JPH0421645A - Preparation of hydroxy aromatic compound - Google Patents
Preparation of hydroxy aromatic compoundInfo
- Publication number
- JPH0421645A JPH0421645A JP2125423A JP12542390A JPH0421645A JP H0421645 A JPH0421645 A JP H0421645A JP 2125423 A JP2125423 A JP 2125423A JP 12542390 A JP12542390 A JP 12542390A JP H0421645 A JPH0421645 A JP H0421645A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic compound
- crystalline aluminosilicate
- catalyst
- chlorobenzene
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 hydroxy aromatic compound Chemical class 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 18
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229910021472 group 8 element Inorganic materials 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical group CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910001464 rare earth metal phosphate Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ハロゲン化芳香族化合物を加水分解し、ヒド
ロキシ芳香族化合物を製造する方法に関する。さらに詳
しくは、結晶性アルミノシリケートと第８族元素の金属
塩の混合物を水蒸気の存在下に加熱処理することにより
鋼製された金属カチオン含有結晶性アルミノシリケート
を加水分解触媒として用いることを特徴とするヒドロキ
シ芳香族化合物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a hydroxyaromatic compound by hydrolyzing a halogenated aromatic compound. More specifically, it is characterized in that a metal cation-containing crystalline aluminosilicate made into steel by heat-treating a mixture of a crystalline aluminosilicate and a metal salt of a Group 8 element in the presence of steam is used as a hydrolysis catalyst. The present invention relates to a method for producing a hydroxy aromatic compound.
（従来の技術）
金属カチオン含有結晶性アルミノシリケートの鋼製方法
としては、金属塩の溶液特に水溶液を用い、液相におい
て結晶性アルミノシリケートと接触させ、カチオン交換
することにより実施されている。また、メタロシリケー
トの合成方法として、金属塩特にハロゲン化合物、塩化
アルミニウム等を高温気相においてハイシリカゼオライ
トと接触させ、結晶格子に金属元素を導入する方法が知
られている。(Prior Art) A method for manufacturing steel from crystalline aluminosilicate containing metal cations is carried out by using a solution, particularly an aqueous solution, of a metal salt, bringing it into contact with crystalline aluminosilicate in the liquid phase, and exchanging the cations. Furthermore, as a method for synthesizing metallosilicates, a method is known in which metal salts, particularly halogen compounds, aluminum chloride, etc. are brought into contact with high-silica zeolite in a high-temperature gas phase to introduce metal elements into the crystal lattice.
ハロゲン化芳香族化合物から気相で加水分解し、フェノ
ール類を製造する方法としては、銅を担持した希土類金
属リン酸塩を触媒に用いる方法（特開昭４７−２７９３
６号公報）、金属成分含有の結晶性アルミノシリケート
を触媒として用いる方法（特開昭６２−１９２３３’０
−号公報、特開昭６２−２８１８３４号公報）、結晶性
ボロシリケートを触媒とする方法（特開昭６２−２４０
６３５号公報）、結晶性鉄シリケートを触媒にする方法
（特開昭６２−２４０６３６号公報）、結晶性クロモシ
リケートを触媒に用いる方法（特開昭６２−２４０６３
４号公報）が知られている。As a method for producing phenols by hydrolyzing halogenated aromatic compounds in the gas phase, a method using a copper-supported rare earth metal phosphate as a catalyst (Japanese Unexamined Patent Publication No. 47-2793
6), a method using crystalline aluminosilicate containing a metal component as a catalyst (Japanese Patent Application Laid-Open No. 1982-19233'0
JP-A No. 62-281834), a method using crystalline borosilicate as a catalyst (JP-A No. 62-240
635), a method using crystalline iron silicate as a catalyst (Japanese Unexamined Patent Publication No. 62-240636), a method using crystalline chromosilicate as a catalyst (Japanese Unexamined Patent Publication No. 62-24063)
4) is known.
（発明が解決しようとする課題）
しかしながら、金属塩の溶液を用いてイオン交換する方
法は、特にハイシリカゼオライトにおいては多価カーチ
オンの導入は難しい等の問題点を有している。従来の銅
成分を主な活性成分とするへロベンゼンの加水分解触媒
は、反応中に銅が飛散減少し、活性低下をもたらす問題
点を有している。(Problems to be Solved by the Invention) However, the method of ion exchange using a metal salt solution has problems such as difficulty in introducing polyvalent cations, especially in high silica zeolite. Conventional helobenzene hydrolysis catalysts containing copper as the main active ingredient have a problem in that copper scatters and decreases during the reaction, resulting in a decrease in activity.
