JPH04117333A - Production of 1-chloro-1,2,-trifluoroethylene and 1,2,2-trifluoroethylene - Google Patents
Production of 1-chloro-1,2,-trifluoroethylene and 1,2,2-trifluoroethyleneInfo
- Publication number
- JPH04117333A JPH04117333A JP2241691A JP24169190A JPH04117333A JP H04117333 A JPH04117333 A JP H04117333A JP 2241691 A JP2241691 A JP 2241691A JP 24169190 A JP24169190 A JP 24169190A JP H04117333 A JPH04117333 A JP H04117333A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- 3fcl
- selectivity
- metal
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 title claims abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 claims abstract 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 5
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 10
- 230000000996 additive effect Effects 0.000 abstract description 10
- 239000010953 base metal Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- -1 etc. Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 64
- 150000003839 salts Chemical class 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101100273751 Caenorhabditis elegans cdc-42 gene Proteins 0.000 description 1
- 244000201986 Cassia tora Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- NCAIGTHBQTXTLR-UHFFFAOYSA-N phentermine hydrochloride Chemical compound [Cl-].CC(C)([NH3+])CC1=CC=CC=C1 NCAIGTHBQTXTLR-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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１
本発明は、１，１．２−１−ジクロロ−１，２’、２−
トリフルオロエタン（１１３）から１−クロロ−１，２
，２−トリフルオロエチレン（３ＦＯＬ）および１．２
．２−トリフルオロエチレン（３ＦＨ）を−工程で製造
する方法に関する。これらの生成物は、それぞれ原料モ
ノマー、代替フロンの原料として有用である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to 1,1,2-1-dichloro-1,2',2-
1-chloro-1,2 from trifluoroethane (113)
, 2-trifluoroethylene (3FOL) and 1.2
．． The present invention relates to a method for producing 2-trifluoroethylene (3FH) in -steps. These products are useful as raw material monomers and raw materials for CFC substitutes, respectively.
［従来の技術および発明が解決しようとする課題］活性
炭にパラジウムを担持させた触媒（Ｐ ｄ／活性炭）の
存在下、原料としての１１３と水素を２００〜３００℃
で反応させて３ＦＨを製造する方法が特公昭４３−８４
５４号公報に記載されている。この方法によれば、３Ｆ
Ｈと同時に３ＦＣＬも生成されるが、３ＦＨ，３ＦＣＬ
以外の化合物の選択率が高く、３ＦＨおよび３ＦＣＬの
選択率は４０〜８５％と低い。また、アルカリフッ化マ
グネシウムを触媒として、１１３と水素から３ＦＨおよ
び３ＦＣＬを製造する方法（Ｅ Ｐ−Ａ−６３６５７）
によれば、これらのオレフィンを９０％以上の高選択率
で得ることができるが、その反応温度は５００℃と高い
。また、反応温度をより低く（２００〜３００℃）し、
上記触媒に０．５％のパラジウムを添加した触媒を用い
た反応においては、オレフィン選択率が７０〜９０％と
低い。[Prior art and problems to be solved by the invention] In the presence of a catalyst in which palladium is supported on activated carbon (Pd/activated carbon), 113 as a raw material and hydrogen are heated at 200 to 300°C.
The method for producing 3FH by reacting with
It is described in Publication No. 54. According to this method, 3F
3FCL is also generated at the same time as H, but 3FH, 3FCL
The selectivity of other compounds is high, and the selectivity of 3FH and 3FCL is as low as 40-85%. Also, a method for producing 3FH and 3FCL from 113 and hydrogen using alkali magnesium fluoride as a catalyst (E P-A-63657).
According to the method, these olefins can be obtained with a high selectivity of 90% or more, but the reaction temperature is as high as 500°C. In addition, the reaction temperature is lowered (200 to 300°C),
In a reaction using a catalyst prepared by adding 0.5% palladium to the above catalyst, the olefin selectivity is as low as 70 to 90%.
本発明の課題は、工業的ｌ二有利である比較的低温で、
３ＦＨおよび３ＦＣＬを、両者の生成比率を制御しつつ
高選択率で製造することのできる方法を提供することに
ある。The object of the present invention is to achieve a relatively low temperature which is advantageous for industrial use.
The object of the present invention is to provide a method capable of producing 3FH and 3FCL with high selectivity while controlling the production ratio of both.
