KR920703444A - Zeolite (B) SSZ-24 - Google Patents

Zeolite (B) SSZ-24

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KR920703444A
KR920703444A KR1019920700023A KR920700023A KR920703444A KR 920703444 A KR920703444 A KR 920703444A KR 1019920700023 A KR1019920700023 A KR 1019920700023A KR 920700023 A KR920700023 A KR 920700023A KR 920703444 A KR920703444 A KR 920703444A
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zeolite
oxide
boron
contacted
conditions
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아이. 죤스 스태시
엘. 홀터만 데니스
에이. 인스 로버트
에스. 산틸리 도날드
테흐 유엔 런
엔.지머 제임스
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원본미기재
셰브런 리써취 앤드 테크놀로지 캄파니
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
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    • 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
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
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    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
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    • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
    • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/86—Borosilicates; Aluminoborosilicates

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  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

내용 없음.No content.

Description

지올라이트 (B) SSZ-24Zeolite (B) SSZ-24

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

Claims (34)

산화실리콘, 산화게르마늄 및 이들의 혼합물 중에서 선택되는 산화물 대 산화붕소 또는 산화 알루미늄, 산화칼륨 및 산화철과 산화붕소의 혼합물중에서 선택되는 산화물의 몰비가 20 : 1 내지 100 : 1이고, 표 I의 X-레이회절선을 지는 지올라이트.The molar ratio of oxide selected from silicon oxide, germanium oxide and mixtures thereof to boron oxide or oxide selected from aluminum oxide, potassium oxide and a mixture of iron oxide and boron oxide is 20: 1 to 100: 1, and X- Zeolite with Ray Diffraction Line. 산화실리콘 대 산화붕소의 몰비가 20 : 1 내지 100 : 1이고, 표 I의 X-레이회절선을 지니는 지올라이트.Zeolite having a molar ratio of silicon oxide to boron oxide of 20: 1 to 100: 1 and having an X-ray diffraction line of Table I. 산화실리콘 대 산화알루미늄의 몰비가 20 : 1 내지 100 : 1이고, 표 I의 X-레이회절선을 지니는 지올라이트.Zeolite having a molar ratio of silicon oxide to aluminum oxide of 20: 1 to 100: 1 and having an X-ray diffraction line of Table I. 하기와 같은 산화물의 몰비의 조성을 지니고 표 I의 X-레이회절선을 지니는 무수상태의 지올라이트,Anhydrous zeolite having the composition of the molar ratio of oxide as follows and having the X-ray diffraction line of Table I, (1.0 내지 5)Q2O : (0.1 내지 1.0)M2O : W2O3: (20 내지 100)YO2 (1.0 to 5) Q 2 O: (0.1 to 1.0) M 2 O: W 2 O 3 : (20 to 100) YO 2 상기식에서, M은 알칼리금속 양이온이고, W는 붕소이고, Y는 실리콘, 게르마늄 및 이들의 혼합물 중에서 선택되고, Q는 아다만탄 4차 암모늄이온이다.Wherein M is an alkali metal cation, W is boron, Y is selected from silicon, germanium and mixtures thereof, and Q is adamantane quaternary ammonium ion. 제4항의 지올라이트를 약 200℃ 내지 820℃의 온도에서 열적으로 처리함으로서 제조되는 지올라이트.A zeolite prepared by thermally treating the zeolite of claim 4 at a temperature of about 200 ° C. to 820 ° C. 6. 