JPH0314306B2 - - Google Patents
Info
- Publication number
- JPH0314306B2 JPH0314306B2 JP59234083A JP23408384A JPH0314306B2 JP H0314306 B2 JPH0314306 B2 JP H0314306B2 JP 59234083 A JP59234083 A JP 59234083A JP 23408384 A JP23408384 A JP 23408384A JP H0314306 B2 JPH0314306 B2 JP H0314306B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- indoles
- regeneration
- oxygen
- 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
- 239000003054 catalyst Substances 0.000 claims description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 150000002475 indoles Chemical class 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 150000001448 anilines Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 description 21
- 238000011069 regeneration method Methods 0.000 description 16
- 230000008929 regeneration Effects 0.000 description 14
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 5
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 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
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 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
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000010714 indole synthesis reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Indole Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(産業上の利用分野)
本発明は、アニリン類とエチレングリコール類
よりインドール類を製造する方法において、反応
に使用した劣化触媒を再生して繰り返し使用する
方法に関する。
(従来技術およびその問題点)
インドール類は化学工業原料として知られ、特
にインドールは近年香料やアミノ酸合成原料とし
て重要な物質となつてきている。
従来より、インドール類を合成しようとする試
みは数多くあつたが、いずれも副生物が多い原料
が高価である、製造工程が複雑であるなどの問題
点を有していた。
最近に至り、安価な原料であるアニリン類とエ
チレングリコール類を用い、かつ短い工程でイン
ドール類を合成する反応に有効な触媒系が見出さ
れてきた。例えば、Cu−Cr、Cu−Co、Pd/
SiO2、Pt/SiO2、Cdsなどが挙げられるが、いず
れの触媒系も反応活性低下が激しい、反応活性が
低いなどの欠点を有してり、実用触媒としての使
用に耐えない。本発明者らは、この反応について
種々の検討を加え、既に反応系に水を添加するこ
と、反応を加圧で実施することなどにより反応の
パフオーマンスを向上させうることを明らかにし
てきた。さらに、本発明者らは元素の周期律表第
b族の元素、例えば、Cu,AgおよびAu等のい
ずれかを有効成分として含む触媒系がインドール
類の製造に有効であり、長時間にわたり反応を実
施しうることを見出した。
しかしながらこれらの触媒を用いても反応時間
の経過とともに触媒が劣化し、触媒活性およびイ
ンドール類への選択性が低下して、インドール類
の収率が悪くなることは避けられない。
したがつて、この方法の工業的実施のために
は、反応に使用して劣化した触媒を再生し、繰り
返し使用できることが重要である。
触媒の再生法は、触媒の物性により異なり、ま
た最近開発された方法、すなわちアニリン類とエ
チレングリコール類よりインドール類を製造する
方法であるこの方法については、劣化した触媒の
再生について適切な方法が末だ提案されていな
い。
本発明の課題は、アニリン類とエチレングリコ
ール類よりインドール類を製造する方法に使用し
た劣化触媒を再生し、繰り返し使用するインドー
ル類の工業的製造方法を提供することである。
(問題点を解決するための手段)
本発明者らは、上記の課題について鋭意検討
し、アニリン類とエチレングリコール類からイン
ドール類を製造するのに使用する触媒、とくに元
素の周期律表第b族金属含有触媒の劣化の一因
が、アニリン類とエチレングリコール類を反応さ
せる際、それらが触媒上に吸着され、反応時間の
経過とともに、炭素が析出することにあるのを見
出し、このように劣化した触媒を適切な方法で再
生し、インドール類の製造に繰り返し使用する本
発明の方法に到達した。
すなわち、本発明は、元素の周期律表第b族
金属含有触媒の存在下でアニリン類とエチレング
リコール類からインドール類を製造する方法にお
いて、反応に使用して劣化した触媒を200〜450℃
の温度範囲の酸素を5vol%以下含有する不活性ガ
スと接触させて再生し、繰り返し使用することを
特徴とするインドール類の製造方法である。
本発明の方法で使用されるアニリン類は、一般
式()
(式中、Rは水素原子、ハロゲン原子、水酸
基、アルキル基またはアルコキシ基を示す)で表
わされる化合物である。例えば、アニリン、o
−・m−・もしくはp−トルイジン、o−・m・
もしくはp−ハロアニリン、o−・m−・もしく
はp−ヒドロキシアニリン、o−・m−・もしく
はp−アニシジン等があげられる。
またエチレングリコール類か、エチレングリコ
ール、プロピレングリコール、1,2−ブタンジ
オール、1,2,4−ブタントリオール、グリセ
ロール、2,3−ブタンジオール、ジエチレング
リコール等である。
本発明の方法に使用される触媒は、元素の周期
律表第b族元素であるCu、Ag及びAuの内、選
ばれた一種以上を有効成分として含有する触媒系
であり、これらと複合可能な元素として、B,
C,O,Mg,Al,Si,P,S,Ca,Ti,Cr,
Mn,Fe,Co,Ni,Zn,Ga,Ge,Se,Sr,Zr,
Mo,Ru,Rh,Pd,Cd,In,Sn,Sb,Te,
Ba,La,Ce,W,Ir,Pt,Tl,Pb,Bi,Th,
