JP6807958B2 - Method for Purifying and Producing Carbonyl Fluoride - Google Patents
Method for Purifying and Producing Carbonyl Fluoride Download PDFInfo
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- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 title claims description 107
- 238000000034 method Methods 0.000 title claims description 42
- 239000007789 gas Substances 0.000 claims description 239
- 238000006243 chemical reaction Methods 0.000 claims description 151
- 239000012535 impurity Substances 0.000 claims description 58
- 239000003054 catalyst Substances 0.000 claims description 51
- 239000012043 crude product Substances 0.000 claims description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- 239000011737 fluorine Substances 0.000 claims description 28
- 238000000746 purification Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- 229910052709 silver Inorganic materials 0.000 claims 2
- 239000004332 silver Substances 0.000 claims 2
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 87
- 229910001220 stainless steel Inorganic materials 0.000 description 38
- 239000010935 stainless steel Substances 0.000 description 38
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 28
- 238000001514 detection method Methods 0.000 description 20
- 238000009835 boiling Methods 0.000 description 16
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 15
- KNSWNNXPAWSACI-UHFFFAOYSA-N chlorine pentafluoride Chemical compound FCl(F)(F)(F)F KNSWNNXPAWSACI-UHFFFAOYSA-N 0.000 description 12
- 238000005530 etching Methods 0.000 description 11
- 229940096017 silver fluoride Drugs 0.000 description 10
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 10
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 9
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 9
- 239000011698 potassium fluoride Substances 0.000 description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- 235000013024 sodium fluoride Nutrition 0.000 description 6
- 239000011775 sodium fluoride Substances 0.000 description 6
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 5
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HPNURIVGONRLQI-UHFFFAOYSA-K trifluoroeuropium Chemical compound F[Eu](F)F HPNURIVGONRLQI-UHFFFAOYSA-K 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910016655 EuF 3 Inorganic materials 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000012025 fluorinating agent Substances 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 229910016569 AlF 3 Inorganic materials 0.000 description 3
- 229910016509 CuF 2 Inorganic materials 0.000 description 3
- 101100441092 Danio rerio crlf3 gene Proteins 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
- 238000002474 experimental method Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- MGGVALXERJRIRO-UHFFFAOYSA-N 4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-2-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-1H-pyrazol-5-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)O MGGVALXERJRIRO-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- -1 CO 2 Chemical compound 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000004341 Octafluorocyclobutane Substances 0.000 description 1
- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- KWVVTSALYXIJSS-UHFFFAOYSA-L silver(ii) fluoride Chemical compound [F-].[F-].[Ag+2] KWVVTSALYXIJSS-UHFFFAOYSA-L 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B9/00—General methods of preparing halides
- C01B9/08—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、化学工業の技術分野に関し、特に、フッ化カルボニルの精製方法及び製造方法に関する。 The present invention relates to the technical field of the chemical industry, and more particularly to a method for purifying and producing carbonyl fluoride.
現在、半導体および液晶製造の分野において、パーフルオロカーボンをエッチングガス及びクリーニングガスとすることが多いが、上記ガスは、一般的に地球温暖化係数（ＧＷＰ， Ｇｌｏｂａｌ Ｗａｒｍｉｎｇ Ｐｏｔｅｎｔｉａｌ）値が比較的高く、温室効果を低減するために、ＧＷＰの低い代替製品を開発する必要がある。
フッ化カルボニル（ＣＯＦ２）は、比較的低いＧＷＰを有する半導体用エッチングガス、半導体用クリーニングガス、及び有機合成におけるフッ素化剤ないし重要な中間体である。
Currently, in the field of semiconductor and liquid crystal manufacturing, perfluorocarbon is often used as an etching gas and a cleaning gas, but the above gas generally has a relatively high global warming potential (GWP) value and is a greenhouse. In order to reduce the effect, it is necessary to develop alternative products with low GWP.
Carbonyl fluoride (COF 2 ) is an etching gas for semiconductors having a relatively low GWP, a cleaning gas for semiconductors, and a fluorinating agent or an important intermediate in organic synthesis.
現在、フッ化カルボニルの製造方法は、一般的に以下の４種類に分けられる。
１）一酸化炭素又は二酸化炭素をフッ素ガス、ジフルオロ銀（ＩＩ）などのフッ素化剤と反応させる方法であり、当該方法は、爆発が起こりやすく、かつ高価な耐食性材料が必要であり、製造されたフッ化カルボニルの収率と純度が低い。
２）ホスゲン（ＣＯＣｌ２）をフッ化水素、三フッ化アンチモン、三フッ化ヒ素、フッ化ナトリウムなどのフッ素化剤と反応させる方法であり、当該方法が使用する原料のホスゲンは、毒性の高い物質であり、かつ製造されたフッ化カルボニルの純度が低い。
３）トリフルオロメタンを酸素ガスと反応させる方法であり、当該方法は、反応条件が過酷であり、５００℃以上の高温が必要である。
４）テトラフルオロエチレンを酸素ガスと反応させる方法であり、当該方法は、反応中において非常に大きな反応熱を生じ、爆発の危険性がある。
Currently, methods for producing carbonyl fluoride are generally classified into the following four types.
1) A method of reacting carbon monoxide or carbon dioxide with a fluorinating agent such as fluorine gas or difluorosilver (II), which is prone to explosion and requires an expensive corrosion-resistant material, and is manufactured. The yield and purity of carbonyl fluoride are low.
2) A method of reacting phosgene (COCl 2 ) with a fluorinating agent such as hydrogen fluoride, antimony trifluoride, arsenic trifluoride, and sodium fluoride. The raw material phosgene used in this method is highly toxic. It is a substance and the purity of the produced carbonyl fluoride is low.
3) A method of reacting trifluoromethane with oxygen gas, in which the reaction conditions are harsh and a high temperature of 500 ° C. or higher is required.
4) A method of reacting tetrafluoroethylene with oxygen gas, which generates a very large heat of reaction during the reaction and has a risk of explosion.
また、以上の異なるＣＯＦ２の製造方法と反応条件により製造されたフッ化カルボニルＣＯＦ２の粗生成物ガスは、一般的に、ＨＣｌ、ＨＦ、ホスゲン（ＣＯＣｌ２）、ＣＦ４、ＣＯ２、ＣＯ、Ｈ２Ｏ、Ｎ２Ｏ、空気中のＮ２及びＯ２などの不純物を含むことが多い。中でも、ＣＯＦ２の沸点は−８４．５７℃であり、ＣＯ２の沸点は−７８．４５℃であり、沸点が近く、沸点の差はたった約６℃と小さく、かつＣＯＦ２とＣＯ２分子の物理的化学的性質、分子サイズは比較的近いため、通常の吸着法、精留法による精製分離は困難である。同時にそれらはいずれもアルカリ性物質と反応しやすいために、中和による分離も困難である。現在では、国内外でＣＯＦ２中のＣＯ２の精製について、報告された特許はほとんどない。 Further, the crude product gas of carbonyl fluoride COF 2 produced by the above-mentioned different COF 2 production methods and reaction conditions is generally such as HCl, HF, phosgene (COCl 2 ), CF 4 , CO 2 , CO. , H 2 O, N 2 O, and often contains impurities such as N 2 and O 2 in the air. Among them, the boiling point of COF 2 is -84.57 ° C, the boiling point of CO 2 is -78.45 ° C, the boiling points are close, the difference between the boiling points is as small as about 6 ° C, and the COF 2 and CO 2 molecules Since the physical and chemical properties and molecular size of carbon dioxide are relatively close to each other, it is difficult to purify and separate them by ordinary adsorption methods and rectification methods. At the same time, they are all easy to react with alkaline substances, so they are difficult to separate by neutralization. At present, there are few patents reported on the purification of CO 2 in COF 2 at home and abroad.
上記の問題点に鑑みて、本発明の解決しようとする技術的課題は、製造されたフッ化カルボニルガスが高純度であるフッ化カルボニルの精製方法及び製造方法を提供することにある。 In view of the above problems, a technical problem to be solved by the present invention is to provide a method for purifying and producing carbonyl fluoride having a high purity of the produced carbonyl fluoride gas.
本発明は、
精製ガスをフッ化カルボニル粗生成物ガス中の不純物と反応させ、フッ化カルボニル粗生成物ガス中の不純物を除去し、前記精製ガスは、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種であることを含む、フッ化カルボニルの精製方法を提供する。
好ましくは、前記反応の温度は、−９９℃〜４９９℃であり、前記反応の圧力は、−０．０９ＭＰａ〜５ＭＰａである。
好ましくは、前記反応の温度は、−４９℃〜２９９℃であり、前記反応の圧力は、−０．０５ＭＰａ〜１ＭＰａである。
好ましくは、前記反応の温度は、１℃〜１９９℃であり、前記反応の圧力は、−０．０５ＭＰａ〜１ＭＰａである。
好ましくは、前記反応は、さらに、反応終了後、蒸留、精留、又は凍結真空排気のような方法により精製ガス及び反応で発生する不純物を除去することを含む。
好ましくは、前記フッ化カルボニル粗生成物ガスにおける不純物は、ＣＯ２、ＣＯ、Ｈ２Ｏ、ＣＯＣｌ２、Ｎ２Ｏの不純物ガスの少なくとも１つを含む。
好ましくは、前記反応は、さらに触媒を含み、前記触媒は、セシウムのフッ化物、ナトリウムのフッ化物、カリウムのフッ化物、ユウロピウムのフッ化物、銅のフッ化物、アルミニウムのフッ化物、及び銀のフッ化物のいずれか１種又は複数種を含む。
好ましくは、前記精製ガスとフッ化カルボニル粗生成物ガスとのモル比は、１００〜０．００１： １である。
The present invention
The purified gas is reacted with impurities in the crude carbonyl fluoride product gas to remove impurities in the crude carbonyl fluoride product gas, and the purified gas is one of ClF, ClF 3 , ClF 5 , and F 2 . Provided is a method for purifying carbonyl fluoride, which comprises one or more kinds.
