JPH0735351B2 - Manufacturing method of aryl hydroxide - Google Patents
Manufacturing method of aryl hydroxideInfo
- Publication number
- JPH0735351B2 JPH0735351B2 JP61082250A JP8225086A JPH0735351B2 JP H0735351 B2 JPH0735351 B2 JP H0735351B2 JP 61082250 A JP61082250 A JP 61082250A JP 8225086 A JP8225086 A JP 8225086A JP H0735351 B2 JPH0735351 B2 JP H0735351B2
- Authority
- JP
- Japan
- Prior art keywords
- hours
- chlorobenzene
- water
- reaction
- catalyst
- 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
- -1 aryl hydroxide Chemical compound 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 150000001555 benzenes Chemical class 0.000 claims description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 229960003742 phenol Drugs 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001502 aryl halides Chemical class 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 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
- NVLHGZIXTRYOKT-UHFFFAOYSA-N 1-chloro-2,3-dimethylbenzene Chemical group CC1=CC=CC(Cl)=C1C NVLHGZIXTRYOKT-UHFFFAOYSA-N 0.000 description 1
- DANMWBNOPFBJSZ-UHFFFAOYSA-N 1-iodo-2,3-dimethylbenzene Chemical group CC1=CC=CC(I)=C1C DANMWBNOPFBJSZ-UHFFFAOYSA-N 0.000 description 1
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 1
- HMJBXEZHJUYJQY-UHFFFAOYSA-N 4-(aminomethyl)octane-1,8-diamine Chemical compound NCCCCC(CN)CCCN HMJBXEZHJUYJQY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910001464 rare earth metal phosphate Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、各種ポリマー原料として有用なフエノール類
の製造法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing phenols useful as various polymer raw materials.
（従来の技術） アリールハロゲン化物を水の存在下、気相において加水
分解してアリール水酸化物に転化する方法は、古くから
フエノール合成におけるラシヒ法の後段反応として知ら
れている。(Prior Art) A method of hydrolyzing an aryl halide in the gas phase in the presence of water to convert it into an aryl hydroxide has long been known as a post-stage reaction of the Raschig method in the phenol synthesis.
このアリールハロゲン化物の加水分解の触媒としては、
銅を含むリン酸カルシウムアパタイト（USP3,148,222
号、USP2,988,573号）、銅を含むリン酸ジルコニウム
（特公昭51-6108号）、希土類金属リン酸塩及びその銅
を含んだ物（特開昭47-27936号）等が知られている。As a catalyst for the hydrolysis of this aryl halide,
Calcium phosphate apatite containing copper (USP3,148,222
, USP2,988,573), copper-containing zirconium phosphate (Japanese Patent Publication No. 51-6108), rare earth metal phosphates and their copper-containing products (JP-A-47-27936), etc. .
（発明が解決しようとする問題点） これまでの触媒は、活性が低いため、高転化率を得るた
めには、500℃以上の高温で反応させるか、又は非常に
低いSVで反応させる必要があつた。(Problems to be solved by the invention) Since the conventional catalysts have low activity, it is necessary to react them at a high temperature of 500 ° C. or higher or at a very low SV in order to obtain a high conversion rate. Atsuta
（問題を解決するための手段） 本発明者らは、高活性な触媒を開発すべく鋭意検討した
結果、周期律表上のIB族及び又はVIII族の金属を含有す
る無水の状態で下記の組成を有する結晶性クロモシリケ
ートが高活性である事を見い出し、本発明を完成するに
至つた。(Means for Solving the Problem) As a result of intensive studies to develop a highly active catalyst, the present inventors have shown the following in an anhydrous state containing a Group IB and / or a Group VIII metal on the periodic table. It was found that the crystalline chromosilicate having a composition has high activity, and the present invention has been completed.
