JPH02178237A - Fluorination of perchloroethylene - Google Patents
Fluorination of perchloroethyleneInfo
- Publication number
- JPH02178237A JPH02178237A JP63328974A JP32897488A JPH02178237A JP H02178237 A JPH02178237 A JP H02178237A JP 63328974 A JP63328974 A JP 63328974A JP 32897488 A JP32897488 A JP 32897488A JP H02178237 A JPH02178237 A JP H02178237A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- perchloroethylene
- preparation example
- fluorination
- 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
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000003682 fluorination reaction Methods 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 9
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 239000011651 chromium Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000423 chromium oxide Inorganic materials 0.000 abstract description 6
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 7
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 2
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- -1 aluminum halides Chemical class 0.000 description 2
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- JQZFYIGAYWLRCC-UHFFFAOYSA-N 1-chloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)(F)Cl JQZFYIGAYWLRCC-UHFFFAOYSA-N 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
- 239000004340 Chloropentafluoroethane Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 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
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910001055 inconels 600 Inorganic materials 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
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product 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
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１．１．２− トリクロロ−２，２，−ジフル
オロエタン（Ｒ−１２２）、１．１−ジクロロ−２，２
，２−トリフルオロエタン（Ｒ−１２３）、１−クロロ
−１，２，２，２−テトラフルオロエタン（Ｒ−１２４
）、およびペンタフルオロエタン（Ｒ−１２５）の製造
方法に関するものである。Ｒ−１２３、Ｒ−１２４およ
びＲ−１２５は、オゾン層を破壊する疑いのあるそれぞ
れトリクロロフルオロエタン（Ｒ−１１）、ジクロロジ
フルオロエタン（Ｒ−１２）、クロロペンタフルオロエ
タン（Ｒ−１１５）の代替フロンとしての使用が検討さ
れている。Detailed Description of the Invention [Industrial Application Field] The present invention relates to 1.1.2-trichloro-2,2-difluoroethane (R-122), 1.1-dichloro-2,2
, 2-trifluoroethane (R-123), 1-chloro-1,2,2,2-tetrafluoroethane (R-124)
), and a method for producing pentafluoroethane (R-125). R-123, R-124 and R-125 are substitutes for trichlorofluoroethane (R-11), dichlorodifluoroethane (R-12) and chloropentafluoroethane (R-115), respectively, which are suspected of destroying the ozone layer. Its use as a fluorocarbon is being considered.
［従来の技術及び問題点］
従来より、パークロロエチレンの気相フッ素化反応にハ
ロゲン化アルミニウム、ハロゲン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。 （例えば、米国
特許第４７６６２６０号明細書などを参照、）シかるに
従来の触媒には、かならずしも目的とする化合物が選択
的に得られないことや、触媒寿命が短いことなどの難点
がある。[Prior Art and Problems] It has been known that aluminum halides, chromium halides, and the like are effective as catalysts for the gas-phase fluorination reaction of perchlorethylene. (See, for example, US Pat. No. 4,766,260, etc.) However, conventional catalysts have drawbacks such as not necessarily being able to selectively obtain the desired compound and having a short catalyst life.
［問題点を解決するための手段］
本発明者は、酸化クロムを含む触媒について鋭意検討を
重ねた結果、酸化クロムを活性成分とする複合酸化物触
媒が、酸化クロム単味の触媒に比べ活性が高く、かつ目
的とする生成物の選択率を向上させることができること
を見いだした。すなわち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
を含む酸化物からなるフッ素化触媒の存在下、パークロ
ロエチレンを気相フッ素化するにあたり、ハロゲン化ク
ロムや酸化クロム単味の触媒に比べ活性、選択性が著し
く向上することを見い出した。[Means for Solving the Problems] As a result of intensive studies on catalysts containing chromium oxide, the present inventor found that a composite oxide catalyst containing chromium oxide as an active ingredient has higher activity than a catalyst containing only chromium oxide. It has been found that the selectivity of the desired product can be improved. That is, along with Cr, Ai, Mg,
In gas phase fluorination of perchloroethylene in the presence of a fluorination catalyst made of an oxide containing at least one element selected from the group consisting of Ca, Ba, Sr, Fe, Ni, Co, and Mn, halogen It was discovered that the activity and selectivity of this catalyst were significantly improved compared to catalysts containing only chromium oxide or chromium oxide.
