JPH0678256B2 - Fluorophenol manufacturing method - Google Patents
Fluorophenol manufacturing methodInfo
- Publication number
- JPH0678256B2 JPH0678256B2 JP63150103A JP15010388A JPH0678256B2 JP H0678256 B2 JPH0678256 B2 JP H0678256B2 JP 63150103 A JP63150103 A JP 63150103A JP 15010388 A JP15010388 A JP 15010388A JP H0678256 B2 JPH0678256 B2 JP H0678256B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- catalyst
- parafluorochlorobenzene
- fluorophenol
- silica
- 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.)
- Expired - Lifetime
Links
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 title description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- CGPVLUCOFNAVGV-UHFFFAOYSA-N copper;pentahydrate Chemical compound O.O.O.O.O.[Cu] CGPVLUCOFNAVGV-UHFFFAOYSA-N 0.000 description 2
- 150000005171 halobenzenes Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 1
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical compound FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 description 1
- RBAHXNSORRGCQA-UHFFFAOYSA-N 1-chloro-2-fluoro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1F RBAHXNSORRGCQA-UHFFFAOYSA-N 0.000 description 1
- MHXNHUSVBYUTJL-UHFFFAOYSA-N 1-chloro-2-fluoro-4-methylbenzene Chemical compound CC1=CC=C(Cl)C(F)=C1 MHXNHUSVBYUTJL-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-AHCXROLUSA-N copper-60 Chemical compound [60Cu] RYGMFSIKBFXOCR-AHCXROLUSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000008423 fluorobenzenes Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- -1 vanazine Chemical compound 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)
- Catalysts (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、フルオロフェノール類の製造方法に関する。
さらに詳しくは、フルオロクロロベンゼン類を銅含有結
晶性シリカおよび／または銅を含有し、珪素／メタル原
子比が10以上（ただし、メタルがアルミニウムの場合は
50以上）の結晶性メタロシリケートを触媒とし、選択的
に加水分解してフルオロフェノール類を製造する方法に
関する。TECHNICAL FIELD The present invention relates to a method for producing fluorophenols.
More specifically, fluorochlorobenzenes contain copper-containing crystalline silica and / or copper and have a silicon / metal atomic ratio of 10 or more (however, when the metal is aluminum,
(50 or more) using a crystalline metallosilicate as a catalyst to selectively hydrolyze to produce fluorophenols.
（従来の技術） 従来、フルオロフェノールの製造方法としては、例え
ば、（１）ブロモフルオロベンゼンを水酸化カルシウム
および水の存在下でアルカリ分解する方法、（２）アミ
ノフェノールをジアゾニウム塩とした後、分解する方
法、（３）フェノールをフッ素でフッ素化する方法等が
知られている。また、一方、ハロベンゼンの加水分解に
よるフェノールの製造法も、例えば、特開昭47−27936
号、特開昭62−192330号、特開昭62−281834号公報等に
おいて知られている。(Prior Art) Conventionally, as a method for producing fluorophenol, for example, (1) a method in which bromofluorobenzene is alkali-decomposed in the presence of calcium hydroxide and water, (2) after aminophenol is converted to a diazonium salt, A method of decomposing, (3) a method of fluorinating phenol with fluorine, etc. are known. On the other hand, a method for producing phenol by hydrolysis of halobenzene is also disclosed in, for example, JP-A-47-27936.
JP-A-62-192330, JP-A-62-281834 and the like.
（発明が解決しようとする課題） しかしながら、従来のフルオロフェノールの合成方法
は、高温、高圧の反応条件を必要とするとか、複雑な反
応工程を必要とするとか、反応そのものに問題を有して
いる上、オルト、メタ、パラの異性体のうち特定の異性
体を選択率よく合成することができない等、工業的に満
足できるレベルにない。また、公知のハロベンゼンの加
水分解法で、選択的にフルオロフェノールを製造する方
法は知られていない。(Problems to be Solved by the Invention) However, the conventional method for synthesizing fluorophenol has a problem that the reaction itself requires high-temperature, high-pressure reaction conditions, a complicated reaction step, or the like. In addition, specific isomers of ortho, meta, and para isomers cannot be synthesized with high selectivity, which is not industrially satisfactory. Further, there is no known method for selectively producing fluorophenol by a known halobenzene hydrolysis method.
