CN101039892A - 环烷烃氧化和环烷基氢过氧化物分解的催化剂 - Google Patents
环烷烃氧化和环烷基氢过氧化物分解的催化剂 Download PDFInfo
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- CN101039892A CN101039892A CNA200580035352XA CN200580035352A CN101039892A CN 101039892 A CN101039892 A CN 101039892A CN A200580035352X A CNA200580035352X A CN A200580035352XA CN 200580035352 A CN200580035352 A CN 200580035352A CN 101039892 A CN101039892 A CN 101039892A
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Classifications
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- 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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
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- C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
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Abstract
环状酮/醇混合物通过催化氧化相应的环烷烃,或催化分解相应的环烷基氢过氧化物制备。负载于含有少于约2%重量铝的多孔结晶硅酸盐或结晶磷酸盐的金用作催化剂。该载体材料任选含有一种或多种杂原子。
Description
发明领域
本发明涉及环烷烃的催化氧化和环烷基氢过氧化物的催化分解,形成含有相应酮和醇的混合物。
发明背景
已用几种不同的方法将环己烷氧化成含环己酮和环己醇的产物混合物。此类产物混合物通常称为KA(酮/醇)混合物。KA混合物易于氧化产生己二酸,而己二酸在制备某些缩合聚合物,尤其是聚酰胺的过程中是一种重要的反应物。已知在这些和其他方法中消耗大量的己二酸,因此对制备己二酸及其前体的成本效果方法存在需求。
目前用于环己烷氧化的一种技术采用偏硼酸作为催化剂。虽然偏硼酸多少是有效的氧化催化剂,但是某些缺点与其使用相关。主要缺点是需要催化剂回收,催化剂回收典型地涉及反应混合物的水解、水相与有机相的分离及硼酸的脱水。这些步骤将相当的复杂性和费用引入到整个方法中。
有机钴盐,例如辛酸钴已广泛用于将环己烷氧化成KA混合物中。各种单一金属催化剂也已被建议用于氧化环烷烃,例如铬、铁和锰的盐,在环己烷转化和酮/醇的选择性方面具有不同的结果。
两步方法也被用于环烷烃氧化。在一种典型的两步法的第一步骤中,环己烷被氧化形成含环己基氢过氧化物(CHHP)的反应混合物。在第二步骤中,用或不用催化剂,CHHP被分解形成KA混合物。在Druliner等的美国专利6,284,927中描述了两步法的实例,其中在Au、Ag、Cu或含有Fe、Ni、Cr、Co、Zr、Ta、Si、Mg、Nb、Al和Ti特定组合的溶胶-凝胶化合物的多相催化剂存在下,烷基或芳族氢过氧化物被氧化,其中这些金属中的某些与氧化物组合。建议用于两步氧化法的第二步骤的其他催化剂包括锰、铁、钴、镍和铜的盐。
WO 00/53550及Druliner等的伴随美国专利6,160,183描述了用于所谓的环烷烃直接氧化形成KA混合物的多相催化剂。所描述的催化剂包括金、金溶胶-凝胶化合物及含有Cr、Co、Zr、Ta、Si、Mg、Nb、Al和Ti特定组合的溶胶-凝胶化合物,其中这些金属中的某些与氧化物组合。
中国科学院兰州化学物理研究所Fan等的“经沸石包裹的Au催化剂,环己烷和烯烃用空气的环境良性氧化”中公开了用于环己烷和烯烃氧化的催化剂。当用作环己烷的氧化催化剂时,据说Au/NaY产生高周转频率和产物选择性。
对将环烷烃氧化成KA混合物的成本效果方法仍有需求,特别是对采用催化剂的方法存在需求,所述催化剂能产生高环烷烃转化率、高酮和醇选择性及相对低的环烷基氢过氧化物浓度。
发明概述
本发明涉及将反应混合物中的环烷烃氧化,形成含有相应醇和酮的产物混合物的方法。该方法包括将反应混合物在催化有效量的金存在下与氧源接触,该金负载于多孔结晶硅酸盐或磷酸盐载体上。
本发明也涉及催化分解环烷基氢过氧化物,形成含有相应醇和酮的产物混合物的方法。该方法包括将含有环烷基氢过氧化物的反应混合物与催化有效量的金接触,该金负载于含有少于约2%(重量)铝的多孔结晶硅酸盐或结晶磷酸盐载体上。
多孔结晶硅酸盐任选可含有一种和多种杂原子,并可由通式:(El2On)xSiO2描述,其中x=0-0.13,El为周期系中第2、3、4和5周期除铝外的至少一种元素,n为该元素El的化合价。
多孔结晶磷酸盐任选可含有一种和多种杂原子,并可由通式:(El2On)x(Al2O3)yP2O5描述,其中x≤0.27,y≤1.0,El为至少一种周期系中第2、3、4和5周期的元素,n为该元素El的化合价。