すなわち、本発明は、アリールハロゲン化物を水の存在
下、気相において加水分解してアリール水酸化物に転化
する際に、触媒として周期律表のIB族及び又はVIII族の
金属を含有する無水の状態で下記の組成を有する結晶性
クロモシリケートを用いる事を特徴とするアリール水酸
化物の製法に関するものである。That is, the present invention is an anhydride containing a metal of Group IB and / or Group VIII of the periodic table as a catalyst when an aryl halide is hydrolyzed in the gas phase in the presence of water to be converted into an aryl hydroxide. In this state, a crystalline chromosilicate having the following composition is used, and the present invention relates to a process for producing an aryl hydroxide.
本発明に用いられる結晶性クロモシリケートとは、一般
にゼオライトと呼ばれる結晶性アルミノシリケートと同
様な剛性の三次元構造を有する無機結晶体である。この
結晶性クロモシリケートはSiO4とCrO4又はAlO4が酸素原
子を介して交さ結合しており、このクロム原子とアルミ
ニウム原子とケイ素原子の和と酸素原子との比は1:2で
あり、またクロム又はアルミニウムを含有する四面体の
電子価は結晶内に種々のカチオンを含有することによつ
て平衡が保たれている。The crystalline chromosilicate used in the present invention is an inorganic crystal body having a three-dimensional structure of rigidity similar to that of crystalline aluminosilicate generally called zeolite. In this crystalline chromosilicate, SiO 4 and CrO 4 or AlO 4 are cross-bonded through an oxygen atom, and the ratio of the sum of chromium atom, aluminum atom, silicon atom and oxygen atom is 1: 2. The electron valence of the tetrahedron containing chromium or aluminum is balanced by the inclusion of various cations in the crystal.
本発明に用いられる結晶性クロモシリケートは無水の状
態で以下の組成式で表わされる。The crystalline chromosilicate used in the present invention is represented by the following composition formula in an anhydrous state.
M2/nO・xSiO2・yAl2O3・zCr2O3 （ただし、Ｍはｎ価の少なくとも一種のカチオンを示
し、ｙ＋ｚ＝1,y≧0,z＞0,xは10〜1000である。） ここで示されるｘは、10〜1000であるが好ましいのは20
〜500、さらに好ましいのは30〜200の範囲である。M 2 / nO ・ xSiO 2・ yAl 2 O 3・ zCr 2 O 3 (where M represents at least one cation having an n valence, y + z = 1, y ≧ 0, z> 0, x is 10 to 1000 X shown here is 10 to 1000, but 20 is preferable.
~ 500, more preferably 30-200.
本発明に用いられる結晶性クロモシリケートはクロム原
子を必ず含むが、その量は、好ましくは式中のｚの値で
0.2〜1.0、さらに好ましくは、0.3〜1.0の範囲である。The crystalline chromosilicate used in the present invention always contains a chromium atom, but the amount thereof is preferably the value of z in the formula.
The range is 0.2 to 1.0, and more preferably 0.3 to 1.0.
この様な結晶性クロモシリケートとしては、ゼオライト
ZSM-5類似のクロモシリケート（特開昭57-169434号）、
結晶性クロモシリケートAZ-3（特開昭60-226411号）等
が挙げられる。Such crystalline chromosilicates include zeolite
Chromosilicate similar to ZSM-5 (JP-A-57-169434),
Examples thereof include crystalline chromosilicate AZ-3 (JP-A-60-226411).
本発明に用いられる結晶性クロモシリケートは周期律表
上のIB族及び又はVIII族の金属を含有する必要がある。
周期律表上のIB族とは、銅、銀、金であり、VIII族と
は、ニツケル、パラジウム、白金、コバルト、ロジウ
ム、イリジウム、鉄、ルテニウム、オスミウムである
が、これらの中で好ましいのは、銅、ニツケル、コバル
ト、パラジウムであり、特に好ましいのは銅である。The crystalline chromosilicate used in the present invention must contain a metal of Group IB and / or Group VIII on the periodic table.
Group IB on the Periodic Table is copper, silver and gold, and Group VIII is nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium and osmium, among which preferred Are copper, nickel, cobalt and palladium, with copper being particularly preferred.
