CN102309989B - 混合床聚合物催化剂 - Google Patents
混合床聚合物催化剂 Download PDFInfo
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- CN102309989B CN102309989B CN201110192501.0A CN201110192501A CN102309989B CN 102309989 B CN102309989 B CN 102309989B CN 201110192501 A CN201110192501 A CN 201110192501A CN 102309989 B CN102309989 B CN 102309989B
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- Prior art keywords
- catalyst
- metal
- exchange resin
- ion exchange
- mixed bed
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
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- 239000003456 ion exchange resin Substances 0.000 claims abstract description 34
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 239000010948 rhodium Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010931 gold Substances 0.000 claims abstract description 6
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 6
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Abstract
一种混合床聚合物催化剂,以及该催化剂的应用,该催化剂包含10-90重量%的第一催化剂,该第一催化剂包含加载了金属的离子交换树脂,所述金属是钯、铂、铱、铑、钌、铜、金和/或银;以及10-90重量%的第二催化剂,所述第二催化剂包括缺少金属的强酸性离子交换树脂,所述金属均匀地分布在混合床中。
Description
技术领域
本发明涉及混合床聚合物催化剂。更具体来说,本发明涉及金属掺杂的离子交换树脂催化剂和强阳离子型离子交换树脂催化剂的混合床。
背景技术
在填充床中使用金属掺杂的离子交换树脂催化剂是已知的。例如,在美国专利第6,977,314号中,金属掺杂的多磺化阳离子型离子交换树脂催化剂形成催化剂床,用来制备酮。英国专利第GB 994137号和第GB1191113号也揭示了含金属的强酸性阳离子型催化剂。英国专利第GB994137号还揭示了在填充床内使用活性炭或活性氧化铝。但是,在离子交换床中难以实现活性炭或氧化铝的良好混合,导致选择性低,由于产生小颗粒而发生设备的堵塞,在氢化过程中会造成压降。
本发明力图对现有技术进行改进,本发明提供了一种混合床聚合物催化剂,该催化剂同时包含金属掺杂的离子交换树脂催化剂和强酸离子交换树脂催化剂,其具有非常有利的反应转化率,以及金属在催化剂床中的均一分布。本发明还允许针对实验条件,例如工艺流速、温度和其他条件对金属加载进行调节。
发明内容
在本发明的第一方面,提供了一种混合床聚合物催化剂,其包含10-90重量%的第一催化剂,该第一催化剂包含加载了金属的离子交换树脂,所述金属是钯、铂、铱、铑、钌、铜、金和/或银;以及10-90重量%的第二催化剂,所述第二催化剂包括缺少金属的强酸性离子交换树脂。所述金属均匀分布在混合床中。
在本发明的第二方面,提供了本发明的催化剂用于以下基团的氢化的应用:炔、烯、醛、酮、醇、腈、胺和/或硝基。
在本发明的第三个方面,提供了一种制备酮的方法,该方法包括提供聚合物催化剂的混合床,所述聚合物催化剂包含:10-90重量%的第一催化剂,该第一催化剂包含加载了金属的离子交换树脂,所述金属是以下的一种或多种:钯、铂、铱、铑、钌、铜、金和/或银;以及10-90重量%的第二催化剂,所述第二催化剂包括缺少金属的强酸性离子交换树脂,所述金属均匀分布在所述混合床中;将所述金属均匀分布在所述混合床中;合成酮,以获得0.1-60%的产率。
