JPH01301630A - Production of 1,1,1,2-tetrafluoroethane - Google Patents
Production of 1,1,1,2-tetrafluoroethaneInfo
- Publication number
- JPH01301630A JPH01301630A JP63132395A JP13239588A JPH01301630A JP H01301630 A JPH01301630 A JP H01301630A JP 63132395 A JP63132395 A JP 63132395A JP 13239588 A JP13239588 A JP 13239588A JP H01301630 A JPH01301630 A JP H01301630A
- Authority
- JP
- Japan
- Prior art keywords
- freon
- tetrafluoroethane
- hydrogen
- range
- reaction
- 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
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- BAMUEXIPKSRTBS-UHFFFAOYSA-N 1,1-dichloro-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Cl)Cl BAMUEXIPKSRTBS-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003507 refrigerant Substances 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 10
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- QCMJBECJXQJLIL-UHFFFAOYSA-L chromium(6+);oxygen(2-);difluoride Chemical compound [O-2].[O-2].[F-].[F-].[Cr+6] QCMJBECJXQJLIL-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本Ｑ明は１，１，２，Ｌ２−テトラフルオロエタン（以
下フロン１３４ａと記す）の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 1,1,2,L2-tetrafluoroethane (hereinafter referred to as Freon 134a).
フロン１３４ａは冷媒として有用な化合物である。Freon 134a is a compound useful as a refrigerant.
フロン１３４ａの製造方法としては、■１−クロロー２
．２．２− ）リフルオロエタンヲ酸化クロム触媒存
在下、無水フッ化水素を用いてフッ素化する方法（米国
特許第４，１２９，６０３号等）、■１−クロロー２．
２．２− トリフロロエタンをフッ化カリウムを用い
て液相下でフッ素化する方法（米国特許第４．３１Ｌ８
６３号）、■トリフルオロエチレンをオキシフッ化クロ
ム触媒存在下、無水フッ化水素と反応させる方法（特公
昭６２−２３７２８号）、■１，１−ジクロロー１、２
．２．２−テトラフルオロエタンを活性炭担持パラジウ
ム触媒の存在下、水素と反応させる方法（特公昭５６−
３８１３１号）、■１−クロローＬ２，２．２−テトラ
フルオロエタンを活性炭担持パラジウム触媒の存在下、
水素と反応させる方法（特公昭５６−３８１３１号）等
が知られている。The method for producing Freon 134a is as follows: ■1-Chloro2
．． 2.2-) Method of fluorinating refluoroethane using anhydrous hydrogen fluoride in the presence of a chromium oxide catalyst (US Pat. No. 4,129,603, etc.), ■1-chloro2.
2.2 - Fluorination of trifluoroethane with potassium fluoride in liquid phase (U.S. Pat. No. 4.31L8)
63), ■ A method of reacting trifluoroethylene with anhydrous hydrogen fluoride in the presence of a chromium oxyfluoride catalyst (Japanese Patent Publication No. 62-23728), ■ 1,1-dichloro 1,2
．． 2. A method of reacting 2-tetrafluoroethane with hydrogen in the presence of a palladium catalyst supported on activated carbon (Japanese Patent Publication No. 1983-
38131), ■ 1-chloroL2,2,2-tetrafluoroethane in the presence of an activated carbon-supported palladium catalyst,
A method of reacting with hydrogen (Japanese Patent Publication No. 56-38131) is known.
しかしながら、■の方法は収率が約１０〜３０％と低い
こと、■の方法は、高温、高圧での反応であり、また塩
化カリウムが剛性すること、■、■の方法では収率が高
い（約９５〜９９％）ものの原料のトリフロロエチレン
、１−クロロ−Ｌ２，２．２−テトラフルオロエタンが
高価であることから必ずしも工集的に有利な製造法とは
言えないものである。However, method (■) has a low yield of about 10 to 30%, method (■) requires a reaction at high temperature and high pressure, and potassium chloride is rigid, and methods (■) and (■) have a high yield. (approximately 95 to 99%) Since the raw materials trifluoroethylene and 1-chloro-L2,2,2-tetrafluoroethane are expensive, it cannot necessarily be said that this is an industrially advantageous manufacturing method.