Preferably, the temperature of the reaction is −99 ° C. to 499 ° C. and the pressure of the reaction is −0.09 MPa to 5 MPa.
Preferably, the temperature of the reaction is −49 ° C. to 299 ° C. and the pressure of the reaction is −0.05 MPa to 1 MPa.
Preferably, the temperature of the reaction is 1 ° C to 199 ° C and the pressure of the reaction is −0.05 MPa to 1 MPa.
Preferably, the reaction further comprises removing the purified gas and impurities generated in the reaction by methods such as distillation, rectification, or freezing vacuum exhaust after completion of the reaction.
Preferably, the impurity gas in the carbonyl fluoride crude product gas contains at least one of the impurity gas of CO 2 , CO, H 2 O, COCl 2 and N 2 O.
Preferably, the reaction further comprises a catalyst, the catalyst of which is cesium fluoride, sodium fluoride, potassium fluoride, europium fluoride, copper fluoride, aluminum fluoride, and silver fluoride. Includes any one or more of the fluorides.
Preferably, the molar ratio of the purified gas to the crude carbonyl fluoride product gas is 100 to 0.001: 1.
本発明は、さらに、
ＣＯ、ＣＯ２のいずれか１種又は複数種をフッ素含有ガスと反応させ、フッ化カルボニルを調製し、前記フッ素含有ガスは、ＣｌＦ、ＣｌＦ３、及びＣｌＦ５のいずれか１種又は複数種であり、
あるいは、ＣＯＦＣｌをフッ素含有ガスと反応させ、フッ化カルボニルを調製し、前記フッ素含有ガスは、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種ことを含む、フッ化カルボニルの製造方法を提供する。
好ましくは、前記反応の温度は、−９９℃〜４９９℃であり、前記反応の圧力は、−０．０９ＭＰａ〜５ＭＰａである。
好ましくは、前記反応の温度は、−４９℃〜２９９℃であり、前記反応の圧力は、−０．０５ＭＰａ〜１ＭＰａである。
好ましくは、前記反応の温度は、１℃〜１９９℃であり、前記反応の圧力は、−０．０５ＭＰａ〜１ＭＰａである。
好ましくは、前記フッ素含有ガスとＣＯ、ＣＯ２のいずれか１種又は複数種、又はＣＯＦＣｌとのモル比は、１００〜０．００１： １である。
好ましくは、前記反応は、さらに触媒を含み、前記触媒は、セシウムのフッ化物、ナトリウムのフッ化物、カリウムのフッ化物、ユウロピウムのフッ化物、銅のフッ化物、アルミニウムのフッ化物、及び銀のフッ化物のいずれか１種又は複数種を含む。
The present invention further
One or more of CO and CO 2 are reacted with a fluorine-containing gas to prepare fluorinated carbonyl, and the fluorine-containing gas is one or more of ClF, ClF 3 , and ClF 5. Yes,
Alternatively, reacting the COFCl with fluorine-containing gas, to prepare a carbonyl fluoride, the fluorine-containing gas, ClF, ClF 3, ClF 5, and that any one or more of F 2, carbonyl fluoride Providing a manufacturing method for.
Preferably, the temperature of the reaction is −99 ° C. to 499 ° C. and the pressure of the reaction is −0.09 MPa to 5 MPa.
Preferably, the temperature of the reaction is −49 ° C. to 299 ° C. and the pressure of the reaction is −0.05 MPa to 1 MPa.
Preferably, the temperature of the reaction is 1 ° C to 199 ° C and the pressure of the reaction is −0.05 MPa to 1 MPa.
Preferably, the molar ratio of the fluorine-containing gas to any one or more of CO and CO 2 or COFCl is 100 to 0.001: 1.
Preferably, the reaction further comprises a catalyst, the catalyst of which is cesium fluoride, sodium fluoride, potassium fluoride, europium fluoride, copper fluoride, aluminum fluoride, and silver fluoride. Includes any one or more of the fluorides.
本発明は、従来技術と比較して、精製ガスをフッ化カルボニル粗生成物ガス中の不純物と反応させ、フッ化カルボニル粗生成物ガス中の不純物を除去し、前記精製ガスは、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種であることを含むフッ化カルボニルの精製方法を提供する。本発明が提供する精製方法は、フッ化カルボニルの反応粗生成物を精製し、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種を精製ガスとし、精製装置でフッ化カルボニルの反応粗生成物と反応させ、フッ化カルボニル以外の様々な不純物、特に、ＣＯ２、ＣＯ、Ｈ２Ｏ、ホスゲン（ＣＯＣｌ２）、Ｎ２Ｏなどの不純物を除去し、不純物の含有量を大きく低減させる。精製されたフッ化カルボニル精製ガスは、ＣＯＦ２純度≧９９．９５％、ＣＯ２含有量≦１５０×１０-６（体積比）、ＣＯＣｌ２含有量≦１５０×１０-６（体積比）である。 In the present invention, as compared with the prior art, the purified gas is reacted with impurities in the carbonyl fluoride crude product gas to remove impurities in the carbonyl fluoride crude product gas, and the purified gas is ClF, ClF. A method for purifying carbonyl fluoride, which comprises any one or more of 3 , ClF 5 , and F 2 , is provided. In the purification method provided by the present invention, a crude reaction product of carbonyl fluoride is purified, and any one or more of ClF, ClF 3 , ClF 5 , and F 2 are used as a purification gas, and fluoride is used in a purification apparatus. Reaction with carbonyl reaction crude product to remove various impurities other than carbonyl fluoride, especially impurities such as CO 2 , CO, H 2 O, phosgene (COCl 2 ), N 2 O, and the content of the impurities. Is greatly reduced. The purified carbonyl fluoride purified gas has COF 2 purity ≧ 99.95%, CO 2 content ≦ 150 × 10 -6 (volume ratio), and COCl 2 content ≦ 150 × 10 -6 (volume ratio). ..
本発明は、さらに、ＣＯ、ＣＯ２のいずれか１種又は複数種をフッ素含有ガスと反応させ、フッ化カルボニルを調製する（前記フッ素含有ガスは、ＣｌＦ、ＣｌＦ３、及びＣｌＦ５のいずれか１種又は複数種である）、又は、ＣＯＦＣｌとフッ素含有ガスと反応させ、フッ化カルボニルを調製する（前記フッ素含有ガスは、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種である）ことを含むフッ化カルボニルの製造方法を提供する。本発明は、上記ガスを原料として使用し、調製されたフッ化カルボニルガスが、高い収率及び純度を有する。同時に、より高い安定性と経済的利益がある。 The present invention further reacts one or more of CO and CO 2 with a fluorine-containing gas to prepare a fluoride carbonyl (the fluorine-containing gas is any one of ClF, ClF 3 , and ClF 5 ). One or more types), or COFCl is reacted with a fluorine-containing gas to prepare carbonyl fluoride (the fluorine-containing gas is any one of ClF, ClF 3 , ClF 5 , and F 2 or Provided is a method for producing carbonyl fluoride, which comprises (multiple species). In the present invention, the carbonyl fluoride gas prepared by using the above gas as a raw material has a high yield and purity. At the same time, there is higher stability and economic benefits.
本発明は、精製ガスをフッ化カルボニル粗生成物ガス中の不純物と反応させ、フッ化カルボニル粗生成物ガス中の不純物を除去する（上記精製ガスは、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種である）ことを含むフッ化カルボニルの精製方法を提供する。
本発明が提供する精製方法は、フッ化カルボニルの反応粗生成物を精製し、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種を精製ガスとし、フッ化カルボニル粗生成物ガスと接触させることにより、精製装置で精製ガスをフッ化カルボニルの反応粗生成物中の不純物と反応させ、フッ化カルボニル以外の様々な不純物、特に、ＣＯ２、ＣＯ、Ｈ２Ｏ、ホスゲン（ＣＯＣｌ２）、Ｎ２Ｏなどの不純物を除去し、不純物の含有量を大きく低減させ、操作プロセスが簡単であるとともに、フッ化カルボニルの収率を向上させる。
The present invention reacts the purified gas with impurities in the crude carbonyl fluoride product gas to remove impurities in the crude carbonyl fluoride product gas (the purified gases are ClF, ClF 3 , ClF 5 , and F). Provided is a method for purifying carbonyl fluoride, which comprises any one or more of 2 ).
The purification method provided by the present invention purifies a reaction crude product of carbonyl fluoride and uses any one or more of ClF, ClF 3 , ClF 5 , and F 2 as a purified gas to crudely produce carbonyl fluoride. By contacting with a substance gas, the purification device reacts the purified gas with impurities in the reaction crude product of carbonyl fluoride, and various impurities other than carbonyl fluoride, particularly CO 2 , CO, H 2 O, and phosgen. It removes impurities such as (COCl 2 ) and N 2 O, greatly reduces the content of impurities, simplifies the operation process, and improves the yield of carbonyl fluoride.
本発明にかかるフッ化カルボニル粗生成物ガスは、ＣＯ２、ＣＯ、Ｈ２Ｏ、ＣＯＣｌ２、Ｎ２Ｏの不純物ガスを含むことが好ましく、ＣＯ２、ＣＯＣｌ２含有量の多いガスを含むことがより好ましい。上記不純物の含有量≦１０％（体積比）であることが好ましい。上記ＣＯ２不純物ガスの含有量≦５％（体積比）であることがより好ましく、上記ＣＯＣｌ２不純物ガスの含有量≦５％（体積比）であることがさらに好ましい。
本発明は、かかるＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２には特に制限はないが、当該分野における通常のＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２であればよい。
The crude carbonyl fluoride product gas according to the present invention preferably contains impurity gases of CO 2 , CO, H 2 O, COCl 2 , and N 2 O, and contains a gas having a high content of CO 2 and COCl 2. Is more preferable. The content of the impurities is preferably ≤10% (volume ratio). The content of the CO 2 impurity gas is more preferably ≦ 5% (volume ratio), and the content of the COCl 2 impurity gas is more preferably ≦ 5% (volume ratio).
