CN1325458C - 金属掺杂的磺化离子交换树脂催化剂 - Google Patents
金属掺杂的磺化离子交换树脂催化剂 Download PDFInfo
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- CN1325458C CN1325458C CNB021570191A CN02157019A CN1325458C CN 1325458 C CN1325458 C CN 1325458C CN B021570191 A CNB021570191 A CN B021570191A CN 02157019 A CN02157019 A CN 02157019A CN 1325458 C CN1325458 C CN 1325458C
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Abstract
本发明公开了一种与以前的催化反应相比以更大的产率和选择性制备酮的方法,其中使用金属掺杂的聚磺化离子交换树脂催化剂进行酸催化缩合反应。例如,与使用常规单磺化离子交换树脂催化剂相比,使用具有至少5.0毫当量磺酸基团/克催化剂并载有金属,如钯的聚磺化离子交换树脂可增加丙酮缩合反应的甲基异丁基酮产率。
Description
背景
本发明涉及通过其它酮的催化缩合反应制备具有至少6个碳原子的酮的方法。尤其是本发明涉及金属掺杂的聚磺化离子交换树脂催化剂的用途,所述催化剂与以前使用的缩合催化剂相比以更大的产率和选择性提供所需酮。
醛醇缩合反应包括,通过将一种羰基化合物的α-碳加成到另一羰基化合物的羰基碳上而进行羰基化合物(醛或酮)的二聚反应,提供β-羟基羰基化合物。如果在存在酸性催化剂下缩合两个酮,通常在二聚反应之后发生脱水以提供α,β-不饱和酮;可以使用常规技术还原双键以提供饱和酮加成物。
例如,U.S.专利No.6,008,416公开了一个通过使用载有0.05%钯的单磺化酸性催化剂(AmmberlystTM 15离子交换树脂)进行丙酮二聚反应/脱水/氢化以提供亚异丙基丙酮,和最终的甲基异丁基酮(MIBK)的工作实施例。磺酸基团用作缩合/脱水催化剂且钯用作双键氢化反应的催化剂。
本发明解决的问题是克服用于制备酮的已有方法的缺陷,其中通过使用所选催化剂材料向所需饱和酮加成物提供较高的产率和选择性。
发明的描述
本发明提供一种用于制备具有6或更多碳原子的酮的方法,包括,将酮反应物与氢在一种聚磺化离子交换树脂催化剂的存在下接触,其中催化剂包含(a)1-85%聚合交联剂单元,基于催化剂干重;(b)5.0-7.0毫当量磺酸基团/克,基于催化剂干重;和(c)0.1-2%的分布其中且选自一种或多种钯,铂,铱,铑,钌,锇,铜,镍和锆的金属离子,基于催化剂干重。
另一方面,本发明提供了一种聚磺化离子交换树脂组合物,包含(a)10-25%聚合交联剂单元,基于催化剂的干重;(b)5.2-6.0毫当量磺酸基团/克,基于催化剂的干重;和(c)0.5-1.5%的分布其中且选自一种或多种钯,铂,铱,铑,钌,锇,铜,镍和锆的金属离子,基于催化剂干重。
详细描述
本发明人已经发现一种在氢存在下,基于使用金属掺杂的聚磺化催化剂通过其它酮的催化缩合反应来制备具有至少6个碳原子的酮的方法,这样与以前使用的单磺化缩合催化剂相比以更大的产率和选择性提供所需酮。
在整个说明书中使用的以下术语应该具有以下含义,除非在本文中清楚地另有所指。