結晶性クロモシリケート中に含まれるこれらの金属の状
態は、カチオン、酸化物、ハロゲン化物等の塩、還元金
属いずれの状態でも構わないが、好ましいのは、カチオ
ンの状態である。The state of these metals contained in the crystalline chromosilicate may be any of cations, oxides, salts such as halides, and reduced metals, but the state of cations is preferred.
これらの金属の含有量は特に制限はないが、あまり少な
いと活性が低く、多すぎると選択性が低くなるので、通
常は結晶性クロモシリケートに対して、0.005〜50wt
％、好ましくは0.01〜20wt％、さらに好ましくは0.1〜1
0wt％の範囲である。The content of these metals is not particularly limited, but if it is too small, the activity is low, and if it is too large, the selectivity is low, so it is usually 0.005 to 50 wt% with respect to the crystalline chromosilicate.
%, Preferably 0.01 to 20 wt%, more preferably 0.1 to 1
It is in the range of 0 wt%.
結晶性クロモシリケートに、これらの金属を含有させる
方法としては、通常のイオン交換法、含浸法等が用いら
れる。As a method of incorporating these metals into the crystalline chromosilicate, an ordinary ion exchange method, an impregnation method or the like is used.
本発明におけるアリールハロゲン化物とは、例えば、ク
ロルベンゼン、ブロムベンゼン、ヨードベンゼン、ジク
ロルベンゼン、ジブロムベンゼン、ジヨードベンゼン、
クロルトルエン、ブロムトルエン、ヨードトルエン、ク
ロルキシレン、ブロムキシレン、ヨードキシレン等が挙
げられる。The aryl halide in the present invention includes, for example, chlorobenzene, brombenzene, iodobenzene, dichlorobenzene, dibromobenzene, diiodobenzene,
Examples thereof include chlorotoluene, bromotoluene, iodotoluene, chlorxylene, bromoxylene, and iodoxylene.
本発明における水とアリールハロゲン化物の比は、通
常、水／アリールハロゲン化物モル比で0.5〜100、好ま
しくは、１〜50、さらに好ましくは２〜20の範囲であ
る。The ratio of water to aryl halide in the present invention is usually in the range of 0.5 to 100, preferably 1 to 50, more preferably 2 to 20 in terms of water / aryl halide molar ratio.
本発明におけるアリール水酸化物とは、原料がモノハロ
ゲン化ベンゼンの場合は、対応するヒドロキシベンゼン
であり、原料がジハロゲン化物の場合は、モノヒドロキ
シベンゼン及び又は、ジヒドロキシベンゼンである。The aryl hydroxide in the present invention is a corresponding hydroxybenzene when the raw material is a monohalogenated benzene, and is monohydroxybenzene and / or dihydroxybenzene when the raw material is a dihalide.
本発明における反応温度は、通常250〜600℃、好ましく
は300〜550℃、さらに好ましくは350〜500℃の範囲であ
る。The reaction temperature in the present invention is usually in the range of 250 to 600 ° C, preferably 300 to 550 ° C, more preferably 350 to 500 ° C.
本発明における圧力は、減圧、常圧、加圧いずれでも良
い。The pressure in the present invention may be any of reduced pressure, normal pressure and increased pressure.
（発明の効果） 本発明における触媒は、従来の触媒に比べて活性が高
い。この事は、工業的に行う上で非常に有利となる。(Effects of the Invention) The catalyst of the present invention has higher activity than conventional catalysts. This is very advantageous for industrial use.
（実施例） 次に本発明を実施例を用いて説明する。(Example) Next, this invention is demonstrated using an Example.