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、
Ａ１．Ｍｇ、 Ｃａ、 Ｂａ、 Ｓｒ、 Ｆｅ
、Ｎｉ、Ｃｏ、およびＭｎからなる群がら選ばれる少な
くとも１種の元素を含む酸化物が使用できる。As the fluorination catalyst in the present invention, together with Cr,
A1. Mg, Ca, Ba, Sr, Fe
An oxide containing at least one element selected from the group consisting of , Ni, Co, and Mn can be used.
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
反応温度は気相中常圧もしくは加圧下で、２゜Ｏ℃〜５
５０℃、特に好ましくは、２５０℃〜４００℃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
媒寿命が粗くなり、反応温度が低すぎるとパークロロエ
チレン転化率が低下する。It is desirable for all of the above catalysts to be 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. The temperature is between 2°C and 5°C under normal pressure or pressure in the gas phase.
It is appropriate to conduct the reaction at a temperature range of 50°C, particularly preferably 250°C to 400°C. If the reaction temperature is too high, the catalyst life will be shortened, and if the reaction temperature is too low, the perchlorethylene conversion rate will decrease. .
接触時間は、通常０．１〜３００秒、特に好ましくは５
〜６０秒である。The contact time is usually 0.1 to 300 seconds, particularly preferably 5 seconds.
~60 seconds.
フッ化水素とパークロロエチレン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５等量のフ
ッ化水素を使用して塩素原子を置換する。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
１０モルまたはそれ以上のフッ化水素を使用し得る。The proportions of hydrogen fluoride and perchlorethylene can vary widely. However, typically stoichiometric to 5 equivalents of hydrogen fluoride are used to replace the chlorine atoms. Significantly more than stoichiometric amounts of hydrogen fluoride may be used, for example 10 moles or more, based on the total number of moles of starting materials.
また触媒活性維持のため酸素または塩素をパークロロエ
チレンに対して０．１〜１０％共存させて反応を行なう
こともできる。The reaction can also be carried out in the presence of 0.1 to 10% oxygen or chlorine based on perchloroethylene in order to maintain the catalyst activity.
［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 Ｏｔ） ３・９
Ｎ２０．１２５ｇのＣｒ （Ｎ０３） ３ ・９ Ｎ２
０、および４０ｇのＭｇ （Ｎｏｒ） ２・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２０００ｇｆ！：ｆ９１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 1100g special grade reagent A I (N Ot) 3.9
N20.125g Cr (N03) 3 ・9 N2
0, and 40 g of Mg (Nor) 2.6H20 dissolved in 2.5 liters of water, and 2000 gf of a 28% aqueous solution of ammonium hydroxide! :f91 was added to 4 liters of heated water while stirring to obtain 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、３００〜４５０°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 300 to 450°C in a hydrogen fluoride/nitrogen mixed gas stream before the reaction, and then further chlorinated at 250 to 300°C in a trichlorofluoromethane/hydrogen fluoride mixed gas stream. Fluorinated and activated.
調製例２〜４
Ｍｇ（ＮＯｉ＞２・６Ｈ２０のかわりに、それぞれＢ
ａ （、Ｎｏｖ） ２の４０ｇ、Ｓｒ （ＮＯ３）２の
５０ｇ、Ｃａ （ＮＯ３） ・４Ｈ２０の４０ｇを用い
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 Mg (instead of NOi>2・6H20, B
A catalyst was prepared in the same manner as in Preparation Example 1, except that 40 g of a (, Nov) 2, 50 g of Sr (NO3) 2, and 40 g of Ca (NO3) 4H20 were used.
調製例５
Ａ Ｉ （ＮＯ３） ３・９Ｈ２０，Ｃｒ （ＮＯ３）
３・９Ｈ２０、およびＭ ｇ （Ｎ０ａ） ２ ・６
Ｎ２０ノかわりに、 Ｆｅ （ＮＯａ） ２・９Ｈ
２０の６００ｇ、Ｃｒ（ＮＯｓ）３・９Ｈ２０の１５０
ｇ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 5 A I (NO3) 3・9H20, Cr (NO3)
3・9H20, and M g (N0a) 2 ・6
Instead of N20, Fe (NOa) 2.9H
600g of 20, 150g of Cr(NOs)3.9H20
A catalyst was prepared in the same manner as in Preparation Example 1 except that g was used.