具体实施方式
本发明涉及一种混合床聚合物催化剂。所述混合床催化剂包括第一和第二催化剂,所述第一催化剂包含金属,所述第二催化剂缺乏金属。所述第一催化剂是加载了金属的离子交换树脂。所述第二催化剂是强酸性离子交换树脂。“强酸性离子交换树脂”中的“强酸性”表示树脂在水中的pKa小于2。所述强酸性离子交换树脂包括苯乙烯类强酸阳离子型树脂,其水份保持容量为10-90%,粒度为100-2000微米,体积容量为0.5-7毫当量/升(毫当量每升)。离子交换树脂的例子包括磺化不足(undersulfonated)的树脂以及多磺化树脂。在一个优选的实施方式中,离子交换树脂包括多磺化阳离子型离子交换树脂,其中芳族基团/磺基比例为10∶1至1∶2。1∶2是磺化极限。可以用于催化的其它树脂包括丙烯酸类主链树脂,例如弱酸阳离子型树脂,弱碱阴离子型树脂,强碱阴离子型树脂以及强酸阳离子型树脂。
第一和第二催化剂中的离子交换树脂可以为胶体树脂或大孔珠粒的形式。较佳的是,所述离子交换树脂催化剂是大孔球形珠粒的形式,其平均粒径为100微米至2毫米,更优选为150微米至1.5毫米,最优选为250微米至1毫米。当所述离子交换树脂是多磺化的阳离子型离子交换树脂的时候,以多磺化阳离子型离子交换树脂的干重为基准计,所述磺酸基的含量优选约为5.0-7.0,更优选约为5.1-6.5,最优选约为5.2-6.0meq/g(毫当量每克),以所述多磺化阳离子型离子交换树脂的干重为基准计,金属或金属离子的加载量优选约为0.1-10%,更优选约为0.5-5%,最优选约为0.7-2%。
较佳的是,所述第一和第二催化剂的离子交换树脂的表面积约为10-1000,更优选约为15-500,最优选约为0.1-50平方米/克(m2/g),优选其总孔隙率约为0.1-0.9,更优选约为0.2-0.7,最优选约为0.25-0.5立方厘米/克聚合物(cm3/g),平均孔径优选约为50-2,500埃,更优选约为150-1000埃。
所述第一和第二催化剂的离子交换树脂可以由交联的大孔共聚物制备,所述交联的大孔共聚物表示由单体或单体混合物聚合形成的聚合物或共聚物,以单体总重量为基准计,所述单体或单体混合物包含至少1重量%的多乙烯基不饱和单体。通过在存在成孔剂(也称作“相扩展剂”或“沉淀剂”)的条件下,通过悬浮聚合在共聚物珠粒中引入孔隙,所述成孔剂是单体的溶剂,但是并非聚合物的溶剂。
例如,交联的大孔共聚物的制备可以包括制备包含悬浮助剂(例如分散剂,保护胶体和缓冲剂)的连续水相溶液,然后与包含以下组分的单体混合物混合:1-85%的多乙烯基芳族单体,自由基引发剂,以及优选约0.2-5份、更优选约0.3-3份、最优选约0.4-1份的成孔剂(例如甲苯,二甲苯,(C4-C10)-链烷醇,(C6-C12)-饱和烃或聚亚烷基二醇)/1份单体。然后使得所述单体与成孔剂的混合物在升高的温度下聚合,然后通过各种方法将成孔剂从制得的聚合物珠粒中除去;例如,可以通过蒸馏或者溶剂洗涤除去甲苯、二甲苯和(C4-C10)醇,可以通过水洗除去聚亚烷基二醇。然后通过常规的方式,例如脱水、然后干燥,分离制得的大孔共聚物。
可以用来制备交联的共聚物的合适的多乙烯基芳族单体包括例如,选自以下的一种或多种单体: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,以及它们的混合物;需要理解上述各种交联剂的任意各种位置异构体也是合适的。在一个优选的实施方式中,所述多乙烯基芳族单体是二乙烯基苯。较佳的是,所述交联的共聚物包含约1-85%,更优选约5-55%,最优选约10-25%的多乙烯基芳族单体单元。
任选的,除了多乙烯基芳族交联剂以外,还可以使用非芳族交联单体,例如二丙烯酸乙二醇酯,二甲基丙烯酸乙二醇酯,三丙烯酸三羟甲基丙酯,三甲基丙烯酸三羟甲基丙酯,二乙二醇二乙烯基醚和三乙烯基环己烷。当使用非芳族交联单体的时候,以用来形成大孔共聚物的单体总重量为基准计,所述非芳族交联单体优选占大孔聚合物的大约0-10%,更优选大约0-5%,最优选大约0-2%,作为聚合单元。