The present invention, according ClF, ClF 3, ClF 5, and is not particularly limited to F 2, conventional ClF in the art, ClF 3, ClF 5, and may be a F 2.
上記精製ガスは、単独で用いてもよいし、順番に用いてもよく、例えば、本発明における幾つかの具体的な実施例において、まず、三フッ化塩素（ＣｌＦ３）で精製し、さらに、一フッ化塩素（ＣｌＦ）で精製し、本発明における他の幾つかの実施例において、まず、一フッ化塩素（ＣｌＦ）で精製し、さらに、三フッ化塩素（ＣｌＦ３）で精製する。
ここで、常圧下（１０１．３２５ｋＰａ）、ＣＯＦ２の沸点は−８４．５７℃であり、ホスゲン（ＣＯＣｌ２）の沸点は７．５６℃であり、ＣＯ２の沸点は−７８．４５℃であり、ＣＯの沸点は−１９１．４５℃であり、Ｈ２の沸点は−２５２．７６℃であり、Ｈ２Ｏの沸点は１００℃であり、Ｏ２の沸点は−１８２．９８℃であり、Ｃｌ２の沸点は−３４．０３℃であり、ＣｌＦ３の沸点は１１．７５℃であり、ＣｌＦの沸点は−１００．１℃であり、ＣｌＦ５の沸点は−１３．１ ℃であり、Ｆ２の沸点は−１８８．２℃である。精製ガスにより精製された後、フッ化カルボニル粗生成物ガス中の複数種の不純物は反応して除去され、特に、ＣＯ２などの分離しにくい不純物と精製ガスとは反応して精製しやすい不純物となる。
The purified gas may be used alone or in sequence. For example, in some specific examples of the present invention, the purified gas is first purified with chlorine trifluoride (ClF 3 ) and then further purified. , Purify with chlorine monofluoride (ClF), and in some other examples of the present invention, first purify with chlorine monofluoride (ClF) and then with chlorine trifluoride (ClF 3 ). ..
Here, under normal pressure (101.325 kPa), the boiling point of COF 2 is −84.57 ° C., the boiling point of phosgen (COCl 2 ) is 7.56 ° C., and the boiling point of CO 2 is −78.45 ° C. The boiling point of CO is -191.45 ° C, the boiling point of H 2 is -252.76 ° C, the boiling point of H 2 O is 100 ° C, and the boiling point of O 2 is 182.98 ° C. , Cl 2 has a boiling point of −34.03 ° C., ClF 3 has a boiling point of 11.75 ° C., ClF has a boiling point of −100.1 ° C., and ClF 5 has a boiling point of -13.1 ° C. , F 2 has a boiling point of -188.2 ° C. After purification with a purification gas, a plurality of types of impurities in the carbonyl fluoride crude product gas are reacted and removed, and in particular, impurities that are difficult to separate such as CO 2 and impurities that are easy to purify by reacting with the purification gas. It becomes.
上記反応中において、かかる反応の温度は、−９９℃〜４９９℃であることが好ましく、−４９℃〜２９９℃であることがより好ましく、１℃〜１９９℃であることが最も好ましく、かかる反応の圧力は、−０．０９ＭＰａ〜５ＭＰａであることがことが好ましく、−０．０５ＭＰａ〜１ＭＰａであることがより好ましい。かかる圧力の数値は、ゲージ圧である。
好ましくは、かかるＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種、即ち精製ガスの全量とフッ化カルボニル粗生成物ガスとのモル比は、１００〜０．００１： １であり、より好ましくは、５０〜０．１： １である。
During the above reaction, the temperature of the reaction is preferably −99 ° C. to 499 ° C., more preferably −49 ° C. to 299 ° C., and most preferably 1 ° C. to 199 ° C. The pressure of is preferably −0.09 MPa to 5 MPa, more preferably −0.05 MPa to 1 MPa. The numerical value of such pressure is the gauge pressure.
Preferably, any one or more of such ClF, ClF 3 , ClF 5 , and F 2 , that is, the molar ratio of the total amount of purified gas to the crude carbonyl fluoride product gas is 100 to 0.001: 1. It is more preferably 50 to 0.1: 1.
反応終了後で得られたものは、フッ化カルボニル精製ガスと残った精製ガスと反応副生成物との混合物であり、本発明は、さらに通常の蒸留、精留、又は凍結真空排気の方法により、残った精製ガス及び反応中において発生する不純物を除去することが好ましい。
本発明は、好ましくは、上記反応が、さらに、セシウムのフッ化物（好ましくは、ＣｓＦ）、ナトリウムのフッ化物（好ましくは、ＮａＦ）、カリウムのフッ化物（好ましくは、ＫＦ）、ユウロピウムのフッ化物（好ましくは、ＥｕＦ３）、銅のフッ化物（好ましくは、ＣｕＦ２）、アルミニウムのフッ化物（好ましくは、ＡｌＦ３）和銀のフッ化物（好ましくは、ＡｇＦ）のいずれか１種又は複数種を含むことが好ましい触媒を含む。
What was obtained after completion of the reaction was a mixture of the carbonyl fluoride purified gas, the remaining purified gas and the reaction by-product, and the present invention was further carried out by a conventional distillation, rectification, or freeze-vacuum exhaust method. It is preferable to remove the remaining purified gas and impurities generated during the reaction.
In the present invention, the above reaction is preferably carried out in addition to fluoride of cesium (preferably CsF), fluoride of sodium (preferably NaF), fluoride of potassium (preferably KF), fluoride of europium. One or more of (preferably EuF 3 ), copper fluoride (preferably CuF 2 ), aluminum fluoride (preferably AlF 3 ) and Japanese silver fluoride (preferably AgF). Includes a catalyst preferably comprising.
本発明は、上記触媒の用量には特に制限はないが、触媒の通常の用量であってもよいし、又は実験に従って自分で決定されてもよい。
本発明で得られたフッ化カルボニル精製ガスは、ＣＯＦ２の純度≧９９．９５％、ＣＯ２含有量≦１５０×１０-６（体積比）、ＣＯＣｌ２含有量≦１５０×１０-６（体積比）である。
The present invention is not particularly limited in the dose of the catalyst, but may be a normal dose of the catalyst, or may be determined by oneself according to an experiment.
The carbonyl fluoride purified gas obtained in the present invention has COF 2 purity ≧ 99.95%, CO 2 content ≦ 150 × 10 -6 (volume ratio), and COCl 2 content ≦ 150 × 10 -6 (volume). Ratio).
本発明は、さらに、
ＣＯ、ＣＯ２のいずれか１種又は複数種をフッ素含有ガスと反応させ、フッ化カルボニルを調製し、上記フッ素含有ガスは、ＣｌＦ、ＣｌＦ３、及びＣｌＦ５のいずれか１種又は複数種であり、
或いは、ＣＯＦＣｌをフッ素含有ガスと反応させ、フッ化カルボニルを調製し、上記フッ素含有ガスは、ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種であることを含むフッ化カルボニルの製造方法を提供する。
The present invention further
One or more of CO and CO 2 are reacted with a fluorine-containing gas to prepare fluorinated carbonyl, and the above-mentioned fluorine-containing gas is one or more of ClF, ClF 3 , and ClF 5. Yes,
Alternatively, COFCl is reacted with a fluorine-containing gas to prepare fluorinated carbonyl, and the fluorine-containing gas is fluorinated including any one or more of ClF, ClF 3 , ClF 5 , and F 2 . A method for producing carbonyl is provided.
本発明は、ＣＯ、ＣＯ２、及びＣＯＦＣｌのいずれか１種又は複数種、並びにＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種を原料として、調製されたフッ化カルボニルガスが、高い収率及び純度を有する。同時に、より高い安全性と経済的利益がある。
本発明は、上記ＣＯ、ＣＯ２、及びＣＯＦＣｌには特に制限はないが、当該分野における通常のＣＯ、ＣＯ２、及びＣＯＦＣｌであればよい。
本発明は上記ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２には特に制限はないが、当該分野における通常のＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２であればよい。
The present invention is a carbonyl fluoride prepared from any one or more of CO, CO 2 , and COFCl, and any one or more of ClF, ClF 3 , ClF 5 , and F 2 as raw materials. The gas has high yield and purity. At the same time, there are higher safety and economic benefits.
The present invention is not particularly limited to the above CO, CO 2 and COF Cl, but may be ordinary CO, CO 2 and COF Cl in the art.
The present invention is not particularly limited to the above ClF, ClF 3 , ClF 5 , and F 2 , but may be ordinary ClF, ClF 3 , ClF 5 , and F 2 in the art.
上記ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２原料ガスは、単独で用いてもよいし、順番に用いてもよく、例えば、本発明における幾つかの具体的な実施例において、まず、三フッ化塩素（ＣｌＦ３）を使用して調製し、さらに一フッ化塩素（ＣｌＦ）を使用して調製し、本発明における他の幾つかの実施例において、まず、一フッ化塩素（ＣｌＦ）を使用して調製し、さらに三フッ化塩素（ＣｌＦ３）を使用して調製する。 The ClF, ClF 3 , ClF 5 , and F 2 source gases may be used alone or in sequence. For example, in some specific examples of the present invention, first, three hooks are used. Prepared using chlorine fluoride (ClF 3 ) and further prepared using chlorine monofluoride (ClF), and in some other examples of the present invention, first chlorine monofluoride (ClF). Prepared using, and further prepared using chlorine trifluoride (ClF 3 ).