Seなどをあげることができる。前述の触媒は単
独、あるいは通常の担体であるケイソウ土、活性
白土、ゼオライト、シリカ、アルミナ、シリカ−
アルミナ、チタニア、クロミア、トリア、マグネ
シア、カルシア、酸化亜鉛、などに担持し使用さ
れる。
b族金属の原料としては、Cu及びAgの場
合、硝酸塩、硫酸塩、リン酸塩、炭酸塩、ハロゲ
ン化物、有機酸塩等、Auの場合は、塩化金塩、
塩化金酸アルカリ金属類、シアン化金、シアン化
金アルカリ金属類等が一般的に使用できる。
触媒の調整法としては、通常の混練法、共沈
法、含浸法及び前述の各法を組み合わせた方法な
どが適用可能である。例えば、各種の原料を混合
し、少量の水を添加し、ニーダー等で混練する方
法、各種原料を水溶液とし、これに沈澱剤を加
え、不溶性の沈澱として共沈させる方法、各種担
体に対し各種の原料を含浸させる方法などで調製
できる。
得られた触媒組成物は、通常180℃以下で乾燥
し、適当な造粒添加剤、成形助剤などを添加し成
形したり、あるいは触媒組成物をそのまま破砕し
て使用する。
本発明の方法では、このような触媒は反応時間
の経過とともに徐々に劣化するので、この劣化触
媒を後述の再生法で再生して、繰り返し使用す
る。
本発明の方法において、アニリン類とエチレン
グリコール類との反応は、触媒の存在下気相で実
施されるが、固定床、流動床または移動床のいず
れの反応様式でも可能である。
反応装置に導入するアニリン類とエチレングリ
コール類は、アニリン類1モルに対してエチレン
グリコール類0.01〜5モルの範囲、好ましくは
0.05〜1モルの範囲である。
原料であるアニリン類とエチレングリコール類
の導入量は、液空間速度(LHSV)で0.01〜
10hr-1の範囲であり、あらかじめ蒸発器にて気化
後反応装置に導入する。またその際に、水蒸気、
水素、一酸化炭素、二酸化炭素、メタン、窒素、
ネオン、アルゴンなどをキヤリアガスとして同伴
させても良い。中でも水蒸気、水素、一酸化炭素
は触媒のサービスライフを増大させる効果を有す
る為好ましい。
反応温度は200〜600℃の範囲、好ましくは250
〜500℃の範囲である。
反応圧力は減圧、常圧、加圧のいずれでも実施
可能であるが、常圧及び加圧状態の方が好まし
い。
本発明の方法に用いられる再生触媒は、上記の
ような反応条件によるインドール類の製造に用い
られた劣化触媒を、5vol%以下の酸素を含有する
不活性ガス中で20〜450℃で熱処理する方法が再
生したものである。
劣化した触媒の再生は、劣化触媒を反応器に充
填したまま行なうのが便利であるが、触媒を反応
器外に取り出して行なつてもよい。
この熱処理は、触媒の劣化の一因である反応中
に沈着した炭素質を取りのぞくことにあるが、通
常これは燃焼反応であり発熱する。したがつて、
供給ガスの温度(入口温度)は、200℃〜450℃、
好ましくは250℃〜400℃にする必要がある。温度
が高すぎると、熱処理中の触媒の温度が燃焼発熱
反応で上がりすぎてしまい、触媒中の有効成分が
シンタリングを起こし触媒活性の低下をまねく。
また、逆に温度が低すぎると、燃焼反応が起らな
いかあるいは起りにくくなり、十分再生されな
い。
再生に用いられるガスは酸素を容量で5%以
下、好ましくは2%以下含有する不活性ガスであ
る。酸素濃度が高すぎると燃焼反応が早く進み過
ぎ、触媒活性の低下をまねく。酸素濃度の下限は
特にないが、あまり酸素濃度を低くすると再生時
間が長くなり、経済的に不利である。不活性ガス
としては、N2,Ar,He,CO2,H2O等が使用で
きるが、経済的な理由から所定の酸素量を含有す
るように窒素と空気とを混合したガスを再生に用
いることが好ましい。ガス供給流量は、触媒層で
の圧力損失や再生所要時間を考慮して決められる
が、通常5m/sec以下、特に1cm/secから1m/
secの範囲が用いられる。ガス供給方法は酸素含
有不活性ガスをワン・パスで供給しても良いし、
不活性ガスを系内に循環させながら所定の酸素量
を供給する方法でも良く、特に制限はない。
これら再生操作を行なうことにより、触媒に沈
着した炭素質を取りのぞくことができるが、再生
効果をより顕著にするため、前記の再生操作に引
続いて酸素含有ガス、好ましくは空気雰囲気下、
温度を450℃〜600℃、好ましくは480℃〜550℃に
し、5時間以上、好ましくは約10〜20時間熱処理
を行なうことが好ましい。この操作を行なうこと
によつて触媒の安定性が増加し長時間にわたり経
時変化なく反応を実施できる。
(作用および発明の効果)
アニリン類とエチレングリコール類との反応で
インドール類を製造する際に用いられる周期律表
第b族金属含有触媒は、反応時間の経過ととも
に、徐々に析出した炭素質が沈着して劣化する。
この劣化触媒を5vol%以下の酸素を含有する不
活性ガスに200〜470℃の温度で熱処理することに
より、効果的に炭素質が取り除かれて触媒活性が
回復する。
本発明の方法は、アニリン類とエチレングリコ
ール類によりインドール類の製造に有効な第b
族金属含有触媒について、反応に使用して劣化し
た触媒を最適の条件で再生し、再生した触媒を繰
り返し使用してなるインドール類の工業的製造方
法を提供するものである。
(実施例)
以下、本発明の方法を実施例および比較例によ
り詳しく説明する。
実施例1および比較例1
内径20mmのステンレス製反応管に市販の打錠成
形した直径3mm、高さ2.5mmのSiO2に銀を13%担
持したペレツト状触媒400c.c.を充填した。反応管
を350℃に保ち、あらかじめ気化させたアニリン、
エチレングリコールおよび水のモル比でで12:
1:30の原料を300g/hrで、また同時に水素ガ
スを60lSTP/hrで反応管に供給しインドール合
成反応を行なつた。なお、反応は常圧で行なつ
た。
一定時間反応させた後、触媒の再生を行なつ
た。再生条件は表1に示した。なお、酸素含有ガ
スの空筒線速度は15Ncm/secであつた。
再生後500℃、空気雰囲気下15時間、触媒の熱
処理を行なつた後再生前と同じ条件で再び反応を
行なつた。
再生前後の反応でのエチレングリコールの転化
率および生成したインドールの収率を表1に示し
た。なお、エチレングリコール類の転化率および
インドールの収率は以下の定義に従う。
エチレングリコールの転化率=消
費されたエチレングリコールのモル数/供給したエチレ
ングリコールのモル数×100
インドールの収率=生成したイン
ドールのモル数/供給したエチレングリコール類のモル
数×100
また、表中転化率および収率は反応25時間目
(但し、( )中は50時間目)のものを示す。
