JPS6343372B2 - - Google Patents
Info
- Publication number
- JPS6343372B2 JPS6343372B2 JP54050891A JP5089179A JPS6343372B2 JP S6343372 B2 JPS6343372 B2 JP S6343372B2 JP 54050891 A JP54050891 A JP 54050891A JP 5089179 A JP5089179 A JP 5089179A JP S6343372 B2 JPS6343372 B2 JP S6343372B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- oxide
- catalyst
- hours
- catalysts
- 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
Links
- 239000003054 catalyst Substances 0.000 claims description 51
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 150000002989 phenols Chemical class 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- -1 phenol compound Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PXSSNPBEHHJLDH-UHFFFAOYSA-N 2,3,4,5-tetramethylphenol Chemical class CC1=CC(O)=C(C)C(C)=C1C PXSSNPBEHHJLDH-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical class CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical class CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical class CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-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
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
-
- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は還元性ガスにより前処理をした金属酸
化物含有触媒を用いて、フエノール核の水素原子
をアルキル化し、少なくとも１個以上のアルキル
基をもつアルキル化フエノール類の製造に関する
ものである。
アルキル化フエノール類の製造方法に関して
は、特にオルトアルキル化物である２，６−ジメ
チルフエノールが有用なプラスチツクスであるポ
リフエニレンエーテル（PPE）製造用の原料と
なるので、数多くの研究がなされている。
フエノール類のアルキル化方法としては、既
に、酸化アルミニウム、酸化マグネシウム、酸化
マンガン、酸化鉄、酸化クロム、ゼオライトな
ど、およびそれらに各種の成分を添加したものを
触媒として使用し、フエノール類とアルコール類
を接触反応させる方法が公知であるが、これらの
触媒はいずれも触媒寿命の点で欠点を有し、十分
な触媒とは言い難い。
本発明者らは、このアルキル化方法について
種々の検討を加えた結果、還元性ガスにより前処
理をした金属酸化物含有触媒は、未処理の場合と
比較して、触媒寿命の点においてすぐれているこ
とを見出し、本発明の方法に到達したものであ
る。
本発明において使用されるフエノール類とは、
１個以上の水素原子を芳香族環上に有するフエノ
ール化合物で、一般式（）
（式中、R1〜R5は、水素、炭素原子数１〜４の
炭化水素基、または非置換もしくは置換のフエニ
ル、ナフチルなどの芳香族炭化水素基であり、そ
の内少なくとも１個以上は水素原子である）で表
わされる。
例えば、フエノール、クレゾール類、キシレノ
ール類、トリメチルフエノール類、テトラメチル
フエノール類、各種のエチルフエノール類、ｎ−
iso−またはtert−のブチルフエノール類、フエ
ニルフエノール類、ナフチルフエノール類などが
本発明に使用でき、同様に異種の官能基が芳香族
環に１個以上置換したフエノール化合物も使用で
きる。
本発明に使用されるアルコール類とは、炭素原
子数１〜４の低級アルコールであり、例えばメタ
ノール、エタノール、ｎ−プロパノール、iso−
プロパノール、ｎ−ブタノール、iso−ブタノー
ル、tert−ブタノールなどである。
本発明の方法で用いられる還元性ガスで前処理
される触媒とは、フエノール類とアルコール類を
接触反応させ、アルキル化フエノール類を合成す
る際に使用される触媒系が一般に有効であり、例
えば酸化アルミニウム含有触媒、酸化マグネシウ
ム含有触媒、酸化マンガン含有触媒、酸化鉄含有
触媒などがあげられる。すなわち、(1)酸化アルミ
ニウム含有触媒とは、酸化アルミニウム単独およ
びそれを主成分とし、酸化ケイ素などを含むも
の、(2)酸化マグネシウム含有触媒とは、酸化マグ
ネシウム単独およびそれを主成分とし、酸化錫、
酸化マンガン、酸化銅、ランタニド、アクチニ
ド、酸化ビスマスおよび酸化ホウ素から選ばれた
一種もしくは二種以上を含むもの、(3)酸化マンガ
ン含有触媒とは、酸化マンガン単独およびそれを
主成分とし、酸化ケイ素、アルカリ金属類、アル
カリ土類金属類および硫酸根から選ばれた一種も
しくは二種以上を含むもの、(4)酸化鉄含有触媒と
は、酸化鉄単独およびそれを主成分とし、酸化ケ
イ素、酸化クロム、酸化亜鉛、酸化マンガン、酸
化バナジウム、アルカリ金属類およびアルカリ土
類金属類から選ばれた一種もしくは２種以上を含
むものである。上記の酸化アルミニウム含有触
媒、酸化マグネシウム含有触媒、酸化マンガン含
有触媒、酸化鉄含有触媒において、「主成分」の
語彙は、それぞれ酸化アルミニウムを50モル％以
上含有するもの、酸化マグネシウムを50モル％以
上含有するもの、酸化マンガンを50モル％以上含
有するもの、酸化鉄を50モル％以上含有するもの