また、■については、フロン１３４ａの収率は約７２％
であるものの選択率は約７８％と低く、副生物であるＬ
ｌ、１−１−リフルオロエタン（フロン１４３ａと記す
。沸点−４７，６°Ｃ）、フロン１３４ ａの前駆体で
ある１−クロロ−１，２，２，２−テトラフルオロエタ
ン（フロン１２４と記す。沸点−１２°Ｃ）が各々約１
０％程度生成する。また、原料中に異性体である１、２
−ジクＩコロー１．，１，２．２−テトラフルオロエタ
ン（フロン１１４と記す。）が存在すると、１，１゜２
．２−テトラフルオロエタン（フロン１３４と記す。Regarding ■, the yield of Freon 134a is approximately 72%.
However, the selectivity of the by-product L is as low as about 78%.
l, 1-1-lifluoroethane (referred to as Freon 143a, boiling point -47.6°C), 1-chloro-1,2,2,2-tetrafluoroethane (referred to as Freon 124), which is a precursor of Freon 134a. Boiling point -12°C) is approximately 1
About 0% is generated. In addition, there are isomers 1 and 2 in the raw materials.
-Jiku I Coro 1. , 1,2.2-tetrafluoroethane (denoted as Freon 114), 1,1°2
．． 2-Tetrafluoroethane (referred to as Freon 134).
沸点−１９，７°Ｃ）、１−クロロ−１，Ｌ２，２−テ
トラフルオロエタン（フロン１２４ａと記ず。沸点−１
０，２’ｃ ＞が副生ずる。通常フロン１１４ａは１，
１．２−トリクロロ−１，２，２−トリフルトロエタン
（フロン１１３と記す。） 、１，１．１．− ）ジク
ロロ−２，２，２−トリフルオロエタン（フロン１１３
ａと記す。）と無水フッ化水素との反応により工業的に
製造されるが約１０〜２５％のフロン１１４の混入は避
けられない。Boiling point -19.7°C), 1-chloro-1,L2,2-tetrafluoroethane (noted as Freon 124a. Boiling point -1
0,2'c> is produced as a by-product. Usually Freon 114a is 1,
1.2-Trichloro-1,2,2-triflutroethane (referred to as Freon 113), 1,1.1. -) Dichloro-2,2,2-trifluoroethane (Freon 113
It is written as a. ) and anhydrous hydrogen fluoride, but the contamination of about 10 to 25% Freon 114 is unavoidable.
また、反応生成物中に目的物であるフロン１３４ａ（沸
点−２６，５°Ｃ）と沸点の近いフロン１３４、フロン
１２４、フロン１２４ａが含まれると、分離、精製十問
題があり、フロン１３４ａを効率よく製造することがで
きない。例えば、通常の蒸留法では、フロン１３４ａと
フロン１２４との分離、精製には約４０段の蒸留塔が必
要となり、この場合、フロン１３４ａとフロン１３４、
フロン１２４とフロン１２４ａは分離できない。このた
め、フロン１３４ａの純度およびフロン１２４の反応系
への再循環という点で問題が生じる。In addition, if the reaction product contains Freon 134, Freon 124, and Freon 124a, which have boiling points close to the target product Freon 134a (boiling point -26.5°C), there will be problems in separation and purification. cannot be manufactured efficiently. For example, in a normal distillation method, approximately 40 stages of distillation columns are required to separate and purify the Freon 134a and the Freon 124.
Freon 124 and Freon 124a cannot be separated. Therefore, problems arise in terms of the purity of the Freon 134a and the recirculation of the Freon 124 to the reaction system.
本発明者らは、かかる従来技術の問題に鑑み、鋭意検討
の結果フロン１１４を含有するフロン１１４ａを出発原
料として高選択率でフロン１３４ａを製造できる方法を
見出したものである。すなわち本発明は１，２−ジクロ
ロ−１，Ｌ２，２−テトラフルオロエタンを含む１１１
−ジクロロ−Ｌ２．２．２−テトラフルオロエタンを活
性アルミナ担持パラジウム触媒の存在下、１２０℃から
２００°Ｃ未満の温度範囲で水素と反応させることを特
徴とする１，１，２，Ｌ２−テトラフルオロエタンの製
造法である。In view of the problems of the prior art, the inventors of the present invention have conducted intensive studies and discovered a method that allows the production of fluorocarbon 134a with high selectivity using fluorocarbon 114a containing fluorocarbon 114 as a starting material. That is, the present invention provides 111 containing 1,2-dichloro-1,L2,2-tetrafluoroethane.
