2 It can be produced by reacting with FCClF 2 . Or 20~
Hydrogen fluoride at 450℃, sulfur fluoride ( SF4 , SF6, etc.), sulfuryl fluoride, thionyl fluoride at 300-500℃, ammonium fluoride (acidic ammonium fluoride, neutral fluoride) at 20-450℃ It can be produced by reacting with an inorganic fluoride (such as ammonium) and then reacting with a chlorofluorohydrocarbon or a chlorohydrocarbon. In the present invention, the hydrogen-containing chlorofluorohydrocarbon used as a starting material has 2 carbon atoms and 1 or 2 hydrogen atoms, and the others are aliphatic hydrocarbons substituted with chlorine or fluorine. For example,
CHClFCCl 2 F, CHClFCClF 2 and CHClFCHClF. These undergo the following transfer reaction. CHClFCCl 2 F→CHCl 2 CClF 2 CHClFCClF 2 →CHCl 2 CF 3 CHClFCHClF→CHCl 2 CHF 2 The temperature and pressure of the rearrangement reaction may be selected so that the starting material and target material are gases, and the maximum temperature is about 300°C. It is. The formation of liquid on the catalyst is undesirable because it reduces activity and the starting materials decompose at temperatures above about 300°C. Contact time depends on temperature, pressure and type of starting materials. Usually 0.02 minutes to 2 minutes. The coexistence of oxygen or air is effective in preventing a decrease in the activity of the catalyst due to precipitation of carbon atoms. The amount of coexisting oxygen is 0.1 mol% to 300 mol%, preferably, based on the starting material.
It is 1 mol% to 50 mol%. In one embodiment of the present invention, the perchlorohydrocarbon or perchlorofluorohydrocarbon is a saturated aliphatic hydrocarbon having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, in which all hydrogens have been replaced with chlorine or fluorine. . Under the transfer reaction conditions and at the partial pressure of the additive in the amount shown below, it is preferred that it exists in the form of a gas. Particularly preferred examples include carbon tetrachloride, trichlorofluoromethane, 1, 1, 2
-Trichloro-1,2,2-trifluoroethane, 1,1,1-trichloro-2,2,2-trifluoroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, 1. 1・1・2-
Tetrachloro-2,2-difluoroethane. The amount added should be at least 1 mole of starting material.
0.01 mole is required. Although there is no particular upper limit to the amount added, it is preferably 3 mol or less in view of industrially obtaining the target substance. Furthermore, when perchlorofluorohydrocarbon is passed through an activated alumina bed or aluminum chloride bed together with hydrogen-containing fluorocarbons at temperatures above 100°C for a considerable period of time, chlorinated fluorinated alumina or chlorinated fluorinated aluminum having the above-mentioned composition is produced. . Therefore, it then behaves as if activated alumina or aluminum chloride were catalyzing the transfer reaction according to the invention. However, this is due to the production of the catalyst according to the present invention. The present invention will be explained below with reference to Examples. In the examples, isomers were confirmed by infrared spectroscopy and mass spectrometry. Comparative Example 1 Activated alumina (Neobead C-4 manufactured by Mizusawa Chemical Co., Ltd.
4mmφ) to 1,1,2-trichloro-1,2,2
- Chlorinated fluorinated alumina obtained by treatment with trifluoroethane (weight composition: Al 49.8%, Cl 0.5
%, F9.5%, O4 0.2%) was filled into a glass reaction tube (diameter 24 mm, length 1000 mm) and kept at 100°C. Nitrogen (200c.c./min) and CHClFCClF 2
(60 c.c./min) was introduced into the reaction tube from the upper part of the reaction tube and reacted at 100° C. under atmospheric pressure, and the gas discharged from the reaction tube was analyzed by gas chromatography. The results were as shown in the table below.
【表】
実施例 １
比較例１で用いたのと同じ新たな塩素化フツ素
化アルミナを用いて、つぎの点を除き比較例１と
同様に操作した。
窒素（140c.c.／分）、CHClFCClF2（60c.c.／
分）およびCCl3F（60c.c.／分）を前記反応管の上
部から反応管に導入した。結果は、つぎの表のと
おりであつた。[Table] Example 1 Using the same new chlorinated fluorinated alumina as used in Comparative Example 1, the same procedure as in Comparative Example 1 was carried out except for the following points. Nitrogen (140c.c./min), CHClFCClF 2 (60c.c./min)
min) and CCl 3 F (60 c.c./min) were introduced into the reaction tube from the top of the reaction tube. The results were as shown in the table below.