［課題を解決するための手段］
本発明の要旨は、１，１．２−トリクロロ−１゜２．２
−トリフルオロエタンと水素とを触媒存在下に反応させ
ることによって１−クロロ−１，２゜２−トリフルオロ
エチレンおよび１．２．２−トリフルオロエチレンを製
造する方法であって、触媒としてパラジウム、ロジウム
およびルテニウムから選ばれる少なくとも１種の金属と
水銀、鉛、カドミウム、錫、インジウム、鋼、ビスマス
、タリウムおよび銀から選ばれる少なくとも１種の金属
（ただし、後者の金属がタリウムのとき、前者の金属が
ロジウムに限る）とをＡｌ１．０！またはＳｉＯ２に担
持させた触媒を使用することを特徴とする方法に存する
。[Means for Solving the Problems] The gist of the present invention is that 1,1,2-trichloro-1°2.2
- A method for producing 1-chloro-1,2゜2-trifluoroethylene and 1.2.2-trifluoroethylene by reacting trifluoroethane and hydrogen in the presence of a catalyst, the method comprising palladium as a catalyst. , rhodium, and ruthenium and at least one metal selected from mercury, lead, cadmium, tin, indium, steel, bismuth, thallium, and silver (however, when the latter metal is thallium, the former metal is limited to rhodium) and Al1.0! Alternatively, the present invention resides in a method characterized by using a catalyst supported on SiO2.
本発明の方法で起こる反応を以下に示す。The reactions that occur in the method of the invention are shown below.
ＣＣＱＪＣＦ２ＣＱ＋Ｈｘ
−ＣＣｌ２Ｆ−ＣＦ２＋２８（１２
ＣＣＱＪＣＦ、ＣＱ＋２Ｈｚ
→ ＣＦＨ−ＣＦ、＋３ＨＣＱ
本発明の方法において用いる触媒は、アルミナまたはシ
リカゲルに、パラジウム、ロジウムおよびルテニウムか
ら選ばれる少なくとも１種の金属（以下、ベース金属と
称する。）とさらに水銀、鉛、カドミウム、錫、インジ
ウム、銅、ビスマス、タリウムおよび銀から選ばれる少
なくとも１種の金属（以下、添加金属と称する。）を担
持させて得られるものである。ベース金属と添加金属の
担持体への担持は、ベース金属先付けでもベース金属と
添加金属の同時付けでもよい。触媒のベース金属の含量
は０．１−１０％、好ましくは０．５〜５％である。CCQJCF2CQ+Hx -CCl2F-CF2+28 (12 CCQJCF, CQ+2Hz → CFH-CF, +3HCQ ) and at least one metal selected from mercury, lead, cadmium, tin, indium, copper, bismuth, thallium, and silver (hereinafter referred to as additive metal).Base metal The base metal and the additive metal may be supported on the support either by applying the base metal first or by simultaneously applying the base metal and the additive metal.The content of the base metal in the catalyst is 0.1-10%, preferably 0.5-5%. .
上記添加金属を担持させるために上記添加金属の硝酸塩
、炭酸塩、硫酸塩、ハロゲン化物、水酸化物、リン酸塩
、過塩素酸塩、有機金属化合物および有機酸塩等の化合
物が用いられる。それらは触媒中に主としてメタル状で
存在するが表面は部分的に塩化物あるいはフッ化物で覆
われている可能性が高い。In order to support the additive metal, compounds such as nitrates, carbonates, sulfates, halides, hydroxides, phosphates, perchlorates, organometallic compounds, and organic acid salts of the additive metal are used. They exist mainly in the form of metal in the catalyst, but the surface is likely to be partially covered with chloride or fluoride.
添加金属とベース金属とのモル比は、添加金属がビスマ
ス以外の場合０．５以上であることが必要であり、添加
金属がビスマスの場合０．０５以上であることが必要で
ある。例えば、Ｈｇ／Ｐｄモル比が０．５より低くなる
と３ＦＨの選択率が大幅に低下し、オレフィン全体の選
択率も低下してしまう。また、このモル比は大きくなっ
ても選択率には大きな影響を与えないが、大きすぎると
反応率が低下するので４以下に押さえることが好ましい
。さらには、オレフィンの中でも３ＦＣＬの選択率の高
い金属の場合は、ベース金属とのモル比を４以下の適当
な値にすることにより３ＦＨの選択率を高くすることも
できる。The molar ratio of the added metal to the base metal needs to be 0.5 or more when the added metal is other than bismuth, and needs to be 0.05 or more when the added metal is bismuth. For example, if the Hg/Pd molar ratio is lower than 0.5, the selectivity of 3FH will decrease significantly, and the selectivity of the entire olefin will also decrease. Further, even if this molar ratio becomes large, it does not have a large effect on the selectivity, but if it is too large, the reaction rate will decrease, so it is preferable to keep it to 4 or less. Furthermore, in the case of a metal that has a high selectivity for 3FCL among olefins, the selectivity for 3FH can be increased by setting the molar ratio with the base metal to an appropriate value of 4 or less.
また上記添加金属の種類を選択することにより３ＦＣＬ
／３ＦＨ生成比を変えることができる。In addition, by selecting the type of additive metal mentioned above, 3FCL
/3FH production ratio can be changed.
例えば、その添加金属を、水銀、鉛、銅とした場合、３
ＦＣＬ／３ＦＨ生成比は代表的にはそれぞれ０．１１，
０．５８．５．８となる。For example, if the additive metals are mercury, lead, and copper, 3
The FCL/3FH production ratio is typically 0.11, respectively.