実施例１ Q brandケイ酸塩水溶液(Na2O 8.9wt%,SiO2 28.9wt%、H2O
62.2wt%)300gに10wt％テトラプロピルアンモニウムハ
イドロキサイド水溶液200gを加え、さらに水100gにCr(N
O3)3・9H2O23gを溶かした溶液を加えて均質な溶液を得
た。さらに硝酸をかきまぜながら滴下してpHを約11に調
整して均質なゲルを得た。このゲルをテフロン内張りオ
ートクレーブに仕込み、かきまぜながら180℃、24時間
結晶化させた。Example 1 Q brand silicate aqueous solution (Na 2 O 8.9 wt%, SiO 2 28.9 wt%, H 2 O
62.2 wt%) 300 g, 10 wt% tetrapropylammonium hydroxide aqueous solution 200 g was added, and water (100 g) was added with Cr (N
O 3) was added to 3 · 9H 2 solution of O23g obtain a homogeneous solution. Furthermore, nitric acid was added dropwise with stirring to adjust the pH to about 11 to obtain a homogeneous gel. This gel was placed in a Teflon-lined autoclave and crystallized at 180 ° C. for 24 hours while stirring.
得られた生成物を濾過、洗浄、120℃で４時間乾燥、500
℃で６時間空気中で焼成した。この生成物は、Ｘ線回折
分析より、ゼオライトZSM5類似の結晶性クロモシリケー
トである事が分つた。又、1Nの硝酸でイオン交換した
後、乾燥した状態で、ケイ光Ｘ線分析より求めたこの結
晶性シリケートの無水の状態での組成式は H2O・50SiO2・0.05Al2O3・0.95Cr2O3であつた。The product obtained is filtered, washed and dried at 120 ° C. for 4 hours, 500
It was calcined in air for 6 hours. This product was found by X-ray diffraction analysis to be a crystalline chromosilicate similar to zeolite ZSM5. The composition formula of this crystalline silicate in an anhydrous state obtained by fluorescent X-ray analysis after being ion-exchanged with 1N nitric acid is H 2 O · 50SiO 2 · 0.05Al 2 O 3 ·. It was 0.95Cr 2 O 3 .
得られた結晶性クロモシリケートを20wt% CuCl2・2H2O水
溶液中で一日室温でイオン交換を行い、濾過、洗浄後、
120℃で４時間乾燥、400℃で５時間焼成した。この触媒
のCu含有率をケイ光Ｘ線を用いて測定した結果、もとの
結晶性クロモシリケートに対して、0.51wt％であつた。The obtained crystalline chromosilicate was subjected to ion exchange in a 20 wt% CuCl 2 · 2H 2 O aqueous solution at room temperature for one day, filtered, washed, and then
It was dried at 120 ° C. for 4 hours and calcined at 400 ° C. for 5 hours. The Cu content of this catalyst was measured by fluorescent X-ray, and as a result, it was 0.51 wt% with respect to the original crystalline chromosilicate.
この触媒を用いてクロルベンゼンの加水分解反応を行つ
た。Using this catalyst, chlorobenzene was hydrolyzed.
反応条件は、水／クロルベンゼンモル比＝2.6WHSV（ク
ロルベンゼン基準）＝3.0hr-1、反応温度＝450℃、常圧
で行つた。The reaction conditions were water / chlorobenzene molar ratio = 2.6 WHSV (chlorobenzene standard) = 3.0 hr −1 , reaction temperature = 450 ° C., and atmospheric pressure.
反応開始後、１〜２時間の成績を表１に示す。The results of 1 to 2 hours after the start of the reaction are shown in Table 1.
実施例２ 実施例１で得られた触媒を用いて、下記の条件でクロル
ベンゼンの加水分解反応を行つた。 Example 2 Using the catalyst obtained in Example 1, a hydrolysis reaction of chlorobenzene was carried out under the following conditions.
水／クロルベンゼンモル比＝６、WHSV（クロルベンゼン
基準）＝0.5hr-1、反応温度＝400℃、常圧。Water / chlorobenzene molar ratio = 6, WHSV (chlorobenzene standard) = 0.5 hr −1 , reaction temperature = 400 ° C., atmospheric pressure.
反応開始後、１〜２時間の結果は、クロルベンゼン転化
率＝30.0％、フエノール選択率＝95.5％、ベンゼン選択
率＝4.5％であつた。After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 30.0%, the phenol selectivity was 95.5%, and the benzene selectivity was 4.5%.
