JPH02172933A - Method for fluorinating 1-chloro-2,2,2-trifluoroethane - Google Patents
Method for fluorinating 1-chloro-2,2,2-trifluoroethaneInfo
- Publication number
- JPH02172933A JPH02172933A JP63323668A JP32366888A JPH02172933A JP H02172933 A JPH02172933 A JP H02172933A JP 63323668 A JP63323668 A JP 63323668A JP 32366888 A JP32366888 A JP 32366888A JP H02172933 A JPH02172933 A JP H02172933A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- trifluoroethane
- chloro
- reaction
- amount
- 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
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 150000004820 halides Chemical class 0.000 claims abstract description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 239000011651 chromium Substances 0.000 abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910001055 inconels 600 Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-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 1
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 1
- 239000011475 Accrington brick Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000931705 Cicada Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 101000762967 Homo sapiens Lymphokine-activated killer T-cell-originated protein kinase Proteins 0.000 description 1
- 102100026753 Lymphokine-activated killer T-cell-originated protein kinase Human genes 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000206608 Pyropia tenera Species 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は１．１．１．２−テトラフルオロエタン（Ｒ−
１３４ａ）の製造方法に関するものである。Ｒ−１３４
ａは、オゾン層を破壊する疑いのあるジクロロジフルオ
ロエタン（Ｒ−１２つの代替品として冷媒等への使用が
検討されている。Detailed Description of the Invention [Industrial Application Field] The present invention relates to 1.1.1.2-tetrafluoroethane (R-
134a). R-134
a is dichlorodifluoroethane (R-12), which is suspected of destroying the ozone layer, and its use as a refrigerant is being considered as a substitute for R-12.
［従来の技術及び問題点コ
従来より、１−クロロ−２，２，２−トリフルオロエタ
ン（Ｒ−１３３ａ）の気相フッ素化反応に、酸化クロム
、フッ化クロムなどが触媒として有効であることが知ら
れている０例えば、米国特許第４１２９６０３号明細書
、西ドイツ特許２９３２２９３４号などを参照、しかる
に従来の触媒には、触媒寿命が短いという厨久性での難
点、および反応活性が低いという難点がある。このフッ
素化反応は平衡反応であり、その平衡は原糸に片寄って
いる。[Prior art and problems] Conventionally, chromium oxide, chromium fluoride, etc. have been effective as catalysts in the gas phase fluorination reaction of 1-chloro-2,2,2-trifluoroethane (R-133a). For example, see U.S. Pat. No. 4,129,603, West German Patent No. 2,932,934, etc. However, conventional catalysts have problems with durability such as short catalyst life and low reaction activity. There are some difficulties. This fluorination reaction is an equilibrium reaction, and the equilibrium is biased towards the filament.
ＣＦｓＣＨ２Ｃ１＋ＨＦ；’ＣＦｓＣＨ２Ｆ＋ＨＣ１こ
の平衡を生成系へ移動させるためには、反応温度を高く
すること、また供給ＨＦ／Ｒ−１３３ａモル比を高くす
ることが必要である。しかし反応温度が高いと触媒寿命
が短くなること、ＨＦ／Ｒ−１３３ａ供給比率を高くす
ると単位体積当りのＲ−１３４ａ収率が低下し実用触媒
として問題が生じるたぬｚれらの方策は必ずしも効果的
ではない。CFsCH2C1+HF;'CFsCH2F+HC1 In order to shift this equilibrium to the production system, it is necessary to increase the reaction temperature and the feed HF/R-133a molar ratio. However, if the reaction temperature is high, the catalyst life will be shortened, and if the HF/R-133a supply ratio is increased, the R-134a yield per unit volume will decrease, causing problems as a practical catalyst. Not effective.