It becomes 0.58.5.8.
また、反応に用いる水素と１１３のモル比は０゜５〜４
．０が好ましい。この値が大きくなっても、水素化され
たパラフィン系化合物の生成は起こりにくく、オレフィ
ン（３ＦＣＬと３ＦＨ）の高選択率は保持される。しか
し４．０より大きいと不経済である。In addition, the molar ratio of hydrogen and 113 used in the reaction is 0°5 to 4
．． 0 is preferred. Even if this value becomes large, hydrogenated paraffinic compounds are less likely to be produced, and a high selectivity for olefins (3FCL and 3FH) is maintained. However, if it is larger than 4.0, it is uneconomical.
接触時間に相当するＷ／Ｆ（Ｗ：触媒重量Ｌ Ｆ：標準
状態における総流量ｍＱ／秒）は、１．３〜１１．４の
範囲内においては選択率に大きな影響を与えない。W/F (W: catalyst weight L F: total flow rate mQ/sec under standard conditions), which corresponds to the contact time, does not have a significant effect on the selectivity within the range of 1.3 to 11.4.
反応温度は、１５０〜４００℃、好ましくは２００〜３
００℃である。The reaction temperature is 150-400°C, preferably 200-300°C.
It is 00℃.
本発明によれば２００〜３００℃の比較的低い温度での
反応により３ＦＣＬおよび３ＦＨを８７〜１００％の高
選択率で得ることができる。According to the present invention, 3FCL and 3FH can be obtained at a high selectivity of 87 to 100% by reaction at a relatively low temperature of 200 to 300°C.
［寅施例］ 担持方法 水３０ｍ１２に添加金属の金属塩を溶かし、ＡＱ。[Tora example] Support method Dissolve the metal salt of the additive metal in 30 ml of water and prepare AQ.
０、にパラジウム０．５％を担持させてなる直径３゜２
＋ｎ、高さ３．２ｍｍのペレット状パラジウム触媒［
触媒ａ］ ５ｇ、そのペレット状触媒を６０メツシユ以
下に粉砕した触媒［触媒ｂ］４ｇ、カーボン（活性炭）
にパラジウム２％を担持させてなる粉末状触媒［触媒ｃ
１またはＡｌ２Ｏ３またはＳｉＯ２ｆｆｉＯ，にベース
金属５％を担持させてなる粉末状触媒［触媒ｄｌ ４ｇ
のいずれか〔いずれも市販触媒：Ｎ、Ｅ、ケミカル・カ
タリスト（ＣＨＥＭＩＣＡＬ ＣＡＴＡＬＹＳＴ）製
〕およびホルマリン０．２ｇを添加し、５０℃で２〜３
時間熟成させた。上記金属塩の量は、添加金属とベース
金属のモル比が目的の値となるようにした。その後、ロ
ータリーエバポレーターで水を除去し、さらに空気中１
００℃で１２時間乾燥させた。得られた触媒ａ、ｂ、ｃ
を、反応前に、水素気流中３００〜４００℃で２時間前
処理した。但し、ビスマスを添加したものは、３００℃
酸素気流中で２時間前処理した。Diameter 3゜2 made by supporting 0.5% palladium on
+n, 3.2 mm height pelleted palladium catalyst [
Catalyst a] 5g, catalyst obtained by crushing the pelleted catalyst into 60 meshes or less [Catalyst B] 4g, carbon (activated carbon)
Powdered catalyst made by supporting 2% palladium [catalyst c
1 or Al2O3 or SiO2ffiO, with 5% of the base metal supported [catalyst dl 4g
[all commercially available catalysts: N, E, manufactured by CHEMICAL CATALYST] and 0.2 g of formalin were added, and the mixture was heated at 50°C for 2 to 3 hours.
Aged for time. The amount of the metal salt was determined so that the molar ratio of the added metal to the base metal would be a desired value. After that, water was removed using a rotary evaporator, and 1
It was dried at 00°C for 12 hours. Obtained catalysts a, b, c
was pretreated at 300-400°C for 2 hours in a hydrogen stream before the reaction. However, for those with bismuth added, the temperature is 300℃.
Pretreatment was carried out for 2 hours in an oxygen stream.
実施例１
担持金属塩としてＨｇＣ（２，を触媒中のＨｇ／Ｐｄモ
ル比−４となる量にして用いた。内径２０ｍｍのハステ
ロイ製反応管に触媒ａ４ｇを充填し、１１３と水素を、
モル比ｌ：２、総流量２１ｉ／分として流通させて２０
０℃で反応させた。Example 1 HgC (2,) was used as a supported metal salt in an amount such that the Hg/Pd molar ratio in the catalyst was −4. A Hastelloy reaction tube with an inner diameter of 20 mm was filled with 4 g of catalyst a, and 113 and hydrogen were
Flowed at a molar ratio of 1:2 and a total flow rate of 21 i/min.
The reaction was carried out at 0°C.