术语“交联聚合物基质”是指任何被适宜官能化以提供聚磺化芳族环的交联聚合物基材;通常交联聚合物基质是交联苯乙烯聚合物,其中芳族环经受聚磺化条件以提供可用于本发明方法的催化剂。术语“共聚物”是指包含两种或多种不同的单体(包括位置异构体)的单元的聚合物组合物。术语“交联大孔共聚物”表示由单体或包含基于总单体重量至少1%重量(%)聚乙烯基不饱和单体的单体混合物聚合的聚合物或共聚物。术语“(甲基)丙烯酸烷基酯”是指相应的丙烯酸酯或甲基丙烯酸酯;类似地,术语“(甲基)丙烯酸”是指丙烯酸或甲基丙烯酸和相应的衍生物,如酯或酰胺。所提及的所有的百分数表示为%重量(%),基于所涉及的聚合物或组合物的总重,除非另有所指。本文使用以下简称:g=克,μm=微米,cm=厘米,mm=毫米,m=米,ml=毫升,meq/g=毫当量/克,L=升,1巴压力=105帕斯卡或105Pa。除非另有所指,所列举的范围要理解为包含性的和可合并的且温度是摄氏度(℃)。
尽管金属掺杂的聚磺化离子交换树脂一般可应用于采用强酸阳离子交换树脂作为催化剂的酸催化缩合反应,它们特别有利地用于其中产物是衍生自其它酮反应物底物的二聚反应/脱水/氢化反应的酮的那些缩合反应。
使用本发明方法,表示为化合物A(参见式1)的酮反应物在聚磺化催化剂B的存在下二聚反应。随着形成二聚的β-羟基酮加成物C,它经历脱水成为α,β-不饱和酮衍生物D(参见式2)。在氢和金属称作聚磺化催化剂B的存在下,α,β-不饱和酮衍生物D转化成饱和酮加成物E(参见式3)。
R’=苯基,H或C1-C4烷基
R=C1-C4烷基或苯基
Rz=交联聚合物基质
(SO3H)x=聚磺酸基团,其中x=>1<2,表示每个芳环的磺酸基团的平均数
M=选自Pd,Pt,Ir,Rh,Ru,Os,Cu,Ni,Zr的金属或金属离子
可用于本发明方法的酸催化剂是具有聚磺酸盐官能度的强酸阳离子交换树脂;即,承载催化剂位的交联聚合物基质包含具有一个以上磺酸基团/芳族环的芳环。通常至少10%,优选至少15%和更优选至少20%的芳族环包含一个以上的磺酸基团/芳族环。
可用于本发明方法的聚磺化阳离子交换树脂可以是凝胶或大孔珠的形式。优选,聚磺化阳离子交换树脂催化剂是具有平均颗粒直径100μm-2mm,优选150μm-1.5mm和更优选250μm-1mm的大孔球形珠粒形式;具有磺酸基团含量5.0-7.0,优选5.1-6.5和更优选5.2-6.0meq/g,基于催化剂的干重;载有0.1-2%,优选0.5-1.5%和更优选0.8-1.2%的金属或金属离子,基于催化剂的干重;通常具有表面积10-100,优选15-75和更优选20-50平方米/克(m2/g);和总孔隙率0.1-0.9,优选0.2-0.7和更优选0.25-0.5立方厘米孔/克聚合物(cm3/g),具有平均孔直径50-2,500埃单位和优选150-1000埃单位。孔隙率根据IUPAC(国际理论和应用化学联合会)命名法定义如下:
微孔隙率=低于20埃单位的孔
中孔隙率=20-500埃单位的孔
大孔隙率=大于500埃单位的孔
对于聚磺化阳离子交换树脂催化剂的表面积和孔隙率,如果表面积太低(低于约10m2/g),催化剂的氢化活性受影响且对所需饱和酮加成物的选择性下降。如果孔尺寸下降且表面积超过约100m2/g,反应结果是反应物不好地扩散通过催化剂床,导致所需饱和酮加成物的生产率下降。
聚磺化阳离子交换树脂通常由如描述于U.S.专利No.4,382,124中的交联大孔共聚物制备,其中孔隙率通过在孔原(也称作“相增量剂”或“沉淀剂”),即,用于单体的溶剂但是用于聚合物的非溶剂的存在下悬浮聚合反应而引入共聚物珠粒。
典型的交联大孔共聚物制备,例如可包括,制备包含悬浮助剂(如分散剂,保护胶体和缓冲剂)的连续水相溶液,随后与包含1-85%聚乙烯基芳族单体,自由基引发剂和通常0.2-5,优选0.3-3和更优选0.4-1份孔原(如甲苯,二甲苯,(C4-C10)-烷醇,(C6-C12-饱和烃或聚亚烷基二醇)/1份单体的单体混合物混合。单体和孔原的混合物随后在升高的温度下聚合且孔原随后通过各种方式从所得聚合物珠粒中去除;例如,甲苯,二甲苯和(C4-C10)醇可通过蒸馏或溶剂洗涤,和聚亚烷基二醇通过水洗涤而去除。所得大孔共聚物随后通过常规方式,如脱水后干燥而分离。