已发现用于环烷基氧化的本发明负载型金催化剂能产生其特征为高环烷烃转化率、高酮和醇选择性及相对低环烷基氢过氧化物浓度的产物混合物。这些催化剂因此在环烷烃氧化中表现出异常的性能。另外,不溶性多相催化剂比使用硼酸作为催化剂提供了明显简化的操作。不溶性多相催化剂也可以本领域技术人员已知的任何其他形式使用,例如浆料、在催化剂筐中、固定床、负载于栅板或蜂巢结构上等形式。例如,如果使用催化剂筐等,催化剂回收可能是不必要的。如果催化剂以浆料形式使用,它可以通过过滤、离心或任何常规方法容易地回收。
已发现,用于环烷基氢过氧化物分解的本发明负载型金催化剂能产生其特征为高环烷基氢过氧化物分解活性、高酮和醇选择性的产物混合物。用于环烷基氢过氧化物分解的负载型金催化剂,可以与上述用于环烷基氧化的负载型金催化剂相同的形式使用。
发明详述
本发明涉及环烷烃的催化氧化方法。如本文使用,术语“环烷烃”指具有3-约10个碳原子,更通常是约5-约8个碳原子的饱和环烃。环烷烃的非限定性实例包括环戊烷、环己烷、环庚烷和环辛烷。
本发明也涉及环烷基氢过氧化物的催化分解方法。如本文使用,术语“环烷基氢过氧化物”指具有3-约10个碳原子,更通常是约5-约8个碳原子的饱和环烃。环烷基的非限定性实例包括环戊基、环己基、环庚基和环辛基氢过氧化物。
本发明的催化剂包含负载于含有少于约2%(重量)铝的多孔结晶硅酸盐或结晶磷酸盐载体的金。金可以任何合适的形式提供。例如,它可通过浸渍、沉淀、沉积-沉淀、离子交换、溶液的阴离子或阳离子吸附及蒸气相沉积,沉积在载体上。另外,含有金的催化剂可通过在载体材料的水热合成阶段引入金源制备。当使用上述及其他可能的方法时,所引入金的量在最高达约10%(重量)的宽范围内变化。催化剂典型地含有直径为约3-约15nm的超细大小金颗粒。
多孔结晶硅酸盐可具有各种结构,其非限定性实例包括BEA、FAU、MFI、MEL、MOR、MTW、MTT、MCM-22、MCM-41、MCM-48和NU-1。结晶硅酸盐中硅的部分可由一种或多种杂原子同构或非同构替换,所述杂原子选自B、Be、Ga、In、Ge、Sn、Ti、Zr、Hf、V、Cr、Mn、Fe、Co、P、Mo和W系,或周期系中第2、3、4和5周期中除铝外的任何其他元素。多孔结晶硅酸盐中的铝含量应在约2%(重量)以下,优选在约1%(重量)以下。如果替换是同构的并且替换元素的化合价与硅的化合价不相等,则相应结晶硅酸盐可在阳离子位置含有氢阳离子,和/或碱金属阳离子(Li+、Na+、K+等),和/或碱土金属阳离子(Mg2+、Ca2+、Sr2+等),和/或任一过渡金属的阳离子和/或氧化阳离子(oxycations)(例如Cu+、Zn2+、VO+、FeO+等)。
也可用多孔结晶磷酸盐载体制备含金催化剂,该催化剂在环烷烃氧化和环烷基氢过氧化物分解中提供最佳催化剂性能。多孔结晶磷酸盐载体可具有各种结构,其非限定性实例包括AFI、AEL、AFO、AFR、AFS、AFT,AFY、ATN、ATO、ATS、ATT、ATV、AWW。结晶硅酸盐中磷的部分可由一种或多种杂原子同构或非同构替换,所述杂原子选自Al、Si、B、Be、Ga、In、Ge、Sn、Ti、Zr、Hf、V、Cr、Mn、Fe、Co、Mo、W系。
脱铝化沸石载体也可用作用于含金催化剂制备的结晶多孔硅酸盐,该含金催化剂在环烷烃氧化和环烷基氢过氧化物分解中提供最佳催化剂性能。脱铝化沸石载体可具有各种结构,其非限定性实例包括AFI、AEL、AFO、AFR、AFS、AFT,AFY、ATN、ATO、ATS、ATT、ATV和AWW。脱铝化程度应使残余铝含量在1%(重量)以下,并优选在0.1%(重量)以下。
本发明优选的催化剂在最高达约6-7%的环己烷转化中提供约90%的选择性。在无空气的存在下,催化剂以接近100%的选择性,将环己基氢过氧化物(CHHP)分解成环己醇和环己酮。本发明优选的催化剂比已知含金催化剂证明具有明显更高的性能稳定性。
多孔结晶硅酸盐或磷酸盐材料的结晶结构通过四面体片段(例如[SiO4]4-、[PO4]3+)形成,该四面体片段通过它们的共同顶点结合成为具有空穴和通道的三维结构。上述制备含金催化剂的方法提供了超细大小金颗粒在载体微孔空间的通道和空穴中,或在催化剂外表面的孔入口中的排列。金颗粒的该排列防止了其在催化剂热处理中的烧结,并且增加了催化剂的操作稳定性。
多孔结晶硅酸盐或磷酸盐载体可按照本领域技术人员众所周知的方法制备(J.Weitkamp,L.Puppe(编著)Catalysis and Zeolites.Fundamentals and Applications.Springer,p.1-52)。例如,多孔结晶硅酸盐可通过以下方法制备。将由硅源、Eln+源(如果需要)、碱性有机表面活性剂及在某些情况下的晶种组成的混合物匀化,然后置于高压釜中,其中在热水条件下,在80℃-200℃的温度范围内保持10小时-30天。在用作载体之前,固体产物可在450℃-800℃的温度范围内煅烧。改变混合物的化学组成、水热合成的温度和时间,人们可制备出所期望结构的硅酸盐。如果具有沸石结构的铝硅酸盐用作制备本发明多孔结晶硅酸盐的前体,其铝含量需要降低到约2%(重量)铝以下,优选约1%(重量)以下。这可使用本领域技术人员众所周知的方法,例如通过在具有含气体蒸气的高温下处理载体来实现。