제2항에 있어서, 아다만탄 4차 암모늄이온이 하기 일반식(a) 또는 (b) 아다만탄 화합물로 부터 유도되는 지올라이트.The zeolite according to claim 2, wherein the adamantane quaternary ammonium ion is derived from the following general formula (a) or (b) adamantane compound. 상기 식에서, Y1, Y2및 Y3는 각각 독립적으로 저급 알킬이고, Aθ는지올라이트의 형성에 유해하지 않은 음이온이고, R1, R2및 R3는 각각 독립적으로 수소 또는 저급알킬이고, R4, R5및 R6는 각각 독립적으로 수소 또는 저급알킬이다.Wherein Y 1 , Y 2 and Y 3 are each independently lower alkyl, A θ zi is an anion that is not harmful to the formation of the zeolite, and R 1 , R 2 and R 3 are each independently hydrogen or lower alkyl , R 4 , R 5 and R 6 are each independently hydrogen or lower alkyl. 제6항에 있어서, 일반식(a)에서 Y1, Y2및 Y3는 각각 독립적으로 메틸 또는 에틸이고, Aθ는 OH 또는 할로겐이고, R1, R2및 R3는 각각 수소이고, 일반식(b)에서 Y1, Y2및 Y3는 각각 독립적으로 메틸 또는 에틸이고, Aθ가 OH 또는 할로겐이고, R4, R5및 R6는 각각 수소인 지올라이트.The compound of claim 6, wherein in formula (a), Y 1 , Y 2 and Y 3 are each independently methyl or ethyl, A θ is OH or halogen, R 1 , R 2 and R 3 are each hydrogen, Y 1 , Y 2 and Y 3 in formula (b) are each independently methyl or ethyl, A θ is OH or halogen, and R 4 , R 5 and R 6 are each hydrogen. 제6항에 있어서, Y1, Y2및 Y3가 동일하고 각각 메틸이며, Aθ가 OH 또는 요드인 지올라이트.The zeolite of claim 6, wherein Y 1 , Y 2 and Y 3 are the same and each is methyl and A θ is OH or iodine. 제1항 또는 제2항에 있어서, 하소후 수소, 암모늄, 회토류금속, IIA족 금속 또는 VII족 금속이온으로 이온 교환시킨 지올라이트.The zeolite according to claim 1 or 2, which is ion-exchanged with hydrogen, ammonium, rare earth metal, Group IIA metal or Group VII metal ion after calcination. 제1항 내지 제2항에 있어서, 회토류금속, VII족 금속 또는 VIII족 금속이 지올라이트내에 흡착되는 지올라이트.The zeolite according to claim 1, wherein the rare earth metal, the Group VII metal, or the Group VIII metal is adsorbed in the zeolite. 제1항 또는 제2항의 지올라이트 및 무기 메트릭스를 함유하는 지올라이트 조성물.A zeolite composition comprising the zeolite of claim 1 or 2 and an inorganic matrix. (a) 아다만탄 4차 암모늄이온의 공급원, 붕소 실리케이트 형태인 산화 붕소 및 산화실리콘, 산화게르마늄 및 이들의 혼합물 중에서 선택되는 산화물을 함유하는 수성 혼합물을 제조하고, (b) 이 혼합물을 140℃이상의 온도에서 유지하여 상기 지올라이트의 결정을 형성시키고, (c) 상기 결정을 회수함을 특징으로 하여, 제1항의 지올라이트를 제조하는 방법.(a) preparing an aqueous mixture containing a source of adamantane quaternary ammonium ion, boron oxide in the form of boron silicate and an oxide selected from silicon oxide, germanium oxide and mixtures thereof, (b) the mixture at 140 ° C Maintaining at the above-mentioned temperature to form the crystal of the zeolite, and (c) recovering the crystal, characterized in that the method of producing a zeolite of claim 1. 제12항에 있어서, 붕소 실리케이트가 붕소 실리케이트 유리 또는 붕소 베타 지올라이트 또는 다른 붕소 지올라이트인 방법.13. The method of claim 12, wherein the boron silicate is boron silicate glass or boron beta zeolite or other boron zeolite. 제12항에 있어서, 수성 혼합물이 하기 범위에 해당하는 산화물의 몰비의 조성을 지니는 방법.13. The method of claim 12, wherein the aqueous mixture has a composition of molar ratios of oxides in the following ranges. YO2/W2O2, 20 내지 100 ; Q/YO2, 0.05 : 1 내지 0.50 : 1YO 2 / W 2 O 2 , 20 to 100; Q / YO 2 , 0.05: 1 to 0.50: 1 상기 식에서, Y는 실리콘, 게르마늄 및 이들의 혼합물중에서 선택되고, W는 붕소이고, Q는 아다만탄 화합물이다.Wherein Y is selected from silicon, germanium and mixtures thereof, W is boron and Q is an adamantane compound. 