を示す。また、ここに記載された「含有触媒」
は、化学的な意味での「含有触媒」ではなく、物
理的な意味での「含有触媒」である。すなわち、
「含有触媒」は当該成分を物理的に主として含む
（換言すれば50モル％以上含有する）触媒を表す。
これらの触媒に用いられる各種酸化物の原料と
しては、それぞれの金属の酸化物、水酸化物、ハ
ロゲン化物、硝酸塩、硫酸塩、炭酸塩、有機酸塩
など、通常の化合物が使用可能である。
触媒の調製方法としては、各種の原料を混合
し、少量の水を添加し、ニーダー、ミクサーなど
で混練させる方法、あるいは各種原料を水溶液と
し、これに塩基性成分を加え、不溶性の沈澱とし
て共沈させる方法など、各種の一般的方法が適用
可能である。得られた触媒組成物は通常180℃以
下の温度で乾燥し、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してもよい。
本発明の方法で使用される金属酸化物含有触媒
の還元処理は、つぎの２つの方法によるが、どち
らの方法でもよい。
() 触媒組成物の乾燥品を、還元性ガス雰囲気
下にて焼成し、使用する方法。
() 空気あるいは、窒素などのいわゆる不活性
ガス雰囲気下にて、あらかじめ焼成されている
触媒組成物を、還元性ガス雰囲気下にて再焼成
し、使用する方法。
ここで使用される還元性ガスとは、水素、一酸
化炭素、アンモニア、メタノール、エタノール、
メタン、エタン、プロパン、ブタンおよびそれら
の混合物があげられるが、水素、一酸化炭素およ
びそれらの混合物がより好ましい。また上記還元
性ガスを窒素などの不活性ガスで希釈して使用し
ても良い。通常、上記還元処理は100〜800℃、好
ましくは200〜600℃の温度範囲で、（）の場合、
0.3〜30時間、（）の場合では0.5〜50時間行な
われる。反応に使用して活性の低下した触媒は、
酸素および水蒸気によつて賦活化させた後、前記
還元処理を行なう。
本発明における還元処理の役割は、通常の空気
中または窒素などの雰囲気下で焼成されたとき、
触媒表面上に存在するを考えられる反応性に富ん
だ酸素種を取り去ることにある。これにより、反
応開始時でのこれらの酸素種と原料の間の副反応
の抑制、誘導期の短縮および吸着炭化水素種の量
を減少させることが可能となり、本発明の方法を
実施しない場合と比較して大巾に触媒再生サイク
ルの長期化がはかれる。
本発明の方法を実施する場合、フエノール類と
アルコール類の供給モル比率は１：１〜１：10が
適当で１：１〜１：８がより好ましい。気相で反
応させる場合、原料の反応系への供給に窒素、炭
酸ガス、アルゴンまたは本発明を実施した際に発
生するガスをキヤリアーとして使用することは、
反応を円滑に進行させる。また、反応原料中に水
を混入させ反応を実施させることは触媒寿命をさ
らに延ばす効果およびアルコール類の不必要な分
解を抑制する効果がある。
本発明の方法では、反応温度は290〜580℃、好
ましくは310〜530℃の範囲である。通常、反応温
度これ以上の高温側にすると反応の選択性が低下
したり、高沸分の生成が増加したりして好ましく
ない。また、これ以下の低温側では、通常の反応
形式では転化率が低く、実用的でない。
反応は液相、加圧、常圧、減圧いずれの場合で
も実施でき反応形式も固定床、流動床または移動
床のいずれもが可能であるが、固定床方式が一般
的である。
以下、実施例によつて本発明を説明する。
実施例 １
硝酸マンガン６水塩100ｇ、水ガラス３号２ｇ
を水２中に溶解させ、アンモニア水を加え沈澱
を生成させた。これを水洗、過し、170℃で乾
燥させた。それを破砕し、６〜12メツシユの粒径
にそろえ、得られた触媒７mlを、ガラス製反応管
に充填し空気流通下430℃で３時間焼成した後、
400℃で水素と窒素のモル比１：１の混合ガスを
50分間流し、反応に用いた。
フエノールとメタノールのモル比１：６に混合
した反応液を240℃にて加熱気化させた後、内温
を410℃に調節した反応管に１時間当り3.1ｇ導入
し反応を行なつた。
反応開始時より、生成物はあまり着色せず澄ん
でおり、高沸分の生成が少ないことが示唆され
た。結果は、反応開始後５時間の時点でフエノー
ル転化率100％、Ｏ−クレソール、2.6−キシレノ
ールの選択率はそれぞれ3.1％、92.8％であり、
反応開始後200時間の時点においても、内温422℃
でフエノール転化率99.8％、Ｏ−クレゾール、
2.6−キシレノールの選択率はそれぞれ4.9％、
91.7％であつた。
実施例 ２
硝酸鉄９水塩100ｇ、硝酸クロム９水塩１ｇ、
水ガラス３号0.5ｇを水２中に溶解させ、アン
モニア水を加え沈澱を生成させた。これを水洗、
過し、170℃で乾燥させた。それを破砕し、６
〜12メツシユの粒径にそろえ、得られた触媒８ml
を空気流通下400℃で３時間焼成した後、実施例
１と同様の水素−窒素の混合ガスを30分間流し、
反応に用いた。
フエノールとメタノールのモル比１：６に混合
した反応液を240℃にて加熱気化させた後、内温
を360℃に調節した反応管に１時間当り3.2ｇ導入
し、反応を行なつた。
反応開始時より生成物はあまり着色せず澄んで
おり、高沸分の生成が少ないことが示唆された。
結果は、反応開始始後５時間の時点で、フエノー
ル転化率100％、Ｏ−クレゾール、2.6−キシレノ
ールの選択率はそれぞれ、2.3％、95.6％であり、
反応開始後150時間の時点においても、内温366℃
でフエノール転化率99.4％、Ｏ−クレソール、
2.6−キシレノールの選択率はそれぞれ8.1％、
91.3％であつた。
実施例 ３
水酸化マグネシウム50ｇおよび塩化錫10ｇに、
水30mlを加え、３時間良くらいかい混練させた後
170℃にて乾燥させた。それを破砕し、６〜12メ
ツシユの粒径にそろえ得られた触媒７mlをガラス
製反応管に充填し、480℃、一酸化炭素、水素お
よび窒素のモル比１：１：８の混合ガスを流し、
３時間焼成し反応に用いた。
フエノールとメタノールのモル比１：６に混合
した反応液を240℃にて加熱気化させた後、内温
を440℃に調節した反応管に１時間当り3.0.ｇ導
入し、反応を行なつた。
結果は、反応開始後５時間の時点で、フエノー
ル転化率100％、Ｏ−クレゾール、2.6−キシレノ
ールの選択率はそれぞれ5.4％、93.0％であり、
反応開始後150時間の時点においても、内温455℃
でフエノール転化率99.7％、Ｏ−クレゾール、
2.6−キシレノールの選択率はそれぞれ8.8％、