（課題を解決するための手段）
本発明者らは、ハロゲン化芳香族化合物の加水分解によ
りヒドロキシ芳香族化合物を製造する方法について鋭意
検討を加えた結果、驚（べきことに、第８族元素の金属
塩と結晶性アルミノシリケートの混合組成物を水蒸気の
存在下に加熱処理し、鋼製した金属カチオン含有結晶性
アルミノシリケートを加水分解触媒として用いることに
より、ハロゲン化芳香族化合物の加水分解によるヒドロ
キシ芳香族化合物が高収率で、かつ、安定的に製造でき
ることを見出し、本発明を完成するに至ったのである。(Means for Solving the Problems) The present inventors have conducted intensive studies on a method for producing a hydroxy aromatic compound by hydrolysis of a halogenated aromatic compound, and have surprisingly found that a group 8 element A mixed composition of a metal salt and a crystalline aluminosilicate is heat-treated in the presence of steam, and a steel-made metal cation-containing crystalline aluminosilicate is used as a hydrolysis catalyst. They discovered that hydroxy aromatic compounds can be produced stably in high yield and completed the present invention.
本発明に用いられる結晶性アルミノシリケートとしては
、ペンタシル構造を有するハイシリカの結晶性アルミノ
シリケートが好ましい。例えば、ＺＳＭ−５、ＺＳＭ−
１１、ＡＺ−１（特開昭５９−１２８２１号）を挙げる
ことができる。シリカ／アルミナ比としては２０以上、
１００以下のものが好ましい。The crystalline aluminosilicate used in the present invention is preferably a high-silica crystalline aluminosilicate having a pentasil structure. For example, ZSM-5, ZSM-
11, AZ-1 (Japanese Unexamined Patent Publication No. 59-12821). The silica/alumina ratio is 20 or more,
Preferably, it is 100 or less.
本発明に用いられる金属の塩としては、第８族の金属の
塩であって、例えば、金属カチオンとしては鉄、コバル
ト、ニッケル、ルテニウム、ロジウム、パラジウム、白
金等のカチオンが、陰イオンとしてはハロゲン根、硫酸
根、リン酸根、硝酸根、水酸板、炭酸根等無機の陰イオ
ンが用いられる。特に金属成分としてはニッケルが、陰
イオンとしてはハロゲン根が好ましい。The metal salt used in the present invention is a Group 8 metal salt, for example, the metal cation is iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, etc., and the anion is iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, etc. Inorganic anions such as halogen, sulfate, phosphate, nitrate, hydroxyl, carbonate, etc. are used. In particular, nickel is preferred as the metal component, and halogen radicals are preferred as the anion.
第８族金属の含有量としては０．０１〜２０重量％、好
ましくは０．１〜１０重量％、さらに好ましくは０．２
〜５重量％が用いられる。The content of Group 8 metal is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.2% by weight.
~5% by weight is used.
加熱処理の温度としては３００°Ｃ〜６５０°Ｃが好ま
しく、４００°Ｃ〜５５０°Ｃが特に好ましい。The temperature of the heat treatment is preferably 300°C to 650°C, particularly preferably 400°C to 550°C.
温度が余り高過ぎると、結晶性アルミノシリケートの構
造の破壊、格子中のアルミニウムの脱離が大きくなり好
ましくなく、温度が低すぎると、充分な所望イオンの含
有が達成できない。If the temperature is too high, the structure of the crystalline aluminosilicate will be destroyed and the aluminum in the lattice will be largely eliminated, which is undesirable. If the temperature is too low, sufficient desired ion content cannot be achieved.
本発明方法による触媒鋼製の一例を示すと、結晶性アル
ミノシリケート粉末と金属の塩例えば塩化ニッケル粉末
を、乳鉢により均一に混合した後、圧縮成型し、適度の
粒度としたものを加熱処理容器に入れ、水蒸気の存在下
に所定温度に加熱することにより実施できる。An example of catalytic steel made by the method of the present invention is that crystalline aluminosilicate powder and a metal salt, such as nickel chloride powder, are mixed uniformly in a mortar and then compression molded to give an appropriate particle size. This can be carried out by heating the mixture to a predetermined temperature in the presence of water vapor.