제12항 또는 제13항에 있어서, 아다만탄 4차 암모늄이온이 하기 일반식(a) 또는 (b)의 아다만탄 화합물로 부터 유도되는 방법.The process according to claim 12 or 13, wherein the adamantane quaternary ammonium ion is derived from an adamantane compound of the general formula (a) or (b). 상기 식에서, Y1, Y2및 Y3는 각각 독립적으로 저급 알킬이고, Aθ는 지올라이트의 형성에 유해하지 않은 음이온이고, R1, R2및 R3는 각각 독립적으로 수소 또는 저급알킬이고, R4, R5및 R6는 각각 독립적으로 수소 또는 저급알킬이다.Wherein Y 1 , Y 2 and Y 3 are each independently lower alkyl, A θ is an anion that is not harmful to the formation of zeolites, and R 1 , R 2 and R 3 are each independently hydrogen or lower alkyl , R 4 , R 5 and R 6 are each independently hydrogen or lower alkyl. 제14항에 있어서, 일반식(a)에서 Y1, Y2및 Y3가 각각 독립적으로 메틸 또는 에틸이고, Aθ가 OH 또는 할로겐이고, R1, R2및 R3는 각각 수소이고, 일반식(b)에서 Y1, Y2및 Y3는 각각 독립적으로 메틸 또는 에틸이고, Aθ가 OH 또는 할로겐이고, R4, R5및 R6는 각각 수소인 방법.The compound of claim 14, wherein in formula (a), Y 1 , Y 2 and Y 3 are each independently methyl or ethyl, A θ is OH or halogen, R 1 , R 2 and R 3 are each hydrogen, Y 1 , Y 2 and Y 3 in formula (b) are each independently methyl or ethyl, A θ is OH or halogen, and R 4 , R 5 and R 6 are each hydrogen. 제15항에 있어서, Y1, Y2및 Y3가 동일하며, 각각 메틸이고, Aθ가 OH 또는 요오드인 방법.The method of claim 15, wherein Y 1 , Y 2 and Y 3 are the same, each is methyl, and A θ is OH or iodine. 제5항의 붕소함유 지올라이트를 IIIA족 금속 또는 전이금속의 수용액과 접촉시킴을 특징으로 하여, 제5항의 지올라이트중의 붕소를 치환시키는 방법.The boron-containing zeolite of claim 5 is brought into contact with an aqueous solution of a Group IIIA metal or a transition metal, so that the boron in the zeolite of claim 5 is substituted. 탄화수소성 공급 원료를 탄화수소 전화조건하에서 제1항의 지올라이트와 접촉시킴을 특징으로 하여, 탄화수소를 전화시키는 방법.A process for converting hydrocarbons, characterized in that the hydrocarbonaceous feedstock is contacted with the zeolite of claim 1 under hydrocarbon conversion conditions. 제19항에 있어서, 탄화수소공급원료를 수소화크래킹 조건하에서 제1항의 지올라이트와 접촉시킴을 특징으로 하는 수소화 크래킹법.20. The hydrogenation cracking method of claim 19, wherein the hydrocarbon feedstock is contacted with the zeolite of claim 1 under hydrogenation cracking conditions. 제19항에 있어서, (a) 약 40℃이상 내지 약 200℃미만의 비등점 범위를 지니는 직쇄 및 약간 측쇄의 탄화수소를 함유하는 탄화수소성 공급원료를 방향족 전화조건하에서 산성이 거의 없는 제1항의 지올라이트와 접촉시키고, (b) 방향족 함유 유출물을 회수함을 특징으로 하여, 방향족 함량이 증가된 생성물을 제조하는 방법.20. The zeolite of claim 19, wherein (a) the hydrocarbonaceous feedstock containing straight and slightly branched hydrocarbons having a boiling point range of at least about 40 [deg.] C. to less than about 200 [deg.] C. is substantially free of acid under aromatic conversion conditions. And (b) recovering the aromatic containing effluent, thereby producing a product having increased aromatic content. 제21항에 있어서, 지올라이트가 VIII족 금속성분을 함유하는 방법.The method of claim 21 wherein the zeolite contains a Group VIII metal component. 제19항에 있어서, 탄화수소성 공급원료를 탈납조건하에서 제1항의 지올라이트와 접촉시킴을 특징으로 하는 탈납법.20. The dewaxing process of claim 19 wherein the hydrocarbonaceous feedstock is contacted with the zeolite of claim 1 under dewaxing conditions. 