可以用来制备所述交联共聚物的合适的单烯键式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(例如二溴苯乙烯和三溴苯乙烯),乙烯基萘以及乙烯基蒽。较佳的是,所述单不饱和乙烯基芳族单体选自苯乙烯、(C1-C4)烷基取代的苯乙烯以及它们的混合物。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。应当理解,上述各种乙烯基芳族单体的任意各种位置异构体也是合适的。较佳的是,所述共聚物包含约15-99%,更优选约75-90%的单不饱和乙烯基芳族单体单元。
任选的,除了乙烯基芳族单体以外,还可以使用非芳族单不饱和乙烯基单体,例如脂族不饱和单体,例如氯乙烯,丙烯腈,(甲基)丙烯酸和(甲基)丙烯酸烷基酯。当使用的时候,以用来形成大孔共聚物的单体总重量为基准计,所述非芳族单不饱和乙烯基单体优选占大孔聚合物的大约0-10%,更优选大约0-5%,最优选大约0-2%,作为聚合单元。
可以用来制备大孔共聚物的成孔剂包括疏水性成孔剂,例如(C7-C10)芳族烃和(C6-C12)饱和烃;以及亲水性成孔剂,例如(C4-C10)链烷醇和聚亚烷基二醇。合适的(C7-C10)芳族烃包括例如以下的一种或多种:甲苯,乙基苯,邻二甲苯,间二甲苯和对二甲苯;需要理解,上述各种烃的任何各种位置异构体也是合适的。较佳的是,所述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)饱和烃包括例如己烷、庚烷和异辛烷中的一种或多种;优选所述饱和烃是异辛烷。合适的(C4-C10)链烷醇包括例如以下的一种或多种:异丁醇,叔戊醇,正戊醇,异戊醇,甲基异丁基甲醇(4-甲基-2-戊醇),己醇和辛醇;优选的是,所述链烷醇选自一种或多种(C5-C8)链烷醇,例如甲基异丁基甲醇和辛醇。
可以用来制备共聚物的聚合引发剂包括可溶于单体的引发剂,例如过氧化物、氢过氧化物和相关的引发剂;例如过氧化苯甲酰基,氢过氧化叔丁基,过氧化枯烯,过氧化萘满,过氧化乙酰基,过氧化己酰基,过辛酸叔丁酯(也被称为叔丁基过氧基-2-乙基己酸酯),过辛酸叔戊酯,过苯甲酸叔丁酯,二过邻苯二甲酸叔丁酯,过氧化二碳酸二环己酯,过氧化二碳酸二(4-叔丁基环己基)酯以及过氧化甲基乙基酮。还可以使用偶氮类引发剂,例如偶氮二异丁腈,偶氮二异丁酰胺,2,2′-偶氮-二(2,4-二甲基戊腈),偶氮-二(α-甲基丁腈)以及二甲基-,二乙基-或二丁基偶氮-二(甲基戊酸酯)。优选的过氧化物引发剂是过氧化二酰基,例如过氧化苯甲酰基,以及过酸酯,例如过辛酸叔丁酯和过苯甲酸叔丁基酯;更优选的是,所述引发剂是过氧化苯甲酰基。以乙烯基单体的总重量为基准计,过氧化物引发剂的用量优选约为0.3-5%,更优选约为0.5-3%,最优选约为0.7-2%。
较佳的是,用作催化剂的基材的所述交联的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。可以采用本领域普通技术人员已知用于多磺化的常规方法,用强酸官能团对这些交联的共聚物进行官能化,例如用三氧化硫(SO3),发烟硫酸(包含三氧化硫的浓硫酸)以及氯磺酸进行磺化。或者,还可以对单磺化的阳离子型离子交换树脂采用常规的多磺化条件,以提供多磺化的阳离子型离子交换树脂催化剂。
第一催化剂中的示例性的金属包括钯(Pd)、铂(Pt)、铱(Ir)、铑(Rh)、钌(Ru)、铜(Cu)、金(Au)、银(Ag),以及它们的混合物。所述催化剂可以用均匀地分散在树脂中的零价态金属制备的。较佳的是,以催化剂的干重为基准计,所述离子交换树脂催化剂包含0.1-15%的金属。
较佳的是,所述混合床聚合物催化剂包含10-90重量%的第一催化剂和10-90重量%的第二催化剂。根据所需的结果,以混合床聚合物催化剂的总重量为基准计,所述第一催化剂的含量可以最低为1%,最高为99%。但是,因为包含金属的第一催化剂更昂贵,优选第一催化剂用量较少。更优选的,所述混合床聚合物催化剂包含15-25重量%的第一催化剂和75-85重量%的第二催化剂,最优选所述混合床聚合物催化剂包含19-21重量%的第一催化剂以及79-81重量%的第二催化剂。
所述混合床聚合物催化剂实现了所需的反应转化率以及双功能催化剂(第一催化剂)和酸催化剂(第二催化剂)在催化剂床内的均匀分布。可以针对实验条件对所需的金属加载量进行调节。所述混合床聚合物催化剂可能的反应包括但不限于以下基团的氢化:炔、烯、醛、酮、醇、腈、胺和硝基,可以相应地调节金属加载量。