另外,含金催化剂可经历合成后处理,包括但不限于用酸或螯合剂洗涤、用还原性、氧化性或惰性气体或具有还原性、氧化性或惰性气体的蒸气混合物处理。
多孔结晶磷酸盐可使用任何已知方法制备(J.Weitkamp,L.Puppe(编著)Catalysis and Zeolites.Fundamentals and Applications.Springer,p.53-80)。例如,将由磷源、铝源和/或Eln+源(如果需要)、碱性有机表面活性剂及在某些情况下的晶种组成的混合物匀化,然后置于高压釜中,其中在热水条件下,在80℃-200℃的温度范围内保持10小时-30天。在用作载体之前,固体产物可在450℃-800℃的温度范围内煅烧,以除去有机内含物。改变磷源和铝源、有机表面活性剂的性质、水热合成的温度和时间,人们可制备出给定结构的结晶磷酸盐。
在本发明的实施中,催化剂可通过配制成催化剂床,与环烷烃例如环己烷接触,安排该催化剂床以提供催化剂和反应物之间的充分接触。或者,催化剂可用本领域已知的技术与反应混合物一起浆化。本发明的方法适用于分批或连续的环烷烃氧化。这些方法可在各种条件下实施,这对本领域普通技术人员而言是显而易见的。
用于本发明方法的合适反应温度通常在约130℃至约200℃的范围内,更通常在约150℃至约180℃的范围内。反应压力通常在约69kPa至约2760kPa(53-400psia)的范围内,更通常在约552kPa至约1380kPa(80-200psia)的范围内(为了保持在液相中)。环烷烃反应器停留时间通常以与反应温度成反比关系变化,并且一般小于120分钟。
用于氧化的氧源可为分子氧本身,但是适宜为空气;或氮与氧的其他混合物,具有比空气中更高或更低的氧比例,例如通过将氧或氮与空气混合获得的混合物。然而,优选空气。在反应器中空气与液相接触的时间在0.05-5分钟内变化,更通常为约0.2至约1.5分钟。
除了被用于环烷烃氧化反应器中外,催化剂也可用于单独的反应器中,以促进在氧化期间形成的环烷烃氢过氧化物向环烷醇和环烷酮的转化。在该情况下,使在环烷烃与分子氧的氧化期间产生的反应混合物在50-200℃,优选100-170℃的温度下与催化剂接触。于方法温度下,压力维持在足够使环烷烃保持在液相的水平。一般压力维持在100-1380kPa(15-200psig),优选172-830kPa(25-120psig)的范围内。将环烷基氢过氧化物转化成环烷醇和环烷酮所需的时间取决于催化剂、反应物与催化剂的比率、温度和其他参数。在本发明优选的实施方案中,时间通常不超过10秒钟。
以下实施例仅为举例说明目的提供,并且不应被认为是限制本发明。
实施例1
硅沸石(Silicalite)-1载体的制备
硅沸石-1按Flanigen E.M.,Bennett J.M.,Grose R.W.,Cohen J.P.,Patton R.L.,Kirchner R.M.,Smith J.V.(1978)Nature 271,512中描述的方法制备。将含40%SiO2的硅溶胶(36g)加入到220ml 0.1M氢氧化四丙基铵溶液中。搅拌该混合物30分钟,并向其中滴加4ml 10MNaOH水溶液。将所得混合物室温搅拌1小时,并于170℃保持72小时。将沉淀过滤,用蒸馏水洗涤,并于100℃干燥24小时。XRD分析证实了所得产物的MFI结构。
Au/硅沸石-1催化剂的制备
该实施例举例说明了用硅沸石-1—多孔结晶硅酸盐作为载体制备含金催化剂。将硅沸石-1(3g)悬浮于50ml水中,并向该悬浮液中滴加7.9ml 0.05M HAuCl4。用6%氨水调节所得浆状物的pH至7;再搅拌该浆状物2小时。将沉淀过滤,于100℃干燥10小时,并于200℃锻烧2小时。
实施例2
该实施例举例说明了用具有以下组成(TiO2)0.025(SiO2)的MFI结构的钛硅酸盐TS-1制备金催化剂。该催化剂根据实施例1制备,其中结晶钛硅酸盐TS-1用作载体。
TS-1载体的制备
将四乙基原硅酸盐(91g)在惰性气氛中置于玻璃烧瓶中。搅拌下加入四乙基钛酸盐(3g)。加入氢氧化四丙基铵(25%水溶液,160g),室温搅拌该混合物1小时,并于80-90℃搅拌5小时。之后,将该混合物转移到高压釜中,并于175℃保持10天。将产物冷却,过滤并用蒸馏水洗涤。通过于550℃锻烧3小时除去有机模板。X-射线衍射分析显示该产物为MFI结构。
实施例3
该实施例举例说明了用具有以下组成(B2O3)0.0083(SiO2)的MFI结构的硼硅酸盐制备金催化剂。该催化剂根据实施例1制备,其中硼硅酸盐用作载体。
硼硅酸盐载体的制备
将氢氧化四丙基铵(25%水溶液,61g)在惰性气氛中置于玻璃烧瓶中。搅拌下加入硼酸(9.3g)。加入四乙基原硅酸盐(93.75g),并将该混合物逐渐加热到60℃,并于该温度下恒定搅拌12小时。之后,加入KOH(0.09g)和蒸馏水以使总体积为150ml。将该混合物转移到高压釜中,并于145℃保持12天。将产物冷却,过滤并用蒸馏水洗涤,并于120℃干燥。通过于750℃锻烧除去有机模板。X-射线衍射分析显示该产物具有MFI结构。该材料下面称为B-ZSM-5。
实施例4
该实施例举例说明了在FAU结构的脱铝化铝硅酸盐(Na2O)0.0025(Al2O3)0.023SiO2上的金催化剂的制备。该样品含有的铝比典型的Y沸石少7倍。该催化剂根据实施例1制备,其中0.03M HAuCl4水溶液用作金源。该载体按照Kerr G.T.,J.Phys.Chem 71(1967)4155中描述的方法制备。