本発明に用いられるハロゲン化芳香族化合物としては、
塩素原子、臭素原子のいずれか１つ以上が芳香族核に直
接置換したものであって、例えば、クロロベンゼン、ジ
クロロヘンゼン、プロモヘンゼン、ジプロモヘンゼン、
クロロトルエン、ブロモトルエン、クロロキシレン、ブ
ロモキシレン等のハロゲン置換ヘンガン類、クロロナフ
タレン、ブロモナフタレン等のハロゲン置換ナフタレン
類等を挙げることができる。The halogenated aromatic compounds used in the present invention include:
One or more of a chlorine atom or a bromine atom is directly substituted on an aromatic nucleus, such as chlorobenzene, dichlorohenzene, promohenzene, dipromohenzene,
Examples include halogen-substituted hemanganese such as chlorotoluene, bromotoluene, chloroxylene, and bromoxylene, and halogen-substituted naphthalenes such as chloronaphthalene and bromonaphthalene.
さらに、本発明に用いる結晶性アルミノシリケートは、
前処理としてスチーム存在下で２００〜７００“Ｃの温
度で処理するか、スチーム非存在下で６００〜８５０°
Ｃの温度下で熱処理したものが反応生成物の選択性、触
媒の安定性から好ましく用いられる。Furthermore, the crystalline aluminosilicate used in the present invention is
Pre-treatment at a temperature of 200-700"C in the presence of steam or 600-850"C in the absence of steam
A catalyst heat-treated at a temperature of C is preferably used in view of the selectivity of the reaction product and the stability of the catalyst.
ハロゲン化芳香族化合物の加水分解条件としては、原料
ハロゲン化芳香族化合物により異なるが、通常２５０°
Ｃ〜６００°Ｃの温度、好ましくは３００°Ｃ〜５５０
°Ｃの温度、さらに好ましくは３５０°Ｃ〜５００°Ｃ
の反応温度が、水のハロゲン化芳香族化合物に対するモ
ル比としては０．５〜１００、好ましくは１〜５０、さ
らに好ましくは２〜２０が用いられる。原料ハロゲン化
芳香族化合物の供給速度としては、重量時間空間速度（
ＷＨ３Ｖ）で０．０５〜２０ｕｒ−’、好ましくは０．
１〜１０Ｈｒ−’が用いられる。The hydrolysis conditions for halogenated aromatic compounds vary depending on the raw material halogenated aromatic compound, but are usually 250°
Temperature from 300°C to 550°C, preferably from 300°C to 550°C
temperature of °C, more preferably 350°C to 500°C
The molar ratio of water to the halogenated aromatic compound is from 0.5 to 100, preferably from 1 to 50, more preferably from 2 to 20. The feed rate of the raw material halogenated aromatic compound is the weight hourly space velocity (
WH3V) from 0.05 to 20 ur-', preferably 0.
1 to 10 Hr-' is used.
（発明の効果）
本発明の方法によれば、ハロゲン化芳香族化合物よりヒ
ドロキシ芳香族化合物を高選択率、高収率で、かつ、安
定的に製造することができる。(Effects of the Invention) According to the method of the present invention, a hydroxy aromatic compound can be stably produced from a halogenated aromatic compound with high selectivity and high yield.
（実施例）
以下に本発明の実施例を挙げて具体的に説明するが、本
発明は、これに限定されるものではない。(Example) The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.
実施例１
公知の方法によりＺＳＭ−５（ＳｉＯ□／ＡＺＺＯｚ＝
４５）を水熱合成し、次いで、常法により塩化ナトリウ
ム水溶液を用いてナトリウム型とし、これに塩化ニッケ
ルをニッケルとして０．６重量％添加し、自動乳鉢で約
３０分間混合し、圧縮成型した後、８〜２０メツシユに
破砕した。このものを１０■径の石英製反応管に１０ｇ
充填し、加熱炉により４５０℃に加熱し、水を２ｃｃ／
ｈｒの速度で供給し、２時間加熱処理した。次いで、定
量ポンプでクロロベンゼン、水を各々所定量供給し、加
水分解反応を実施した。Example 1 ZSM-5 (SiO□/AZZOz=
45) was hydrothermally synthesized, and then made into a sodium form using a sodium chloride aqueous solution by a conventional method, 0.6% by weight of nickel chloride was added as nickel, mixed for about 30 minutes in an automatic mortar, and compression molded. After that, it was crushed into 8 to 20 mesh pieces. Put 10g of this into a 10cm diameter quartz reaction tube.
Fill it, heat it to 450℃ in a heating furnace, and add 2cc/water.