1,1,2,L2- characterized by reacting 2-dichloro-L2.2-tetrafluoroethane with hydrogen in the presence of an activated alumina-supported palladium catalyst in the temperature range from 120°C to less than 200°C. This is a method for producing tetrafluoroethane.
本発明において使用するフロン１１４ａ中のフロン１１
４の含有量は約１０〜２５％の範囲が好ましい。２５％
以上になるとフロン１３４ａの収率が低くなる。また、
１０％以下のものは工業的に製造することが困難である
。本発明はフロン１１４を含有した原料を用いてフロン
１１４ａの転化率を大きくするとともに、フロン１１４
が反応してフロン１２４ａおよびさらに水素化されたフ
ロン１３４を生成することを防いで、目的のフロン１３
４ａの収率を可及的に大きくするために、特定の温度範
囲すなわち１２０℃から２００℃未満の温度範囲をとる
ものである。また、水素化触媒としてはパラジウム触媒
が好ましく、特に活性アルミナに担持して使用する。活
性炭担持触媒も活性は十分であるが、目的のフロン１３
４ａの選択率を高くすることができない。パラジウムの
担持量は特に限定されないが０．２〜５％の範囲が好ま
しい。また、原料であるフロン１．１４ａ、フロン１１
４で前処理し活性アルミナを部分的にフッ素化すること
により過水素化されたフロン１４３ａの生成量を低く抑
えることができるものである。前処理の条件は２００℃
以上で２０時間程度が好ましい。ちなみに反応条件にも
よるが、前処理をおこなった触媒を用いた場合と未処理
の触媒を用いた場合では反応生成物中のフロン１４３ａ
の量は前者が４〜６％であるのに対して後者では１０％
程度と約２倍である。水素の量は原料のフロン１１４ａ
とフロン１１４の混合物に対してモル比で２〜４倍の範
囲が好ましく、２倍以下では反応率が低くなり、フロン
１３４ａの収率は低下する。また、４倍以上では反応率
は変わらないが水素の回収を考えると好ましくない。反
応温度は、１２０℃から２００℃未満が好ましく１２０
°Ｃ以下では反応率が低くフロン１３４ａの収量が低く
好ましくない。また、２００°Ｃ以上ではフロン１２４
ａ、さらにはフロン１３４の生成量が増大し、フロン１
３４ａの選択率が低くなり好ましくない。Freon 11 in Freon 114a used in the present invention
The content of 4 is preferably in the range of about 10 to 25%. 25%
If the amount exceeds that amount, the yield of Freon 134a will decrease. Also,
If it is less than 10%, it is difficult to produce it industrially. The present invention uses a raw material containing Freon 114 to increase the conversion rate of Freon 114a, and also increases the conversion rate of Freon 114a.
The target fluorocarbon 13 is prevented from reacting to produce fluorocarbon 124a and further hydrogenated fluorocarbon 134.
In order to maximize the yield of 4a, a specific temperature range, ie, a temperature range from 120°C to less than 200°C, is adopted. Further, as the hydrogenation catalyst, a palladium catalyst is preferable, and in particular, it is used supported on activated alumina. Activated carbon-supported catalyst also has sufficient activity, but the target CFC 13
It is not possible to increase the selectivity of 4a. The amount of palladium supported is not particularly limited, but is preferably in the range of 0.2 to 5%. In addition, the raw materials Freon 1.14a and Freon 11
By pre-treating with Step 4 and partially fluorinating activated alumina, the amount of perhydrogenated Freon 143a produced can be suppressed to a low level. Pretreatment conditions are 200℃
The above time period is preferably about 20 hours. By the way, although it depends on the reaction conditions, CFC 143a in the reaction product is different when a pretreated catalyst is used and when an untreated catalyst is used.
The amount of is 4-6% in the former, but 10% in the latter.