（課題を解決するための手段） 本発明者らは、高選択率で、かつ、簡単なプロセスによ
りフルオロフェノールを製造する方法について鋭意検討
を加えた結果、フルオロクロロベンゼン類を銅含有結晶
性シリカおよび／または銅を含有し、珪素／メタル原子
比が10以上（ただし、メタルがアルミニウムの場合は50
以上）の結晶性メタロシリケートを触媒に用いて加水分
解することにより、極めて選択的にクロル基のみが加水
分解され、フルオロフェノールが生成することを見出し
たものである。特に工業的に有用なパラフルオロフェノ
ールをパラフルオロクロロベンゼンより得ることができ
る。(Means for Solving the Problem) The inventors of the present invention have made earnest studies on a method of producing fluorophenol with a high selectivity and a simple process, and as a result, have determined that fluorochlorobenzenes are used as copper-containing crystalline silica and / Or contains copper and has a silicon / metal atomic ratio of 10 or more (however, when the metal is aluminum, it is 50
It was discovered that by hydrolyzing the crystalline metallosilicate of the above) as a catalyst, only the chloro group is hydrolyzed very selectively to produce fluorophenol. Particularly useful industrially useful parafluorophenol can be obtained from parafluorochlorobenzene.
本発明で用いられるフルオロクロロベンゼン類として
は、一般式 で示されるもので、Ｒは置換基を示し、例えば、水素、
アルキル基、ニトロ基、ニトリル基、カルボキシル基等
である。具体的には、パラフルオロクロロベンゼン、オ
ルトフルオロクロロベンゼン、メタフルオロクロロベン
ゼン、４−メチル−２−フルオロクロロベンゼン、４−
ニトロ−２−フルオロクロロベンゼン等を挙げることが
できる。The fluorochlorobenzenes used in the present invention have the general formula And R represents a substituent, for example, hydrogen,
Examples thereof include an alkyl group, a nitro group, a nitrile group and a carboxyl group. Specifically, parafluorochlorobenzene, orthofluorochlorobenzene, metafluorochlorobenzene, 4-methyl-2-fluorochlorobenzene, 4-
Examples thereof include nitro-2-fluorochlorobenzene.
本発明で用いられる触媒は、銅含有結晶性シリカあるい
は結晶性メタロシリケートであって、好ましい構造は、
ZSM−５、ZSM−11、AZ−１（特開昭59−128210号公報）
類似のものである。The catalyst used in the present invention is a copper-containing crystalline silica or crystalline metallosilicate, and a preferred structure is
ZSM-5, ZSM-11, AZ-1 (JP-A-59-128210)
Is similar.
これら銅含有メタロシリケートの構成元素としては、
銅、珪素、酸素を必須成分とし、それにアルミニウム、
ホウ素、クロム、チタン、バナジン、鉄、希土類元素等
公知のメタロシリケートに用いられる成分を含むもので
ある。結晶性シリカは前記必須成分のみ含み、これらの
後者の成分を実質上含まないものである。銅の含有量と
しては0.1〜10重量％、好ましくは0.2〜２重量％が用い
られる。結晶性メタロシリケートの珪素と銅以外のメタ
ル成分の原子比としては、あるアルミニウムの場合は50
以上、好ましくは100以上が、それ以外のメタル成分の
場合は10以上、好ましくは20以上が用いられる。As the constituent elements of these copper-containing metallosilicates,
Copper, silicon and oxygen are essential components, and aluminum,
It contains components used in known metallosilicates such as boron, chromium, titanium, vanazine, iron, and rare earth elements. Crystalline silica contains only the above-mentioned essential components and substantially does not include these latter components. The copper content is 0.1 to 10% by weight, preferably 0.2 to 2% by weight. The atomic ratio of the metal components other than copper in the crystalline metallosilicate is 50 in the case of certain aluminum.
As described above, preferably 100 or more is used, and in the case of other metal components, 10 or more, preferably 20 or more is used.