実施例３ 実施例１で得られた触媒を用いて、下記の条件でブロム
ベンゼンの加水分解反応を行つた。Example 3 Using the catalyst obtained in Example 1, a hydrolysis reaction of bromobenzene was carried out under the following conditions.
反応条件は、水／ブロムベンゼンモル比＝4.0WHSV（ブ
ロムベンゼン基準）＝1.0hr-1、反応温度＝450℃、常圧
で行つた。The reaction conditions were water / brominebenzene molar ratio = 4.0 WHSV (brominebenzene standard) = 1.0 hr −1 , reaction temperature = 450 ° C., and atmospheric pressure.
反応開始後、１〜２時間の結果は、ブロムベンゼン転化
率＝13.0％、フエノール選択率＝90.0％、ベンゼン選択
率＝5.0％であつた。After 1 to 2 hours from the start of the reaction, the bromobenzene conversion rate was 13.0%, the phenol selectivity was 90.0%, and the benzene selectivity was 5.0%.
実施例４ 実施例１で得られた結晶性クロモシリケートを周期律表
上のIB族及びVIII族の各種金属でイオン交換した触媒を
用いてクロルベンゼンの加水分解反応を下記の条件で行
つた。Example 4 A hydrolysis reaction of chlorobenzene was carried out under the following conditions using a catalyst in which the crystalline chromosilicate obtained in Example 1 was ion-exchanged with various metals of Group IB and Group VIII on the periodic table.
水／クロルベンゼンモル比＝2.6、WHSV（クロルベンゼ
ン基準）＝3.0hr-1、反応温度＝450℃、常圧で行つた。Water / chlorobenzene molar ratio = 2.6, WHSV (chlorobenzene standard) = 3.0 hr −1 , reaction temperature = 450 ° C., and normal pressure.
反応開始後、１〜２時間の成績を表２に示す。The results of 1 to 2 hours after the start of the reaction are shown in Table 2.
実施例５ 特開昭60-226411号に従つて結晶性クロモシリケートAZ-
3を下記の手順で合成した。 Example 5 According to JP-A-60-226411, crystalline chromosilicate AZ-
3 was synthesized by the following procedure.
1,8−ジアミノ−４−アミノメチルオクタン10g、Cr(N
O3)3・9H2O1.1g、水酸化ナトリウム0.5gを水15gにとか
し、さらにシリカゾル（30％SiO2）20gを加えて均質な
溶液を得た。この溶液にかきまぜながら20％硫酸を滴下
してpH約11.5に調整して均質なゲルを得た。さらにこの
ゲルをミキサーに入れ、5000rpmで10分間混合しゲル化
を促進した。このゲルをテフロン製試験管に仕込みステ
ンレス製耐圧容器中で170℃、48時間静置して結晶化を
行つた。1,8-diamino-4-aminomethyloctane 10 g, Cr (N
O 3) 3 · 9H 2 O1.1g , sodium hydroxide 0.5g was dissolved in water 15 g, to obtain a homogeneous solution by addition of further silica sol (30% SiO 2) 20g. While stirring this solution, 20% sulfuric acid was added dropwise to adjust the pH to about 11.5 to obtain a homogeneous gel. Further, this gel was put into a mixer and mixed at 5000 rpm for 10 minutes to promote gelation. This gel was placed in a Teflon test tube and allowed to stand in a stainless steel pressure vessel at 170 ° C. for 48 hours for crystallization.
得られた生成物を濾過、洗浄、120℃で４時間乾燥、550
℃で４時間空気中で焼成した。この生成物は、Ｘ線回折
分析よりAZ-3と同定された。又、1N塩酸中でイオン交換
した後、120℃で４時間乾燥して、ケイ光Ｘ線分析より
求めた組成は無水の状態で、 H2O・80SiO2・0.02Al2O3・0.98Cr2O3であつた。The product obtained is filtered, washed and dried at 120 ° C. for 4 hours, 550
It was calcined in air for 4 hours. This product was identified as AZ-3 by X-ray diffraction analysis. After ion exchange in 1N hydrochloric acid, it was dried at 120 ° C for 4 hours, and the composition determined by fluorescent X-ray analysis was H 2 O ・ 80SiO 2・ 0.02Al 2 O 3・ 0.98Cr It was 2 O 3 .