【表】
比較例 ２
塩化アルミニウムを30℃の液状１・１・２−ト
リクロロ−１・２・２−トリフルオロエタンに浸
漬して乾操後、塩素５重量％を含有する塩素化弗
素化アルミニウムを得た。直径５mm、長さ５mmの
ペレツトに成形した。そのペレツト50c.c.を実施例
１と同じ反応管に充填して200℃に保つた。空気
（200c.c.／分）およびCHClFCClF2（60c.c.／分）
を通じて、前記反応管の上部から反応管に導入
し、反応管から排出されたガスを比較例１と同様
に分析した。結果は、つぎの表のとおりであつ
た。[Table] Comparative Example 2 After immersing aluminum chloride in liquid 1,1,2-trichloro-1,2,2-trifluoroethane at 30°C and drying it, chlorinated aluminum fluoride containing 5% by weight of chlorine was obtained. I got it. The pellets were formed into pellets with a diameter of 5 mm and a length of 5 mm. 50 c.c. of the pellets were filled into the same reaction tube as in Example 1 and kept at 200°C. Air (200c.c./min) and CHClFCClF 2 (60c.c./min)
The gas was introduced into the reaction tube from the upper part of the reaction tube through the reaction tube, and the gas discharged from the reaction tube was analyzed in the same manner as in Comparative Example 1. The results were as shown in the table below.
【表】
実施例 ２
比較例２で用いたのと同じ新たな塩素化弗素化
アルミニウムを用いて、つぎの点をを除き比較例
２と同様に操作した。空気（194c.c.／分）、
CHClFCClF2（60c.c.／分）およびCCl3F（６c.c.／
分）を通じた。ガスクロマトグラフ分析の結果
は、つぎの表のとおりであつた。[Table] Example 2 Using the same new chlorinated fluorinated aluminum as used in Comparative Example 2, the same procedure as in Comparative Example 2 was carried out except for the following points. Air (194c.c./min),
CHClFCClF 2 (60c.c./min) and CCl 3 F (6c.c./min)
minutes). The results of gas chromatography analysis were as shown in the table below.
Claims (1)
ロ炭化水素の共存下に、水素含有クロロフルオロ
炭化水素を、式AlClxFyOz（式中、ｘ＋ｙ＋ｚ
＝３、０＜ｘ＜３、０＜ｙ＜３、０≦ｚ＜3/2で
ある）で示される触媒に接触せしめて転位反応さ
せることを特徴とする異性化された水素含有クロ
ロフルオロ炭化水素の製法。1 Hydrogen-containing chlorofluorohydrocarbon in the coexistence of perchlorohydrocarbon or perchlorofluorohydrocarbon with the formula AlClxFyOz (where x+y+z
=3, 0<x<3, 0<y<3, 0≦z<3/2) isomerized hydrogen-containing chlorofluorocarbonization characterized by bringing the rearrangement reaction into contact with a catalyst. Hydrogen production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3630277A JPS53121710A (en) | 1977-03-30 | 1977-03-30 | Preparation of isomerized chlorofluorohydrocarbon containing hydrogne |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3630277A JPS53121710A (en) | 1977-03-30 | 1977-03-30 | Preparation of isomerized chlorofluorohydrocarbon containing hydrogne |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53121710A JPS53121710A (en) | 1978-10-24 |
| JPS6127375B2 true JPS6127375B2 (en) | 1986-06-25 |
Family
ID=12466014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3630277A Granted JPS53121710A (en) | 1977-03-30 | 1977-03-30 | Preparation of isomerized chlorofluorohydrocarbon containing hydrogne |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53121710A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1139269B (en) * | 1981-10-21 | 1986-09-24 | Montedison Spa | PROCESS FOR THE PREPARATION OF 1,1-DIALO-1,2,2,2-TETRAFLUOROETANI |
| GB8824571D0 (en) * | 1988-10-20 | 1988-11-23 | Ici Plc | Chemical process |
| US4902838A (en) * | 1988-12-28 | 1990-02-20 | E. I. Du Pont De Nemours And Company | Isomerization of saturated fluorohydrocarbons |
| US5157171A (en) * | 1989-10-16 | 1992-10-20 | E. I. Du Pont De Nemours And Company | Process for chlorofluoropropanes |
| JPH03284637A (en) * | 1990-03-31 | 1991-12-16 | Du Pont Mitsui Fluorochem Co Ltd | Isomerization of hydrochlorofluorocarbon |
| US5030372A (en) * | 1990-07-31 | 1991-07-09 | E. I. Du Pont De Nemours And Company | Catalytic equilibration to improve the relative yield of selected halocarbons |
| IT1251957B (en) * | 1991-10-18 | 1995-05-27 | Ausimont Spa | PROCEDURE FOR ISOMERIZING 1,1,2-TRIFLUORO-1,2-DICHLOROETHANE TO 1,1,1- TRIFLUORO-2,2, -DICHLOROETHANE |
| JP5598910B2 (en) * | 2010-06-14 | 2014-10-01 | 独立行政法人産業技術総合研究所 | Method for producing fluorine compound |
| JP7036024B2 (en) * | 2016-11-01 | 2022-03-15 | Ａｇｃ株式会社 | Method for isomerizing an organic compound and method for producing an isomer of an organic compound |
| CN113292392B (en) * | 2021-04-16 | 2022-10-28 | 台州益普高分子材料有限公司 | Rearrangement reaction between saturated hydrochlorofluorocarbons and method for preparing fluoroalcohol by using rearrangement reaction |
-
1977
- 1977-03-30 JP JP3630277A patent/JPS53121710A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53121710A (en) | 1978-10-24 |
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