上記反応中において、かかる反応の温度は、−９９℃〜４９９℃であることが好ましく、−４９℃〜２９９℃であることがより好ましく、１℃〜１９９℃である最も好ましく、かかる反応の圧力は、−０．０９ＭＰａ〜５ＭＰａであることが好ましく、−０．０５ＭＰａ〜１ＭＰａであることがより好ましい。上記圧力の数値は、ゲージ圧である。
好ましくは、かかるＣｌＦ、ＣｌＦ３、及びＣｌＦ５のいずれか１種又は複数種、即ちフッ素含有ガスの全量とＣＯ、ＣＯ２のいずれか１種又は複数種とのモル比は、１００〜０．００１： １であることが好ましく、５０〜１： １であることがより好ましい。
During the above reaction, the temperature of the reaction is preferably −99 ° C. to 499 ° C., more preferably −49 ° C. to 299 ° C., most preferably 1 ° C. to 199 ° C., and the pressure of the reaction. Is preferably −0.09 MPa to 5 MPa, more preferably −0.05 MPa to 1 MPa. The numerical value of the above pressure is a gauge pressure.
Preferably, the molar ratio of any one or more of such ClF, ClF 3 , and ClF 5 , that is, the total amount of the fluorine-containing gas to any one or more of CO and CO 2 is 100 to 0. It is preferably 001: 1 and more preferably 50 to 1: 1.
上記ＣｌＦ、ＣｌＦ３、ＣｌＦ５、及びＦ２のいずれか１種又は複数種、即ちフッ素含有ガスの全量とＣＯＦＣｌとのモル比は、１００〜０．００１： １であることが好ましく、５０〜１： １であることがより好ましい。
反応終了後で得られたものは、フッ化カルボニル精製ガスと残た原料ガスと反応で発生する他のガスとの混合物であり、本発明は、通常の蒸留、精留、又は凍結真空排気の方法により残た原料ガス及び反応で発生する他のガスを除去することが好ましい。
Any one or more of ClF, ClF 3 , ClF 5 , and F 2 , that is, the molar ratio of the total amount of the fluorine-containing gas to COFCl is preferably 100 to 0.001: 1, and is preferably 50 to 0.001: 1. It is more preferably 1: 1.
What was obtained after the reaction was completed was a mixture of the carbonyl fluoride purified gas, the remaining raw material gas, and other gases generated by the reaction, and the present invention is obtained by ordinary distillation, rectification, or freezing vacuum exhaust. It is preferable to remove the raw material gas remaining by the method and other gases generated by the reaction.
本発明では、好ましくは、上記反応が、さらに、セシウムのフッ化物（好ましくは、ＣｓＦ）、ナトリウムのフッ化物（好ましくは、ＮａＦ）、カリウムのフッ化物（好ましくは、ＫＦ）、ユウロピウムのフッ化物（好ましくは、ＥｕＦ３）、銅のフッ化物（好ましくは、ＣｕＦ２）、アルミニウムのフッ化物（好ましくは、ＡｌＦ３）、及び銀のフッ化物（好ましくは、ＡｇＦ）のいずれか１種又は複数種を含むことが好ましい触媒を含む。
本発明は、上記触媒の用量には特に制限はないが、触媒の通常の用量であってもよく、又は実験に従って自分で決定してもよい。
In the present invention, preferably, the above reaction is further carried out with fluoride of cesium (preferably CsF), fluoride of sodium (preferably NaF), fluoride of potassium (preferably KF), fluoride of europium. One or more of (preferably EuF 3 ), copper fluoride (preferably CuF 2 ), aluminum fluoride (preferably AlF 3 ), and silver fluoride (preferably AgF). Includes a catalyst preferably containing a seed.
The present invention is not particularly limited in the dose of the catalyst, but may be a normal dose of the catalyst, or may be determined by oneself according to an experiment.
本発明は、調製されたフッ化カルボニルの用途には特に制限はないが、例えば、半導体製造装置のクリーニングガス及びエッチングガス、有機合成におけるフッ素化剤、原料、中間体などの他の広い分野に用いられることが好ましい。中でも、純度が高いため、半導体製造装置のクリーニングガス及びエッチングガスにさらに適用することができる。エッチング及びクリーニング条件は、プラズマエッチング、気相エッチング、イオンビームエッチング、マイクロ波エッチング、反応性エッチングなどのエッチング条件、及び対応するクリーニング条件であってもよい。上記フッ化カルボニルは、単独又は他のエッチングガス、クリーニングガスと混合物として用いてもよく、他のガスは、例えば、三フッ化窒素（ＮＦ３）、四フッ化炭素（ＣＦ４）、ヘキサフルオロエタン（Ｃ２Ｆ６）、オクタフルオロプロパン（Ｃ３Ｆ８）、オクタフルオロシクロブタン（Ｃ４Ｆ８）、１、３-ブタジエン、フッ化水素（ＨＦ）、塩化水素（ＨＣｌ）、臭化水素（ＨＢｒ）、塩素ガス（Ｃｌ２）、六フッ化硫黄（ＳＦ６）、四フッ化ケイ素（ＳｉＦ４）、ＣＨＦ３、ＣＣｌＦ３、Ｃ２ＣｌＦ５、ＢＣｌ３、ＨＦＣｌ２、フッ素ガス（Ｆ２）などのガス、及び上記ガスと不活性ガス、希釈用ガス（例えば、Ｈｅ、Ｎ２、Ａｒ、Ｏ２、Ｈ２など）との混合ガスである。混合する量の割合は特に制限されず、用途に応じて適宜選択することができる。 The present invention is not particularly limited in the use of the prepared carbonyl fluoride, but is used in a wide range of other fields such as cleaning gas and etching gas for semiconductor manufacturing equipment, fluorinating agents in organic synthesis, raw materials, and intermediates. It is preferable to be used. Above all, since it has high purity, it can be further applied to cleaning gas and etching gas of semiconductor manufacturing equipment. The etching and cleaning conditions may be etching conditions such as plasma etching, vapor phase etching, ion beam etching, microwave etching, and reactive etching, and corresponding cleaning conditions. The above-mentioned carbonyl fluoride may be used alone or as a mixture with another etching gas or cleaning gas, and other gases include, for example, nitrogen trifluoride (NF 3 ), carbon tetrafluoride (CF 4 ), and hexafluoro. Ethan (C 2 F 6 ), Octafluoropropane (C 3 F 8 ), Octafluorocyclobutane (C 4 F 8 ), 1,3-butadiene, Hydrogen Fluoride (HF), Hydrogen Chloride (HCl), Hydrogen Bromide (HBr), Chlorine gas (Cl 2 ), Sulfur hexafluoride (SF 6 ), Silicon tetrafluoride (SiF 4 ), CHF 3 , CClF 3 , C 2 ClF 5 , BCl 3 , HFCl 2 , Fluorine gas (F) 2 ) and the like, and a mixed gas of the above gas with an inert gas and a diluting gas (for example, He, N 2 , Ar, O 2 , H 2 and the like). The ratio of the amount to be mixed is not particularly limited, and can be appropriately selected depending on the intended use.
以下、本発明をさらに説明するために、本発明が提供するフッ化カルボニルの精製方法及び製造方法を、実施例を用いて詳細に説明する。
本発明において、上記圧力とは、特に言及しなければ、いずれもゲージ圧を意味する。
収率とは、ある生成物の理論収量に対する実際に得られた収量の割合を意味する。収率の計算は、使用量が不足である原料に基づいて計算する。
ここで、実施例１〜２４は、フッ化カルボニル粗生成物ガスの精製プロセスの実施例であり、実験の必要に応じて上記特定の不純物を含むフッ化カルボニル粗生成物ガスを配合する。中でも、フッ化カルボニル粗生成物ガス中のＣＯ２、ＣＯ、ホスゲン（ＣＯＣｌ２）、Ｎ２Ｏ不純物の含有量は、それぞれ２００×１０-６（体積比）である。
Hereinafter, in order to further explain the present invention, the method for purifying and producing carbonyl fluoride provided by the present invention will be described in detail with reference to Examples.
In the present invention, the above-mentioned pressure means a gauge pressure unless otherwise specified.
Yield means the ratio of the actually obtained yield to the theoretical yield of a product. Yield calculations are based on raw materials that are in short supply.
Here, Examples 1 to 24 are examples of the purification process of the carbonyl fluoride crude product gas, and the carbonyl fluoride crude product gas containing the above-mentioned specific impurities is blended as necessary for the experiment. Above all, the contents of CO 2 , CO, phosgene (COCl 2 ), and N 2 O impurities in the crude carbonyl fluoride product gas are 200 × 10 -6 (volume ratio), respectively.
実施例１
ＣＯＦ２粗生成物ガス５モルを乾燥された５Ｌのステンレス製反応釜に導入し、その後、三フッ化塩素を導入して反応させ、ＣｌＦ３とフッ化カルボニル粗生成物ガスとのモル比は、１：１である。反応温度は４９９℃であり、反応圧力は５ＭＰａであり、上記反応釜の排気口から反応生成物を排出し、温度が−１１０℃の低温冷却トラップに導入し、凍結真空排気の方法により不純物を除去し、精製されたガスをフッ化カルボニル精製ガスの貯蔵タンクに収集し、精製されたガスを検出した。
具体的には、精製されたガスをガスクロマトグラフ−質量分析計（ＧＣ−ＭＳ、型番：株式会社島津製作所製ＧＣ−２０１４）とフーリエ変換赤外分光光度計（ＦＴ−ＩＲ、型番：Ｎｉｃｏｌｅｔ６７００）に導入し、その組成を分析した。収集されたガスは、ＧＣ−ＭＳ及びＦＴ−ＩＲによりフッ化カルボニルと確認され、ガスクロマトグラフのデータ結果の主成分の積分面積から主成分の純度を算出した。
Example 1
5 mol of COF 2 crude product gas was introduced into a dried 5 L stainless steel reaction vessel, and then chlorine trifluoride was introduced to react, and the molar ratio of ClF 3 to carbonyl fluoride crude product gas was It is 1: 1. The reaction temperature is 499 ° C., the reaction pressure is 5 MPa, the reaction product is discharged from the exhaust port of the reaction vessel, introduced into a low-temperature cooling trap having a temperature of −110 ° C., and impurities are removed by the method of freeze-vacuum exhaust. The removed and purified gas was collected in a storage tank for carbonyl fluoride purified gas and the purified gas was detected.