このAZ-3を、10wt% CuCl2・2H2O水溶液に浸漬した後、蒸
発乾固し、さらに450℃で３時間空気中で焼成してCu担
持AZ-3を調製した。この触媒のケイ光Ｘ線で測定したCu
含有率は、1.8wt％であつた。This AZ-3 was immersed in a 10 wt% CuCl 2 · 2H 2 O aqueous solution, evaporated to dryness, and then calcined in air at 450 ° C for 3 hours to prepare Cu-supported AZ-3. Cu measured by fluorescent X-ray of this catalyst
The content rate was 1.8 wt%.
この触媒を用いて、クロルベンゼンの加水分解反応を下
記の条件で行つた。Using this catalyst, the hydrolysis reaction of chlorobenzene was carried out under the following conditions.
水／クロルベンゼンモル比＝3.0、WHSV（クロルベンゼ
ン基準）＝0.8hr-1、反応温度＝450℃常圧。Water / chlorobenzene molar ratio = 3.0, WHSV (chlorobenzene standard) = 0.8 hr −1 , reaction temperature = 450 ° C. normal pressure.
反応開始後、１〜２時間の成績は、クロルベンゼン転化
率＝35.0％、フエノール選択率＝96.5％、ベンゼン選択
率＝3.5％であつた。After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 35.0%, the phenol selectivity was 96.5%, and the benzene selectivity was 3.5%.
実施例６ Q brandケイ酸塩水溶液(Na2O 8.9wt%、SiO2 28.9wt%、H2O
62.2wt%)300gに10wt％テトラプロピルアンモニウムハ
イドロキサイド水溶液200gを加え、さらに水100gに硝酸
アルミニウム(Al(NO3)3・9H2O)3gとCr(NO3)3・9H2O15.0g
を溶かした溶液を加えて均質な溶液を得た。さらに硝酸
をかきまぜながら滴下してpHを約11に調整して均質なゲ
ルを得た。このゲルをテフロン内張りオートクレーブに
仕込み、かきまぜながら180℃、36時間結晶化させた。Example 6 Q brand silicate aqueous solution (Na 2 O 8.9 wt%, SiO 2 28.9 wt%, H 2 O
62.2wt%) to 10 wt% tetrapropylammonium hydroxide key side solution 200g was added to 300 g, further aluminum nitrate (Al (NO 3) in water 100g 3 · 9H 2 O) 3g and Cr (NO 3) 3 · 9H 2 O15. 0g
Was added to obtain a homogeneous solution. Furthermore, nitric acid was added dropwise with stirring to adjust the pH to about 11 to obtain a homogeneous gel. This gel was placed in a Teflon-lined autoclave and crystallized at 180 ° C. for 36 hours while stirring.
得られた生成物を濾過、洗浄、120℃で４時間乾燥、500
℃で６時間空気中で焼成した。この生成物は、Ｘ線回折
分析よりゼオライトZSM-5類似の結晶性クロモシリケー
トと同定された。The product obtained is filtered, washed and dried at 120 ° C. for 4 hours, 500
It was calcined in air for 6 hours. The product was identified as crystalline chromosilicate similar to zeolite ZSM-5 by X-ray diffraction analysis.
又、これを、1Nの塩酸中でイオン交換して、120℃で乾
燥後、ケイ光Ｘ線分析より求めた無水の状態の組成は、 H2O・35SiO2・0.4Al2O3・0.6Cr2O3であつた。The composition in an anhydrous state obtained by fluorescent X-ray analysis after being ion-exchanged in 1N hydrochloric acid and dried at 120 ° C was H 2 O · 35SiO 2 · 0.4Al 2 O 3 · 0.6. It was Cr 2 O 3 .