适用于制备交联共聚物的聚乙烯基芳族单体包括,例如,一种或多种选自二乙烯基苯,三乙烯基苯,二乙烯基甲苯,二乙烯基萘和二乙烯基二甲苯的单体;要理解,每种前述交联剂的各种位置异构体都是合适的;优选聚乙烯基芳族单体是二乙烯基苯。通常交联共聚物包含1-85%,优选5-55%和更优选10-25%的聚乙烯基芳族单体单位。
除了聚乙烯基芳族交联剂,也可视需要使用非芳族交联单体,如乙二醇二丙烯酸酯,乙二醇二甲基丙烯酸酯,三羟甲基丙烷三丙烯酸酯,三羟甲基丙烷三甲基丙烯酸酯,二甘醇二乙烯基醚和三乙烯基环己烷。如果使用,非芳族交联单体通常包含0-10%,优选0-5%,和更优选0-2%大孔聚合物作为聚合单元,基于用于形成大孔共聚物的总单体重量。
适用于制备交联共聚物的单不饱和乙烯基芳族单体包括,例如,苯乙烯,α-甲基苯乙烯,(C1-C4)烷基取代的苯乙烯,卤素取代的苯乙烯(如二溴苯乙烯和三溴苯乙烯),乙烯基萘和乙烯基蒽;优选单不饱和乙烯基芳族单体选自一种或多种苯乙烯和(C1-C4)烷基取代的苯乙烯。合适的(C1-C4)烷基取代的苯乙烯包括,例如,乙基乙烯基苯,乙烯基甲苯,二乙基苯乙烯,乙基甲基苯乙烯和二甲基苯乙烯;要理解,每种前述乙烯基芳族单体的各种位置异构体都是合适的。优选共聚物包含15-99%,和更优选75-90%的单不饱和乙烯基芳族单体单位。
除了乙烯基芳族单体,也可视需要使用非芳族单不饱和乙烯基单体,如脂族不饱和单体,例如,氯乙烯,丙烯腈,(甲基)丙烯酸和(甲基)丙烯酸烷基酯。如果使用,非芳族单不饱和乙烯基单体通常包含0-10%,优选0-5%,和更优选0-2%大孔共聚物作为聚合单元,基于用于形成大孔共聚物的总单体重量。
有用的用于制备大孔共聚物的孔原包括憎水孔原,如(C7-C10)芳族烃和(C6-C12)饱和烃;和亲水孔原,如(C4-C10)烷醇和聚亚烷基二醇。合适的(C7-C10)芳族烃包括,例如,一种或多种甲苯,乙基苯,邻-二甲苯,间-二甲苯和对-二甲苯;要理解,每种前述烃的各种位置异构体都是合适的。优选芳族烃是甲苯或二甲苯或二甲苯混合物或甲苯和二甲苯的混合物。合适的(C6-C12)饱和烃包括,例如,一种或多种己烷,庚烷和异辛烷;优选,饱和烃是异辛烷。合适的(C4-C10)烷醇包括,例如,一种或多种异丁基醇,叔-戊基醇,n-戊基醇,异戊基醇,甲基异丁基甲醇(4-甲基-2-戊醇),己醇和辛醇;优选,烷醇选自一种或多种(C5-C8)烷醇,如甲基异丁基甲醇和辛醇。
有用的在制备共聚物的聚合反应引发剂包括单体溶性引发剂如过氧化物,氢过氧化物和相关引发剂;例如过氧化苯甲酰,氢过氧化叔丁基,过氧化枯烯,过氧化四氢萘,过氧化乙酰基,过氧化己基,过辛酸叔-丁基酯(也称作过氧-2-乙基己酸叔-丁基酯),过辛酸叔-戊基酯,过苯甲酸叔-丁基酯,过邻苯二甲酸氢叔-丁基酯,过氧二碳酸二环己基酯,过氧二碳酸二(4-叔-丁基环己基)盐和甲基乙基酮过氧化物。另外有用的是偶氮引发剂如偶氮二异丁腈,偶氮二异丁酰胺,2,2’-偶氮-二(2,4-二甲基戊睛),偶氮-二(α-甲基丁腈)和二甲基-,二乙基或偶氮-二(甲基戊酸二丁基酯)。优选的过氧化物引发剂是过氧化二酰基,如过氧化苯甲酰,和过氧酯,如过辛酸叔-丁基酯和过苯甲酸叔-丁基酯;更优选,引发剂是过氧化苯甲酰。过氧化物引发剂的典型用量是0.3%-5%,优选0.5-3%和更优选0.7-2%,基于乙烯基单体的总重。
优选,交联共聚物选自二乙烯基苯共聚物,苯乙烯-二乙烯基苯共聚物,二乙烯基苯乙基乙烯基苯共聚物和苯乙烯-乙基乙烯基苯-二乙烯基苯共聚物,用作本发明方法所用聚磺化催化剂的基材。