The mixture was supplied at a rate of 2 hours and heat treated for 2 hours. Next, predetermined amounts of chlorobenzene and water were supplied using a metering pump to carry out a hydrolysis reaction.
反応条件として、４５０°Ｃ１水／クロロベンゼンモル
比６、クロロベンゼンの供給ＩＷ ＨＳ Ｖ トして０
、 ３ Ｈｒ−’、希釈剤として窒素ガスをクロロベ
ンゼンと当モル量供給し反応させた。通液開始後１〜２
時間目のサンプリング液の分析より、クロロベンゼンの
転化率５０％、フェノール収率４４ｍｏ／！％であり、
副生物はベンゼンがほとんどで、ベンゼンとフェノール
の合計の選択率は９９％を示した。The reaction conditions were 450°C, 1 water/chlorobenzene molar ratio 6, and chlorobenzene supply IW HS V to 0.
, 3 Hr-', nitrogen gas was supplied as a diluent in an equimolar amount to chlorobenzene, and the reaction was caused. 1-2 after starting liquid passage
Analysis of the sampled liquid at the 1st hour revealed that the conversion rate of chlorobenzene was 50% and the phenol yield was 44 mo/! %,
Most of the by-products were benzene, and the total selectivity for benzene and phenol was 99%.
実施例２
実施例１と同様に、ただし、塩化ニッケルの替わりに硫
酸ニッケルを用いた他は、同様の方法条件で触媒を鋼製
し、クロロベンゼンの加水分解触媒として用いた。加水
分解条件は実施例１と同じで、その結果はクロロベンゼ
ンの転化率３６％、フェノールの収率３２．５％であっ
た。Example 2 A catalyst was made of steel and used as a chlorobenzene hydrolysis catalyst in the same manner as in Example 1, except that nickel sulfate was used instead of nickel chloride. The hydrolysis conditions were the same as in Example 1, and the results were a chlorobenzene conversion of 36% and a phenol yield of 32.5%.
実施例３
実施例１と同様に、ただし、塩化ニッケルの替わりに硝
酸ニッケルを用いた他は、同様の方法条件で触媒を鋼製
し、クロロベンゼンの加水分解触媒に用いた。加水分解
条件は実施例１と同じで、その結果は、クロロベンゼン
の転化率４５％、フェノール選択率８５．８％、ベンゼ
ン選択率１３゜５％であった。Example 3 A catalyst was made of steel and used as a chlorobenzene hydrolysis catalyst in the same manner as in Example 1, except that nickel nitrate was used instead of nickel chloride. The hydrolysis conditions were the same as in Example 1, and the results were a chlorobenzene conversion of 45%, a phenol selectivity of 85.8%, and a benzene selectivity of 13.5%.
比較例１
実施例１のＮａ交換２３Ｍ−５を常法により硝酸ニッケ
ルの水溶液と接触させ、ニッケル交換のＺＳＭ−５触媒
を得た。このものは、ニッケルとして０．４５重量％含
有していた。Comparative Example 1 The Na-exchanged 23M-5 of Example 1 was brought into contact with an aqueous solution of nickel nitrate in a conventional manner to obtain a nickel-exchanged ZSM-5 catalyst. This material contained 0.45% by weight of nickel.
このニッケル交換触媒を、実施例１と同様にクロロベン
ゼンの加水分解触媒に用いた。その結果はクロロベンゼ
ンの転化率４６％、フェノール選択率８４％を示した。This nickel exchange catalyst was used as a chlorobenzene hydrolysis catalyst in the same manner as in Example 1. The results showed a chlorobenzene conversion rate of 46% and a phenol selectivity of 84%.
比較例２
実施例１のＮａ交換２３Ｍ−５に硝酸ニッケル水溶液を
含浸、蒸発乾固後、１００℃で３時間乾燥、次いで、５
００°Ｃで２時間空気中において仮焼後、成型し、ニッ
ケルとして０． ５重量％を含有する触媒を鋼製し、実
施例１と同様にクロロベンゼンの加水分解触媒に供した
。その結果は、クロロベンゼンの転化率３３％、フェノ
ールの選択率８３％であった。Comparative Example 2 Na-exchanged 23M-5 of Example 1 was impregnated with a nickel nitrate aqueous solution, evaporated to dryness, dried at 100°C for 3 hours, and then
After calcination in the air at 00°C for 2 hours, it is molded and the nickel is 0. A catalyst containing 5% by weight was made of steel and used as a chlorobenzene hydrolysis catalyst in the same manner as in Example 1. The results were a chlorobenzene conversion rate of 33% and a phenol selectivity of 83%.
