KR970707061A - 톨루엔 메틸화 반응에 의한 파라-크실렌의 선택적 제조 방법(selective paraxylene production by toluene methylation) - Google Patents

톨루엔 메틸화 반응에 의한 파라-크실렌의 선택적 제조 방법(selective paraxylene production by toluene methylation) Download PDF

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KR970707061A
KR970707061A KR1019970703115A KR19970703115A KR970707061A KR 970707061 A KR970707061 A KR 970707061A KR 1019970703115 A KR1019970703115 A KR 1019970703115A KR 19970703115 A KR19970703115 A KR 19970703115A KR 970707061 A KR970707061 A KR 970707061A
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toluene
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xylene
para
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미즈라히 사디
아담스 웨어 로버트
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맬컴 디. 킨
모빌 오일 코오포레이숀
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/865—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an ether
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/868—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains sulfur as hetero-atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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
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    • 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

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

본 발명은 촉매의 선택화 과정 이전에 측정한 제한 치수가 약 1 내지 약 12인 미공성 물질을 함유한 촉매의 존재하에 툴루엔을 메틸화제와 반응시킴으로써 파라-크실렌을 선택적으로 제조하고, 상기 촉매의 선택화 과정은 하기 (a) 내지 (c) 단계를 통해 이루어지는 방법 : (a) 약 800℃ 이상의 온도에서 약 10분 이상동안 촉매를 미리 증기처리하는 단계; (b) 상기 촉매상에 약 1 내지 약 20중량%의 코크스를 증착시키는 단계; 및 (c) 상기 촉매상의 코크스 중량%를 약 1 내지 약 20중량%로 연속 조절하는 단계.

Description

톨루엔 메틸화 반응에 의한 파라-크실렌의 선택적 제조 방법(SELECTIVE PARAXYLENE PRODUCTION BY TOLUENE METHYLATION)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (16)

  1. 촉매의 선택화 과정 이전에 측정한 제한 지수가 약 1 내지 약 12인 미공성 물질을 함유한 촉매의 존재하에 톨루엔을 메틸화제와 반응시킴으로써 파라-크실렌을 선택적으로 제조하고, 상기 촉매의 선택화 과정은 하기 (a) 내지 (c) 단계를 통해 이루어지는 방법 : (a) 약 800℃ 이상의 온도에서 약 10분 이상동안 촉매를 미리 증기처리하는 단계; (b) 상기 촉매상에 약 1 내지 약 20중량%의 코크스를 증착시키는 단계; 및 (c) 상기 촉매상의 코크스 중량%를 약 1 내지 약 20중량%로 연속 조절하는 단계.
  2. 제1항에 있어서, 상기 메틸화제가 메탄올, 메틸클로라이드, 메틸브로마이드, 디메틸에테르 또는 디메틸설파이드인 방법.
  3. 제1항에 있어서, 톨루엔과 메틸화제의 반응 단계를 약 300℃ 내지 약 750℃의 온도, 약 1기압 내지 1000psig의 압력, 약 0.5 내지 약 1000의 중량 시간당 공간 속도(WHSV)하에 수행하고, 메틸화제 대 툴루엔의 몰비는 약 5 미만인 방법.
  4. 제1항에 있어서, 상기 촉매가, 실리카/알루미나의 비가 30을 초과하는 것을 특징으로 하는 결정형 알루미노실리케이트 제올라이트를 포함하는 방법.
  5. 제4항에 있어서, 상기 결정형 알루미노실리케이트 제올라이트가 ZSM-5의 구조를 갖는 방법.
  6. 제1항에 있어서, 상기 촉매를, 약 800℃ 내지 약 1050℃의 온도에서 약 10분 내지 약 100시간동안 증기-함유 대기로 전-처리하는 방법.
  7. 제6항에 있어서, 상기 촉매가 ZSM-5의 구조를 가진 결정형 알루미노실리케이트를 포함하는 방법.
  8. 제6항에 있어서, 상기 메틸화제가 메탄올인 방법.
  9. 제6항에 있어서, 툴루엔과 메틸화제의 반응 단계를 약 300℃ 내지 약 750℃의 온도, 약 1기압 내지 1000psig의 압력, 약 0.5 내지 1000의 중량 시간당 공간 속도(WHSV)에서 수행하고, 메틸화제대 툴루엔의 몰비는 약 0.05 내지 약 5인 방법.
  10. 제9항에 있어서, 상기 온도가 약 500℃ 내지 약 700℃인 방법.
  11. 제9항에 있어서, 상기 메틸화제가 메탄올이며, 그 존재량은 약 0.1 내지 약 2이 메탄올/툴루엔의 몰비에 상응하는 양인 방법.
  12. 제1항에 있어서, 상기 촉매의 존재하에 툴루엔과 메틸화제의 혼합물을 반응시킴으로써 1회 사이클당 5중량% 이상의 상기 툴루엔을 약 90중량% 이상이 파라-크실렌을 함유한 생성물 혼합물로 전환시키는 단계를 부가로 포함하는 방법.
  13. 제12항에 있어서, 1회 사이클당 상기 톨루엔 7중량% 이상을 약 90중량% 이상의 파라-크실렌을 함유한 생성물 혼합물로 전환시키는 단계를 부가로 포함하는 방법.
  14. 제12항에 있어서, 1회 사이클당 상기 톨루엔 5중량% 이상을 약 94중량% 이상이 파라-크실렌을 함유한 생성물 혼합물로 전환시키는 단계를 부가로 포함하는 방법.
  15. 제12항에 있어서, 산화조건하에서 상기 촉매를 연속 재생시킴으로써 촉매상의 코크스 부하수준을 약 1 내지 약 15중량%로 제공하는 단계를 부가로 포함하는 방법.
  16. 제15항에 있어서, 산화조건하에선 상기 촉매를 연속 재생시킴으로써 파라-크실렌 선택도를 약 94중량% 이상의 수준으로 제공하는 단계를 부가로 포함하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019970703115A 1994-11-10 1995-11-09 톨루엔 메틸화 반응에 의한 파라-크실렌의 선택적 제조 방법(selective paraxylene production by toluene methylation) KR970707061A (ko)