根据本领域普通技术人员已知的常规聚磺化方法,这些交联共聚物可用强酸官能团官能化,例如用三氧化硫(SO3),发烟硫酸或发烟硫酸(包含三氧化硫的浓硫酸)和氯磺酸磺化;另外,单磺化阳离子交换树脂聚合物也可经受常规聚磺化条件以提供聚磺化阳离子交换树脂催化剂。
聚磺化阳离子交换树脂通常通过将金属离子的水溶液与阳离子交换树脂的氢形式以间歇或柱模式接触而载有所需金属离子。通常金属离子以金属盐,例如,氯化物,溴化物,硝酸盐,硫酸盐和乙酸盐的形式提供。所载的阳离子交换树脂随后漂洗去除残余的盐或酸。金属盐的用量选择使得金属或金属离子最终的存在量是阳离子交换树脂的约1-15g/L(0.1-2%加载量),优选约4-10g/L(0.5-1.5%加载量)和更优选约6-8g/L(0.8-1.2%加载量),且可通过常规分析试验方法确定。如果聚磺化催化剂上的金属浓度大于约2%加载量(基于催化剂干重),羰基基团可发生还原并降低所需酮加成物(式3中的E)的总体产率。适用作本发明方法所用聚磺化催化剂的一部分的金属离子包括,例如,钯(Pd),铂(Pt),铑(Rh),铱(Ir),钌(Ru),锇(Os),铜(Cu),镍(Ni)和锆(Zr)。优选,聚磺化阳离子交换树脂催化剂包含0.5-1.5%钯,基于催化剂干重。
对于聚磺化阳离子交换树脂催化剂上的加载量,如果金属加载量太低(低于约0.1%),催化剂不具有足够的氢化反应活性且对饱和酮加成物的选择性不令人满意。如果金属加载量太高(以上约2%),氢化活性太高并导致所需饱和加成物产率下降。
以下描述聚磺化阳离子交换树脂的金属加载量的例子。例如,将1升氢(H)形式的聚磺化阳离子离子交换树脂倒入10-50g硝酸钯在0.5-2升蒸馏水中的溶液,使钯吸收到阳离子交换树脂上约1-4小时并随后将溶液从树脂中倾析。另外,聚磺化阳离子交换树脂可通过将金属盐的水溶液经过聚磺化阳离子交换树脂柱直至该树脂已保留所需量的金属离子而载有金属-随后用水充分洗涤以去除在加载方法过程中产生的残余的盐和酸。
优选,催化剂通过还原包含金属离子的聚磺化离子交换树脂以沉积催化剂中的元素形式的金属而制成。此时,加载的树脂可通过将加载树脂暴露于氢(通常在室温和低氢分压,例如,低于1巴的压力下)经受‘活化’(还原)。另外,活化可最高约120℃的温度和在氢压力约2-50巴下进行。包含还原形式的金属的加载催化剂可随后理想地用于缩合反应。
另外,加载的树脂(离子形式的金属)可就在用于缩合反应之前被‘活化’成还原的金属形式。例如,如果缩合反应包括丙酮至MIBK的二聚反应,丙酮通常在液体小时空间速度(LHSV)约0.5h-1(即,0.5体积丙酮/体积催化剂树脂/小时)下抽吸通过包含载有金属离子的聚磺化催化剂的柱反应器。反应器的压力随后用氢增加至约30巴。在确立流过反应器的所需氢流量之后,温度随后升至约90℃和保持约10-16小时。反应器可随后加热至所需反应温度,通常110-150℃,同时所需丙酮和氢流动以引发丙酮转化成MIBK。
如果Pd,Pt,Rh,Ir,Ru或Os用作催化剂的金属组分,优选的是,加载的树脂在用于缩合反应之前被活化成还原金属形式。
除了本文所述的酮缩合反应,金属掺杂的聚磺化阳离子交换树脂催化剂可用于促进是烯烃和醇醚化成用于马达燃料的高辛烷氧化添加剂(醚),例如描述于U.S.专利Nos.4,330,679和5,395,981。
在本发明的一个优选的实施方案中,金属掺杂的聚磺化阳离子交换树脂催化剂的物理形式是包含在容器中的珠粒,所述珠粒构成催化剂床。酮反应物,如丙酮的加料流与催化剂床在氢(作为单独的加料流)存在下接触足够的时间和温度以发生酮缩合反应。将包含反应产物(饱和酮加成物),副产物(不饱和酮加成物)和可存在的任何未反应的酮反应物的冷凝的液体物流从催化剂床中分离,并通过常规分离方式(如蒸馏)将所需酮加成物从液体物流中回收。本领域熟练技术人员能够选择合适的条件,如(1)间歇操作,例如,其中催化剂床在氢存在下载有液体物流,随后在已发生所需反应之后从催化剂中去除液体物流,或(2)更优选的连续操作,例如,其中在停留时间足以使催化剂床发生所需反应的速率下将液体物流连续加料到柱反应器(与氢)的一端,同时冷凝的液体物流从床的另一端连续去除。类似地,反应设备,对反应物物流经过床的方向的上流或下流选择,反应时间和温度,特殊反应物,和回收酮加成物的方法往往根据本文所提供的指导以及本领域熟练技术人员可得的知识而选择。