反応率は１７．２％で、３ＦＣＬおよび３ＦＨがそれぞ
れ選択率２４．６％および７５．４％で得られた。The reaction rate was 17.2%, and 3FCL and 3FH were obtained with selectivities of 24.6% and 75.4%, respectively.
５Ｉ！施例２
担持金属塩としてＰ ｂ（Ｎ Ｏり３を用い（Ｐｂ／Ｐ
ｄモル比−４）、反応温度を２８０℃とした以外は、実
施例１と同様の反応を行った。5I! Example 2 Using Pb (N O 3) as a supported metal salt (Pb/P
The same reaction as in Example 1 was carried out except that the molar ratio d was -4) and the reaction temperature was 280°C.
反応率は４６．８％で、３ＦＣＬ、３ＦＨ１１２３ａ（
ＣＨＣＩ２ＦＣＣ４Ｆｇ）、ｌ ４１ ａ（ＣＨＣ（２
＊ＣＨ，Ｆ）、１６０（ＣＨ，ＣｆｆＣＨ，）および１
４２（ＣＨＦ、ＣＨバＩ）がそれぞれ選択率２３，４％
、７１．０％、２．７％、１．１％、０．６％および０
゜３％で得られた。The reaction rate was 46.8%, and 3FCL, 3FH1123a (
CHCI2FCC4Fg), l 41 a(CHC(2
*CH,F), 160(CH,CffCH,) and 1
42 (CHF, CH-I) had a selection rate of 23 and 4%, respectively.
, 71.0%, 2.7%, 1.1%, 0.6% and 0
It was obtained at 3%.
実施例３
担持金属塩としてＣｄＣ４２を用い（Ｃｄ／Ｐｄモル比
−４）、反応温度を２８０℃とした以外は実施例１と同
様の反応を行った。Example 3 The same reaction as in Example 1 was carried out except that CdC42 was used as the supported metal salt (Cd/Pd molar ratio -4) and the reaction temperature was 280°C.
反応率は２１．６％で、３ＦＣＬ、３ＦＨ，１６０，１
２３ａ、１４２および１４１ａがそれぞれ選択率３３．
４％、５８．８％、２．０％、１．９％、１．６％およ
び１．５％で得られた。The reaction rate was 21.6%, 3FCL, 3FH, 160,1
23a, 142 and 141a each have a selectivity of 33.
4%, 58.8%, 2.0%, 1.9%, 1.6% and 1.5%.
実施例４
担持金属塩としてＳ ｎＣ（ｈを用い（Ｓｎ／Ｐｄモル
比−４）、反応温度を２５０℃とした以外は実施例１と
同様の反応を行った。Example 4 The same reaction as in Example 1 was carried out except that SnC (h) was used as the supported metal salt (Sn/Pd molar ratio -4) and the reaction temperature was 250°C.
反応率は１５．９％で、３ＦＣＬ、３ＦＨおよび１４２
がそれぞれ選択率７９．３％、１５．３％および２．５
％で得られた。The reaction rate was 15.9%, and 3FCL, 3FH and 142
The selectivity was 79.3%, 15.3% and 2.5 respectively.
Obtained in %.
里簾匹ｉ
担持金属塩としてＩｎｃｈ、を用い（Ｉｎ／Ｐｄモル比
−４）、反応温度を２５０℃とした以外は実施例１と同
様の反応を行った。The same reaction as in Example 1 was carried out except that Inch was used as the supported metal salt (In/Pd molar ratio -4) and the reaction temperature was 250°C.
反応率は１０．４％で、３ＦＣＬ、３ＦＨ，１４２，１
６０，１２３および１４１ａがそれぞれ選択率７１，９
％、１６，１％、４．６％、２，９％、２．３％および
１．３％で得られた。The reaction rate was 10.4%, 3FCL, 3FH,142,1
60, 123 and 141a have selectivity of 71 and 9 respectively
%, 16.1%, 4.6%, 2.9%, 2.3% and 1.3%.
実施例６
担持金属塩としてＣｕＣ（２，を用い（Ｃｕ／Ｐｄモル
比−４）、反応温度を２５０℃とした以外は実施例１と
同様の反応を行った。Example 6 The same reaction as in Example 1 was carried out, except that CuC(2,) was used as the supported metal salt (Cu/Pd molar ratio -4) and the reaction temperature was 250°C.
反応率は１８．７％で、３ＦＣＬ、３ＦＨおよび１４２
がそれぞれ選択率７９．５％、１７．１％および１．９
％で得られた。The reaction rate was 18.7%, with 3FCL, 3FH and 142
The selectivity was 79.5%, 17.1% and 1.9 respectively.
Obtained in %.