銅の含有方法としては、公知のメタロシリケートあるい
は結晶性シリカの水熱合成時に銅化合物を存在させ、水
熱合成するのが好ましいが、通常用いられる含浸法、蒸
発乾固法、イオン交換法等の手段で銅を含まない結晶性
メタロシリケートあるいは結晶性シリカに銅を含有させ
る方法も用いることができる。As a method for containing copper, it is preferable to allow a copper compound to be present during hydrothermal synthesis of a known metallosilicate or crystalline silica, and perform hydrothermal synthesis, but a commonly used impregnation method, evaporation dryness method, ion exchange method, etc. It is also possible to use a method of incorporating copper into a crystalline metallosilicate or crystalline silica containing no copper by the above means.
本発明における反応条件としては通常250〜600℃、好ま
しくは300〜550℃の温度、水と原料フルオロクロロベン
ゼンのモル比としては0.5〜100、好ましくは１〜50が用
いられ、反応圧力としては通常大気圧で実施されるが減
圧、加圧下でも実施できる。原料フルオロクロロベンゼ
ンの供給量は、重量時間空間速度（WHSV）として0.05〜
10hr-1、好ましくは0.1〜5hr-1が用いられる。The reaction conditions in the present invention are usually 250 to 600 ° C., preferably a temperature of 300 to 550 ° C., a molar ratio of water to raw material fluorochlorobenzene is 0.5 to 100, preferably 1 to 50, and a reaction pressure is usually It is carried out at atmospheric pressure, but it can also be carried out under reduced pressure or pressure. The feed rate of the raw material fluorochlorobenzene is 0.05 to 50 as the weight hourly space velocity (WHSV).
10 hr -1, preferably 0.1～5Hr -1 is used.
（発明の効果） 本発明の方法によれば、フルオロクロロベンゼンより簡
単なプロセスで選択率よく、フルオロフェノールを製造
することができる。特に工業的に有用なパラフルオロフ
ェノール類を高選択率で製造することができる。(Effect of the Invention) According to the method of the present invention, fluorophenol can be produced with a simpler process and higher selectivity than fluorochlorobenzene. Particularly, industrially useful parafluorophenols can be produced with a high selectivity.
（実施例） 以下、実施例を挙げて本発明を具体的に示すが、本発明
は、これに限定されるものではない。(Examples) Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
実施例１ シリカゾル（シリカ固形分30重量％）256gに、硫酸第２
銅５水塩5.6gおよびテトラプロピルアンモニウムブロマ
イド60gを純水220gに溶解した水溶液を、強撹拌下に添
加し、ついで、15重量％のカ性ソーダ水溶液20gを添加
し均一ゲル化したものを、１のテフロン内張りのオー
トクレーブに仕込み、170℃、600rpm条件下で60時間水
熱合成した。生成スラリーを濾過、水洗し、ついで、11
0℃、４時間乾燥後、500℃空気中で焼成し、銅含有結晶
性シリケートを得た。このもののＸ線回析は、ZSM−５
類似のパターンを示し、また、銅の含有量は1.5重量％
であった。Example 1 To 256 g of silica sol (silica solid content: 30% by weight) was added sulfuric acid second
An aqueous solution prepared by dissolving 5.6 g of copper pentahydrate and 60 g of tetrapropylammonium bromide in 220 g of pure water was added under vigorous stirring, and then 20 g of a 15 wt% caustic soda aqueous solution was added to form a uniform gel. The mixture was placed in a Teflon-lined autoclave No. 1 and hydrothermally synthesized at 170 ° C. and 600 rpm for 60 hours. The resulting slurry is filtered, washed with water, then 11
After drying at 0 ° C. for 4 hours, it was baked in air at 500 ° C. to obtain a copper-containing crystalline silicate. The X-ray diffraction of this product is ZSM-5
Shows a similar pattern with a copper content of 1.5% by weight
Met.
この触媒を圧縮成形し、９〜20メッシュに破砕したもの
（触媒Ａ）を石英ガラス製反応管（15mmφ×300ml）に5
g充填し、電気炉で400℃に加熱し、水およびパラフルオ
ロクロロベンゼンを各々1.3ml/Hrで定量供給し、加水分
解反応を行った。その結果、パラフルオロクロロベンゼ
ンの転化率は5.2％で、パラフルオロフェノールの選択
率は98％であった。This catalyst was compression molded and crushed to 9 to 20 mesh (Catalyst A) in a quartz glass reaction tube (15 mmφ × 300 ml).