通常,柱反应器内的温度和压力选择使得酮反应物在催化剂床中处于其沸点。酮反应物的温度/压力改变可用于提供所需反应温度和条件的组合,使得缩合反应发生在催化剂床中的液相。可以改变条件以提供气体相条件的催化剂床;但优选的是,这些条件使得缩合反应是在液体相中进行。
本发明的金属掺杂的聚磺化阳离子交换树脂催化剂可用于缩合反应,其中酮反应物和氢在间歇反应条件或在连续反应条件下接触。在一个实施方案中本发明,该方法是一种基于催化蒸馏方法的连续方法,其中将酮反应物加入就在再沸器阶段之上的柱反应器的底部;在这种情况下产物级分或物流从蒸馏装置的再沸器部分中连续取出以用于进一步处理(对于催化蒸馏方法的进一步一般和特定细节,参见U.S.专利No.6,008,416)。优选,将要经历缩合反应的酮反应物向下加料通过催化剂床并将氢气流以相同方向经过反应区。但可以使用,其它的变型以引入反应物加料流,如并流和逆流氢流动,液泛方法和气相方法。
对于连续方法,催化剂相对反应物量的用量通常涉及反应的生产量,例如表示为反应物每单位时间相对催化剂体积的LHSV(液体小时空间速度)或液体流速。通常,高LHSV对于最大利用设备和生成产物是理想的;但满足该目标必须抵消原料的%转化率和对所需产物的%选择性。如果LHSV太低,所需产物的生产速率(空间产率)下降且该方法变得不经济。如果LHSV太高,催化剂活性不足以提供所需转化率水平(该方法变得“动力学受限”)。合适的LHSV值通常为0.5-10h-1,优选1-8h-1和更优选2.5-6h-1。
通常,酮反应物与氢在催化剂存在下在温度110-170℃和在氢压力1-100巴下接触。适用于进行本发明催化缩合反应的温度是110-170℃,优选120-160℃和更优选130-150℃。在较低温度(低于约110℃)下,催化剂不具有足够的活性以提供理想的转化率和产率。在超过约170℃的温度下,该反应对所需饱和酮加成物的选择性下降,且催化剂寿命受不利影响。一般来说,酮反应物和氢的反应区保持在氢压力1-100巴,优选5-60巴和更优选10-40巴下。通常,缩合反应以氢/酮反应物摩尔比0.1-1和优选0.15-0.5进行。
在另一实施方案中本发明,该方法可以是间歇的,其将酮反应物在催化蒸馏装置的再沸器部分阶段加入反应器柱(类似于上述)。该方法可随后在酮加成物在再沸器部分中实现所需产物组成时终止。另外,缩合可在间歇高压釜反应器下进行特定的时间,随后冷却并通过蒸馏或其它常规方式回收所需酮加成物。
本发明的一些实施方案在以下实施例中详细描述。除非另有所指,所有的比率,份数和百分数表示为重量,且除非另有所指,所有的所用试剂都具有商业质量。用于实施例和表的简称和相应的说明在以下列出:
MIBK=甲基异丁基酮(4-甲基-2-戊酮)
LHSV=液时空速(h-1)
DVB=二乙烯基苯(金属/对异构体混合物)
cm3/g=立方厘米/克
实施例1
使用固定床反应器评估用于将丙酮缩合成亚异丙基丙酮并最终缩合成甲基异丁基酮(MIBK)的各种阳离子交换树脂催化剂。管式反应器是具有内径10mm和长度45cm的柱的形式。使用25ml阳离子交换树脂催化剂的催化剂加料用于每个实验并用插入反应器的可调热电偶监控温度。在引发缩合反应之前,金属掺杂的催化剂通过将丙酮在LHSV 0.5h-1下抽吸经过反应器,并加入氢至压力30巴而活化(钯还原成金属形式)。温度随后升至90℃并在此保持10-16小时,然后升温至所需试验温度(130-150℃)并开始加入反应物(丙酮和氢)。通常反应器在设计条件下运行一段时间(通常1-2天)以确保稳定态操作,并随后对流出的物流取样分析。