〔問題点を解決するための手段］
本発明者は、気相フッ素化に作用する触媒成分としてク
ロムを用いた系について戸々の検討を重ねた結果、Ｃｒ
とともにＡＩ、 Ｍｇ、 Ｃａ、 Ｂａ、Ｓｒ、
Ｆｅ、Ｎｉ、Ｃｏ、およびＭｎからなる群から選ば
れる少なくとも１種の元素を含むハロゲン化物または酸
化物からなるフッ素化触媒が有効であることを見いだｊ
７た。[Means for Solving the Problems] As a result of repeated studies on systems using chromium as a catalyst component that acts on gas phase fluorination, the inventor found that Cr
Along with AI, Mg, Ca, Ba, Sr,
It has been discovered that a fluorination catalyst consisting of a halide or oxide containing at least one element selected from the group consisting of Fe, Ni, Co, and Mn is effective.
7.
すなわち本発明はフッ素化に作用する触媒成分としてＣ
ｒとともに、Ａｌ、Ｍｇ、 Ｃａ、Ｂａ、Ｓｒ、
Ｆｅ、 Ｎｉ、Ｃｏ、およびＭｎからなる群から選ば
れる少なくとも１種の元素を含むハロゲン化＃＠または
酸化物触媒の存在下、 １−クロロ−２゜２２−トリフ
ルオロエタン（Ｒ−１３３ａ＞を気相フッ素化する方法
を新規に提供するものである。That is, the present invention uses C as a catalyst component that acts on fluorination.
Along with r, Al, Mg, Ca, Ba, Sr,
In the presence of a halogenated #@ or oxide catalyst containing at least one element selected from the group consisting of Fe, Ni, Co, and Mn, 1-chloro-2゜22-trifluoroethane (R-133a> The present invention provides a new method for vapor phase fluorination.
本発明方法によれば、酸化クロム単独に比して、耐久性
が著しく向上する。さらに活性の点でも優れている９例
えば、酸化クロム触媒では、反応温度が比較的低い場合
には）・ン素化活性が不十分であり、高温にすると結晶
化が進行して触媒耐久性が著しく低下する。これに対し
て、本発明においては、比Ｉ咬的低い温度でも高活性を
維持することが可能である。また、耐久性についても酸
化クロム単独では２週間程度の分合であるのに対して、
本発明においては弁台が６ケ月以上と大幅に改善される
。さらに、従来の３５０から４００℃程度の反応温度よ
りも低い、３００から３５０°Ｃ程度の温度でも、比較
的高いフッ素化活性が得られる。According to the method of the present invention, durability is significantly improved compared to using chromium oxide alone. Furthermore, chromium oxide catalysts are superior in terms of activity.9 For example, when the reaction temperature is relatively low, the chromium oxidation activity is insufficient, and when the reaction temperature is raised, crystallization progresses and the catalyst durability deteriorates. Significantly decreased. In contrast, in the present invention, high activity can be maintained even at relatively low temperatures. In addition, regarding durability, chromium oxide alone only lasts about two weeks.
In the present invention, the valve stand is significantly improved to last more than 6 months. Furthermore, relatively high fluorination activity can be obtained even at a temperature of about 300 to 350°C, which is lower than the conventional reaction temperature of about 350 to 400°C.
以下、反応の詳細について説明する。The details of the reaction will be explained below.
本発明におけるフッ素化触媒としては、Ｃｒとともに、
Ａｌ、Ｍｇ、 Ｃａ、Ｂａ、 Ｓｒ、 Ｆｅ、Ｎ
ｉ、Ｃｏ、およびＭｎからなる群から遷ばれる少なくと
も１種の元素を含むハロゲン化物または酸化物が使用で
きる。上記のあらゆる触媒は、反応に供せられる前にフ
ッ化水素やＲ−１１，Ｒ−１１３など、少なくともフッ
素原子を１個含むハロゲン化メタン、ハロゲン化エタン
等により活性化しておくことが望ましい。As the fluorination catalyst in the present invention, together with Cr,
Al, Mg, Ca, Ba, Sr, Fe, N
Halides or oxides containing at least one element from the group consisting of i, Co, and Mn can be used. All of the above catalysts are preferably activated with hydrogen fluoride, R-11, R-113, halogenated methane, halogenated ethane, etc. containing at least one fluorine atom, before being subjected to the reaction.
反応温度は気相中常圧もしくは加圧下で、２００℃〜５
５０℃、特に好ましくは、２５０℃〜４００°Ｃの温度
範囲で行なうことが適当である０反応源度が高すぎると
触蝉寿命が短くなり、反応温度が低すぎるとＲ−１３４
ａ収量が低下する。The reaction temperature is 200°C to 5°C in the gas phase at normal pressure or under increased pressure.