調製例６
ＡＩ （ＮＯ３）ｚ・９Ｈ２０、Ｃｒ （ＮＯ３） ｚ
・９Ｈ２０、およびＭｇ （ＮＯｓ） ２・６Ｈ２０の
かわりに、 Ｃｒ （ＮＯ３）ｓ・９Ｈ２０の１５
０ｇ、ＡＩ（ＮＯａ）ｘ・９Ｈ２０（７）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 AI (NO3)z・9H20, Cr (NO3)z
・Instead of 9H20 and Mg (NOs) 2・6H20, 15 of Cr (NO3)s・9H20
A catalyst was prepared in the same manner as in Preparation Example 1, except that 1,300 g of AI(NOa)x·9H20(7) was used.
調製例７
Ａ Ｉ （Ｎ０３） ｚ ・９ Ｎ２０、Ｃｒ （Ｎｏ
ｖ）ｓ・９Ｈ２０、およびＭｇ （ＮＯ３） ２・６Ｈ
２０のかわりに、５００ ｇ （７） Ｃｒ （Ｎ Ｏ
３） ｓ ・９ Ｈ２０、および４０ ｇ （７） Ｍ
ｇ （Ｎ Ｏｘ ） ２ ・６ Ｈｅ Ｏ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 A I (N03) z ・9 N20, Cr (No
v) s・9H20, and Mg (NO3) 2・6H
Instead of 20, 500 g (7) Cr (N O
3) s 9 H20, and 40 g (7) M
A catalyst was prepared in the same manner as in Preparation Example 1, except that g (NOx) 2 .6 He 2 O was used.
比較調製例１
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た。Comparative Preparation Example 1 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.
was activated by fluorination.
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０反応結果を表１に示す
。and maintained at 350°C. Table 1 shows the zero reaction results of analyzing the gas composition after acid content was removed using gas chromatography.
表１． Ｃｒ ２０３−Ｍ ｇ Ｏ−Ａ １２０３比較
調製例２
ＣｒＣ１３・６Ｈ２０の２００ｇを２リツトルの水に溶
解した。この溶液に、市販の直径５ｍｍ、高さ５ｍｍの
円筒状に成型したγ−アルミナ１０００ｇを投入した後
乾燥させて水分を除去した。さらに比較調製例１と同様
の活性化方法により活性化した。Table 1. Cr 203-M g O-A 1203 Comparative Preparation Example 2 200 g of CrC13.6H20 was dissolved in 2 liters of water. To this solution was added 1000 g of commercially available γ-alumina molded into a cylindrical shape with a diameter of 5 mm and a height of 5 mm, followed by drying to remove moisture. Furthermore, activation was performed using the same activation method as in Comparative Preparation Example 1.
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。ガス化させたパークロ
ロエチレンを８０ｍ１／分で、酸素を２ｍｌ／分で、フ
ッ酸を３２０ｍ１／分で供ここでＲ−１２３ｍは、１．
１−ジクロロ−２，２，２−）リフルオロエタン（Ｒ−
１２３）、１．２−ジクロロ−１゜２、２− ）リフル
オロエタン（Ｒ−１２３ａ）、１，１−ジクロロ−１，
２，２−トリフルオロエタン（Ｒ−１２３ｂ）の異性体
の総和をさす、またＲ−１２４ｍは、１−クロロ−１，
２，２，２−テトラフルオロエタン（Ｒ−１２４）１−
クロロ−１，１，２，２−テトラフルオロエタン（Ｒ−
１２４ａ）の異性体の総和をさす、 （以下同様）実施
例２
調製例２で調製した触媒を使用して、反応温度を３３０
℃とする他は実施例１と同様の条件で反応を行なった０
反応成績をまとめて表２に示す。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 perchlorethylene was supplied at a rate of 80 ml/min, oxygen at a rate of 2 ml/min, and hydrofluoric acid at a rate of 320 ml/min.