90.1％であつた。
比較例 １〜３
実施例１〜３と同様な方法において、触媒を空
気中で焼成し、還元処理を行なわず反応に用いた
場合について、それぞれ対応させて第１表に示
す。
The present invention relates to the production of alkylated phenols having at least one alkyl group by alkylating hydrogen atoms in phenol nuclei using a metal oxide-containing catalyst pretreated with a reducing gas. Much research has been conducted into the production of alkylated phenols, especially since the orthoalkylated product 2,6-dimethylphenol is a raw material for the production of polyphenylene ether (PPE), a useful plastic. There is. As a method for alkylating phenols, aluminum oxide, magnesium oxide, manganese oxide, iron oxide, chromium oxide, zeolite, etc., as well as various components added thereto, have been used as catalysts to alkylate phenols and alcohols. Although methods for catalytically reacting are known, all of these catalysts have shortcomings in terms of catalyst life and cannot be said to be sufficient catalysts. As a result of various studies on this alkylation method, the present inventors found that a metal oxide-containing catalyst pretreated with a reducing gas has a superior catalyst life compared to an untreated catalyst. The present invention has been developed based on this discovery. The phenols used in the present invention are:
A phenol compound having one or more hydrogen atoms on an aromatic ring, with the general formula () (In the formula, R 1 to R 5 are hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group such as unsubstituted or substituted phenyl or naphthyl, and at least one of them is hydrogen atom). For example, phenols, cresols, xylenols, trimethylphenols, tetramethylphenols, various ethylphenols, n-
Iso- or tert-butylphenols, phenylphenols, naphthylphenols, etc. can be used in the present invention, and similarly, phenol compounds in which one or more different functional groups are substituted on the aromatic ring can also be used. The alcohols used in the present invention are lower alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, iso-
These include propanol, n-butanol, iso-butanol, tert-butanol, and the like. The catalyst that is pretreated with a reducing gas used in the method of the present invention is generally a catalyst system that is used when catalytically reacting phenols and alcohols to synthesize alkylated phenols. For example, Examples include catalysts containing aluminum oxide, catalysts containing magnesium oxide, catalysts containing manganese oxide, and catalysts containing iron oxide. In other words, (1) aluminum oxide-containing catalysts are those containing aluminum oxide alone or aluminum oxide as the main component and containing silicon oxide, etc.; (2) magnesium oxide-containing catalysts are those containing magnesium oxide alone or aluminum oxide as the main component; tin,