It is appropriate to conduct the reaction at a temperature range of 50°C, particularly preferably from 250°C to 400°C. If the reaction temperature is too high, the lifespan of the cicada will be shortened, and if the reaction temperature is too low, R-134
a Yield decreases.
接触時間は、通常０．１〜３００秒、特に好ましくは５
〜３０秒である。The contact time is usually 0.1 to 300 seconds, particularly preferably 5 seconds.
~30 seconds.
フッ化水素とＲ−１３３ａの割合は大幅に変動させ得る
。しかしながら通常、化学量論量から３等量のフッ化水
素を使用して塩素原子を置換する。The proportions of hydrogen fluoride and R-133a can vary widely. However, stoichiometric to 3 equivalents of hydrogen fluoride are usually used to replace the chlorine atoms.
出発物質の全モル数に対して、化学量論量よりかなり多
い量、例えば５モルまたはそれ以上のフッ化水素を使用
し得る。この場合Ｒ−１３３ａの平衡反応率は向上する
が、単位体積あたりの収量は低下する。Significantly more than stoichiometric amounts of hydrogen fluoride may be used, for example 5 moles or more, based on the total number of moles of starting materials. In this case, the equilibrium reaction rate of R-133a improves, but the yield per unit volume decreases.
また酸素または塩素をＲ−１３３ａに対して０゜１〜１
０％共存させて反応を行なうこともできる。Also, add oxygen or chlorine to R-133a at 0°1 to 1
The reaction can also be carried out with 0% coexistence.
［実施例〕 以下、本発明の実施例を示す。[Example〕 Examples of the present invention will be shown below.
調製例１
１１００ｇの特級試薬Ａ Ｉ ＜ Ｎ Ｏｘ） ３ ・
９ Ｈ２Ｏ，１２５ｇのＣｒ （ＮＯｘ） ３・９Ｈ２
０、および４０ｇのＭｇ（ＮＯ３）ｐ・６Ｈ２０を２．
５リツトルの水に溶解し、これと２８％の水酸化アンモ
ニウムの水溶液２０００ｇを攪拌しながら、加熱した４
リツトルの水に添加して水酸化物の沈殿を得た。Preparation example 1 1100 g of special grade reagent A I < N Ox) 3 ・
9 H2O, 125g Cr (NOx) 3.9H2
0, and 40 g of Mg(NO3)p.6H20 2.
It was dissolved in 5 liters of water and heated while stirring this and 2000 g of a 28% ammonium hydroxide aqueous solution.
Addition to a liter of water resulted in a hydroxide precipitate.
これを炉別し、純水による洗浄、および乾燥を行なった
後、４５０℃で５時間焼成して酸化物の粉末を得た。こ
れを打錠成型機を用いて直径５ｍｍ、高さ５ｍｍの円筒
状に成型した。こうして得た触媒を反応前にフッ化水素
／窒素の混合ガス気流中、２５０〜３５０°Ｃでフッ素
化した後、さらにトリクロロフルオロメタン／フッ化水
素混合ガス気流中、２５０〜３００℃で塩素化フッ素化
して、活性化した。This was separated into a furnace, washed with pure water, and dried, and then fired at 450° C. for 5 hours to obtain an oxide powder. This was molded into a cylindrical shape with a diameter of 5 mm and a height of 5 mm using a tablet molding machine. The catalyst thus obtained is fluorinated at 250 to 350°C in a hydrogen fluoride/nitrogen mixed gas stream before the reaction, and then chlorinated at 250 to 300°C in a trichlorofluoromethane/hydrogen fluoride mixed gas stream. Fluorinated and activated.
調製例２〜４
Ｍｇ （ＮＯ３）２・６Ｈ２０のかわりに、それぞれＢ
ａ（ＮＯ３＞２の４０ｇ、Ｓｒ （ＮＯ３）２の５０ｇ
、Ｃａ （Ｎ Ｏｓン ・４ＨｚＯの４０ｇを用し）る
他は、調製例１と同様にして触媒を調製した。Preparation Examples 2 to 4 Instead of Mg (NO3)2 and 6H20, B
a (40g of NO3>2, 50g of Sr (NO3)2
A catalyst was prepared in the same manner as in Preparation Example 1, except that 40 g of , Ca (N Osn .4HzO) was used.