1-dichloro-2,2,2-)lifluoroethane (R-
123), 1,2-dichloro-1゜2,2-)lifluoroethane (R-123a), 1,1-dichloro-1,
Refers to the sum of isomers of 2,2-trifluoroethane (R-123b), and R-124m is 1-chloro-1,
2,2,2-tetrafluoroethane (R-124) 1-
Chloro-1,1,2,2-tetrafluoroethane (R-
Refers to the sum of the isomers of 124a). (The same applies hereinafter) Example 2 Using the catalyst prepared in Preparation Example 2, the reaction temperature was set at 330°C.
The reaction was carried out under the same conditions as in Example 1 except that the temperature was 0.
The reaction results are summarized in Table 2.
実施例３
調製例３で調製した触媒を使用して、反応温度を３３０
℃とする他は実施例１と同様の条件で反応を行なった０
反応成績をまとめて表３に示す。Example 3 Using the catalyst prepared in Preparation Example 3, the reaction temperature was increased to 330°C.
The reaction was carried out under the same conditions as in Example 1 except that the temperature was 0.
The reaction results are summarized in Table 3.
表３． Ｃｒ２０３−Ｓ ｒｏ−Ａ １ｔＯａ触媒表２
．Ｃｒ２０３−Ｂ ａ Ｏ−Ａ ｌ ２０３触媒実施例
４
調製例４で調製した触媒を使用して、反応温度を３３０
℃とする他は実施例１と同様の条件で反応を行なった０
反応成績をまとめて表４に示す。Table 3. Cr203-S ro-A 1tOa catalyst table 2
．． Cr203-B a O-A l 203 Catalyst Example 4 Using the catalyst prepared in Preparation Example 4, the reaction temperature was increased to 330°C.
The reaction was carried out under the same conditions as in Example 1 except that the temperature was 0.
The reaction results are summarized in Table 4.
表５． Ｆ ｅ ２０ｓ−Ｃｒ２０ｇ触媒表４．
Ｃｒ２０３Ｃａｏ−Ａ １２０ｇ触媒実施例５
調製例５で調製した触媒を使用して、反応温度を３８０
°Ｃとする他は実施例１と同様の条件で反応を行なった
０反応成績をまとめて表５に示す。Table 5. Fe 20s-Cr20g catalyst Table 4.
Cr203Cao-A 120g Catalyst Example 5 Using the catalyst prepared in Preparation Example 5, the reaction temperature was set to 380
The reaction results were summarized in Table 5 where the reaction was carried out under the same conditions as in Example 1 except that the temperature was changed to °C.
実施例６
調製例６で調製した触媒を使用して、反応温度を３３０
℃とする他は実施例１と同様の条件で反応を行なった０
反応成績をまとめて表６に示す。Example 6 Using the catalyst prepared in Preparation Example 6, the reaction temperature was increased to 330°C.
The reaction was carried out under the same conditions as in Example 1 except that the temperature was 0.
The reaction results are summarized in Table 6.
表６． Ｃｒ ２０３−Ａ Ｉ ２０３触媒表７．０ｒ
２０ｔ−ＭｇＯ触媒
実施例７
調製例７で調製した触媒を使用して、反応温度を３５０
°Ｃとする他は実施例１と同様の条件で反応を行なった
０反応成績をまとめて表７に示す。Table 6. Cr 203-A I 203 Catalyst Table 7.0r
20t-MgO Catalyst Example 7 Using the catalyst prepared in Preparation Example 7, the reaction temperature was raised to 350
The reaction results were summarized in Table 7, where the reaction was carried out under the same conditions as in Example 1, except that the temperature was changed to °C.
比較例１
比較調製例１で調製した触媒を使用して、反応温度を３
３０”Ｃとする他は実施例１と同様の条件で反応を行な
った０反応成績をまとめて表８に示す。Comparative Example 1 Using the catalyst prepared in Comparative Preparation Example 1, the reaction temperature was increased to 3.
Table 8 summarizes the results of the 0 reaction conducted under the same conditions as in Example 1 except that the temperature was 30''C.
表８．Ｃｒ２Ｏ３触媒
表９． Ｃｒ ＣＩ ３−Ａ １２０３ 触媒比較
例２
比較調製例２で調製した触媒を使用して、反応温度を３
３０°Ｃとする他は実施例１と同様の条件で反応を行な
った０反応成績をまとめて表９に示す。Table 8. Cr2O3 catalyst table 9. Cr CI 3-A 1203 Catalyst Comparative Example 2 Using the catalyst prepared in Comparative Preparation Example 2, the reaction temperature was increased to 3
Table 9 summarizes the results of the 0 reaction conducted under the same conditions as in Example 1 except that the temperature was 30°C.