Catalysts containing one or more selected from manganese oxide, copper oxide, lanthanides, actinides, bismuth oxide, and boron oxide; , alkali metals, alkaline earth metals, and sulfuric acid radicals. (4) Iron oxide-containing catalysts include iron oxide alone or iron oxide as the main component, silicon oxide, sulfuric acid, etc. It contains one or more selected from chromium, zinc oxide, manganese oxide, vanadium oxide, alkali metals, and alkaline earth metals. In the above aluminum oxide-containing catalysts, magnesium oxide-containing catalysts, manganese oxide-containing catalysts, and iron oxide-containing catalysts, the term "main component" refers to those containing 50 mol% or more of aluminum oxide, and 50 mol% or more of magnesium oxide, respectively. containing 50 mol% or more of manganese oxide, and 50 mol% or more of iron oxide. In addition, the "containing catalyst" described here
is not a "containing catalyst" in a chemical sense, but a "containing catalyst" in a physical sense. That is,
"Containing catalyst" refers to a catalyst that physically mainly contains (in other words, contains 50 mol% or more) the component. As raw materials for various oxides used in these catalysts, common compounds such as oxides, hydroxides, halides, nitrates, sulfates, carbonates, and organic acid salts of the respective metals can be used. The catalyst can be prepared by mixing various raw materials, adding a small amount of water, and kneading with a kneader or mixer, or by making various raw materials into an aqueous solution, adding a basic component to this, and coagulating it as an insoluble precipitate. Various general methods are applicable, such as a method of precipitation. The obtained catalyst composition is usually dried at a temperature of 180°C or less, and suitable granulation additives, molding aids, etc. are added and molded, or the catalyst composition may be crushed and used as it is. . The metal oxide-containing catalyst used in the method of the present invention may be reduced by the following two methods, and either method may be used. () A method in which a dried catalyst composition is calcined in a reducing gas atmosphere and then used. () A method in which a catalyst composition that has been previously fired in a so-called inert gas atmosphere such as air or nitrogen is re-fired in a reducing gas atmosphere and then used. The reducing gases used here include hydrogen, carbon monoxide, ammonia, methanol, ethanol,
Mention may be made of methane, ethane, propane, butane and mixtures thereof, with hydrogen, carbon monoxide and mixtures thereof being more preferred. Further, the above-mentioned reducing gas may be diluted with an inert gas such as nitrogen before use. Usually, the above reduction treatment is carried out at a temperature range of 100 to 800°C, preferably 200 to 600°C.