It is about twice as large as the average. The amount of hydrogen is the raw material Freon 114a
The molar ratio is preferably in the range of 2 to 4 times that of the mixture of fluorocarbon 134a and chlorofluorocarbon 114. If the molar ratio is less than 2 times, the reaction rate becomes low and the yield of fluorocarbon 134a decreases. In addition, if it is 4 times or more, the reaction rate will not change, but this is not preferable in terms of hydrogen recovery. The reaction temperature is preferably from 120°C to less than 200°C.
If the temperature is below 0.degree. C., the reaction rate is low and the yield of Freon 134a is low, which is not preferable. In addition, at temperatures above 200°C, Freon 124
a, and the amount of fluorocarbon 134 generated increases, resulting in fluorocarbon 1
The selectivity of 34a becomes low, which is not preferable.
接触時間は５〜３０秒の範囲が好ましく、５秒以下では
反応率が低く、フロン１３４ａの収率は低下する。また
、３０秒以上では触媒単位当たりのフロン１３４ａの収
率が低下する。このようにして得られたフロン１３４ａ
は通常、公知の方法、例えば蒸留等により分離、精製す
ることができ、前駆体のフロン１２４は反応系に再循環
される。The contact time is preferably in the range of 5 to 30 seconds; if the contact time is 5 seconds or less, the reaction rate is low and the yield of Freon 134a is decreased. Further, if the heating time is longer than 30 seconds, the yield of Freon 134a per catalyst unit decreases. Freon 134a obtained in this way
can be usually separated and purified by a known method such as distillation, and the precursor Freon 124 is recycled to the reaction system.
以下、本発明を実施例によりさらに具体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１〜４
長さ３０ｃｍ、内径２．５ ｃｍの耐熱ガラス反応管内
に３ｍｍφの球状γ−アルミナ上に担持されたパラジウ
ム触媒（担持量０．５または５重量％） １００ ｃｃ
を充填し、電気炉内に設置した。Examples 1 to 4 Palladium catalyst (supported amount: 0.5 or 5% by weight) 100 cc supported on 3 mmφ spherical γ-alumina in a heat-resistant glass reaction tube with a length of 30 cm and an inner diameter of 2.5 cm.
was filled and placed in an electric furnace.
約１時間、３００〜３５０°Ｃの温度で水素を１００
ｃｃ／ｍｉｎの流量で送入した後、フロン１１４ａとフ
ロン１１４の混合ガスで２００°Ｃｌ２Ｏ時間前処理し
た。次いで所定反応温度とし、水素とジクロロテトラフ
ルオロエタン（フロン１１４ａ／フロン］、 １４．
＝７５ ／２５重量％）を各々１９８ ｃｃ／ｍｉｎ
、 ６６ｃｃ／ｍｉｎ の流量で導入した（Ｈ２／ジク
ロロテトラフルオロエタン−３／１モル比）。100% hydrogen at a temperature of 300-350°C for about 1 hour.
After feeding at a flow rate of cc/min, pretreatment was carried out for 200°CCl2O hours with a mixed gas of Freon 114a and Freon 114. Next, the reaction temperature is set to a predetermined temperature, and hydrogen and dichlorotetrafluoroethane (Freon 114a/Freon) are added.14.
=75/25% by weight) at 198 cc/min each
, at a flow rate of 66 cc/min (H2/dichlorotetrafluoroethane - 3/1 molar ratio).
反応生成物は水洗浄後、排ガス中の有機物質をガスクロ
マトグラフィーにより分析した。反応条件、結果を第１
表に示した。After washing the reaction product with water, organic substances in the exhaust gas were analyzed by gas chromatography. First, check the reaction conditions and results.
Shown in the table.
比較例１
触媒を活性炭（２ｍｍφＸ５ｍｍＨ１円柱状）上に担持
されたパラジウム触媒（担持量０．５重量％）とするほ
かは実施例３と同様にして反応をおこなった。この結果
を第１表に示した。Comparative Example 1 A reaction was carried out in the same manner as in Example 3, except that the catalyst was a palladium catalyst (carrying amount: 0.5% by weight) supported on activated carbon (2 mm φ x 5 mm H 1 cylindrical). The results are shown in Table 1.