(Industrial Application Field) The present invention relates to a method for producing indoles from anilines and ethylene glycols, in which a degraded catalyst used in the reaction is regenerated and used repeatedly. (Prior art and its problems) Indoles are known as raw materials for the chemical industry, and indoles in particular have recently become important substances as raw materials for perfumes and amino acid synthesis. There have been many attempts to synthesize indoles in the past, but all of them had problems such as expensive raw materials with many by-products and complicated manufacturing processes. Recently, a catalyst system has been discovered that is effective in the reaction of synthesizing indoles using inexpensive raw materials anilines and ethylene glycols and in a short process. For example, Cu-Cr, Cu-Co, Pd/
Examples include SiO 2 , Pt/SiO 2 , Cds, etc., but all catalyst systems have drawbacks such as severe reduction in reaction activity and low reaction activity, and cannot be used as practical catalysts. The present inventors have conducted various studies on this reaction and have already clarified that the performance of the reaction can be improved by adding water to the reaction system, carrying out the reaction under pressure, etc. Furthermore, the present inventors have found that a catalyst system containing any of the elements of Group B of the Periodic Table of Elements, such as Cu, Ag, and Au, as an active ingredient is effective for the production of indoles, and the reaction takes a long time. We found that it is possible to implement However, even if these catalysts are used, it is inevitable that the catalyst deteriorates with the passage of reaction time, the catalyst activity and selectivity to indoles decrease, and the yield of indoles deteriorates. Therefore, for industrial implementation of this method, it is important to be able to regenerate and repeatedly use the catalyst that has deteriorated during the reaction. Catalyst regeneration methods vary depending on the physical properties of the catalyst, and a recently developed method, namely a method for producing indoles from anilines and ethylene glycols, requires an appropriate method for regenerating a deteriorated catalyst. The end is not proposed. An object of the present invention is to provide an industrial method for producing indoles in which a degraded catalyst used in a method for producing indoles from anilines and ethylene glycols is regenerated and used repeatedly. (Means for Solving the Problems) The present inventors have diligently studied the above-mentioned problems and have determined that the catalyst used to produce indoles from anilines and ethylene glycols, in particular We discovered that one of the reasons for the deterioration of group metal-containing catalysts is that when anilines and ethylene glycols are reacted, they are adsorbed onto the catalyst, and as the reaction time progresses, carbon precipitates. The method of the present invention has been achieved in which a deteriorated catalyst is regenerated by an appropriate method and used repeatedly for the production of indoles. That is, the present invention provides a method for producing indoles from anilines and ethylene glycols in the presence of a catalyst containing a metal from Group B of the Periodic Table of the Elements, in which the catalyst deteriorated during the reaction is heated at 200 to 450°C.