［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
ム系触媒より高活性であり、パークロロエチレンのフッ
素化を、高効率で行ない得るという効果を有する。[Effects of the Invention] As shown in the examples, the present invention has the effect that it has higher activity than conventionally known chromium-based catalysts and can fluorinate perchlorethylene 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を含む酸化物からなるフッ素化触媒の存
在下、パークロロエチレンとフッ化水素とを反応せしめ
ることを特徴とするパークロロエチレンのフッ素化方法
。 ２、フッ素化反応を気相中常圧もしくは加圧下で、２０
０℃〜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 Mn, and fluorine of perchlorethylene, which is characterized by reacting perchlorethylene and hydrogen fluoride in the presence of a fluorination catalyst comprising an oxide containing Cr and at least one element selected from the group consisting of Mn. method. 2. The fluorination reaction is carried out in the gas phase at normal pressure or under pressure.
Claim 1, which is carried out in a temperature range of 0°C to 550°C
The fluorination method described in Section.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63328974A JP2764980B2 (en) | 1988-12-28 | 1988-12-28 | Perchlorethylene fluorination method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63328974A JP2764980B2 (en) | 1988-12-28 | 1988-12-28 | Perchlorethylene fluorination method |
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| Publication Number | Publication Date |
|---|---|
| JPH02178237A true JPH02178237A (en) | 1990-07-11 |
| JP2764980B2 JP2764980B2 (en) | 1998-06-11 |
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ID=18216196
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63328974A Expired - Fee Related JP2764980B2 (en) | 1988-12-28 | 1988-12-28 | Perchlorethylene fluorination method |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0513823A2 (en) * | 1991-05-17 | 1992-11-19 | Hoechst Aktiengesellschaft | Method for the production of pentafluoroethane (R125) |
| US5523500A (en) * | 1991-12-09 | 1996-06-04 | D'elf Atochem S.A. | Mass catalysts based on chromium and nickel oxides and their application to the fluorination of halogenated hydrocarbons |
| EP0733611A1 (en) * | 1995-03-20 | 1996-09-25 | Hoechst Aktiengesellschaft | Process for the preparation of pentafluorethane (R 125) |
| US5616820A (en) * | 1993-01-27 | 1997-04-01 | Elf Atochem S.A. | Process for the manufacture of 1,1,1,2-tetrafluoro-2-chloroethane and of pentafluoroethane |
| US5659094A (en) * | 1995-08-23 | 1997-08-19 | Korea Institute Of Science And Technology | Process for co-producing 1,1,1,2-tetrafluoroethane pentafluoroethane and 1,1,1-trifluoroethane |
| US5932776A (en) * | 1993-01-27 | 1999-08-03 | Cheminal; Bernard | Process for fluorination of perchloroethylene or of pentachloroethane |
| EP0957074A4 (en) * | 1997-04-23 | 1999-11-17 | ||
| WO2001077048A1 (en) * | 2000-04-12 | 2001-10-18 | Solvay (Société Anonyme) | Method for preparing a hydro(chloro)fluoroalkane and catalyst |
| CN1308072C (en) * | 2005-09-30 | 2007-04-04 | 山东东岳化工有限公司 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
| US8049045B2 (en) | 2005-12-17 | 2011-11-01 | Mexichem Amanco S.A. de C.V. | Process for production of dichlorotrifluoroethane |
| US8058485B2 (en) | 2005-12-17 | 2011-11-15 | Mexichem Amanco S.A. de C.V. | Process for the production of dichlorotrifluoroethane |
| US8236997B2 (en) | 2005-12-17 | 2012-08-07 | Mexichem Amanco Holding S.A. De C.V. | Process for the production of pentafluoroethane |
| US9556079B2 (en) | 2008-09-05 | 2017-01-31 | Mexichem Amanco Holding S.A. De C.V. | Catalyst and process using the catalyst |