調製例５
Ａ Ｉ （Ｎｏｗ）ｚ・９Ｈ２０，Ｃｒ （ＮＯり ３
・９Ｈ２０、およびＭ ｇ （Ｎｏｗ） ２・６ Ｈ２
Ｏ１）かわりに、 Ｆｅ （ＮＯ３） ２・９１−１
２０の６００ｇ、Ｃｒ（Ｎ ０３） ｓ ・９ Ｈ２０
ノ１５０ ｇ ｔ”用イル他ハ、１ｌｌ１例１と同様に
して触媒を調製した。Preparation example 5 A I (Now)z・9H20, Cr (NOri 3
・9H20, and M g (Now) 2・6 H2
O1) Instead, Fe (NO3) 2・91-1
600g of 20, Cr(N 03) s 9 H20
A catalyst for 150 g t'' was prepared in the same manner as in Example 1.
調製例６
Ａ Ｉ （ＮＯ３） ｓ・９Ｈ２０，Ｃｒ （Ｎｏｔ）
ａ・９Ｈ２０、およびＭｇ （ＮＯ３） ２・６Ｈ２
０のかわりに、 Ｃｒ （ＮＯ３） ３・９Ｈ２０の
１５０ｇ、 ＡＩ（Ｎｏｔ）ｔ・９Ｈ２０の１３００ｇ
を用いる他は、調製例１と同様にして触媒を調製した。Preparation example 6 A I (NO3) s・9H20, Cr (Not)
a・9H20, and Mg (NO3) 2・6H2
Instead of 0, 150g of Cr (NO3) 3・9H20, 1300g of AI(Not)t・9H20
A catalyst was prepared in the same manner as in Preparation Example 1, except that the following was used.
調製例７
ＡＩ （Ｎｏりｓ・９Ｈ２０、Ｃｒ （ＮＯｓ） ３
・９Ｈ２０およびＭ ｇ （Ｎ０３） ２ ・６ Ｈｐ
Ｏツカわりに、Ｃｒ （ＮＯ３） ３・９Ｈ２０の５０
０ｇ、 Ｍｇ（Ｎ０３）？・６Ｈ２０の１６０ｇを用
いる他は、調製例１と同様にして触媒を調製した。Preparation Example 7 AI (Noris・9H20, Cr (NOs) 3
・9H20 and M g (N03) 2 ・6 Hp
50 of Cr (NO3) 3.9H20 instead of O
0g, Mg(N03)? - A catalyst was prepared in the same manner as in Preparation Example 1, except that 160 g of 6H20 was used.
調製例８
ＣｒＣＩａ・６Ｈ２０の２００ｇを２リツトルの水に溶
解した。この溶液に、市販のγ−アルミナ１０００ｇを
投入した後乾燥させて水分を除去した。Preparation Example 8 200 g of CrCIa.6H20 was dissolved in 2 liters of water. To this solution, 1000 g of commercially available γ-alumina was added and dried to remove water.
さらに調製例１と同様の活性化方法により活性化した。Furthermore, activation was performed using the same activation method as in Preparation Example 1.
比較調製例
水酸化クロムを打錠成型機を用いて直径５ｍｍ、高さ５
ｍｍの円筒状に成型した。こうして得た触媒を反応前に
フッ化水素／窒素の混合ガス気流中、３００〜４５０℃
でフッ素化して活性化しな。Comparative Preparation Example Chromium hydroxide was made into tablets with a diameter of 5 mm and a height of 5 mm.
It was molded into a cylindrical shape of mm. The thus obtained catalyst was heated at 300 to 450°C in a hydrogen fluoride/nitrogen mixed gas stream before the reaction.
Activate it by fluoridating it.