実施例７
担持金属塩としてＡｇＮ０．を触媒中のＡｇ／Ｐｄモル
比−４になる量にして用いた。内径７ 、２ ＋ｎのス
テンレス製反応管に触媒ｂ１．３ｇを充填し、１１３と
水素を、モル比ｌ：２、総流量２７＋ｏｆｆ／分として
流通させて２５０℃で反応させた。 反応率は３２．２
％で、３ＦＨ，３ＦＣＬ、１４２．１２３ａ％１６０お
よび１４１ａがそれぞれ選択率２９．３％、６７．０％
、１．２％、０．９％、０゜５％および０．３％で得ら
れた。Example 7 AgN0. as supported metal salt. was used in an amount such that the Ag/Pd molar ratio in the catalyst was -4. A stainless steel reaction tube with an inner diameter of 7,2+n was filled with 1.3 g of catalyst b, and 113 and hydrogen were allowed to flow at a molar ratio of 1:2 and a total flow rate of 27+off/min to react at 250°C. The reaction rate is 32.2
%, 3FH, 3FCL, 142.123a%160 and 141a have selectivity of 29.3% and 67.0%, respectively.
, 1.2%, 0.9%, 0.5% and 0.3%.
実施例８
担持金属塩としてＨｇＣＱ２を用い（Ｈｇ／ｐａモル比
＝４）、総流量を６０ｍ１１／分とした以外は実施例７
と同様の反応を行った。Example 8 Example 7 except that HgCQ2 was used as the supported metal salt (Hg/pa molar ratio = 4) and the total flow rate was 60 m11/min.
A similar reaction was performed.
反応率は５４．７％で、３ＦＣＬ、３ＦＨＳ １５２ａ
（ＣＦｚＨＣＨｓ）、１２３ａおよび１４２がそれぞれ
選択率９．３％、８７．４％、２．２％、０．７％およ
び０．４％で得られた。The reaction rate was 54.7%, 3FCL, 3FHS 152a
(CFzHCHs), 123a and 142 were obtained with selectivities of 9.3%, 87.4%, 2.2%, 0.7% and 0.4%, respectively.
実施例９
総流量を２７−７分とした以外は実施例８と同様の反応
を行った。Example 9 The same reaction as in Example 8 was carried out except that the total flow rate was 27-7 minutes.
反応率は４５．２％で、３ＦＨ，３ＦＣＬ、′１２３
ａ、 ｌ ５２ ａ、 １４２および１６０がそれぞれ
選択率８２．７％、７．６％、４．８％、１．５％、０
．６％および０．５％で得られた。The reaction rate was 45.2%, 3FH, 3FCL, '123
a, l 52 a, 142 and 160 have selectivity of 82.7%, 7.6%, 4.8%, 1.5%, 0 respectively
．． 6% and 0.5% were obtained.
実施例１０
１１３と水素のモル比をｌ：４とした以外は実施例９と
同様の反応を行った。Example 10 The same reaction as in Example 9 was carried out except that the molar ratio of 113 and hydrogen was 1:4.
反応率は４０．０％で、３ＦＨ，３ＦＣＬ、１２３ａ、
１４１ａ、１５２ａ、１４２および１６０がそれぞれ選
択率７６．９％、１２．０％、５゜８％、２．１％、１
．７％、０．７％および０．５％で得られた。The reaction rate was 40.0%, 3FH, 3FCL, 123a,
141a, 152a, 142 and 160 have selectivity of 76.9%, 12.0%, 5°8%, 2.1% and 1, respectively.
．． 7%, 0.7% and 0.5% were obtained.
実施例１１
担持金属塩としてＰ ｂ（Ｎ Ｏ３）ｌを用い（Ｐ ｂ
／Ｐｄモル比−４）、１１３と水素のモル比を１＝１１
総流量１８＋＋＋＋２／分とした以外は実施例７と同様
の反応を行っｔ；。Example 11 Using P b (N O3) l as the supported metal salt (P b
/Pd molar ratio -4), the molar ratio of 113 and hydrogen is 1 = 11
The same reaction as in Example 7 was carried out except that the total flow rate was 18+++2/min.
反応率は１１．２％で、３ＦＨ，３ＦＣＬ、１２３ａ、
１５２ａおよび１４２がそれぞれ選択率６０．４％、３
５．１％、２．１％、１．０％および０．９％で得られ
た。The reaction rate was 11.2%, 3FH, 3FCL, 123a,
152a and 142 have selectivity of 60.4% and 3, respectively.
5.1%, 2.1%, 1.0% and 0.9% were obtained.
実施例１２
１１３と水素のモル比を１＝４とした以外は実施例１１
と同様の反応を行った。Example 12 Example 11 except that the molar ratio of 113 and hydrogen was 1=4
A similar reaction was performed.
反応率は１２．０％で、３ＦＨおよび３ＦＣＬがそれぞ
れ選択率５６．３％および４３．７％で得られた。The reaction rate was 12.0%, and 3FH and 3FCL were obtained with selectivities of 56.3% and 43.7%, respectively.
実施例１３
反応温度を３００℃とした以外は実施例１２と同様の反
応を行った。Example 13 The same reaction as in Example 12 was carried out except that the reaction temperature was 300°C.