It is carried out for 0.3 to 30 hours, and in the case of () 0.5 to 50 hours. A catalyst whose activity has decreased after being used in a reaction is
After activation with oxygen and water vapor, the reduction treatment is performed. The role of reduction treatment in the present invention is that when fired in normal air or in an atmosphere such as nitrogen,
The purpose is to remove reactive oxygen species that may be present on the catalyst surface. This makes it possible to suppress side reactions between these oxygen species and raw materials at the start of the reaction, shorten the induction period, and reduce the amount of adsorbed hydrocarbon species, compared to when the method of the present invention is not carried out. In comparison, the catalyst regeneration cycle is significantly longer. When carrying out the method of the present invention, the molar ratio of phenols and alcohols to be supplied is suitably from 1:1 to 1:10, more preferably from 1:1 to 1:8. When reacting in the gas phase, using nitrogen, carbon dioxide, argon, or the gas generated when carrying out the present invention as a carrier for supplying the raw materials to the reaction system,
Make the reaction proceed smoothly. Furthermore, mixing water into the reaction raw materials to carry out the reaction has the effect of further extending the life of the catalyst and suppressing unnecessary decomposition of alcohols. In the method of the invention, the reaction temperature ranges from 290 to 580°C, preferably from 310 to 530°C. Generally, raising the reaction temperature to a higher temperature is not preferable because the selectivity of the reaction decreases or the production of high-boiling components increases. Furthermore, at lower temperatures than this, the conversion rate is low in the normal reaction format, making it impractical. The reaction can be carried out in a liquid phase, under increased pressure, normal pressure, or reduced pressure, and the reaction format can be fixed bed, fluidized bed, or moving bed, although fixed bed method is common. The present invention will be explained below with reference to Examples. Example 1 Manganese nitrate hexahydrate 100g, water glass No. 3 2g
was dissolved in water 2, and aqueous ammonia was added to form a precipitate. This was washed with water, filtered, and dried at 170°C. The catalyst was crushed and adjusted to a particle size of 6 to 12 meshes, and 7 ml of the resulting catalyst was filled into a glass reaction tube and fired at 430°C for 3 hours under air circulation.
A mixed gas of hydrogen and nitrogen at a molar ratio of 1:1 at 400°C.
It was run for 50 minutes and used for reaction. A reaction solution containing phenol and methanol mixed at a molar ratio of 1:6 was heated and vaporized at 240°C, and then 3.1g per hour was introduced into a reaction tube whose internal temperature was adjusted to 410°C to carry out a reaction. From the beginning of the reaction, the product was clear without much coloration, suggesting that less high-boiling components were produced. The results showed that 5 hours after the start of the reaction, the phenol conversion rate was 100%, and the selectivity for O-cresol and 2.6-xylenol was 3.1% and 92.8%, respectively.
Even at 200 hours after the start of the reaction, the internal temperature was 422℃.
99.8% phenol conversion, O-cresol,
The selectivity of 2.6-xylenol was 4.9% and
It was 91.7%. Example 2 Iron nitrate nonahydrate 100g, chromium nitrate nonahydrate 1g,
0.5 g of Water Glass No. 3 was dissolved in Water 2, and aqueous ammonia was added to form a precipitate. Wash this with water,
and dried at 170°C. Crush it and 6
8 ml of the catalyst obtained by adjusting the particle size to ~12 meshes
After firing at 400°C for 3 hours under air circulation, the same hydrogen-nitrogen mixed gas as in Example 1 was flowed for 30 minutes.
Used for reaction. A reaction solution containing phenol and methanol mixed at a molar ratio of 1:6 was heated and vaporized at 240°C, and then 3.2g per hour was introduced into a reaction tube whose internal temperature was adjusted to 360°C to carry out a reaction. From the start of the reaction, the product was clear without much coloration, suggesting that less high-boiling components were produced.