实施例5
该实施例举例说明了在具有以下组成Al2O3·P2O5的ATS结构的结晶铝磷酸盐上金催化剂的制备。该催化剂根据实施例1制备,其中铝磷酸盐用作载体。该载体按照Bennet J.M.,Richardson J.M.,PluthJ.J.,Smith J.V.(1987)Zeolites 7,160中描述的方法制备。
实施例6
该实施例举例说明了用MFI结构的脱铝化铝硅酸盐(NaxO)0.00007(Al2O3)0.0086SiO2制备金催化剂。该催化剂根据实施例1制备,其中结晶多孔硅酸盐用作载体。该载体按照Argauer R.J.,LandoltG.R.(1972)U.S.Pat.3,702,886中描述的方法制备。为了从铝硅酸盐晶格中除去铝并降低酸性,该载体在金沉积之前,于650℃另外用蒸气处理2小时。
实施例7
该实施例举例说明了用MFI结构的铝硅酸盐(Na2O)0.0086(Al2O3)0.0086SiO2制备金催化剂。该催化剂根据实施例1制备,其中铝硅酸盐用作载体。该载体按照Argauer R.J.,Landolt G.R.(1972)U.S.Pat.3,702,886中描述的方法制备。为了从铝硅酸盐晶格中除去铝并降低酸性,该载体在金沉积之前,于650℃另外用蒸气处理2小时。
实施例8-19
实施例8-19举例说明用实施例1-5的催化剂氧化环己烷。
将根据实施例1-5的各催化剂(0.8-0.9g)置于含有环己烷(160g)和环己酮(0或0.70g)的300ml Parr压力反应器中。该反应器用氦气吹扫20分钟(大气压下300cc/min),之后,用氦气加压至130-140psig。将反应器中的内容物加热至150℃或170℃,关闭氦气流,将空气以300cc/min的速率输入反应器,直到达到所期望的环己烷转化率。试验结果如表1所示。
比较实施例20-28
这些比较实施例举例说明不用催化剂氧化环己烷。将环己烷(160g)和环己酮(0或0.70g)置于300ml Parr压力反应器中。该反应器于大气压下用300cc/min氦气吹扫20分钟,之后,用氦气加压至130-140psig。将反应器中的内容物加热至150℃或170℃,关闭氦气流,将空气以300cc/min的速率输入反应器,直到达到所期望的环己烷转化率。试验结果如表1所示。
比较实施例29
该比较实施例举例说明用具有MFI结构的硼硅酸盐B-ZSM-5氧化环己烷,无金作为催化剂。
含硼ZSM-5(B-ZSM-5)按照实施例3的第一部分制备(该催化剂不含金)。按实施例8-19进行该催化剂的环己烷氧化试验。试验结果如表1所示。
比较实施例30
该比较实施例举例说明用具有MFI结构的多孔结晶硅酸盐氧化环己烷,不用金作为催化剂。
硅沸石-1按照实施例1的第一部分制备;该催化剂不含金。按实施例8-19进行硅沸石的环己烷氧化试验。试验结果如表1所示。
比较实施例31
该比较实施例举例说明用具有MFI结构的钛硅酸盐TS-1氧化环己烷,不用金作为催化剂。
钛硅酸盐TS-1按照实施例2的第一部分制备(该催化剂不含金)。按实施例8-19进行钛硅酸盐的环己烷氧化试验。试验结果如表1所示。
比较实施例32
该比较实施例举例说明用结晶铝磷酸盐氧化环己烷,不用金作为催化剂。
结晶铝磷酸盐按照实施例5制备(该催化剂不含金)。按实施例8-19进行催化剂的环己烷氧化试验。试验结果如表1所示。
比较实施例33
该比较实施例举例说明Au/无定形SiO2催化剂的制备,并在环己烷氧化中使用该催化剂。
Au/SiO2催化剂用溶胶-凝胶方法制备。将四乙基原硅酸盐(10.5g)和1.3ml 0.12M HAuCl4溶液溶解于乙醇,加入稀NH3水溶液直到该混合物变浑浊。将该混合物静置15小时;将沉淀过滤,洗涤并干燥。按实施例8-19进行催化剂的环己烷氧化试验。试验结果如表1所示。
比较实施例34
将y-Al2O3(碱性,Alpha Aesar,5.984g)悬浮于117.3g 0.1%AuCl3/0.5%HCl溶液中。该浆状物用9%NH3滴定至pH 7.0。室温下连续搅拌4小时。将该浆状物过滤,沉淀在过滤器上用50ml水洗涤,于110℃干燥过夜,并于450℃煅烧3小时。按实施例8-19进行该催化剂—Au/Al2O3的环己烷氧化试验。试验结果如表1所示。
比较实施例35
该比较实施例举例说明金/NaY沸石催化剂的制备,NaY沸石为FAU结构的铝硅酸盐(Na2O)0.026(Al2O3)0.15SiO2,并在环己烷氧化中使用该催化剂。该催化剂根据实施例1制备,其中0.03M HAuCl4水溶液用作金源。载体按照Breck D.W.的美国专利3,130,007(1964)中的描述制备。按实施例8-19进行该催化剂—Au/NaY的环己烷氧化试验。试验结果如表1所示。
实施例36-39举例说明用实施例1、4、6和7的催化剂进行CHHP分解
将根据实施例1、4、6和7的催化剂在固定床反应器—内径4.5mm的金属管(SS316)中进行试验。为了防止CHHP与反应器的金属壁反应,通过用Na4P2O7溶液处理其表面使该反应器钝化。用注射泵使液体进料经过催化剂床。将反应器中的排放物收集到收集容器中。通常催化剂的用量是0.3g,将该催化剂加入到反应器中,然后以0.6ml/min开始环己烷进料。由于环己烷排出空气,因此系统中的压力逐渐增加。当压力达到170psig的设定点后,加热该反应器。一旦催化剂床中的温度达到所期望的值160℃,将环己烷进料停止,并开始加入含环己基氢过氧化物8.8mol/l、环己酮1.2mol/l、环己醇2.6mol/l及副产物*1.1mol/l的混合物。此时开始计算连续开工期限。反应器中的排放物每30分钟取样一次。样品用气相色谱仪分析。催化剂通常测试3-5小时。