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US33769394A 1994-11-10 1994-11-10
US08/337,693 1994-11-10

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JP (1) JPH10508854A (ko)
KR (1) KR970707061A (ko)
AU (1) AU4107596A (ko)
CA (1) CA2202858A1 (ko)
TW (1) TW318822B (ko)
WO (1) WO1996015083A1 (ko)

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Publication number Priority date Publication date Assignee Title
US20040097769A1 (en) 2002-11-14 2004-05-20 Ou John D. Y. Para-xylene production process employing in-situ catalyst selectivation
US7368410B2 (en) * 2005-08-03 2008-05-06 Saudi Basic Industries Corporation Zeolite catalyst and method of preparing and use of zeolite catalyst
US8115041B2 (en) * 2008-04-02 2012-02-14 Saudi Basic Industries Corporation Pretreatment of a phosphorus-modified zeolite catalyst for an aromatic alkylation process
US8344197B2 (en) * 2009-10-21 2013-01-01 Exxonmobil Chemical Patents Inc. Production of para-xylene by the methylation of benzene and/or toluene
US20110137099A1 (en) * 2009-12-08 2011-06-09 Saudi Basic Industries Corporation Aromatic alkylation process
US10246383B2 (en) * 2016-10-06 2019-04-02 Exxonmobil Chemical Patents Inc. Process for producing paraxylene by methylation of benzene and/or toluene
BR112019006899A2 (pt) * 2016-10-06 2019-07-02 Exxonmobil Chemical Patents Inc processo para metilar hidrocarbonetos aromáticos
US11084767B1 (en) 2020-02-18 2021-08-10 Uop Llc Toluene disproportionation using an enhanced UZM-44 aluminosilicate zeolite

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US3965207A (en) * 1975-01-06 1976-06-22 Mobil Oil Corporation Selective production of para-xylene
US4001346A (en) * 1975-01-06 1977-01-04 Mobil Oil Corporation Selective production of para-xylene
US4128592A (en) * 1977-11-23 1978-12-05 Mobil Oil Corporation Selective production of para dialkyl benzene
US4384155A (en) * 1980-04-11 1983-05-17 Mobil Oil Corporation Shape selective reactions with cadmium-modified zeolite catalysts
US4380685A (en) * 1980-05-19 1983-04-19 Mobil Oil Corporation Shape selective reactions with zeolite catalysts modified with iron and/or cobalt
US4365104A (en) * 1981-06-26 1982-12-21 Mobil Oil Corporation Para-selective zeolite catalysts treated with sulfur compounds
US5043502A (en) * 1990-03-16 1991-08-27 Uop Production of xylenes from light aliphatic hydrocarbons via dehydrocyclodimerization and methylation

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JPH10508854A (ja) 1998-09-02
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WO1996015083A1 (en) 1996-05-23
TW318822B (ko) 1997-11-01

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