对于在LHSV 2.8下进行的缩合反应,酮反应物加料流在70ml/小时下和氢在4.1L/小时下加入;对于LHSV 5.6,酮反应物加料速率是140ml/小时且氢流量是5.8L/小时。
酮反应物加料物流包含96%丙酮,1%异丙醇,约2%C9-烃杂质和1%水。氢物流在提供氢/丙酮摩尔比0.19/1的速率下加料。缩合反应产物物流通过常规气体色谱分析进行分析以确定%丙酮转化率,%MIBK选择性和总体MIBK产率。MIBK生产率表示为“ml MIBK产物/ml催化剂/小时”。除了使基本缩合/氢化反应的转化率和选择性最大化,高“MIBK生产率”值是理想的,优选大于1.0和更优选大于1.4。
评估三个催化剂并将结果汇总于表1和2。
催化剂1(对比):具有4.8meq/g磺酸容量的单磺化苯乙烯/DVB(12%)共聚物,%钯=基于催化剂干重的0.7%,%水分=47-54%,平均颗粒尺寸=0.85-1.0mm,表面积=35m2/g,孔隙率=0.24cm3/g,平均孔直径=150埃单位。
催化剂2:具有5.2meq/g磺酸容量的聚磺化苯乙烯/DVB(18%)共聚物,%水分=51-57%,%钯=基于催化剂干重的0.75%,平均颗粒尺寸=0.7-0.95mm,表面积=45m2/g,孔隙率=0.34cm3/g,平均孔直径=240埃单位。
催化剂3:具有5.2meq/g磺酸容量的聚磺化苯乙烯/DVB(18%)共聚物,%水分=51-57%,%钯=基于催化剂干重的1.0%,平均颗粒尺寸=0.7-0.95mm,表面积=45m2/g,孔隙率=0.34cm3/g,平均孔直径=240埃单位。
表1MIBK生产@130℃
LHSV=2.8h-1 | %转化率a | %选择性b | %产率c | MIBK生产率d |
催化剂1(对比)相对催化剂1*催化剂2相对催化剂1*催化剂3相对催化剂1*LHSV=5.6h-1催化剂1(对比)相对催化剂1*催化剂2相对催化剂1*催化剂3相对催化剂1* | 39.9(1.0)44.01.1039.40.9932.6(1.0)35.71.1038.41.18 | 91.2(1.0)98.21.08101.81.1285.6(1.0)95.91.1293.71.09 | 36.4(1.0)43.21.1940.11.1027.9(1.0)34.21.2336.01.29 | 0.84(1.0)0.991.180.921.101.28(1.0)1.571.231.651.29 |
a=丙酮转化率
b=MIBK产物的选择性
C=MIBK基于转化的丙酮的产率
d=总体反应效率(ml MIBK/ml催化剂/小时)
*=与催化剂1相比在转化率,选择性,产率和生产率上的相对增加
表2
MIBK生产@140℃/150℃和LHSV=5.6h-1
温度=140℃ | %转化率a | %选择性b | %产率c | MIBK生产率d |
催化剂1(对比)相对催化剂1*催化剂2相对催化剂1*温度=150℃催化剂1(对比)相对催化剂1*催化剂2相对催化剂1* | [34.8]**(1.0)37.61.0837.1(1.0)39.31.06 | [84.2]**(1.0)94.61.1282.9(1.0)93.21.12 | [29.3]**(1.0)35.51.2130.7(1.0)36.61.19 | [1.34]**(1.0)1.631.221.41(1.0)1.681.19 |
a=丙酮转化率
b=MIBK产物的选择性