The results showed that 5 hours after the start of the reaction, the phenol conversion rate was 100%, and the selectivity of O-cresol and 2.6-xylenol was 2.3% and 95.6%, respectively.
Even at 150 hours after the start of the reaction, the internal temperature remained at 366℃.
phenol conversion rate of 99.4%, O-cresol,
The selectivity of 2.6-xylenol is 8.1% and
It was 91.3%. Example 3 50 g of magnesium hydroxide and 10 g of tin chloride,
Add 30ml of water and mix well for 3 hours.
It was dried at 170°C. The catalyst was crushed and adjusted to a particle size of 6 to 12 meshes, and 7 ml of the resulting catalyst was filled into a glass reaction tube, and a mixed gas of carbon monoxide, hydrogen, and nitrogen in a molar ratio of 1:1:8 was heated at 480°C. sink,
It was calcined for 3 hours and used for reaction. A reaction mixture of phenol and methanol in a molar ratio of 1:6 was heated and vaporized at 240°C, and then 3.0g per hour was introduced into a reaction tube whose internal temperature was adjusted to 440°C to carry out the reaction. . The results showed that 5 hours after the start of the reaction, the phenol conversion rate was 100%, and the selectivity of O-cresol and 2.6-xylenol was 5.4% and 93.0%, respectively.
Even at 150 hours after the start of the reaction, the internal temperature remained at 455℃.
phenol conversion rate of 99.7%, O-cresol,
The selectivity of 2.6-xylenol is 8.8% and
It was 90.1%. Comparative Examples 1 to 3 In the same manner as Examples 1 to 3, the catalysts were calcined in air and used in the reaction without being subjected to reduction treatment, as shown in Table 1.
【表】
実施例 ４
市販の酸化アルミニウム（表面積200m2／ｇ）
の錠剤を破砕し、６〜12メツシユの粒径にそろえ
得られた触媒６mlをガラス製反応管に充填し、
430℃、一酸化炭素、水素および窒素のモル比
１：１：８の混合ガスを流し、１時間焼成し、反
応に用いた。
ｍ−クレゾールとメタノールのモル比１：４に
混合した反応液を、240℃にて加熱気化させた後、
内温を330℃に調節した反応管に１時間当り3.3ｇ
導入し、反応を行なつた。
結果は、反応開始後10時間の時点で、ｍ−クレ
ゾール転化率99.9％、50時間、100時間の時点で、
それぞれ99.9％、99.7％であつた。
比較例 ４
実施例４と同様な方法において、酸化アルミニ
ウムを空気中、430℃で焼成し、反応に用いた。
結果は、反応開始後10時間の時点で、ｍ−クレ
ゾール転化率99.8％、50時間、100時間の時点で、
それぞれ99.4％、98.7％であつた。
実施例 ５〜８
市販の特級試薬をそれぞれ成型後粉砕して、６
〜12メツシユの粒径にそろえ、得られた触媒７ml
をガラス製反応管に充填し空気流通下450℃で５
時間焼成した。その後に400℃で水素と窒素との
モル比が１：１である混合ガスを２時間流し、反
応に用いた。反応器内温をそれぞれの適温に調節
した以外は、実施例１と同様の方法で反応を行つ
た。結果を第２表に示す。
比較例 ５〜８
実施例５〜８と同様な方法において、触媒を焼
成後に還元処理を行わずにそれぞれ対応させて反
応を行つた。結果を第２表に示す。[Table] Example 4 Commercially available aluminum oxide (surface area 200m 2 /g)
Crush the tablets, adjust the particle size to 6 to 12 meshes, and fill a glass reaction tube with 6 ml of the resulting catalyst.
A mixed gas of carbon monoxide, hydrogen and nitrogen in a molar ratio of 1:1:8 was flowed at 430°C, and the mixture was calcined for 1 hour and used for the reaction. After heating and vaporizing a reaction mixture of m-cresol and methanol at a molar ratio of 1:4 at 240°C,
3.3g per hour into a reaction tube whose internal temperature was adjusted to 330℃
was introduced and the reaction was carried out. The results showed that the m-cresol conversion rate was 99.9% at 10 hours after the start of the reaction, and at 50 hours and 100 hours.