Specifically, the purified gas was applied to a gas chromatograph-mass spectrometer (GC-MS, model number: GC-2014 manufactured by Shimadzu Corporation) and a Fourier transform infrared spectrophotometer (FT-IR, model number: Nicolet6700). It was introduced and its composition was analyzed. The collected gas was confirmed to be carbonyl fluoride by GC-MS and FT-IR, and the purity of the principal component was calculated from the integrated surface integral of the principal component as a result of the gas chromatograph data.
ここで、ガスクロマトグラフによる測定には、Ｐｏｒａｐａｋカラム、モレキュラーシーブ１３Ｘカラムを使用し、キャリアガスとしてＨｅガスを使用し、ＴＣＤ検出器を使用し、Ｈｅキャリアガスの流速が６０ｍＬ／ｍｉｎであり、カラム温度が２３℃であり、注入口温度が６０℃であり、ＴＣＤ温度が６０℃である。ガスクロマトグラムの最大のピークは、フッ化カルボニルに由来するピークである。
精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜５０×１０-６（体積比）、ＣＯＣｌ２含有量＜５０×１０-６（体積比）、ＣＯ含有量＜５×１０-６（体積比）、Ｎ２Ｏ含有量＜５×１０-６（体積比）であることが明らかになった。
Here, for the measurement by the gas chromatograph, a Porapak column and a molecular sieve 13X column are used, He gas is used as the carrier gas, a TCD detector is used, and the flow velocity of the He carrier gas is 60 mL / min. The temperature is 23 ° C., the inlet temperature is 60 ° C., and the TCD temperature is 60 ° C. The largest peak in the gas chromatogram is the peak derived from carbonyl fluoride.
Was detected with the purified gas, the purified gas is carbonyl fluoride, a purity of 99.95%, impurity CO 2 content <50 × 10 -6 (volume ratio), COCl 2 content <50 × 10 - 6 (volume ratio), CO content of <5 × 10 -6 (volume ratio), it was found to be a N 2 O content of <5 × 10 -6 (volume ratio).
実施例２
反応釜において、反応温度は−９９℃であり、反応圧力は−０．０９ＭＰａであり、反応中において、触媒としてセシウムのフッ化物（ＣｓＦ）２ｇを使用し、ＣｌＦ３とフッ化カルボニル粗生成物ガスとのモル比は１０００：１となった以外は、実施例１と同様にした。
実施例１の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１５０×１０-６（体積比）、ＣＯＣｌ２含有量＜１５０×１０-６（体積比）、ＣＯ含有量＜１５×１０-６（体積比）、Ｎ２Ｏ含有量＜１５×１０-６（体積比）であることが明らかになった。
Example 2
In the reaction vessel, the reaction temperature was -99 ° C., the reaction pressure was -0.09 MPa, and during the reaction, 2 g of fluoride (CsF) of cesium was used as a catalyst, and ClF 3 and a crude product of carbonyl fluoride were used. It was the same as in Example 1 except that the molar ratio with gas was 1000: 1.
When the purified gas was detected under the detection conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <150 × 10 -6 (volume ratio), and COCl 2 It was clarified that the content was <150 × 10 -6 (volume ratio), the CO content was <15 × 10 -6 (volume ratio), and the N 2 O content was <15 × 10 -6 (volume ratio). ..
実施例３
反応釜において、反応温度は２９９℃であり、反応圧力は１ＭＰａであり、触媒としてナトリウムのフッ化物（ＮａＦ）２ｇを使用し、ＣｌＦ３とフッ化カルボニル粗生成物ガスとのモル比は０．００１：１となった以外は、実施例１と同様にした。
実施例１の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜７０×１０-６（体積比）、ＣＯＣｌ２含有量＜７０×１０-６（体積比）、ＣＯ含有量＜７×１０-６（体積比）、Ｎ２Ｏ含有量＜７×１０-６（体積比）であることが明らかになった。
Example 3
In the reaction vessel, the reaction temperature was 299 ° C., the reaction pressure was 1 MPa, 2 g of sodium fluoride (NaF) was used as a catalyst, and the molar ratio of ClF 3 to the crude carbonyl fluoride product gas was 0. This was the same as in Example 1 except that the ratio was 001: 1.
When the purified gas was detected under the detection conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <70 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <70 × 10 -6 (volume ratio), the CO content was <7 × 10 -6 (volume ratio), and the N 2 O content was <7 × 10 -6 (volume ratio). ..
実施例４
反応釜において、反応温度は１９９℃であり、反応圧力は−０．０５ＭＰａであり、触媒としてカリウムのフッ化物（ＫＦ）２ｇを使用した以外は、実施例１と同様にした。
実施例１の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜８０×１０-６（体積比）、ＣＯＣｌ２含有量＜８０×１０-６（体積比）、ＣＯ含有量＜８×１０-６（体積比）、Ｎ２Ｏ含有量＜８×１０-６（体積比）であることが明らかになった。
Example 4
In the reaction kettle, the reaction temperature was 199 ° C., the reaction pressure was −0.05 MPa, and the same procedure as in Example 1 was carried out except that 2 g of fluoride (KF) of potassium was used as a catalyst.
When the purified gas was detected under the detection conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <80 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <80 × 10 -6 (volume ratio), the CO content was <8 × 10 -6 (volume ratio), and the N 2 O content was <8 × 10 -6 (volume ratio). ..
実施例５
反応釜において、反応温度は１℃であり、反応圧力は１ＭＰａであり、触媒としてユウロピウムのフッ化物（ＥｕＦ３）２ｇを使用した以外は、実施例１と同様にした。
実施例１の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１００×１０-６（体積比）、ＣＯＣｌ２含有量＜１００×１０-６（体積比）、ＣＯ含有量＜１０×１０-６（体積比）、Ｎ２Ｏ含有量＜１０×１０-６（体積比）であることが明らかになった。
Example 5
In the reaction kettle, the reaction temperature was 1 ° C., the reaction pressure was 1 MPa, and the same procedure as in Example 1 was carried out except that 2 g of europium fluoride (EuF 3 ) was used as a catalyst.
When the purified gas was detected under the detection conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <100 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <100 × 10 -6 (volume ratio), the CO content was <10 × 10 -6 (volume ratio), and the N 2 O content was <10 × 10 -6 (volume ratio). ..
実施例６
反応釜において、反応温度は−４９℃であり、反応圧力は５ＭＰａであり、触媒として銅のフッ化物（ＣｕＦ２）２ｇを使用した以外は、実施例１と同様にした。
実施例１の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１２０×１０-６（体積比）、ＣＯＣｌ２含有量＜１２０×１０-６（体積比）、ＣＯ含有量＜１２×１０-６（体積比）、Ｎ２Ｏ含有量＜１２×１０-６（体積比）であることが明らかになった。
Example 6
In the reaction kettle, the reaction temperature was −49 ° C., the reaction pressure was 5 MPa, and the same procedure as in Example 1 was carried out except that 2 g of copper fluoride (CuF 2 ) was used as a catalyst.
When the purified gas was detected under the detection conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <120 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <120 × 10 -6 (volume ratio), the CO content was <12 × 10 -6 (volume ratio), and the N 2 O content was <12 × 10 -6 (volume ratio). ..
実施例７
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入して反応させ、反応温度は４９９℃であり、反応圧力は５ＭＰａであり、実施例１と同様にした。
実施例１の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜５０×１０-６（体積比）、ＣＯＣｌ２含有量＜５０×１０-６（体積比）、ＣＯ含有量＜５×１０-６（体積比）、Ｎ２Ｏ含有量＜５×１０-６（体積比）であることが明らかになった。
Example 7
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine monofluoride was introduced and reacted. The reaction temperature was 499 ° C. and the reaction pressure was 5 MPa. , The same as in Example 1.
When the purified gas was detected under the detection conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <50 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <50 × 10 -6 (volume ratio), the CO content was <5 × 10 -6 (volume ratio), and the N 2 O content was <5 × 10 -6 (volume ratio). ..
実施例８
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入して反応させ、反応中において触媒としてアルミニウムのフッ化物（ＡｌＦ３）２ｇを使用した以外は、実施例２と同様にした。
実施例２の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１５０×１０-６（体積比）、ＣＯＣｌ２含有量＜１５０×１０-６（体積比）、ＣＯ含有量＜１５×１０-６（体積比）、Ｎ２Ｏ含有量＜１５×１０-６（体積比）であることが明らかになった。
Example 8
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine monofluoride was introduced to react, and 2 g of aluminum fluoride (AlF 3 ) was used as a catalyst during the reaction. Was used, but was the same as in Example 2.
When the purified gas was detected under the detection conditions of Example 2, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <150 × 10 -6 (volume ratio), and COCl 2 It was clarified that the content was <150 × 10 -6 (volume ratio), the CO content was <15 × 10 -6 (volume ratio), and the N 2 O content was <15 × 10 -6 (volume ratio). ..