| US9862659B2 (en) | 2008-09-05 | 2018-01-09 | Mexichem Amanco Holding S.A. De C.V. | Catalyst and process using the catalyst |
| CN110563548A (en) * | 2019-08-09 | 2019-12-13 | 福建省杭氟电子材料有限公司 | Isomerization reaction of dichlorotrifluoroethane |
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|---|---|---|---|---|
| US3258500A (en) * | 1959-08-17 | 1966-06-28 | Du Pont | Process for fluorinating halohydro-carbons |
| JPS4943922A (en) * | 1972-08-31 | 1974-04-25 |
-
1988
- 1988-12-28 JP JP63328974A patent/JP2764980B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3258500A (en) * | 1959-08-17 | 1966-06-28 | Du Pont | Process for fluorinating halohydro-carbons |
| JPS4943922A (en) * | 1972-08-31 | 1974-04-25 |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0513823A2 (en) * | 1991-05-17 | 1992-11-19 | Hoechst Aktiengesellschaft | Method for the production of pentafluoroethane (R125) |
| US5523500A (en) * | 1991-12-09 | 1996-06-04 | D'elf Atochem S.A. | Mass catalysts based on chromium and nickel oxides and their application to the fluorination of halogenated hydrocarbons |
| US5616820A (en) * | 1993-01-27 | 1997-04-01 | Elf Atochem S.A. | Process for the manufacture of 1,1,1,2-tetrafluoro-2-chloroethane and of pentafluoroethane |
| US5932776A (en) * | 1993-01-27 | 1999-08-03 | Cheminal; Bernard | Process for fluorination of perchloroethylene or of pentachloroethane |
| EP0733611A1 (en) * | 1995-03-20 | 1996-09-25 | Hoechst Aktiengesellschaft | Process for the preparation of pentafluorethane (R 125) |
| US5659094A (en) * | 1995-08-23 | 1997-08-19 | Korea Institute Of Science And Technology | Process for co-producing 1,1,1,2-tetrafluoroethane pentafluoroethane and 1,1,1-trifluoroethane |
| EP0957074A4 (en) * | 1997-04-23 | 1999-11-17 | ||
| WO2001077048A1 (en) * | 2000-04-12 | 2001-10-18 | Solvay (Société Anonyme) | Method for preparing a hydro(chloro)fluoroalkane and catalyst |
| FR2807751A1 (en) * | 2000-04-12 | 2001-10-19 | Solvay | PROCESS FOR THE PREPARATION OF A HYDRO (CHLORO) FLUOROALCANE AND CATALYST |
| US7067706B2 (en) | 2000-04-12 | 2006-06-27 | Solvay (Societe Anonyme) | Method for preparing a hydro(chloro)fluoroalkane and catalyst |
| CN1308072C (en) * | 2005-09-30 | 2007-04-04 | 山东东岳化工有限公司 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
| US8049045B2 (en) | 2005-12-17 | 2011-11-01 | Mexichem Amanco S.A. de C.V. | Process for production of dichlorotrifluoroethane |
| US8058485B2 (en) | 2005-12-17 | 2011-11-15 | Mexichem Amanco S.A. de C.V. | Process for the production of dichlorotrifluoroethane |
| US8236997B2 (en) | 2005-12-17 | 2012-08-07 | Mexichem Amanco Holding S.A. De C.V. | Process for the production of pentafluoroethane |
| US8415515B2 (en) | 2005-12-17 | 2013-04-09 | Mexichem Amanco Holding S.A. De C.V. | Process for the production of pentafluroethane |
| US10906853B2 (en) | 2008-05-09 | 2021-02-02 | Mexichem Amanco Holding S.A. De C.V. | Catalyst and process using the catalyst |
| US9556079B2 (en) | 2008-09-05 | 2017-01-31 | Mexichem Amanco Holding S.A. De C.V. | Catalyst and process using the catalyst |
| US9862659B2 (en) | 2008-09-05 | 2018-01-09 | Mexichem Amanco Holding S.A. De C.V. | Catalyst and process using the catalyst |
| US10974227B2 (en) | 2008-09-05 | 2021-04-13 | Mexichem Amanco Holding S.A. De C.V. | Catalyst and process using the catalyst |
| CN110563548A (en) * | 2019-08-09 | 2019-12-13 | 福建省杭氟电子材料有限公司 | Isomerization reaction of dichlorotrifluoroethane |
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|---|---|
| JP2764980B2 (en) | 1998-06-11 |
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