This is a method for producing indoles, which is characterized in that they are regenerated by contacting with an inert gas containing 5 vol% or less of oxygen in the temperature range of , and used repeatedly. The anilines used in the method of the present invention have the general formula () (wherein R represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group). For example, aniline, o
-・m-・or p-toluidine, o-・m・
Alternatively, examples thereof include p-haloaniline, o-, m-, or p-hydroxyaniline, o-, m-, or p-anisidine, and the like. Also, ethylene glycols, ethylene glycol, propylene glycol, 1,2-butanediol, 1,2,4-butanetriol, glycerol, 2,3-butanediol, diethylene glycol, and the like. The catalyst used in the method of the present invention is a catalyst system containing as an active ingredient one or more of Cu, Ag, and Au, which are group B elements of the periodic table of elements, and can be combined with these. As an element, B,
C, O, Mg, Al, Si, P, S, Ca, Ti, Cr,
Mn, Fe, Co, Ni, Zn, Ga, Ge, Se, Sr, Zr,
Mo, Ru, Rh, Pd, Cd, In, Sn, Sb, Te,
Ba, La, Ce, W, Ir, Pt, Tl, Pb, Bi, Th,
Se etc. can be given. The aforementioned catalysts may be used alone or in the presence of common carriers such as diatomaceous earth, activated clay, zeolite, silica, alumina, and silica.
It is used supported on alumina, titania, chromia, thoria, magnesia, calcia, zinc oxide, etc. Raw materials for Group B metals include nitrates, sulfates, phosphates, carbonates, halides, organic acid salts, etc. for Cu and Ag; gold chlorides,
Alkali metal chloroaurates, gold cyanide, alkali metal gold cyanide, etc. can generally be used. As a method for preparing the catalyst, the usual kneading method, coprecipitation method, impregnation method, and a combination of the above-mentioned methods can be applied. For example, a method of mixing various raw materials, adding a small amount of water, and kneading with a kneader, etc., a method of making various raw materials into an aqueous solution, adding a precipitant to this, and co-precipitating it as an insoluble precipitate; It can be prepared by impregnating raw materials. The obtained catalyst composition is usually dried at 180° C. or lower, and suitable granulation additives, molding aids, etc. are added and molded, or the catalyst composition is crushed and used as it is. In the method of the present invention, such a catalyst gradually deteriorates with the passage of reaction time, so this deteriorated catalyst is regenerated by the regeneration method described below and used repeatedly. In the method of the present invention, the reaction between anilines and ethylene glycols is carried out in the gas phase in the presence of a catalyst, but any reaction mode such as fixed bed, fluidized bed or moving bed is possible. The anilines and ethylene glycols introduced into the reactor are in the range of 0.01 to 5 mol of ethylene glycol per 1 mol of aniline, preferably
It ranges from 0.05 to 1 mole. The amount of introduced raw materials anilines and ethylene glycols is 0.01 to 0.01 in terms of liquid hourly space velocity (LHSV).