It was charged with g and heated to 400 ° C. in an electric furnace, and water and parafluorochlorobenzene were supplied at a constant rate of 1.3 ml / Hr to carry out a hydrolysis reaction. As a result, the conversion of parafluorochlorobenzene was 5.2% and the selectivity of parafluorophenol was 98%.
実施例２ 実施例１の触媒Ａを用い、実施例１と同様に、ただし、
触媒充填量を20gにし、パラフルオロクロロベンゼンの
加水分解反応を行った。その結果、パラフルオロクロロ
ベンゼンの転化率は21％で、パラフルオロフェノールの
選択率は84％であった。Example 2 Using the catalyst A of Example 1, as in Example 1, except that
The catalyst filling amount was set to 20 g, and the hydrolysis reaction of parafluorochlorobenzene was performed. As a result, the conversion of parafluorochlorobenzene was 21% and the selectivity of parafluorophenol was 84%.
実施例３ シリカゾル（シリカ固形分30重量％）250gに、硫酸第２
銅５水塩5.6g、テトラプロピルアンモニウムブロマイド
65gおよび硝酸クロム９水塩32gを純水220gに溶解した液
を、強撹拌下に添加し、ついで、40重量％カ性ソーダ水
溶液40gを添加したゲル状生成物を、実施例１と同様の
方法で水熱合成し、銅−クロムシリケートを調整した。
このものの銅含有量は0.8重量％、シリカ／クロミアモ
ル比46であった。Example 3 To 250 g of silica sol (silica solid content: 30% by weight) was added sulfuric acid second
Copper pentahydrate 5.6g, tetrapropylammonium bromide
A solution of 65 g and 32 g of chromium nitrate nonahydrate in 220 g of pure water was added under vigorous stirring, and then a 40% by weight aqueous solution of caustic soda (40 g) was added to give a gel product similar to that of Example 1. Hydrothermal synthesis was carried out by the method to prepare copper-chromium silicate.
This had a copper content of 0.8% by weight and a silica / chromia molar ratio of 46.
実施例１と同様に、この触媒（触媒Ｂ）を用い、パラフ
ルオロクロロベンゼンの加水分解反応を行った。その結
果、パラフルオロクロロベンゼンの転化率は8.3％で、
パラフルオロフェノールの選択率は91％であった。Using this catalyst (catalyst B), hydrolysis of parafluorochlorobenzene was carried out in the same manner as in Example 1. As a result, the conversion rate of parafluorochlorobenzene was 8.3%,
The selectivity of parafluorophenol was 91%.
実施例４ 実施例３と同様に、ただし、硝酸クロムの代わりにホウ
酸4.8gを、カ性ソーダ水溶液量を17gとして水熱合成
し、銅−ボロシリケートを調製した。このものの銅含有
量は1.5重量％、珪素／ホウ素原子比は24であった。こ
のものを触媒（触媒Ｃ）に用い、実施例２と同様に、パ
ラフルオロクロロベンゼンの加水分解反応を行った。そ
の結果、転化率18％、パラフルオロフェノール選択率86
％であった。Example 4 In the same manner as in Example 3, except that 4.8 g of boric acid was used instead of chromium nitrate and the amount of aqueous caustic soda solution was 17 g to perform hydrothermal synthesis to prepare a copper-borosilicate. This had a copper content of 1.5% by weight and a silicon / boron atomic ratio of 24. Using this as a catalyst (catalyst C), a hydrolysis reaction of parafluorochlorobenzene was carried out in the same manner as in Example 2. As a result, the conversion rate was 18% and the parafluorophenol selectivity was 86.
%Met.
比較例１ 公知方法にしたがいシリカ／アルミナ比50のNa型ZSM−
５を合成し、塩化第二銅水溶液を用い、公知方法でイオ
ン交換し、CuZSM−５触媒（触媒Ｅ）を調製した。この
ものの銅含有量は1.0重量％であった。この触媒を用
い、実施例１と同様にパラフルオロクロロベンゼンの加
水分解反応を行った。その結果、パラフルオロクロロベ
ンゼンの転化率は15％、パラフルオロフェノールの選択
率は１％で、パラフルオロクロロベンゼンの異性化、脱
フッ素によるフェノール生成がみられた。Comparative Example 1 Na-type ZSM with silica / alumina ratio of 50 according to a known method
5 was synthesized and ion-exchanged by a known method using a cupric chloride aqueous solution to prepare a CuZSM-5 catalyst (catalyst E). The copper content of this product was 1.0% by weight. Using this catalyst, a hydrolysis reaction of parafluorochlorobenzene was carried out in the same manner as in Example 1. As a result, the conversion of parafluorochlorobenzene was 15%, the selectivity of parafluorophenol was 1%, and isomerization of parafluorochlorobenzene and phenol production by defluorination were observed.