実施例９
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入して反応させ、反応中において触媒として銀のフッ化物（ＡｇＦ）２ｇを使用した以外は、実施例３と同様にした。
実施例３の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜７０×１０-６（体積比）、ＣＯＣｌ２含有量＜７０×１０-６（体積比）、ＣＯ含有量＜７×１０-６（体積比）、Ｎ２Ｏ含有量＜７×１０-６（体積比）であることが明らかになった。
Example 9
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine monofluoride was introduced and reacted, and 2 g of silver fluoride (AgF) was used as a catalyst during the reaction. It was the same as in Example 3 except that it was used.
When the purified gas was detected under the detection conditions of Example 3, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <70 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <70 × 10 -6 (volume ratio), the CO content was <7 × 10 -6 (volume ratio), and the N 2 O content was <7 × 10 -6 (volume ratio). ..
実施例１０
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入して反応させ、反応中において触媒としてセシウムのフッ化物（ＣｓＦ）２ｇを使用した以外は、実施例４と同様にした。
実施例４の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜８０×１０-６（体積比）、ＣＯＣｌ２含有量＜８０×１０-６（体積比）、ＣＯ含有量＜８×１０-６（体積比）、Ｎ２Ｏ含有量＜８×１０-６（体積比）であることが明らかになった。
Example 10
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine monofluoride was introduced to react, and 2 g of cesium fluoride (CsF) was used as a catalyst during the reaction. It was the same as in Example 4 except that it was used.
When the purified gas was detected under the detection conditions of Example 4, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <80 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <80 × 10 -6 (volume ratio), the CO content was <8 × 10 -6 (volume ratio), and the N 2 O content was <8 × 10 -6 (volume ratio). ..
実施例１１
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入して反応させ、反応中において触媒としてナトリウムのフッ化物（ＮａＦ）２ｇを使用した以外は、実施例５と同様にした。
実施例５の条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１００×１０-６（体積比）、ＣＯＣｌ２含有量＜１００×１０-６（体積比）、ＣＯ含有量＜１０×１０-６（体積比）、Ｎ２Ｏ含有量＜１０×１０-６（体積比）であることが明らかになった。
Example 11
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine monofluoride was introduced to react, and 2 g of sodium fluoride (NaF) was used as a catalyst during the reaction. It was the same as in Example 5 except that it was used.
When the purified gas was detected under the conditions of Example 5, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <100 × 10 -6 (volume ratio), and the COCl 2 content. It was revealed that the amount <100 × 10 -6 (volume ratio), the CO content <10 × 10 -6 (volume ratio), and the N 2 O content <10 × 10 -6 (volume ratio).
実施例１２
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入して反応させ、反応中において触媒としてカリウムのフッ化物（ＫＦ）２ｇを使用した以外は、実施例６と同様にした。
実施例６の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１２０×１０-６（体積比）、ＣＯＣｌ２含有量＜１２０×１０-６（体積比）、ＣＯ含有量＜１２×１０-６（体積比）、Ｎ２Ｏ含有量＜１２×１０-６（体積比）であることが明らかになった。
Example 12
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine monofluoride was introduced and reacted, and 2 g of fluoride (KF) of potassium was used as a catalyst during the reaction. It was the same as in Example 6 except that it was used.
When the purified gas was detected under the detection conditions of Example 6, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <120 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <120 × 10 -6 (volume ratio), the CO content was <12 × 10 -6 (volume ratio), and the N 2 O content was <12 × 10 -6 (volume ratio). ..
実施例１３
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入して反応させた以外は、実施例１と同様にした。
実施例１の条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜５０×１０-６（体積比）、ＣＯＣｌ２含有量＜５０×１０-６（体積比）、ＣＯ含有量＜５×１０-６（体積比）、Ｎ２Ｏ含有量＜５×１０-６（体積比）であることが明らかになった。
Example 13
The same procedure as in Example 1 was carried out except that 5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction kettle, and then 5 mol of chlorine pentafluoride was introduced and reacted.
When the purified gas was detected under the conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <50 × 10 -6 (volume ratio), and the COCl 2 content. the amount <50 × 10 -6 (volume ratio), CO content of <5 × 10 -6 (volume ratio), it was found to be a N 2 O content of <5 × 10 -6 (volume ratio).
実施例１４
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入して反応させ、反応中において触媒としてユウロピウムのフッ化物（ＥｕＦ３）２ｇを使用した以外は、実施例２と同様にした。
実施例２の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１５０×１０-６（体積比）、ＣＯＣｌ２含有量＜１５０×１０-６（体積比）、ＣＯ含有量＜１５×１０-６（体積比）、Ｎ２Ｏ含有量＜１５×１０-６（体積比）であることが明らかになった。
Example 14
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine pentafluoride was introduced to react, and 2 g of europium fluoride (EuF 3 ) as a catalyst during the reaction. Was used, but was the same as in Example 2.
When the purified gas was detected under the detection conditions of Example 2, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <150 × 10 -6 (volume ratio), and COCl 2 It was clarified that the content was <150 × 10 -6 (volume ratio), the CO content was <15 × 10 -6 (volume ratio), and the N 2 O content was <15 × 10 -6 (volume ratio). ..
実施例１５
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入して反応させ、反応中において触媒として銅のフッ化物（ＣｕＦ２）２ｇを使用した以外は、実施例３と同様にした。
実施例３の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜７０×１０-６（体積比）、ＣＯＣｌ２含有量＜７０×１０-６（体積比）、ＣＯ含有量＜７×１０-６（体積比）、Ｎ２Ｏ含有量＜７×１０-６（体積比）であることが明らかになった。
Example 15
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine pentafluoride was introduced to react, and 2 g of copper fluoride (CuF 2 ) was used as a catalyst during the reaction. Was used, but was the same as in Example 3.
When the purified gas was detected under the detection conditions of Example 3, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <70 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <70 × 10 -6 (volume ratio), the CO content was <7 × 10 -6 (volume ratio), and the N 2 O content was <7 × 10 -6 (volume ratio). ..
実施例１６
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入して反応させ、反応中において触媒としてセシウムのフッ化物（ＣｓＦ）２ｇを使用した以外は、実施例４と同様にした。
実施例４の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜８０×１０-６（体積比）、ＣＯＣｌ２含有量＜８０×１０-６（体積比）、ＣＯ含有量＜８×１０-６（体積比）、Ｎ２Ｏ含有量＜８×１０-６（体積比）であることが明らかになった。
Example 16
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine pentafluoride was introduced to react, and 2 g of cesium fluoride (CsF) was used as a catalyst during the reaction. It was the same as in Example 4 except that it was used.
When the purified gas was detected under the detection conditions of Example 4, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <80 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <80 × 10 -6 (volume ratio), the CO content was <8 × 10 -6 (volume ratio), and the N 2 O content was <8 × 10 -6 (volume ratio). ..
実施例１７
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入して反応させ、反応中において触媒としてアルミニウムのフッ化物（ＡｌＦ３）２ｇを使用した以外は、実施例５と同様にした。
実施例５の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１００×１０-６（体積比）、ＣＯＣｌ２含有量＜１００×１０-６（体積比）、ＣＯ含有量＜１０×１０-６（体積比）、Ｎ２Ｏ含有量＜１０×１０-６（体積比）であることが明らかになった。
Example 17
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine pentafluoride was introduced to react, and 2 g of aluminum fluoride (AlF 3 ) was used as a catalyst during the reaction. Was used, but was the same as in Example 5.
When the purified gas was detected under the detection conditions of Example 5, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <100 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <100 × 10 -6 (volume ratio), the CO content was <10 × 10 -6 (volume ratio), and the N 2 O content was <10 × 10 -6 (volume ratio). ..
実施例１８
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入して反応させ、反応中において触媒として銀のフッ化物（ＡｇＦ）２ｇを使用した以外は、実施例６と同様にした。
実施例６の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１２０×１０-６（体積比）、ＣＯＣｌ２含有量＜１２０×１０-６（体積比）、ＣＯ含有量＜１２×１０-６（体積比）、 Ｎ２Ｏ含有量＜１２×１０-６（体積比）であることが明らかになった。
Example 18
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine pentafluoride was introduced and reacted, and 2 g of silver fluoride (AgF) was used as a catalyst during the reaction. It was the same as in Example 6 except that it was used.
When the purified gas was detected under the detection conditions of Example 6, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <120 × 10 -6 (volume ratio), and COCl 2 It was clarified that the content was <120 × 10 -6 (volume ratio), the CO content was <12 × 10 -6 (volume ratio), and the N 2 O content was <12 × 10 -6 (volume ratio). ..
実施例１９
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入して反応させた以外は、実施例１と同様にした。
実施例１の条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜５０×１０-６（体積比）、ＣＯＣｌ２含有量＜５０×１０-６（体積比）、ＣＯ含有量＜５×１０-６（体積比）、Ｎ２Ｏ含有量＜５×１０-６（体積比）であることが明らかになった。
Example 19
The same procedure as in Example 1 was carried out except that 5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of fluorine gas was introduced and reacted.
When the purified gas was detected under the conditions of Example 1, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <50 × 10 -6 (volume ratio), and the COCl 2 content. the amount <50 × 10 -6 (volume ratio), CO content of <5 × 10 -6 (volume ratio), it was found to be a N 2 O content of <5 × 10 -6 (volume ratio).
実施例２０
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入して反応させ、反応中において触媒としてユウロピウムのフッ化物（ＥｕＦ３）２ｇを使用した以外は、実施例２と同様にした。
実施例２の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１５０×１０-６（体積比）、ＣＯＣｌ２含有量＜１５０×１０-６（体積比）、ＣＯ含有量＜１５× １０-６（体積比）、Ｎ２Ｏ含有量＜１５×１０-６（体積比）であることが明らかになった。
Example 20
5 mol of COF 2 crude product gas is introduced into a dry 5 L stainless steel reaction kettle, then 5 mol of fluorine gas is introduced and reacted, and 2 g of fluoropium fluoride (EuF 3 ) is used as a catalyst during the reaction. This was the same as in Example 2 except that.