进料混合物的组成在通过催化剂时改变。CHHP浓度下降,而环己醇和环己酮的浓度增加,这表明CHHP已转化为KA-油。最初3小时环己基氢过氧化物平均转化率以及酮和醇的总选择性如表2所示。
表2也显示催化剂的减活参数、流出180和60分钟后CHHP的转化率。
*副产物浓度以CHHP当量表示
比较实施例40
该比较实施例举例说明不用催化剂进行CHHP分解。反应条件与实施例36-39中的相同。试验结果如表2所示。
比较实施例41
该比较实施例举例说明用具有MFI结构的多孔结晶硅酸盐—硅沸石-1进行CHHP分解,不用金作为催化剂。
硅沸石-1根据实施例1的第一部分制备(该催化剂不含金)。按照实施例36-39进行该催化剂的CHHP分解试验。试验结果如表2所示。
比较实施例42
该比较实施例举例说明用MFI结构的脱铝化铝硅酸盐(Na2O)0.0086(Al2O3)0.0086SiO2,不用金作为催化剂进行CHHP分解。
脱铝化铝硅酸盐(Na2O)0.0086(Al2O3)0.0086SiO2按照实施例7中载体制备(该催化剂不含金)。按照实施例36-39进行该催化剂的环己烷氧化试验。试验结果如表2所示。
比较实施例43
该比较实施例举例说明用MFI结构的脱铝化铝硅酸盐(Na2O)0.00007(Al2O3)0.0086SiO2,而不用金作为催化剂进行CHHP分解。该实施例与实施例42不同之处在于该实施例中所使用的催化剂被转化成H-形式,并含有少量的钠。
铝硅酸盐(Na2O)0.00007(Al2O3)0.00816SiO2按照实施例4中载体制备(该催化剂不含金)。按照实施例36-39进行该催化剂的环己烷氧化试验。试验结果如表2所示。
比较实施例44
该比较实施例举例说明用金/沸石NaY催化剂进行CHHP分解,该沸石NaY为FAU结构的铝硅酸盐(Na2O)0.15(Al2O3)0.15SiO2。
该催化剂根据实施例1制备,其中0.03M HAuCl4水溶液用作金源。载体按照Breck D.W.的美国专利3,130,007(1964)中的描述制备。按照实施例36-39进行该催化剂的CHHP分解试验。试验结果如表2所示。
比较实施例45
该比较实施例举例说明用金/沸石NaY催化剂进行CHHP分解,该沸石NaY为FAU结构的铝硅酸盐(Na2O)0.026(Al2O3)0.15SiO2。该实施例与实施例44不同之处在于该实施例中所使用的载体在金沉积前被转化成H-形式,并含有少量的钠。
该催化剂根据实施例1制备,其中0.03M HAuCl4水溶液用作金源。载体按照实施例35中的描述制备。按照实施例36-39进行该催化剂的CHHP分解试验。试验结果如表2所示。
比较实施例46
该比较实施例举例说明在CHHP分解中使用Au/SiO2催化剂。
Au/SiO2催化剂根据实施例33制备。按照实施例36-39进行该催化剂的CHHP分解试验。试验结果如表2所示。
比较实施例47
该催化剂—Au/Al2O3按照Druliner等的美国专利6,160,183中的描述制备。按照实施例36-39进行该催化剂的CHHP分解试验。试验结果如表2所示。
如实施例36-47所证明,在CHHP分解成KA油的过程中,本发明负载于多孔结晶硅酸盐的金比负载于结晶铝硅酸盐或其他载体的金具有明显更高的选择性和稳定性。实施例37和44或45的比较显示铝的除去明显改善了催化剂性能的稳定性。
应理解虽然本发明已结合其具体的实施方案进行了描述,但是上述描述和实施例仅用于举例说明,而不是限制本发明的范围。其他方面、优点和修改对本发明涉及领域的技术人员而言将是显而易见的,这些方面和修改在本发明的范围内,其仅由权利要求限定。
表1经Au/硅沸石催化剂用氧氧化环己烷
实施例 | 催化剂 | 载体结构 | T℃ | 反应器中环己酮加料,g | 环己烷转化率% | K+A+CHP的选择性% | 产物分布,% | ||
K | A | CHHP | |||||||
8 | Au0.0046SiO2 | MFI | 170 | 0.7 | 3.39 | 91.4 | 52 | 45 | 4 |
9 | Au0.0046SiO2 | MFI | 150 | 0 | 2.93 | 95.9 | 17.3 | 34.3 | 49.4 |
10 | Au0.0046SiO2 | MFI | 150 | 0 | 6.09 | 88.0 | 22.4 | 43.4 | 34.2 |
11 | Au0.0057(TiO2)0.025(SiO2) | MFI | 170 | 0.7 | 3.20 | 92.0 | 50 | 47 | 3 |
12 | Au0.0057(TiO2)0.025(SiO2) | MFI | 170 | 0.7 | 4.21 | 90.6 | 50 | 47 | 4 |
13 | Au0.0057(TiO2)0.025(SiO2) | MFI | 170 | 0.7 | 6.66 | 88.1 | 53 | 47 | 0 |