さらに、この触媒を20wt% CuCl2・2H2O水溶液中で一日イ
オン交換を行い、濾過、洗浄、120℃で４時間乾燥、400
℃で５時間焼成する操作を２回行つた。この触媒のCu含
有率を、ケイ光Ｘ線分析により測定した結果は、0.75wt
％であつた。Furthermore, this catalyst was subjected to ion exchange in a 20 wt% CuCl 2 · 2H 2 O aqueous solution for one day, filtered, washed, and dried at 120 ° C for 4 hours,
The operation of baking at 5 ° C. for 5 hours was performed twice. The Cu content of this catalyst was measured by fluorescent X-ray analysis and found to be 0.75 wt.
It was in%.
この触媒を用いてクロルベンゼンの加水分解反応を下記
の条件で行つた。Using this catalyst, hydrolysis reaction of chlorobenzene was carried out under the following conditions.
水／クロルベンゼンモル比＝5.5、WHSV（クロルベンゼ
ン基準）＝0.3hr-1、反応温度＝400℃常圧。Water / chlorobenzene molar ratio = 5.5, WHSV (chlorobenzene standard) = 0.3 hr −1 , reaction temperature = 400 ° C. normal pressure.
反応開始後、１〜２時間の成績は、クロルベンゼン転化
率＝33.0％、フエノール収率＝31.5％、フエノール選択
率＝95.5％、ベンゼン選択率＝4.5％であつた。After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 33.0%, the phenol yield was 31.5%, the phenol selectivity was 95.5%, and the benzene selectivity was 4.5%.
比較例１ 特開昭47-27936号に従い、銅含有LaPO4を調製した。Comparative Example 1 Copper-containing LaPO 4 was prepared according to JP-A-47-27936.
La(NO3)3・6H2O＝28.8gを水200ccに溶かした溶液に、(NH
4)2HPO4＝17.6gを水100ccに溶かした溶液を激しく攪拌
しながら加える。その後、アンモニア水でpH6.0に調整
して、濾過、洗浄した後120℃で24時間乾燥、500℃で16
時間空気中で焼成して白色のLaPO4粉末を得た。このLaP
O4＝10gを、Cu(NO3)2・3H2Oの0.2wt％水溶液20cc中に浸
漬して、蒸発乾固した後、450℃で５時間空気中で焼成
した。このCu含有LaPO4中のCu含有率は0.05wt％であつ
た。La a (NO 3) 3 · 6H 2 O = 28.8g to a solution in water 200 cc, (NH
4 ) Add a solution of 2 HPO 4 = 17.6 g in 100 cc of water with vigorous stirring. After that, adjust the pH to 6.0 with ammonia water, filter and wash, then dry at 120 ° C for 24 hours and at 16 ° C at 16 ° C.
Firing in air for hours gave a white LaPO 4 powder. This LaP
O 4 = 10 g was immersed in 20 cc of a 0.2 wt% aqueous solution of Cu (NO 3 ) 2 .3H 2 O, evaporated to dryness, and then baked in air at 450 ° C. for 5 hours. The Cu content in this Cu-containing LaPO 4 was 0.05 wt%.
このCu含有LaPO4を触媒に用いてクロルベンゼンの加水
分解反応を下記の条件で行つた。Using this Cu-containing LaPO 4 as a catalyst, the hydrolysis reaction of chlorobenzene was performed under the following conditions.
水／クロルベンゼンモル比＝2.6、WHSV（クロルベンゼ
ン基準）＝0.6hr-1、反応温度＝450℃、常圧で行つた。Water / chlorobenzene molar ratio = 2.6, WHSV (chlorobenzene standard) = 0.6 hr −1 , reaction temperature = 450 ° C., and normal pressure.