反応率は２２．９％で、３ＦＨ，３ＦＣＬ、１２３ａＳ
１４２および１５２ａがそれぞれ選択率４４．３％、
４９．４％、１．９％、１．４％および１．４％で得ら
れた。The reaction rate was 22.9%, 3FH, 3FCL, 123aS
142 and 152a each had a selectivity of 44.3%,
49.4%, 1.9%, 1.4% and 1.4% were obtained.
実施例１４
触媒ｄ１．３ｇを充填し、Ｈｇ／Ｐｄ−１とした以外は
実施例９と同様にして反応を行った。Example 14 The reaction was carried out in the same manner as in Example 9, except that 1.3 g of catalyst d was charged and the ratio was Hg/Pd-1.
反応率は６０．８％で、３ＦＣＬ、３ＦＨ，１２３ａ−
１３４ａ（ＣＦｓＣＦＨｚ）、１４１ａ、１４２および
１６０がそれぞれ選択率７９．０％、１２．１％、３．
６％、２．４％、１．５％、０．６％および０．５％で
得られた。The reaction rate was 60.8%, 3FCL, 3FH, 123a-
134a (CFsCFHz), 141a, 142 and 160 have selectivity of 79.0%, 12.1%, 3.
6%, 2.4%, 1.5%, 0.6% and 0.5% were obtained.
比較例１
触媒ｃｏ、６ｇを充填し、反応温度を２８０℃とした以
外は実施例８と同様にして反応を行った。Comparative Example 1 The reaction was carried out in the same manner as in Example 8, except that 6 g of catalyst co was charged and the reaction temperature was 280°C.
反応率は６３．９％で、３ＦＨ，３ＦＣＬおよびｌ ２
３ａがそれぞれ選択率１６．０％、６２．２％および２
１．９％で得られた。The reaction rate was 63.9%, and 3FH, 3FCL and l 2
3a has a selectivity of 16.0%, 62.2% and 2, respectively.
It was obtained at 1.9%.
比較例２
触媒ｃｏ、６ｇを充填し、反応温度を２８０℃とし、担
持金属塩としてＰｂ（ＮＯｘ）ｇを用いた（Ｐｂ／Ｐｄ
モル比−４）以外は実施例８と同様にして反応を行った
。 反応率は２８．５％で、３ＦＨ。Comparative Example 2 6g of catalyst co was charged, the reaction temperature was 280°C, and Pb(NOx)g was used as the supported metal salt (Pb/Pd
The reaction was carried out in the same manner as in Example 8 except for the molar ratio -4). The reaction rate was 28.5%, 3FH.
３ＦＣＬおよび１２３ａがそれぞれ選択率６．０％、６
９．２％および２４．８％で得られた。3FCL and 123a have selectivity of 6.0% and 6
9.2% and 24.8% were obtained.
比較例３
パラジウム以外の金属を担持させなかっｔ；以外は実施
例８と同様の反応を行った。Comparative Example 3 The same reaction as in Example 8 was carried out except that no metal other than palladium was supported.
反応率は６４．３％で、３ＦＣＬ、３ＦＨ，１４３，１
４１ａ、１２３ａ、１４２．１６０および１５２ａがそ
れぞれ選択率θ％、２３．０％、４０．２％、１８．７
％、７．０％、６．０％、４゜６％および０．７％で得
られた。The reaction rate was 64.3%, 3FCL, 3FH, 143,1
41a, 123a, 142.160 and 152a have selectivity θ%, 23.0%, 40.2%, 18.7 respectively
%, 7.0%, 6.0%, 4°6% and 0.7%.
比較例４
パラジウム以外の金属を担持させず、反応温度を１５０
℃とした以外は実施例１〜７と同様の反応を行った。Comparative Example 4 No metal other than palladium was supported, and the reaction temperature was set at 150°C.
The same reactions as in Examples 1 to 7 were carried out except that the temperature was changed to ℃.
反応率は２４．７％で、３ＦＨ，１４３，１４１ａ、１
６０．１４２および１２３ａがそれぞれ選択率１．５％
、４４．２％、４１．２％、１．０％、３．７％および
８．５％で得られた。The reaction rate was 24.7%, 3FH, 143, 141a, 1
60.142 and 123a each have a selectivity of 1.5%
, 44.2%, 41.2%, 1.0%, 3.7% and 8.5%.
実施例１５
担持金属塩としてＢｉＣｌ２３を用いた（Ｂ１／Ｐｄモ
ル比−〇、４）触媒ｄｉｇを内径１’Ｏｍｍガラス製反
応管に充填し、１１３と水素をモル比１：３で流通させ
２５０℃で反応させた。反応率は９６．４％で、３ＦＨ
１３ＦＣＬ、１５２ａ、１２３ａがそれぞれ選択率８１
．３％、８．９％、６゜１％、１．３％で得られた。Example 15 A glass reaction tube with an inner diameter of 1'Omm was filled with a catalyst dig using BiCl23 as a supported metal salt (B1/Pd molar ratio - 0, 4), and 113 and hydrogen were passed through at a molar ratio of 1:3. The reaction was carried out at ℃. The reaction rate was 96.4%, and 3FH
13FCL, 152a, and 123a each have a selectivity of 81
．． 3%, 8.9%, 6°1%, and 1.3%.