実施例５ 実施例１と同様の方法で、ただし、硫酸アルミニウムを
添加することにより、銅アルミノシリケートを合成し
た。このものの銅含有量は1.5重量％で、シリカ／アル
ミナ比は300であった。このもの（触媒Ｄ）を用い、実
施例１と同様に、パラフルオロクロロベンゼンの加水分
解反応を行った。その結果、パラフルオロクロロベンゼ
ンの転化率９％、パラフルオロフェノールの選択率95％
であった。Example 5 A copper aluminosilicate was synthesized in the same manner as in Example 1, except that aluminum sulfate was added. This had a copper content of 1.5% by weight and a silica / alumina ratio of 300. Using this product (catalyst D), a hydrolysis reaction of parafluorochlorobenzene was carried out in the same manner as in Example 1. As a result, the conversion rate of parafluorochlorobenzene was 9% and the selectivity of parafluorophenol was 95%.
Met.
比較例２ 触媒として酸化第１銅を用いた以外は、実施例１と同様
の方法によりパラフルオロクロロベンゼンの加水分解反
応を行った。その結果、パラフルオロクロロベンゼンの
転化率は２％で、パラフルオロフェノールの選択率は１
％以下であった。主生成物はハロゲンの異性化したオル
ト、メタフロロクロロベンゼン、脱ハロゲン化したフロ
ロベンゼン、ベンゼン、不均化したジフロオロベンゼ
ン、脱ハロゲン、加水分解されたフェノール等の副生成
物であった。Comparative Example 2 The hydrolysis reaction of parafluorochlorobenzene was carried out in the same manner as in Example 1 except that cuprous oxide was used as the catalyst. As a result, the conversion rate of parafluorochlorobenzene was 2% and the selectivity of parafluorophenol was 1%.
% Or less. The main products were by-products such as halogenated isomerized ortho, metafluorochlorobenzene, dehalogenated fluorobenzene, benzene, disproportionated difluorobenzene, dehalogenated and hydrolyzed phenol.
Claims (1)
フルオロフェノール類に転換するに際し、触媒として銅
含有結晶性シリカおよび／または銅を含有し、珪素／メ
タル原子比が10以上（ただし、メタルがアルミニウムの
場合は50以上）の結晶性メタロシリケートを用いること
を特徴とするフルオロフェノール類の製造方法。1. When hydrolyzing fluorochlorobenzenes to convert them into fluorophenols, copper-containing crystalline silica and / or copper is contained as a catalyst, and the silicon / metal atomic ratio is 10 or more (provided that the metal is aluminum. In the case of, a crystalline metallosilicate of 50 or more) is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63150103A JPH0678256B2 (en) | 1988-06-20 | 1988-06-20 | Fluorophenol manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63150103A JPH0678256B2 (en) | 1988-06-20 | 1988-06-20 | Fluorophenol manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01319448A JPH01319448A (en) | 1989-12-25 |
| JPH0678256B2 true JPH0678256B2 (en) | 1994-10-05 |
Family
ID=15489569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63150103A Expired - Lifetime JPH0678256B2 (en) | 1988-06-20 | 1988-06-20 | Fluorophenol manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678256B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01319447A (en) * | 1988-06-21 | 1989-12-25 | Res Assoc Util Of Light Oil | Production of phenols |
| CN116422364B (en) * | 2023-04-13 | 2024-04-09 | 青岛理工大学 | Catalyst for removing chlorobenzene by utilizing bimetal load modified molecular sieve and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62281834A (en) * | 1985-12-16 | 1987-12-07 | Idemitsu Petrochem Co Ltd | Production of phenolic compound |
-
1988
- 1988-06-20 JP JP63150103A patent/JPH0678256B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01319448A (en) | 1989-12-25 |
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