反応開始後、１〜２時間の結果は、クロルベンゼン転化
率＝13.0％、フエノール収率＝12.5％、フエノール選択
率＝96.5％、ベンゼン転化率＝3.5％であつた。After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 13.0%, the phenol yield was 12.5%, the phenol selectivity was 96.5%, and the benzene conversion rate was 3.5%.
比較例２ 特公昭51-6108号に従つて、銅を含むリン酸ジルコニウ
ムを調製した。Comparative Example 2 According to JP-B-51-6108, a zirconium phosphate containing copper was prepared.
ZrOCl2・8H2O＝24gを水100gに溶かし、さらにCuCl2・2H2O
＝0.6gを溶かした。この溶液を、NaOH＝8.0gと85％H3PO
4＝14.8gを水100gに溶かした溶液に加え、44時間室温で
攪拌を続けた。得られたスラリーを濾過、洗浄した後、
110℃で４時間乾燥、400℃で３時間空気中で焼成を行い
銅含有リン酸ジルコニウムを得た。ZrOCl 2・ 8H 2 O ＝ 24g is dissolved in 100g of water, and then CuCl 2・ 2H 2 O
= 0.6g was melted. This solution, NaOH = 8.0 g and 85% H 3 PO
4 = 14.8g was added to the solution which melt | dissolved in 100g of water, and stirring was continued at room temperature for 44 hours. After filtering and washing the obtained slurry,
It was dried at 110 ° C. for 4 hours and baked at 400 ° C. for 3 hours in air to obtain copper-containing zirconium phosphate.
この銅含有リン酸ジルコニウムを触媒に用いて比較例１
と同じ条件でクロルベンゼンの加水分解反応を行つた。Comparative Example 1 using this copper-containing zirconium phosphate as a catalyst
The hydrolysis reaction of chlorobenzene was carried out under the same conditions as described above.
反応開始後、１〜２時間の成績は、クロルベンゼン転化
率＝9.2％、フエノール収率＝8.9％、フエノール選択率
＝97.0％、ベンゼン＝3.0％であつた。After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 9.2%, the phenol yield was 8.9%, the phenol selectivity was 97.0%, and the benzene was 3.0%.
Claims (1)
おいて加水分解して水酸化ベンゼンに転化する際に、無
水の状態で下記の組成を有する結晶性クロモシリケート
に、銅及び又は周期律表のVIII族の金属を含有せしめた
触媒を用いることを特徴とする水酸化ベンゼンの製造
法。 M2/nO・xSiO2・yAl2O3・zCr2O3 （但し、Ｍはｎ価の少なくとも一種のカチオンを示し、
ｙ＋ｚ＝１、ｙ≧０、ｚ＞０、ｘは10〜1000である。）1. When a halogenated benzene is hydrolyzed in the gas phase in the presence of water to be converted into hydroxylated benzene, a crystalline chromosilicate having the following composition in an anhydrous state is added to the crystalline chromosilicate and copper and / or the periodic table. A process for producing benzene hydroxide, which comprises using a catalyst containing a Group VIII metal in the table. M 2 / n O · xSiO 2 · yAl 2 O 3 · zCr 2 O 3 (However, M represents at least one cation of n valence,
y + z = 1, y ≧ 0, z> 0, and x is 10 to 1000. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61082250A JPH0735351B2 (en) | 1986-04-11 | 1986-04-11 | Manufacturing method of aryl hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61082250A JPH0735351B2 (en) | 1986-04-11 | 1986-04-11 | Manufacturing method of aryl hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62240634A JPS62240634A (en) | 1987-10-21 |
| JPH0735351B2 true JPH0735351B2 (en) | 1995-04-19 |
Family
ID=13769186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61082250A Expired - Lifetime JPH0735351B2 (en) | 1986-04-11 | 1986-04-11 | Manufacturing method of aryl hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0735351B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07110825B2 (en) * | 1993-02-03 | 1995-11-29 | 旭化成工業株式会社 | Phenol manufacturing method |
-
1986
- 1986-04-11 JP JP61082250A patent/JPH0735351B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62240634A (en) | 1987-10-21 |
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