14 | Au0.0057(TiO2)0.025(SiO2) | MFI | 150 | 0 | 4.11 | 91.2 | 28.5 | 52.4 | 19.1 |
15 | Au0.0053(B2O3)0.0083(SiO2). | MPI | 170 | 0.7 | 2.53 | 90.3 | 38 | 45 | 16 |
16 | Au0.0053(B2O3)0.0083(SiO2). | MFI | 170 | 0.7 | 3.11 | 86.6 | 34 | 51 | 15 |
17 | Au0.0053(B2O3)0.0083(SiO2). | MFI | 170 | 0.7 | 4.88 | 87.9 | 46 | 48 | 6 |
18 | Au0.024Al2O3·P2O5 | ATS | 170 | 0.7 | 2.9 | 87 | 28 | 55 | 17 |
19 | Au0.004(Na2O)0.0025(Al2O3)0.023SiO2 | FAU | 170 | 0.7 | 2.6 | 85 | 32.2 | 62.5 | 5.3 |
20 | 无 | 170 | 0 | 1.63 | 87.3 | 7 | 11 | 8 | |
21 | 无 | 170 | 0 | 4.77 | 87.9 | 14 | 27 | 59 | |
22 | 无 | 170 | 0 | 7.35 | 81.5 | 20 | 44 | 36 | |
23 | 无 | 170 | 0.7 | 2.76 | 87.5 | 14 | 29 | 57 | |
24 | 无 | 170 | 0.7 | 3.68 | 84.5 | 16 | 41 | 43 | |
25 | 无 | 170 | 0.7 | 4.94 | 83.0 | 19 | 55 | 26 | |
26 | 无 | 170 | 0.7 | 6.32 | 80.2 | 23 | 57 | 21 | |
27 | 无 | 150 | 0 | 3.56 | 96.6 | 8.2 | 14.9 | 77.0 | |
28 | 无 | 150 | 0 | 8.45 | 88.4 | 14.8 | 27.1 | 58.1 | |
29 | (B2O3)0.0083(SiO2). | MFI | 170 | 0.7 | 2.78 | 87.3 | 15 | 36 | 49 |
30 | SiO2 | MFI | 170 | 0.7 | 3.7 | 88 | 8 | 44 | 48 |
31 | (TiO2)0.025(SiO2) | MFI | 170 | 0.7 | 3.7 | 86 | 11 | 43 | 46 |
32 | Al2O3·P2O5 | ATS | 170 | 0.7 | 3.2 | 85.4 | 10 | 43 | 48 |
33 | Au0.0045SiO2 | 无定形 | 170 | 0.7 | 3.19 | 89.4 | 19 | 32 | 48 |
34 | Au0.0043Al2O3 | 勃姆石 | 170 | 0.7 | 2.56 | 87.7 | 7 | 31 | 62 |
35 | Au0.0045(Na2O)0.026(Al2O3)0.15SiO2 | FAU | 170 | 0.7 | 3.98 | 83 | 27 | 55 | 18 |
表2CHHP经Au/硅沸石催化剂分解
实施例 | 催化剂 | 载体结构 | 平均180min | 减活参数X(180min)/X(60min) | |
CHHP转化率(X),%摩尔 | CHHP对酮和醇的选择性,%摩尔 | ||||
36 | Au0.0046SiO2 | MFI | 98 | 100 | 0.98 |
37 | Au0.004(Na2O)0.0025(Al2O3)0.023SiO2 | FAU | 98 | 63 | 0.99 |
38 | Au0.005(Na2O)0.00007(Al2O3)0.0086SiO2 | MFI | 96 | 91 | 0.92 |
39 | Au0.0043(Na2O)0.0086(Al2O3)0.0086SiO2 | MFI | 97 | 94 | 0.91 |
40 | 无 | 2.3 | 72 | - | |
41 | SiO2 | MFI | 11 | 83 | 0.97 |
42 | (Na2O)0.0086(Al2O3)0.0086SiO2 | MFI | 20 | 83 | 0.8 |
43 | (Na2O)0.00007(Al2O3)0.0086SiO2 | MFI | 52 | 66 | 1.0 |
44 | Au0.005(Na2O)0.15(Al2O3)0.15SiO2 | FAU | 90 | 73 | 0.8 |
45 | Au0.0045(Na2O)0.026(Al2O3)0.15SiO2 | FAU | 87 | 75 | 0.8 |
46 | Au0.0045SiO2 | 无定形 | 27 | 83 | 1.0 |
47 | Au0.005Al2O3 | 勃姆石 | 95 | 93 | 0.8 |
Claims (15)
1.一种将反应混合物中的环烷烃氧化,形成含有相应醇和酮的产物混合物的方法,所述方法包括在催化有效量的金存在下,将所述反应混合物与氧源接触,所述金负载于含有少于约2%重量铝的多孔结晶硅酸盐或结晶磷酸盐上。
2.权利要求1的方法,其中所述环烷烃为环己烷。