제19항에 있어서, 1몰 이상 과량의 방향족 탄화수소를 알킬화 조건하에서 제1항에 따르는 지올라이트의 존재하에 일분이상의 액상 조건의 C2내지 C20올레핀과 접촉시킴을 특징으로 하여, 방향족 탄화수소를 알킬화시키는 방법.The alkylation of an aromatic hydrocarbon according to claim 19, characterized in that at least one molar excess of the aromatic hydrocarbon is contacted with C 2 to C 20 olefins in liquid phase for at least one minute in the presence of the zeolite according to claim 1 under alkylation conditions. How to let. 제19항에 있어서, 하나 이상의 VIII족 금속 및 제1항의 지올라이트를 함유하는 촉매를 이성화조건하에서 직쇄 및 약간 측쇄의 C4내지 C7탄화수소를 함유하는 공급원료와 접촉시킴을 특징으로 하여, C4내지 C7탄화수소를 이성화시키는 방법.20. The catalyst of claim 19 wherein the catalyst containing at least one Group VIII metal and the zeolite of claim 1 is contacted with a feedstock containing straight and slightly branched C 4 to C 7 hydrocarbons under isomerization conditions. Process for isomerizing 4 to C 7 hydrocarbons. 제25항에 있어서, 촉매를 VIII족 금속의 함침 후 스팀/공기 혼합물중에서 승온하에 하소시키는 방법.The method of claim 25, wherein the catalyst is calcined at elevated temperature in a steam / air mixture after impregnation of the Group VIII metal. 제25항에 있어서, VIII족 금속이 백금인 방법.The method of claim 25, wherein the Group VIII metal is platinum. 제19항에 있어서, 방향족 탄화수소를 트랜스알킬화 조건하에서 및 제1항에 따르는 지올라이트 존재하에 일부 이상의 액상조건의 폴리알킬 방향족 탄화수소와 접촉시킴을 특징으로 하여, 방향족 탄화수소를 트랜스알킬화 시키는 방법.20. The process of claim 19, wherein the aromatic hydrocarbon is contacted with at least some liquid phase polyalkyl aromatic hydrocarbon under transalkylation conditions and in the presence of the zeolite according to claim 1. 제28항에 있어서, 방향족 탄화수소 및 폴리알킬 방향족 탄화수소가 각각 약 1 : 1 내지 약25 : 1의 몰비로 존재하는 방법.The method of claim 28, wherein the aromatic hydrocarbon and the polyalkyl aromatic hydrocarbon are each present in a molar ratio of about 1: 1 to about 25: 1. 제19항에 있어서, 올레핀 공급원료를 올리고머화 조건하에서 제1항의 지올라이트와 접촉시킴을 특징으로 하는 올리고머화 방법.20. The process of claim 19, wherein the olefin feedstock is contacted with the zeolite of claim 1 under oligomerization conditions. 제19항에 있어서, 알콜을 전화조건하에서 제1항의 지올라이트와 접촉시킴을 특징으로 하여, 탄소수 1내지 8의 저급 지방족 알콜을 접촉 전화시켜 가솔린 비등점 범위 및 고분자량의 탄화수소를 제조하는 방법.20. The process of claim 19, wherein the alcohol is contacted with the zeolite of claim 1 under inverting conditions to produce a hydrocarbon having a gasoline boiling point range and a high molecular weight by contact inversion of a lower aliphatic alcohol having 1 to 8 carbon atoms. 제19항에 있어서, 탄화수소 공급원료를 반종죤중에서 가한 수소의 부존재하에 접촉크래킹 조건하에서 제1항의 지올라이트 성분 및 거대 세공크기의 결정성 알루미늄 실리케이트 크리킹 성분을 함유하는 촉매조성을 과접촉시킴을 특징으로 하는 접촉크래킹법.20. The catalyst composition according to claim 19, wherein the catalyst composition containing the zeolite component of claim 1 and the macroporous crystalline aluminum silicate cracking component is over-contacted under the contact cracking conditions in the absence of hydrogen to which the hydrocarbon feedstock is added in the anti-jong zone. Contact cracking method. 제32항에 있어서, 촉매 조성물이 두 성분의 물리적 혼합물로 이루어지는 방법.33. The method of claim 32, wherein the catalyst composition consists of a physical mixture of two components. 제32항에 있어서, 두개의 촉매 성분이 무기 메트릭스에 혼입되는 방법.33. The method of claim 32, wherein two catalyst components are incorporated into the inorganic matrix. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
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