When the purified gas was detected under the detection conditions of Example 2, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <150 × 10 -6 (volume ratio), and COCl 2 content <150 × 10 -6 (volume ratio), CO content of <15 × 10 -6 (volume ratio), it was found to be a N 2 O content of <15 × 10 -6 (volume ratio) ..
実施例２１
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入して反応させ、反応中において触媒として銅のフッ化物（ＣｕＦ２）２ｇを使用した以外は、実施例３と同様にした。
実施例３の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜７０×１０-６（体積比）、ＣＯＣｌ２含有量＜７０×１０-６（体積比）、ＣＯ含有量＜７×１０-６（体積比）、Ｎ２Ｏ含有量＜７×１０-６（体積比）であることが明らかになった。
Example 21
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of fluorine gas was introduced to react, and 2 g of copper fluoride (CuF 2 ) was used as a catalyst during the reaction. This was the same as in Example 3 except that.
When the purified gas was detected under the detection conditions of Example 3, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <70 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <70 × 10 -6 (volume ratio), the CO content was <7 × 10 -6 (volume ratio), and the N 2 O content was <7 × 10 -6 (volume ratio). ..
実施例２２
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入して反応させ、反応中において触媒としてセシウムのフッ化物（ＣｓＦ）２ｇを使用した以外は、実施例４と同様にした。
実施例４の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜８０×１０-６（体積比）、ＣＯＣｌ２含有量＜８０×１０-６（体積比）、ＣＯ含有量＜８×１０-６（体積比）、Ｎ２Ｏ含有量＜８×１０-６（体積比）であることが明らかになった。
Example 22
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of fluorine gas was introduced and reacted, and 2 g of cesium fluoride (CsF) was used as a catalyst during the reaction. Other than that, it was the same as in Example 4.
When the purified gas was detected under the detection conditions of Example 4, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <80 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <80 × 10 -6 (volume ratio), the CO content was <8 × 10 -6 (volume ratio), and the N 2 O content was <8 × 10 -6 (volume ratio). ..
実施例２３
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入して反応させ、反応中において触媒としてアルミニウムのフッ化物（ＡｌＦ３）２ｇを使用した以外は、実施例５と同様にした。
実施例５の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９５％であり、不純物ＣＯ２含有量＜１００×１０-６（体積比）、ＣＯＣｌ２含有量＜１００×１０-６（体積比）、ＣＯ含有量＜１０×１０-６（体積比）、Ｎ２Ｏ含有量＜１０×１０-６（体積比）であることが明らかになった。
Example 23
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of fluorine gas was introduced to react, and 2 g of aluminum fluoride (AlF 3 ) was used as a catalyst during the reaction. This was the same as in Example 5 except that
When the purified gas was detected under the detection conditions of Example 5, the purified gas was carbonyl fluoride, the purity was 99.95%, the impurity CO 2 content <100 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <100 × 10 -6 (volume ratio), the CO content was <10 × 10 -6 (volume ratio), and the N 2 O content was <10 × 10 -6 (volume ratio). ..
実施例２４
ＣＯＦ２粗生成物ガス５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入して反応させ、反応中において触媒として銀のフッ化物（ＡｇＦ）２ｇを使用した以外は、実施例６と同様にした。
実施例６の検出条件で精製ガスを検出したところ、精製ガスはフッ化カルボニルであり、純度は９９．９％であり、不純物ＣＯ２含有量＜１２０×１０-６（体積比）、ＣＯＣｌ２含有量＜１２０×１０-６（体積比）、ＣＯ含有量＜１２×１０-６（体積比）、Ｎ２Ｏ含有量＜１２×１０-６（体積比）であることが明らかになった。
Example 24
5 mol of COF 2 crude product gas was introduced into a dry 5 L stainless steel reaction kettle, then 5 mol of fluorine gas was introduced and reacted, and 2 g of silver fluoride (AgF) was used as a catalyst during the reaction. Other than that, it was the same as in Example 6.
When the purified gas was detected under the detection conditions of Example 6, the purified gas was carbonyl fluoride, the purity was 99.9%, the impurity CO 2 content <120 × 10 -6 (volume ratio), and COCl 2 It was revealed that the content was <120 × 10 -6 (volume ratio), the CO content was <12 × 10 -6 (volume ratio), and the N 2 O content was <12 × 10 -6 (volume ratio). ..
実施例２５
ＣＯ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、三フッ化塩素を導入し、ＣｌＦ３とＣＯガスとのモル比は１：１であり、反応釜において、反応温度は４９９℃であり、反応圧力は５ＭＰａであり、上記反応釜の排気口から反応生成物を排出し、温度が-１１０℃の低温冷却トラップに導入し、凍結真空排気の方法により不純物を除去し、精製されたガスをフッ化カルボニル精製ガスの貯蔵タンクに収集し、調製されたガスを検出した。
具体的には、精製されたガスをガスクロマトグラフ-質量分析計（ＧＣ−ＭＳ、型番：株式会社島津製作所製ＧＣ−２０１４）とフーリエ変換赤外分光光度計（ＦＴ−ＩＲ、型番：Ｎｉｃｏｌｅｔ６７００）に導入し、その組成を分析した。収集されたガスは、ＧＣ-ＭＳ及びＦＴ-ＩＲによりフッ化カルボニルと確認され、ガスクロマトグラフのデータ結果の主成分の積分面積により主成分の純度を算出した。
ガスクロマトグラフによる測定には、Ｐｏｒａｐａｋカラム、モレキュラーシーブ １３Ｘ カラムを使用し、キャリアガスとしてＨｅガスを使用し、ＴＣＤ検出器を使用し、Ｈｅキャリアガスの流速が６０ｍＬ／ｍｉｎであり、カラム温度が２３℃であり、注入口温度が６０ ℃であり、ＴＣＤ温度が６０℃である。ガスクロマトグラムの最大のピークは、フッ化カルボニルに由来するピークである。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は９５％であり、純度は９６％であることが明らかになった。
Example 25
5 mol of CO was introduced into a dry 5 L stainless steel reaction vessel, then chlorine trifluoride was introduced, the molar ratio of ClF 3 to CO gas was 1: 1 and the reaction temperature was 499 in the reaction vessel. The temperature is ° C., the reaction pressure is 5 MPa, the reaction product is discharged from the exhaust port of the reaction vessel, introduced into a low-temperature cooling trap having a temperature of -110 ° C., impurities are removed by the method of freezing vacuum exhaust, and purification is performed. The prepared gas was collected in a storage tank for purified fluorinated gas, and the prepared gas was detected.
Specifically, the purified gas was applied to a gas chromatograph-mass spectrometer (GC-MS, model number: GC-2014 manufactured by Shimadzu Corporation) and a Fourier transform infrared spectrophotometer (FT-IR, model number: Nicolet6700). It was introduced and its composition was analyzed. The collected gas was confirmed to be carbonyl fluoride by GC-MS and FT-IR, and the purity of the principal component was calculated from the integrated surface integral of the principal component as a result of the gas chromatograph data.
For the measurement by gas chromatograph, a Porapak column and a molecular sieve 13X column are used, He gas is used as the carrier gas, a TCD detector is used, the flow velocity of the He carrier gas is 60 mL / min, and the column temperature is 23. The temperature is 60 ° C, the inlet temperature is 60 ° C, and the TCD temperature is 60 ° C. The largest peak in the gas chromatogram is the peak derived from carbonyl fluoride.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 95%, and the purity was 96%.
実施例２６
反応釜において、反応温度は−９９℃であり、反応圧力は−０．０９ＭＰａであり、反応中において触媒としてセシウムのフッ化物２ｇを使用し、ＣｌＦ３とＣＯガスとのモル比は１００：１となった以外は、実施例２５と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８３％であり、純度は８８％であることが明らかになった。
Example 26
In the reaction vessel, the reaction temperature was -99 ° C., the reaction pressure was -0.09 MPa, 2 g of fluoride of cesium was used as a catalyst during the reaction, and the molar ratio of ClF 3 to CO gas was 100: 1. It was the same as in Example 25 except that.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 83%, and the purity was 88%.
実施例２７
ＣＯ２ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、５モルの三フッ化塩素を導入し、反応中において触媒としてナトリウムのフッ化物（ＮａＦ）２ｇを使用し、ＣｌＦ３とＣＯ２ガスとのモル比は０．００１：１となった以外は、実施例２５と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は３５％であり、純度は７０％であることが明らかになった。
Example 27
The CO 2 5 moles were introduced into a stainless steel reaction kettle drying 5L, then introduce the 5 moles of chlorine trifluoride, using sodium fluoride (NaF) 2 g as a catalyst in the reaction, and ClF 3 The same as in Example 25 except that the molar ratio with CO 2 gas was 0.001: 1.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 35%, and the purity was 70%.
実施例２８
ＣＯ２ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、５モルの三フッ化塩素を導入し、反応中において触媒としてカリウムのフッ化物（ＫＦ）２ｇを使用した以外は、実施例２６と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は４２％であり、純度は７４％であることが明らかになった。
Example 28
The CO 2 5 moles were introduced into a stainless steel reaction kettle drying 5L, then, except that introduces 5 moles of chlorine trifluoride was used fluoride (KF) 2 g of potassium as a catalyst in the reaction, carried out The same as in Example 26.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 42%, and the purity was 74%.
実施例２９
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、５モルの三フッ化塩素を導入し、反応中において触媒としてユウロピウムのフッ化物ＥｕＦ３ ２ｇを使用した以外は、実施例２５と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８５％、純度は９０％であることが明らかになった。
Example 29
The COFCl 5 moles were introduced into a stainless steel reaction kettle drying 5L, then, except that introduces 5 moles of chlorine trifluoride was used fluoride EuF 3 2 g of europium as a catalyst in the reaction, Example 25 I did the same.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 85%, and the purity was 90%.