It is in the range of 10 hr -1 and is vaporized in an evaporator before being introduced into the reactor. Also, at that time, water vapor,
hydrogen, carbon monoxide, carbon dioxide, methane, nitrogen,
Neon, argon, or the like may be used as a carrier gas. Among them, water vapor, hydrogen, and carbon monoxide are preferable because they have the effect of increasing the service life of the catalyst. The reaction temperature ranges from 200 to 600℃, preferably 250℃
~500℃ range. The reaction can be carried out under reduced pressure, normal pressure, or increased pressure, but normal pressure or increased pressure is preferable. The regenerated catalyst used in the method of the present invention is obtained by heat-treating the degraded catalyst used for the production of indoles under the above reaction conditions at 20 to 450°C in an inert gas containing 5 vol% or less oxygen. That's how it was played. Although it is convenient to regenerate a deteriorated catalyst while the deteriorated catalyst remains in the reactor, it may also be performed by taking the catalyst out of the reactor. The purpose of this heat treatment is to remove carbon deposited during the reaction, which is a cause of catalyst deterioration, but this is usually a combustion reaction and generates heat. Therefore,
Supply gas temperature (inlet temperature) is 200℃~450℃,
The temperature should preferably be 250°C to 400°C. If the temperature is too high, the temperature of the catalyst during heat treatment will rise too much due to the combustion exothermic reaction, causing sintering of the active components in the catalyst and reducing the catalytic activity.
On the other hand, if the temperature is too low, the combustion reaction will not occur or will be difficult to occur, and sufficient regeneration will not occur. The gas used for regeneration is an inert gas containing less than 5% oxygen by volume, preferably less than 2% oxygen. If the oxygen concentration is too high, the combustion reaction will proceed too quickly, leading to a decrease in catalyst activity. Although there is no particular lower limit to the oxygen concentration, if the oxygen concentration is too low, the regeneration time becomes longer, which is economically disadvantageous. N 2 , Ar, He, CO 2 , H 2 O, etc. can be used as the inert gas, but for economical reasons, a mixture of nitrogen and air containing a specified amount of oxygen is used for regeneration. It is preferable to use The gas supply flow rate is determined by considering the pressure loss in the catalyst layer and the time required for regeneration, but it is usually 5 m/sec or less, especially from 1 cm/sec to 1 m/sec.
A range of sec is used. The gas supply method may be to supply oxygen-containing inert gas in one pass, or
A method may also be used in which a predetermined amount of oxygen is supplied while circulating an inert gas within the system, and there is no particular restriction. By performing these regeneration operations, carbonaceous matter deposited on the catalyst can be removed, but in order to make the regeneration effect more pronounced, subsequent to the above regeneration operation, under an oxygen-containing gas, preferably air atmosphere,
It is preferable to carry out the heat treatment at a temperature of 450°C to 600°C, preferably 480°C to 550°C, for 5 hours or more, preferably about 10 to 20 hours. By carrying out this operation, the stability of the catalyst is increased and the reaction can be carried out for a long time without any change over time. (Action and Effect of the Invention) A catalyst containing a group B metal of the periodic table used for producing indoles through the reaction of anilines and ethylene glycols gradually deposits carbonaceous material over the course of the reaction time. Deposits and deteriorates. By heat-treating this deteriorated catalyst in an inert gas containing 5 vol% or less oxygen at a temperature of 200 to 470°C, carbonaceous matter is effectively removed and the catalyst activity is restored. The method of the present invention is effective for producing indoles using anilines and ethylene glycols.