実施例４
実施例１と同様に、ただし、Ｎａ型２３Ｍ−５を４５０
℃、２０時間水蒸気分圧０．Ｂａｔｓ中で加熱処理し、
次いで、硝酸銅水溶液を用いイオン交換、水洗、乾燥し
、０．０８重量％の銅を含むゼオライトを得た。これに
塩化ニッケル粉末をニッケルとして０．６重量％混合し
、実施例１と同様に、ただし、５００°Ｃで処理した。Example 4 Same as Example 1, except that Na type 23M-5 was added to 450
℃, 20 hours water vapor partial pressure 0. Heat treated in Bats,
Next, ion exchange was performed using an aqueous copper nitrate solution, water washing, and drying to obtain a zeolite containing 0.08% by weight of copper. This was mixed with 0.6% by weight of nickel chloride powder as nickel, and treated in the same manner as in Example 1, but at 500°C.
この触媒を、実施例１と同様にクロロベンゼンの加水分
解触媒に用いた０反応条件は４５０°ｃ、ＷＨ３Ｖ＝０
゜２８Ｈｒ−’、水／クロロベンゼフモル比５．８、窒
素／クロロベンゼンモル比９で実施した。その結果は２
〜３時間目のクロロベンゼン転化率４２％、フェノール
選択率９２％を示した。さらに反応を進メ、ｌＯ〜１２
時間目のクロロベンゼン転化率は３５％、フェノール選
択率９３％、２４〜２５時間目の転化率は３０％であっ
た。This catalyst was used as a chlorobenzene hydrolysis catalyst in the same manner as in Example 1. The reaction conditions were 450°C, WH3V=0
The reaction was carried out at a temperature of 28 Hr-', a water/chlorobenzef molar ratio of 5.8, and a nitrogen/chlorobenzene molar ratio of 9. The result is 2
A chlorobenzene conversion rate of 42% and a phenol selectivity of 92% were shown for ~3 hours. Continue the reaction, lO ~ 12
The conversion rate of chlorobenzene at 1 hour was 35%, the phenol selectivity was 93%, and the conversion rate at 24 to 25 hours was 30%.
反応後の触媒を解析したところ、ニッケル、銅とも減少
は認められなかった。When the catalyst was analyzed after the reaction, no decrease was observed in either nickel or copper.
（ほか１名）(1 other person)
Claims (1)
族化合物に転換するに際して、結晶性アルミノシリケー
トと第８族元素の金属塩の混合物を水蒸気の存在下に加
熱処理して鋼製された金属カチオン含有結晶性アルミノ
シリケートを加水分解触媒として用いることを特徴とす
るヒドロキシ芳香族化合物の製造方法。A metal cation-containing steel made by heat-treating a mixture of crystalline aluminosilicate and a metal salt of a Group 8 element in the presence of water vapor when a halogenated aromatic compound is hydrolyzed and converted into a hydroxy aromatic compound. A method for producing a hydroxy aromatic compound, characterized in that a crystalline aluminosilicate is used as a hydrolysis catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2125423A JPH0421645A (en) | 1990-05-17 | 1990-05-17 | Preparation of hydroxy aromatic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2125423A JPH0421645A (en) | 1990-05-17 | 1990-05-17 | Preparation of hydroxy aromatic compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0421645A true JPH0421645A (en) | 1992-01-24 |
Family
ID=14909736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2125423A Pending JPH0421645A (en) | 1990-05-17 | 1990-05-17 | Preparation of hydroxy aromatic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0421645A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069464A (en) * | 1993-02-03 | 1994-01-18 | Asahi Chem Ind Co Ltd | Production of aryl hydroxide compound |
| WO1998007516A1 (en) * | 1996-08-20 | 1998-02-26 | Monsanto Company | Selective introduction of active sites for hydroxylation of benzene |
-
1990
- 1990-05-17 JP JP2125423A patent/JPH0421645A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069464A (en) * | 1993-02-03 | 1994-01-18 | Asahi Chem Ind Co Ltd | Production of aryl hydroxide compound |
| JPH07110825B2 (en) * | 1993-02-03 | 1995-11-29 | 旭化成工業株式会社 | Phenol manufacturing method |
| WO1998007516A1 (en) * | 1996-08-20 | 1998-02-26 | Monsanto Company | Selective introduction of active sites for hydroxylation of benzene |
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