3.一种将反应混合物中的环烷基氢过氧化物分解,形成含有相应醇和酮的产物混合物的方法,所述方法包括将所述反应混合物与催化有效量的金接触,所述金负载于多孔结晶硅酸盐或磷酸盐上。
4.权利要求3的方法,其中所述环烷基氢过氧化物为环己基氢过氧化物。
5.权利要求1或权利要求3的方法,其中所述多孔结晶硅酸盐载体为元素硅酸盐,该元素硅酸盐具有选自BEA、FAU、MFI、MEL、MOR、MTW、MTT、MCM-22、MCM-41、MCM-48、NU-1的结构。
6.权利要求1或权利要求3的方法,其中所述多孔结晶磷酸盐载体为元素磷酸盐,该元素磷酸盐具有选自AFI、AEL、AFO、AFR、AFS、AFT、AFY、ATN、ATO、ATS、ATT、ATV、AWW的结构。
7.权利要求1或3的方法,其中所述结晶硅酸盐载体为脱铝化沸石,该脱铝化沸石具有选自AFI、AEL、AFO、AFR、AFS、AFT、AFY、ATN、ATO、ATS、ATT、ATV、AWW的结构。
8.权利要求1或权利要求3的方法,其中所述多孔结晶硅酸盐或结晶磷酸盐载体包含杂原子。
9.权利要求7的方法,其中所述杂原子选自周期2、3、4和5中除铝外的至少一种元素及其混合物。
10.权利要求5的方法,其中所述多孔结晶硅酸盐载体具有MFI结构。
11.权利要求5的方法,其中所述多孔结晶硅酸盐载体为具有MFI结构的钛硅分子筛(titanosilicalite)。
12.权利要求5的方法,其中所述多孔结晶硅酸盐载体为具有MFI结构的硼硅酸盐。
13.权利要求3的方法,其中所述多孔结晶硅酸盐载体具有FAU结构。
14.权利要求4的方法,其中所述多孔结晶磷酸盐载体具有ATS结构。
15.权利要求1或权利要求3的方法,其中所述多孔结晶硅酸盐含有少于约1%重量的铝。
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US10/920,021 US7081552B2 (en) | 2004-08-17 | 2004-08-17 | Catalysts for cycloalkanes oxidation and decomposition of cycloalkyl hydroperoxide |
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JP (1) | JP4977836B2 (zh) |
KR (1) | KR101208102B1 (zh) |
CN (1) | CN101039892A (zh) |
BR (1) | BRPI0515213A (zh) |
GB (1) | GB2433899B (zh) |
MX (1) | MX2007002077A (zh) |
TW (1) | TW200613057A (zh) |
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Cited By (3)
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CN104736506A (zh) * | 2012-07-26 | 2015-06-24 | 罗地亚经营管理公司 | 环烷烃氧化催化剂以及生产醇和酮的方法 |
CN111655660A (zh) * | 2018-01-30 | 2020-09-11 | 巴斯夫欧洲公司 | 氧化环烷烃的方法 |
CN112961032A (zh) * | 2014-12-22 | 2021-06-15 | 高性能聚酰胺有限公司 | 环烷烃氧化催化剂以及生产醇和酮的方法 |
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US7868201B2 (en) * | 2005-07-01 | 2011-01-11 | Exxonmobil Research And Engineering Company | Process and catalyst for oxidation of hydrocarbons |
CN100435944C (zh) * | 2007-03-13 | 2008-11-26 | 浙江大学 | 一种负载型纳米金催化剂及制备方法 |
US20090159502A1 (en) * | 2007-12-19 | 2009-06-25 | Nemeth Laszlo T | Decomposition of peroxides using iron-containing acidic zeolites |
PT104862A (pt) | 2009-12-07 | 2011-06-07 | Univ Tras Os Montes E Alto Douro | Catalisadores híbridos de vanádio e sua utilização em processos de oxidação selectiva de cicloalcanos |
JP6004528B2 (ja) * | 2011-08-29 | 2016-10-12 | 地方独立行政法人東京都立産業技術研究センター | 多孔質シリカ内包粒子の製造方法および多孔質シリカ |
JP6544118B2 (ja) * | 2015-07-29 | 2019-07-17 | 住友化学株式会社 | ゼオライトの製造方法及びε−カプロラクタムの製造方法 |