実施例１
内径２．５４ｃｍ、長さ１００ｃｍのインコネル６００
製Ｕ字型反応管に調製例１で示したように調製した触媒
を２００ｍ１充填し反応させた。ガス化させた１−クロ
ロ−２，２，２−トリフルオロエタン（Ｒ−１３３ａ）
を１００ｍ１／分で、酸素を２ｍｌ／分で、フッ酸を３
００ｍ１／分で供給し、３５０℃に保持した。酸分を除
去した後のガス組成をガスクロを用いて分析した。その
結果、反応を連続して行い、１週間後の成績はＲ−１３
３ａ転化率２０％、Ｒ−１３４ａ選択率９６％であった
。６力月間同一条件で反応させた後、同様の分析を行な
ったところ、Ｒ−１３３ａ転化率１８％、Ｒ−１３４ａ
選択率９４％の成績を得た。Example 1 Inconel 600 with an inner diameter of 2.54 cm and a length of 100 cm
A U-shaped reaction tube was filled with 200 ml of the catalyst prepared as shown in Preparation Example 1 and reacted. Gasified 1-chloro-2,2,2-trifluoroethane (R-133a)
at 100 ml/min, oxygen at 2 ml/min, and hydrofluoric acid at 3 ml/min.
00ml/min and maintained at 350°C. The gas composition after acid content was removed was analyzed using gas chromatography. As a result, the reaction was performed continuously, and the result after one week was R-13.
The conversion rate of 3a was 20%, and the selectivity of R-134a was 96%. After reacting under the same conditions for 6 months, similar analysis was performed, and the conversion rate of R-133a was 18%, and the R-134a conversion rate was 18%.
A selection rate of 94% was obtained.
実施例 ２〜８
調製例２〜８で調製した触媒を使用して、反応温度を変
更する他は実施例１と同様の条件で、それぞれ反応を行
なった０反応開始後１週間の時点での反応成績と６力月
後の反応成績をまとめて第１表に示す。Examples 2 to 8 Using the catalysts prepared in Preparation Examples 2 to 8, the reactions were carried out under the same conditions as in Example 1 except that the reaction temperature was changed. The reaction results and the reaction results after 6 months are summarized in Table 1.
第１表
Ｒ１３３ａ転化率、Ｒ１３４ａ選択率 ％（）内は６力
月後の成績
比較例
内径２．５４ｃｍ、長さ１００ｃｍのインコネル６００
製Ｕ字型反応管に比較調製例で示したように調製した触
媒を２００ｍ１充填し反応させた。ガス化させた１−ク
ロロ−２，２，２−トリフルオロエタン（Ｒ−１３３ａ
）を１００ｍ１／分で、酸素を２ｍｌ／分で、フッ酸を
３００ｍ１／分で供給し、３５０℃に保持した。酸分を
除去した後のガス組成をガスクロを用いて分析した。そ
の結果、当初Ｒ−１３３ａ転化率１０％、Ｒ−Ｊ３４ａ
選択率９０％の成績を得たが、１週間連続して同一条件
で反応させた後、同様の分析を行なったところ、Ｒ−１
３３ａ転化率７％、Ｒ−１３４ａ選択率８４％の成績と
なり、さらに６力月間反応を継続させたところＲ−１３
３ａ転化率２％、Ｒ−１３４ａ選択率７４％の成績まで
低下しな。Table 1 R133a conversion rate, R134a selection rate % () is a comparative example of results after 6 months Inconel 600 with inner diameter 2.54 cm and length 100 cm
A U-shaped reaction tube was filled with 200 ml of the catalyst prepared as shown in the comparative preparation example, and reacted. Gasified 1-chloro-2,2,2-trifluoroethane (R-133a
) was supplied at a rate of 100 ml/min, oxygen was supplied at a rate of 2 ml/min, and hydrofluoric acid was supplied at a rate of 300 ml/min, and the temperature was maintained at 350°C. The gas composition after acid content was removed was analyzed using gas chromatography. As a result, the initial conversion rate of R-133a was 10%, and the R-J34a conversion rate was 10%.
A selectivity rate of 90% was obtained, but when a similar analysis was performed after one week of continuous reaction under the same conditions, R-1
33a conversion rate was 7% and R-134a selectivity was 84%, and when the reaction was continued for 6 months, R-13
The results did not decrease to 2% 3a conversion and 74% R-134a selectivity.