比較例２．３
反応温度２００°Ｃ１接触時間２８秒（比較例２）、反
応温度２５０℃、接触時間２６秒（比較例３）とするほ
かは実施例１と同様にして反応をおこなった。Comparative Example 2.3 A reaction was carried out in the same manner as in Example 1, except that the reaction temperature was 200° C. and the contact time was 28 seconds (Comparative Example 2), and the reaction temperature was 250° C. and the contact time was 26 seconds (Comparative Example 3).
この結果を第１表に示した。The results are shown in Table 1.
本発明においては工業的に容易に得られるフロン１１４
を含有するフロン１１４ａを原料とし、反応温度を制御
することにより収率よく目的のフロン１３４ａを得るこ
とができるものである。In the present invention, Freon 114, which is easily obtained industrially,
By using Freon 114a containing chlorofluorocarbons as a raw material and controlling the reaction temperature, the desired Freon 134a can be obtained in good yield.
Claims (1)
エタンを含む１，１−ジクロロ−１，２，２，２−テト
ラフルオロエタンを活性アルミナ担持パラジウム触媒の
存在下、１２０℃から２００℃未満の温度範囲で水素と
反応させることを特徴とする１，１，１，２−テトラフ
ルオロエタンの製造法。1,1-dichloro-1,2,2,2-tetrafluoroethane containing 1,2-dichloro-1,1,2,2-tetrafluoroethane was heated from 120°C to 200°C in the presence of an activated alumina-supported palladium catalyst. 1. A method for producing 1,1,1,2-tetrafluoroethane, which comprises reacting with hydrogen in a temperature range below °C.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63132395A JPH0629201B2 (en) | 1988-05-30 | 1988-05-30 | Method for producing 1,1,1,2-tetrafluoroethane |
| US07/357,291 US4996379A (en) | 1988-05-30 | 1989-05-26 | Method of preparing 1,1,1,2-tetrafluoroethane from 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| FR8907005A FR2631959A1 (en) | 1988-05-30 | 1989-05-29 | PROCESS FOR THE PREPARATION OF 1,1,1,2-TETRAFLUOROETHANE FROM 1,1-DICHLORO-1,2,2,2-TETRAFLUOROETHANE |
| IT8920692A IT1230795B (en) | 1988-05-30 | 1989-05-30 | PROCEDURE FOR PREPARING 1,1,1,2 TETRAFLUOROETHANE FROM 1,1 DICHLOR 1,2,2,2 TETRAFLUOROETHANE. |
| GB8912325A GB2219796B (en) | 1988-05-30 | 1989-05-30 | Method of preparing 1,1,1,2-tetrafluoroethane from 1,1-dichloro-1,2,2,2-tetrafluoroethane |
| DE3917573A DE3917573A1 (en) | 1988-05-30 | 1989-05-30 | METHOD FOR PRODUCING 1,1,1,2-TETRAFLUORETHANE FROM 1,1-DICHLOR-1,2,2,2-TETRAFLUORETHANE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63132395A JPH0629201B2 (en) | 1988-05-30 | 1988-05-30 | Method for producing 1,1,1,2-tetrafluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01301630A true JPH01301630A (en) | 1989-12-05 |
| JPH0629201B2 JPH0629201B2 (en) | 1994-04-20 |
Family
ID=15080388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63132395A Expired - Lifetime JPH0629201B2 (en) | 1988-05-30 | 1988-05-30 | Method for producing 1,1,1,2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629201B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638131A (en) * | 1979-09-06 | 1981-04-13 | Kawasaki Heavy Ind Ltd | Contact method betweeen solid and liquid |
| US4319060A (en) * | 1980-12-08 | 1982-03-09 | Allied Chemical Corporation | Process for producing 1,2-dichloro-1,1,2,2-tetrafluoroethane substantially free of 1,1-dichloro-1,2,2,2-tetrafluoroethane |
-
1988
- 1988-05-30 JP JP63132395A patent/JPH0629201B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638131A (en) * | 1979-09-06 | 1981-04-13 | Kawasaki Heavy Ind Ltd | Contact method betweeen solid and liquid |
| US4319060A (en) * | 1980-12-08 | 1982-03-09 | Allied Chemical Corporation | Process for producing 1,2-dichloro-1,1,2,2-tetrafluoroethane substantially free of 1,1-dichloro-1,2,2,2-tetrafluoroethane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0629201B2 (en) | 1994-04-20 |
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