US9822052B2 (en) | 2015-10-01 | 2017-11-21 | Advansix Resins & Chemicals Llc | Nanoparticle catalysts for conversion of cyclohexanol to cyclohexanone |
CN108329190B (zh) * | 2018-01-28 | 2020-03-27 | 江西科因润滑材料有限公司 | 一种环己基过氧化氢催化分解的方法 |
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BE1007904A3 (nl) | 1993-12-23 | 1995-11-14 | Dsm Nv | Werkwijze voor de bereiding van een alkanol en/of een alkanon. |
JP2615432B2 (ja) * | 1994-10-28 | 1997-05-28 | 工業技術院長 | 金−酸化チタン含有触媒による炭化水素の部分酸化方法 |
US5827406A (en) * | 1995-01-31 | 1998-10-27 | The Regents Of The University Of California | Selective photooxidation of hydrocarbons in zeolites by oxygen |
US5914013A (en) | 1995-01-31 | 1999-06-22 | The Regents Of The University Of California | Selective thermal and photooxidation of hydrocarbons in zeolites by oxygen |
IN192732B (zh) | 1995-09-29 | 2004-05-15 | Council Scient Ind Res | |
KR100512672B1 (ko) | 1996-07-01 | 2005-12-21 | 다우 글로벌 테크놀로지스 인크. | 촉매조성물,이의재생방법및이를사용한산화올레핀의제조방법 |
ID22219A (id) | 1997-02-11 | 1999-09-16 | Du Pont | Proses dekomposisi hidroperoksida |
JP4016121B2 (ja) * | 1997-09-05 | 2007-12-05 | 独立行政法人産業技術総合研究所 | 炭化水素部分酸化用触媒及び含酸素有機化合物の製造方法 |
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JP2004506703A (ja) * | 2000-08-18 | 2004-03-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 改良されたヒドロペルオキシド分解触媒 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104736506A (zh) * | 2012-07-26 | 2015-06-24 | 罗地亚经营管理公司 | 环烷烃氧化催化剂以及生产醇和酮的方法 |
CN104736506B (zh) * | 2012-07-26 | 2017-04-12 | 罗地亚经营管理公司 | 环烷烃氧化催化剂以及生产醇和酮的方法 |
CN112961032A (zh) * | 2014-12-22 | 2021-06-15 | 高性能聚酰胺有限公司 | 环烷烃氧化催化剂以及生产醇和酮的方法 |
CN111655660A (zh) * | 2018-01-30 | 2020-09-11 | 巴斯夫欧洲公司 | 氧化环烷烃的方法 |
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GB0703142D0 (en) | 2007-03-28 |
MX2007002077A (es) | 2007-04-23 |
UA86644C2 (ru) | 2009-05-12 |
WO2006023333A1 (en) | 2006-03-02 |
BRPI0515213A (pt) | 2008-07-08 |
GB2433899A (en) | 2007-07-11 |
KR101208102B1 (ko) | 2012-12-04 |
JP4977836B2 (ja) | 2012-07-18 |
KR20070059094A (ko) | 2007-06-11 |
US20060041172A1 (en) | 2006-02-23 |
JP2008510002A (ja) | 2008-04-03 |
GB2433899B (en) | 2008-05-14 |
TW200613057A (en) | 2006-05-01 |
US7081552B2 (en) | 2006-07-25 |
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