実施例１６
触媒中のＴｆｆ／Ｒｈモル比−２となる量にした触媒ｄ
ｉｇを内径１０ｍｍのガラス製反応管に充填し、１１３
と水素をモル比３：４で流通させ２３０℃で反応させた
。反応率は４．５％で、３ＦＣＬ、３ＦＨ，１４３ａ、
１２３ａがそれぞれ選択率７１．８％、１９．３％、２
．６％、２．３％で得られた。Example 16 Catalyst d in an amount such that the Tff/Rh molar ratio in the catalyst is -2
Fill a glass reaction tube with an inner diameter of 10 mm with 113
and hydrogen at a molar ratio of 3:4 to react at 230°C. The reaction rate was 4.5%, 3FCL, 3FH, 143a,
123a had a selectivity of 71.8%, 19.3%, and 2, respectively.
．． 6% and 2.3%.
比較例５
ＴＩ２を添加しないこと以外は実施例１６と同様の反応
を行った。反応率は１２．５％で、３ＦＣＬ、３ＦＨ，
１４３，１４１ａ、１２３ａ、 エタンがそれぞれ選択
率２６．７％、３．７％、２２゜０％、２１．８％、９
．０％、６．６％で得られた。Comparative Example 5 The same reaction as in Example 16 was carried out except that TI2 was not added. The reaction rate was 12.5%, and 3FCL, 3FH,
143, 141a, 123a, ethane selectivity 26.7%, 3.7%, 22°0%, 21.8%, 9
．． 0% and 6.6%.
実施例１７
触媒中のＨｇ／Ｒｕモル比が１となる量にした触媒ｄｉ
ｇを内径１０ｍｍのガラス製反応管に充填し、１１３と
水素をモル比１：２で流通させ、２００℃で反応させた
。反応率は１８．７％で、３ＦＣＬ、 ３ Ｆ Ｈ，ｌ
１３２ａ （ＣＦ ｚ−ＣＨｚ）がそれぞれ選択率８
１．５％、１２．４％、１．２％で得られた。Example 17 Catalyst di in an amount such that the Hg/Ru molar ratio in the catalyst is 1
A glass reaction tube with an inner diameter of 10 mm was filled with 113 and hydrogen at a molar ratio of 1:2, and the mixture was reacted at 200°C. The reaction rate was 18.7%, 3FCL, 3F H,l
132a (CF z-CHz) each has a selectivity of 8
They were obtained at 1.5%, 12.4%, and 1.2%.
［発明の効果］ 本発明によれば、１１３を利用して、ｌ ３４ ａ。[Effect of the invention] According to the present invention, by utilizing 113, l34a.
ＣＴＦＥポリマーの原料となる３ＦＨと３ＦＣＬを高選
択率で製造することができる。また、３００℃以下の温
度においても高い選択率を得ることができ、３ＦＣＬと
３ＦＨの生成比を容易に制御することもできる。3FH and 3FCL, which are raw materials for CTFE polymer, can be produced with high selectivity. Moreover, high selectivity can be obtained even at temperatures of 300° C. or lower, and the production ratio of 3FCL and 3FH can be easily controlled.
特許出願人ダイキン工業株式会社Patent applicant Daikin Industries, Ltd.