［発明の効果］
本発明は、実施例に示した如く、従来知られているクロ
ム系触媒より触媒寿命が長くかつ高活性が長期間維持で
きるため、１．１．１．２−テトラフルオロエタン（Ｒ
−１３４ａ）を、高効率で製造し得るという効果を有す
る。[Effects of the Invention] As shown in the examples, the present invention has a longer catalyst life than conventionally known chromium-based catalysts and can maintain high activity for a long period of time. (R
-134a) can be produced with high efficiency.
Claims (1)
、およびＭｎからなる群から選ばれる少なくとも１種の
元素およびＣｒを含むハロゲン化物または酸化物からな
るフッ素化触媒の存在下、１−クロロ−２，２，２−ト
リフルオロエタンとフッ化水素とを反応せしめることを
特徴とする１−クロロ−２，２，２−トリフルオロエタ
ンのフッ素化方法。 ２、フッ素化反応を気相中常圧もしくは加圧下、２００
℃〜５５０℃の温度範囲で行なう特許請求の範囲第１項
に記載のフッ素化方法。[Claims] 1. Al, Mg, Ca, Ba, Sr, Fe, Ni, Co
, and 1-chloro-2,2,2-trifluoroethane and hydrogen fluoride in the presence of a fluorination catalyst consisting of a halide or oxide containing at least one element selected from the group consisting of Mn and Cr. A method for fluorinating 1-chloro-2,2,2-trifluoroethane, which comprises reacting. 2. The fluorination reaction is carried out in the gas phase at normal pressure or under pressure at 200 °C.
The fluorination method according to claim 1, which is carried out at a temperature range of 550°C to 550°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63323668A JPH02172933A (en) | 1988-12-23 | 1988-12-23 | Method for fluorinating 1-chloro-2,2,2-trifluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63323668A JPH02172933A (en) | 1988-12-23 | 1988-12-23 | Method for fluorinating 1-chloro-2,2,2-trifluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02172933A true JPH02172933A (en) | 1990-07-04 |
Family
ID=18157275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63323668A Pending JPH02172933A (en) | 1988-12-23 | 1988-12-23 | Method for fluorinating 1-chloro-2,2,2-trifluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02172933A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300710A (en) * | 1991-03-20 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane |
| US5300711A (en) * | 1991-03-20 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2,2-dichloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane |
| US5321170A (en) * | 1991-03-20 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 1,1,1,2-tetrafluoroethane |
| US5569795A (en) * | 1993-06-18 | 1996-10-29 | Showa Denko K. K. | Fluorination catalyst and fluorination process |
| US6040486A (en) * | 1991-03-20 | 2000-03-21 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2-chloro-1,1,1-trifluoroethane |
| US6080900A (en) * | 1991-05-23 | 2000-06-27 | Daikin Industries Limited | Process for fluorinating halogenated hydrocarbon |
| US10414704B2 (en) * | 2010-10-22 | 2019-09-17 | Arkema France | Process for the manufacture of 2-chloro-3,3,3-trifluoropropene by gas phase fluorination of pentachloropropane |
-
1988
- 1988-12-23 JP JP63323668A patent/JPH02172933A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300710A (en) * | 1991-03-20 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane |
| US5300711A (en) * | 1991-03-20 | 1994-04-05 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2,2-dichloro-1,1,1-trifluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane and pentafluoroethane |
| US5321170A (en) * | 1991-03-20 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 1,1,1,2-tetrafluoroethane |
| US6040486A (en) * | 1991-03-20 | 2000-03-21 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 2-chloro-1,1,1-trifluoroethane |
| US6080900A (en) * | 1991-05-23 | 2000-06-27 | Daikin Industries Limited | Process for fluorinating halogenated hydrocarbon |
| US5569795A (en) * | 1993-06-18 | 1996-10-29 | Showa Denko K. K. | Fluorination catalyst and fluorination process |
| US10414704B2 (en) * | 2010-10-22 | 2019-09-17 | Arkema France | Process for the manufacture of 2-chloro-3,3,3-trifluoropropene by gas phase fluorination of pentachloropropane |
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