c=MIBK基于转化的丙酮的产率
d=总体反应效率(ml MIBK/ml催化剂/小时)
*=与催化剂1相比在转化率,选择性,产率和生产率上的相对增加
**=通过补充在130℃和150℃下的数据而评估
在其中聚磺化催化剂2或3可直接与单磺化催化剂(催化剂1)比较的六种情况下,通过使用本发明的金属掺杂的聚磺化催化剂,丙酮转化率平均增加约8%,MIBK%选择性平均增加约11%且总体MIBK产率和MIBK生产率平均增加约20%。
Claims (10)
1.制备具有6个或更多碳原子的酮的方法,它包括将酮反应物与氢在一种含芳环的聚磺化离子交换树脂催化剂的存在下接触,所述催化剂中平均每个芳环的磺化基团数大于1但小于2,所述催化剂包含:
(a)1-85%聚合交联剂单元,基于催化剂干重;
(b)5.0-7.0毫当量磺酸基团/克,基于催化剂干重;和
(c)0.1-2%的分布其中且选自一种或多种钯,铂,铱,铑,钌,锇,铜,镍和锆的金属离子,基于催化剂干重。
2.权利要求1的方法,其中催化剂通过还原包含金属离子的聚磺化离子交换树脂以在催化剂中沉积元素形式的金属而制成。
3.权利要求1的方法,其中酮反应物与氢在催化剂存在下在温度110-170℃下和在压力1-100巴下接触。
4.权利要求1的方法,其中催化剂包含5.2-6.0毫当量磺酸基团/克,基于催化剂干重。
5.权利要求1的方法,其中催化剂包含0.5-1.5%钯,基于催化剂干重。
6.权利要求1的方法,其中酮反应物和氢在连续反应条件下接触。
7.权利要求1的方法,其中聚磺化离子交换树脂催化剂的形式是具有总孔隙率0.1-0.9立方厘米/克和表面积10-100平方米/克的大孔珠粒,基于催化剂干重。
8.权利要求7的方法,其中催化剂表面积是20-50平方米/克,基于催化剂干重。
9.一种含芳环的聚磺化离子交换树脂催化剂,所述催化剂中平均每个芳环的磺化基团数大于1但小于2,所述催化剂包含:
(a)1-85%聚合交联剂单元,基于催化剂的干重;
(b)5.0-7.0毫当量磺酸基团/克,基于催化剂 的干重;和
(c)0.1-2%的分布其中且选自一种或多种钯,铂,铱,铑,钌,锇,铜,镍和锆的金属离子,基于催化剂干重。
10.权利要求9所述的催化剂,其特征在于它包含:
(a)10-25%的聚合交联剂单元;
(b)5.2-6.0毫当量磺酸基团/克;和
(c)0.5-1.5%的金属离子。
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CN100427447C (zh) * | 2003-11-17 | 2008-10-22 | 萨索尔溶剂德国有限公司 | 用于制备含羰基产物的缩合和氢化反应 |
DE602005025268D1 (de) * | 2004-02-24 | 2011-01-27 | Rohm & Haas | Verfahren zur Entfernung von Arsen aus Wasser |
CA2579031C (en) * | 2006-03-03 | 2011-03-29 | Rohm And Haas Company | Method for producing an arsenic-selective resin |
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JP5405463B2 (ja) | 2007-07-27 | 2014-02-05 | ダウ グローバル テクノロジーズ エルエルシー | 銅系触媒を用いたmibcならびに/またはibhkおよびtmnの生成方法 |
EP2128118A1 (en) | 2008-05-28 | 2009-12-02 | DSM IP Assets B.V. | Synthesis of mono-ketones from 1,3-diketones |