Claims (1)
ロエタンと水素とを触媒存在下に反応させることによっ
て１−クロロ−１，２，２−トリフルオロエチレンおよ
び１，２，２−トリフルオロエチレンを製造する方法で
あって、触媒としてパラジウム、ロジウムおよびルテニ
ウムから選ばれる少なくとも１種の金属と水銀、鉛、カ
ドミウム、錫、インジウム、銅、ビスマス、タリウムお
よび銀から選ばれる少なくとも１種の金属（ただし、後
者の金属がタリウムのとき、前者の金属がロジウムに限
る）とをＡｌ＿２Ｏ＿３またはＳｉＯ＿２に担持させた
触媒を使用することを特徴とする方法。By reacting 1,1,1,2-trichloro-1,2,2-trifluoroethane with hydrogen in the presence of a catalyst, 1-chloro-1,2,2-trifluoroethylene and 1,2,2 - A method for producing trifluoroethylene, the catalyst comprising at least one metal selected from palladium, rhodium and ruthenium and at least one metal selected from mercury, lead, cadmium, tin, indium, copper, bismuth, thallium and silver. A method characterized by using a catalyst in which a seed metal (when the latter metal is thallium, the former metal is limited to rhodium) is supported on Al_2O_3 or SiO_2.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2241691A JP2887278B2 (en) | 1990-05-31 | 1990-09-11 | Method for producing 1-chloro-1,2,2-trifluoroethylene and 1,2,2-trifluoroethylene |
| EP19910108824 EP0459463B1 (en) | 1990-05-31 | 1991-05-29 | Process for preparing 1-chloro-1,2,2-trifluoroethylene or 1,2,2-trifluoroethylene |
| DE1991603473 DE69103473T2 (en) | 1990-05-31 | 1991-05-29 | Process for the preparation of 1-chloro-1,2,2-trifluoroethylene or 1,2,2-trifluoroethylene. |
| US08/369,259 US5498806A (en) | 1990-05-31 | 1995-01-05 | Process for preparing 1-chloro-1,2,2-trifluoroethylene or 1,2,2-trifluoroethylene |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14305390 | 1990-05-31 | ||
| JP2-143053 | 1990-05-31 | ||
| JP2241691A JP2887278B2 (en) | 1990-05-31 | 1990-09-11 | Method for producing 1-chloro-1,2,2-trifluoroethylene and 1,2,2-trifluoroethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04117333A true JPH04117333A (en) | 1992-04-17 |
| JP2887278B2 JP2887278B2 (en) | 1999-04-26 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2241691A Expired - Fee Related JP2887278B2 (en) | 1990-05-31 | 1990-09-11 | Method for producing 1-chloro-1,2,2-trifluoroethylene and 1,2,2-trifluoroethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2887278B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
| WO2010007968A1 (en) * | 2008-07-18 | 2010-01-21 | 日本ゼオン株式会社 | Method for producing hydrogen-containing fluoroolefin compound |
| JP2014511369A (en) * | 2011-02-04 | 2014-05-15 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | Method for producing perfluorovinyl ether |
| CN109529830A (en) * | 2018-12-18 | 2019-03-29 | 沈阳化工大学 | A kind of dimethyl sulfide carbon monoxide-olefin polymeric preparation method |
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5473716A (en) * | 1977-11-17 | 1979-06-13 | Asahi Chem Ind Co Ltd | Production of carboxylic ester |
| JPS5473717A (en) * | 1977-11-17 | 1979-06-13 | Asahi Chem Ind Co Ltd | Production of carboxylic ester |
| JPS55338A (en) * | 1978-06-19 | 1980-01-05 | Mitsubishi Chem Ind Ltd | Preparation of diacetoxybutene |
| JPH02178238A (en) * | 1988-12-28 | 1990-07-11 | Du Pont Mitsui Fluorochem Co Ltd | Production of fluorine-containing ethylene |
| JPH0413638A (en) * | 1990-04-27 | 1992-01-17 | Central Glass Co Ltd | Preparation of trifluorochloroethylene |
| JPH0499738A (en) * | 1990-08-13 | 1992-03-31 | Nippon Haron Kk | Production of trifluoroethylene |
-
1990
- 1990-09-11 JP JP2241691A patent/JP2887278B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5473716A (en) * | 1977-11-17 | 1979-06-13 | Asahi Chem Ind Co Ltd | Production of carboxylic ester |
| JPS5473717A (en) * | 1977-11-17 | 1979-06-13 | Asahi Chem Ind Co Ltd | Production of carboxylic ester |
| JPS55338A (en) * | 1978-06-19 | 1980-01-05 | Mitsubishi Chem Ind Ltd | Preparation of diacetoxybutene |
| JPH02178238A (en) * | 1988-12-28 | 1990-07-11 | Du Pont Mitsui Fluorochem Co Ltd | Production of fluorine-containing ethylene |
| JPH0413638A (en) * | 1990-04-27 | 1992-01-17 | Central Glass Co Ltd | Preparation of trifluorochloroethylene |
| JPH0499738A (en) * | 1990-08-13 | 1992-03-31 | Nippon Haron Kk | Production of trifluoroethylene |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716590A (en) * | 1993-12-17 | 1998-02-10 | Wacker-Chemie Gmbh | Catalytic hydrodehalogenation of halogen-containing compounds of group IV elements |
| WO2010007968A1 (en) * | 2008-07-18 | 2010-01-21 | 日本ゼオン株式会社 | Method for producing hydrogen-containing fluoroolefin compound |
| US8318991B2 (en) | 2008-07-18 | 2012-11-27 | Zeon Corporation | Method for producing hydrogen-containing fluoroolefin compound |
| JP2014511369A (en) * | 2011-02-04 | 2014-05-15 | ソルヴェイ・スペシャルティ・ポリマーズ・イタリー・エッセ・ピ・ア | Method for producing perfluorovinyl ether |
| US9868684B2 (en) | 2011-02-04 | 2018-01-16 | Solvay Specialty Polymers Italy S.P.A. | Method for manufacturing perfluorovinylethers |
| CN109529830A (en) * | 2018-12-18 | 2019-03-29 | 沈阳化工大学 | A kind of dimethyl sulfide carbon monoxide-olefin polymeric preparation method |
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2887278B2 (en) | 1999-04-26 |
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