実施例３０
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、５モルの三フッ化塩素を導入し、反応中において触媒として銅のフッ化物（ＣｕＦ２）２ｇを使用した以外は、実施例２６と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８４％であり、純度は８９％であることが明らかになった。
Example 30
Except that 5 mol of COFCl was introduced into a dry 5 L stainless steel reaction kettle, then 5 mol of chlorine trifluoride was introduced and 2 g of copper fluoride (CuF 2 ) was used as a catalyst during the reaction. The same as in Example 26.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 84%, and the purity was 89%.
実施例３１
ＣＯ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入し、反応中において触媒としてアルミニウムのフッ化物（ＡｌＦ３）２ｇを使用した以外は、実施例２５と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８０％であり、純度は９２％であることが明らかになった。
Example 31
Examples except that 5 mol of CO was introduced into a dry 5 L stainless steel reaction vessel, then 5 mol of chlorine monofluoride was introduced and 2 g of aluminum fluoride (AlF 3 ) was used as a catalyst during the reaction. It was the same as 25.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 80%, and the purity was 92%.
実施例３２
ＣＯ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入し、反応中において触媒として銀のフッ化物（ＡｇＦ）２ｇを使用した以外は、実施例２６と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は７３％であり、純度は８８％であることが明らかになった。
Example 32
Example 26, except that 5 mol of CO was introduced into a dry 5 L stainless steel reaction vessel, then 5 mol of chlorine monofluoride was introduced and 2 g of silver fluoride (AgF) was used as a catalyst during the reaction. I did the same.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 73%, and the purity was 88%.
実施例３３
ＣＯ２ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入し、反応中において触媒としてセシウムのフッ化物（ＣｓＦ）２ｇを使用した以外は、実施例３１と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は４０％であり、純度は７０％であることが明らかになった。
Example 33
The CO 2 5 moles were introduced into a stainless steel reaction kettle drying 5L, then, except that introduces chlorine monofluoride 5 mol, it was used fluoride (CsF) 2 g of cesium as a catalyst in the reaction, examples It was the same as 31.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 40%, and the purity was 70%.
実施例３４
ＣＯ２ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入し、反応中において触媒としてナトリウムのフッ化物（ＮａＦ）２ｇを使用した以外は、実施例３２と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は４５％であり、純度は７２％であることが明らかになった。
Example 34
The CO 2 5 moles were introduced into a stainless steel reaction kettle drying 5L, then, except that introduces chlorine monofluoride 5 mol, it was used fluoride (NaF) 2 g of sodium as a catalyst in the reaction, examples It was the same as 32.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 45%, and the purity was 72%.
実施例３５
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入し、反応中において触媒としてカリウムのフッ化物２ｇを使用した以外は、実施例３１と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は７７％であり、純度は９０％であることが明らかになった。
Example 35
Same as in Example 31 except that 5 mol of COFCl was introduced into a dry 5 L stainless steel reaction vessel, then 5 mol of chlorine monofluoride was introduced and 2 g of potassium fluoride was used as a catalyst during the reaction. did.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 77%, and the purity was 90%.
実施例３６
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、一フッ化塩素５モルを導入し、反応中において触媒を使用しなかった以外は、実施例３２と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は７６％であり、純度は８９％であることが明らかになった。
Example 36
5 mol of COFCl was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine monofluoride was introduced, and the same procedure as in Example 32 was carried out except that no catalyst was used during the reaction.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 76%, and the purity was 89%.
実施例３７
ＣＯ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入し、反応中において触媒としてセシウムのフッ化物（ＣｓＦ）２ｇを使用した以外は、実施例２５と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は９５％であり、純度は９６％であることが明らかになった。
Example 37
Example 25, except that 5 mol of CO was introduced into a dry 5 L stainless steel reaction vessel, then 5 mol of chlorine pentafluoride was introduced and 2 g of cesium fluoride (CsF) was used as a catalyst during the reaction. I did the same.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 95%, and the purity was 96%.
実施例３８
ＣＯ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入し、反応中において触媒としてユウロピウムのフッ化物（ＥｕＦ３）２ｇを使用した以外は、実施例２６と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８１％であり、純度は８８％であることが明らかになった。
Example 38
Examples except that 5 mol of CO was introduced into a dry 5 L stainless steel reaction kettle, then 5 mol of chlorine pentafluoride was introduced and 2 g of europium fluoride (EuF 3 ) was used as a catalyst during the reaction. It was the same as 26.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 81%, and the purity was 88%.
実施例３９
ＣＯ２ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入し、反応中において触媒として銅のフッ化物（ＣｕＦ２）２ｇを使用した以外は、実施例３７と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は４４％であり、純度は７０％であることが明らかになった。
Example 39
The CO 2 5 moles were introduced into a stainless steel reaction kettle drying 5L, then, except that introduces chlorine pentafluoride 5 moles, copper fluoride as catalyst in the reaction (CuF 2) was used 2g, implementation The same as in Example 37.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 44%, and the purity was 70%.
実施例４０
ＣＯ２ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入し、反応中において触媒としてアルミニウムのフッ化物（ＡｌＦ３）２ｇを使用した以外は、実施例３８と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は４０％であり、純度は７２％であることが明らかになった。
Example 40
The CO 2 5 moles were introduced into a stainless steel reaction kettle drying 5L, then, except that introduces chlorine pentafluoride 5 moles, of aluminum fluoride as a catalyst in the reaction (AlF 3) were used 2g, implementation The same as in Example 38.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 40%, and the purity was 72%.
実施例４１
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入し、反応中において触媒を使用しなかった以外は、実施例３７と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８３％であり、純度は９０％であることが明らかになった。
Example 41
5 mol of COFCl was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of chlorine pentafluoride was introduced, and the same procedure as in Example 37 was carried out except that no catalyst was used during the reaction.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 83%, and the purity was 90%.
実施例４２
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、五フッ化塩素５モルを導入し、反応中において触媒として銀のフッ化物２ｇを使用した以外は、実施例３８と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８２％であり、純度は８９％であることが明らかになった。
Example 42
Similar to Example 38, except that 5 mol of COFCl was introduced into a dry 5 L stainless steel reaction kettle, then 5 mol of chlorine pentafluoride was introduced and 2 g of silver fluoride was used as a catalyst during the reaction. did.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 82%, and the purity was 89%.
実施例４３
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入し、反応中において触媒を使用しなかった以外は、実施例２５と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８１％であり、純度は８８％であることが明らかになった。
Example 43
5 mol of COFCl was introduced into a dry 5 L stainless steel reaction vessel, and then 5 mol of fluorine gas was introduced, and the same procedure as in Example 25 was carried out except that no catalyst was used during the reaction.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 81%, and the purity was 88%.
実施例４４
ＣＯＦＣｌ ５モルを乾燥の５Ｌのステンレス製反応釜に導入し、その後、フッ素ガス５モルを導入し、反応中において触媒として銀のフッ化物２ｇを使用した以外は、実施例２６と同様にした。
調製されたガスを検出したところ、精製ガスはフッ化カルボニルであり、収率は８０％であり、純度は８７％であることが明らかになった。
Example 44
The procedure was the same as in Example 26, except that 5 mol of COFCl was introduced into a dry 5 L stainless steel reaction vessel, then 5 mol of fluorine gas was introduced, and 2 g of silver fluoride was used as a catalyst during the reaction.
When the prepared gas was detected, it was revealed that the purified gas was carbonyl fluoride, the yield was 80%, and the purity was 87%.
上記実施例により、本発明が調製するフッ化カルボニルは、比較的に高い収率、及び純度を有する。
以上、実施例の説明は本発明の方法及びその主旨の理解を助けるためのものに過ぎない。なお、当業者にとっては、本発明は、その原理から逸脱することなく、若干の改良及び修飾も可能であり、それらの改良及び修飾はいずれも本発明の特許請求の範囲によって保護される範囲に包含される。
According to the above examples, the carbonyl fluoride prepared by the present invention has a relatively high yield and purity.
As described above, the description of the examples is merely for assisting in understanding the method of the present invention and its gist. It should be noted that for those skilled in the art, the present invention can be slightly improved and modified without departing from the principle, and all of these improvements and modifications are within the scope of the claims of the present invention. Included.
Claims (13)
又は、ＣＯＦＣｌをＣｌＦ、ＣｌＦ 3 、及びＣｌＦ 5 のいずれか１種又は複数種のフッ素含有ガスと−９９℃〜４９９℃の温度及び−０．０９ＭＰａ〜５ＭＰａの圧力で反応させ、フッ化カルボニルを調製することを含むフッ化カルボニルの製造方法。 One or more of CO and CO 2 are mixed with one or more fluorine-containing gases of ClF, ClF 3 , and ClF 5 and a temperature of -99 ° C to 499 ° C and -0.09 MPa to 5 MPa. Reaction with pressure to prepare carbonyl fluoride,
Alternatively, COFCl is reacted with one or more fluorine-containing gases of ClF, ClF 3 , and ClF 5 at a temperature of -99 ° C to 499 ° C and a pressure of -0.09 MPa to 5 MPa to form carbonyl fluoride. A method for producing carbonyl fluoride, which comprises preparing.
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| CN103213965B (en) * | 2013-04-24 | 2016-02-17 | 邯郸净化设备研究所 | A kind of preparation method of carbonyl fluoride |
| CN103303894B (en) * | 2013-06-17 | 2015-03-11 | 邯郸净化设备研究所 | Carbonyl fluoride purifying method |
| CN105565324B (en) * | 2015-12-23 | 2019-01-04 | 中国船舶重工集团公司第七一八研究所 | A kind of purification process of ocratation |
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