The present invention provides an industrial method for producing indoles by regenerating a group metal-containing catalyst that has deteriorated after being used in a reaction under optimal conditions and repeatedly using the regenerated catalyst. (Examples) Hereinafter, the method of the present invention will be explained in detail with reference to Examples and Comparative Examples. Example 1 and Comparative Example 1 A stainless steel reaction tube with an inner diameter of 20 mm was filled with 400 c.c. of a commercially available tablet-formed SiO 2 catalyst having a diameter of 3 mm and a height of 2.5 mm and carrying 13% silver thereon. Keep the reaction tube at 350℃ and pre-vaporize aniline,
The molar ratio of ethylene glycol and water is 12:
Indole synthesis reaction was carried out by supplying raw materials of 1:30 at 300 g/hr and hydrogen gas at 60 lSTP/hr to the reaction tube at the same time. Note that the reaction was carried out at normal pressure. After reacting for a certain period of time, the catalyst was regenerated. The regeneration conditions are shown in Table 1. Note that the cylinder linear velocity of the oxygen-containing gas was 15 Ncm/sec. After regeneration, the catalyst was heat-treated at 500° C. for 15 hours in an air atmosphere, and then the reaction was performed again under the same conditions as before regeneration. Table 1 shows the conversion rate of ethylene glycol and the yield of the produced indole in the reactions before and after regeneration. Note that the conversion rate of ethylene glycols and the yield of indole follow the definitions below. Conversion rate of ethylene glycol = Number of moles of ethylene glycol consumed/Number of moles of ethylene glycol supplied x 100 Yield of indole = Number of moles of indole produced/Number of moles of ethylene glycols supplied x 100 In addition, in the table The conversion rate and yield are those obtained at the 25th hour of the reaction (however, the values in parentheses indicate the 50th hour).
【表】
実施例2および比較例2
触媒再生条件等実施例1、比較例1に示した方
法に準じ、触媒のみを変化させて反応を行なつ
た。なお、触媒は、実施例1で用いた触媒の担体
と同じものに銅を2.5%担持したものである。
再生前後の反応でのエチレングリコールの転化
率および生成したインドールの収率を表−2に示
した。[Table] Example 2 and Comparative Example 2 A reaction was carried out according to the method shown in Example 1 and Comparative Example 1, including catalyst regeneration conditions, with only the catalyst being changed. The catalyst was the same as the catalyst carrier used in Example 1, with 2.5% copper supported thereon. Table 2 shows the conversion rate of ethylene glycol and the yield of indole produced in the reactions before and after regeneration.
【表】【table】
Claims (1)
も一種を含有する触媒の存在下でアニリン類とエ
チレングリコール類を反応させてインドール類を
製造する方法において、反応に使用して劣化した
触媒を200〜450℃の温度範囲の酸素を5vol%以下
含有する不活性ガスと接触させて再生し、繰り返
し使用することを特徴とするインドール類の製造
方法。1. In a method for producing indoles by reacting anilines and ethylene glycols in the presence of a catalyst containing at least one metal from Group B of the Periodic Table of the Elements, the catalyst degraded during the reaction is A method for producing indoles, which comprises regenerating and repeatedly using oxygen by contacting it with an inert gas containing 5 vol% or less of oxygen in the temperature range of ~450°C.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59234083A JPS61115065A (en) | 1984-11-08 | 1984-11-08 | Production of indole compound |
CA000494544A CA1253507A (en) | 1984-11-08 | 1985-11-04 | Preparation process of indoles |
DE8585114043T DE3581587D1 (en) | 1984-11-08 | 1985-11-05 | MANUFACTURING METHOD FOR INDOLE. |
EP85114043A EP0180957B1 (en) | 1984-11-08 | 1985-11-05 | Preparation process of indoles |
KR1019850008365A KR870000522B1 (en) | 1984-11-08 | 1985-11-08 | Contisuous process preparing indole |
US07/117,904 US4831158A (en) | 1984-11-08 | 1987-11-02 | Preparation process indoles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59234083A JPS61115065A (en) | 1984-11-08 | 1984-11-08 | Production of indole compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61115065A JPS61115065A (en) | 1986-06-02 |
JPH0314306B2 true JPH0314306B2 (en) | 1991-02-26 |
Family
ID=16965337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59234083A Granted JPS61115065A (en) | 1984-11-08 | 1984-11-08 | Production of indole compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61115065A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010279876A (en) * | 2009-06-03 | 2010-12-16 | Jx Nippon Oil & Energy Corp | System for dehydrogenating organic hydride |
-
1984
- 1984-11-08 JP JP59234083A patent/JPS61115065A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS61115065A (en) | 1986-06-02 |
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