CN101417994B (zh) * | 2008-11-25 | 2012-05-02 | 国际香料香精(杭州)有限公司 | 一种4-(3′,4′-亚甲二氧基)苯基-2-丁酮的生产方法 |
CN101579643B (zh) * | 2009-06-11 | 2010-12-29 | 湖州师范学院 | 海藻酸盐包覆二氧化钛纳米粉体的溶胶凝胶原位制备方法 |
JP5554201B2 (ja) * | 2009-11-25 | 2014-07-23 | ローム アンド ハース カンパニー | 金属合金触媒組成物 |
JP5349540B2 (ja) | 2010-06-30 | 2013-11-20 | ローム アンド ハース カンパニー | 不均一系触媒を製造する方法 |
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JP5363532B2 (ja) * | 2010-06-30 | 2013-12-11 | ローム アンド ハース カンパニー | 多反応二官能性ポリマー系触媒 |
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KR101297510B1 (ko) * | 2010-08-20 | 2013-08-16 | 삼성석유화학(주) | 방향족 디카르복실산의 제조방법 |
FR2968002B1 (fr) | 2010-11-30 | 2012-11-23 | Rhodia Poliamida E Especialidades Ltda | Procede pour la production de dibk |
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JP6042278B2 (ja) * | 2012-07-10 | 2016-12-14 | オルガノ株式会社 | 白金族金属担持接触水素化還元触媒及び接触水素化還元方法 |
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CN105188875B (zh) | 2013-03-13 | 2017-03-08 | 陶氏环球技术有限责任公司 | 用于圆柱形过滤元件的拼接纤维增强外壳 |
IN2013MU02838A (zh) * | 2013-08-30 | 2015-07-03 | Godavari Biorefineries Ltd | |
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US6977314B2 (en) | 2005-12-20 |
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JP2003212812A (ja) | 2003-07-30 |
TW200301244A (en) | 2003-07-01 |
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MXPA02012311A (es) | 2005-07-25 |
CN1426990A (zh) | 2003-07-02 |
PL357801A1 (en) | 2003-06-30 |
KR20030051253A (ko) | 2003-06-25 |
US20030139629A1 (en) | 2003-07-24 |
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