They were 99.9% and 99.7%, respectively. Comparative Example 4 In the same manner as in Example 4, aluminum oxide was calcined in air at 430°C and used in the reaction. The results showed that the m-cresol conversion rate was 99.8% at 10 hours after the start of the reaction, and at 50 hours and 100 hours.
They were 99.4% and 98.7%, respectively. Examples 5 to 8 Commercially available special grade reagents were each molded and pulverized to form 6
7 ml of the catalyst obtained by adjusting the particle size to ~12 meshes
Filled into a glass reaction tube and heated at 450℃ under air circulation for 5 minutes.
Baked for an hour. Thereafter, a mixed gas containing hydrogen and nitrogen at a molar ratio of 1:1 was flowed for 2 hours at 400°C and used for the reaction. The reaction was carried out in the same manner as in Example 1, except that the internal temperature of the reactor was adjusted to the appropriate temperature for each. The results are shown in Table 2. Comparative Examples 5 to 8 In the same manner as in Examples 5 to 8, reactions were carried out in the same way as in Examples 5 to 8, without performing reduction treatment after calcination of the catalysts. The results are shown in Table 2.
【表】【table】
Claims (1)
を有するフエノール類を、アルコール類と共に気
相接触反応させ、アルキル化フエノール類を製造
する際、酸化アルミニウムを50モル％以上含有す
る酸化アルミニウム含有触媒、酸化マグネシウム
を50モル％以上含有する酸化マグネシウム含有触
媒、酸化マンガンを50モル％以上含有する酸化マ
ンガン含有触媒または酸化鉄を50モル％以上含有
する酸化鉄含有触媒のうちいずれか１種を還元性
ガスにより前処理して用いることを特徴とするア
ルキル化フエノール類の製造方法。1. An aluminum oxide-containing catalyst containing 50 mol% or more of aluminum oxide when producing alkylated phenols by subjecting a phenol having at least one hydrogen atom on an aromatic ring to a gas phase catalytic reaction with an alcohol. , a magnesium oxide-containing catalyst containing 50 mol% or more of magnesium oxide, a manganese oxide-containing catalyst containing 50 mol% or more of manganese oxide, or an iron oxide-containing catalyst containing 50 mol% or more of iron oxide. 1. A method for producing alkylated phenols, the method comprising pre-treating them with a reactive gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5089179A JPS55143921A (en) | 1979-04-26 | 1979-04-26 | Preparation of alkylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5089179A JPS55143921A (en) | 1979-04-26 | 1979-04-26 | Preparation of alkylphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55143921A JPS55143921A (en) | 1980-11-10 |
| JPS6343372B2 true JPS6343372B2 (en) | 1988-08-30 |
Family
ID=12871349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5089179A Granted JPS55143921A (en) | 1979-04-26 | 1979-04-26 | Preparation of alkylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55143921A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020054068A1 (en) | 2018-09-14 | 2020-03-19 | 日揮グローバル株式会社 | Method for operating liquefied natural gas receiving equipment |
| WO2021005675A1 (en) | 2019-07-08 | 2021-01-14 | 東芝三菱電機産業システム株式会社 | Energy balance adjustment control method and adjustment control device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5838225A (en) * | 1981-08-31 | 1983-03-05 | Sumitomo Chem Co Ltd | Preparation of alkylphenols |
-
1979
- 1979-04-26 JP JP5089179A patent/JPS55143921A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020054068A1 (en) | 2018-09-14 | 2020-03-19 | 日揮グローバル株式会社 | Method for operating liquefied natural gas receiving equipment |
| KR20210058819A (en) | 2018-09-14 | 2021-05-24 | 닛키 글로벌 가부시키가이샤 | How to operate liquefied natural gas import facility |
| WO2021005675A1 (en) | 2019-07-08 | 2021-01-14 | 東芝三菱電機産業システム株式会社 | Energy balance adjustment control method and adjustment control device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55143921A (en) | 1980-11-10 |
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