在一个实施方式中,所述混合床聚合物催化剂用来制备酮。所述金属均匀地分布在第一和第二催化剂的混合床中,合成酮,使得产率为0.1-60%。
所述混合床聚合物催化剂的产率约为5-65%,选择性为85-99%。在一个实施方式中,所述催化剂的产率为30%,选择性为97%。产率是基于制得的酮的量计算的,选择性是基于制得的酮的量相对于全部产物的比例计算的。
在本发明的一个优选实施方式中,所述混合床聚合物催化剂的物理形式是包含在容器中的珠粒,所述珠粒形成所述催化剂的床。在存在氢气(作为独立的进料流)的情况下,在足够的温度条件下,酮类反应物(例如丙酮)或溶剂的进料物流与催化剂床接触足够的时间,以发生酮的缩合反应。将包含反应产物(饱和酮加合物)、副产物(不饱和酮加合物)和可能存在的任何未反应的酮反应物的冷凝的液体流从催化剂床分离出来,通过常规的分离方法(例如蒸馏)从液体流回收所需的酮加合物。
本领域技术人员能够选择合适的条件,例如(1)分批操作,例如其中在存在氢气的条件下对催化剂床加载液体流,或者(2)更优选的连续操作,例如,以一定的速率将液体流(以及氢气)连续地通入柱状反应器的一端,所述速率使得在催化剂床内有足够的停留时间,能够发生所需的反应,冷凝的液体流连续地从床的另一端移出。类似的,本领域技术人员根据本文给出的指导以及公知常识,可以很容易地对反应设备、反应物流通过床的上流和下流方向选择、反应时间和温度、具体的反应物、以及回收酮加合物的方法进行选择。
可以对柱状反应器内的温度和压力进行选择,使得酮反应物在催化剂床内处于其沸点。利用酮反应物的温度/压力变化提供反应温度和条件的所需组合,使得在催化剂床中,缩合反应在液相中发生。可以改变条件,在催化剂床中提供气相条件;所述条件可以使得缩合反应在液相中进行。在一个优选的实施方式中,采用喷淋床条件,在此条件下,液体和气体流过催化剂床。在一个实施方式中,所述气体是氢气,所述平衡液体/蒸气是丙酮。通过选择较高的压力可以提供更多液体。
本发明的混合床聚合物催化剂可以用于缩合反应,其中酮反应物和氢气在间歇反应条件或连续反应条件下接触。在一个实施方式中,所述方法是基于催化蒸馏工艺的连续工艺,其中在与再沸器阶段紧邻的上方的柱状反应器的底部之内引入酮反应物;在此情况下,将产物馏分或物流从蒸馏设备的再沸器部分连续地引出,用于进一步的加工。较佳的是,将要发生缩合反应的酮反应物通过催化剂床向下加入,氢气流沿着相同的方向通过反应区。但是还可以通过其它的不同方式引入反应物进料流,例如同向和反向氢气流,漫溢法和气相法。
对于连续工艺,相对于反应物的量,混合床聚合物催化剂的用量通常与反应的通过速率相关,用反应物的LHSV(液时空速)或者每单位时间内相对于催化剂体积的反应物流速来表示。可以通过高LHSV来尽可能提高设备应用以及产物的生成;但是,为了实现这个目标,原料转化百分数和制备所需产物的选择性百分数之间必须进行平衡。如果LHSV过低,则所需产物的生产率(产率和选择性)会降低,工艺不够经济。如果LHSV过高,则催化剂的活性不足以实现所需的转化率(工艺″动力学受限制″)。合适的LHSV的值通常优选为0.5-10小时-1,更优选为1-8小时-1,最优选为为2-4小时-1。
在存在催化剂的情况下,在温度为65-200℃、氢气压力为1-100巴(0.1-10兆帕)的条件下,使得酮反应物与氢气接触。通常,缩合反应在氢气/酮反应物摩尔比至少为1∶1的条件下进行。
在本发明的另一个实施方式中,所述工艺可以是间歇反应,在催化蒸馏设备的再沸器部分阶段,将酮反应物引入反应器柱内(与上文所述类似)。然后当再沸器部分中实现所需的酮加合物的产物组成的时候,可以终止反应过程。或者,缩合反应可以在间歇式高压釜反应器中进行特定的时间,然后冷却,通过蒸馏或者其它的常规手段回收所需的酮加合物。
在本发明的一个说明性实施例中,由一种加载了0.7重量%的Pd的离子交换树脂以及另一种纯酸形式的离子交换树脂形成离子交换树脂催化剂的混合床。所述较低的总体Pd加载能够有效地减少不利的异丙醇副产物的形成,催化剂混合物的高酸度有助于保持高的MIBK产率。另外,两种催化剂都具有类似的粒度分布,比重和体积变化,由此使得催化剂床内根据需要可以获得稳定的混合物或分层。因此,通过使用混合的Pd-掺杂的/酸树脂催化剂体系能够通过减少IPA的形成提高MIBK选择性,每个催化剂床使用较少的Pd,维持具有较高的Pd加载的催化剂相当的高产率,在催化剂床上保持均匀的金属分布。
提供下面的实施例以进一步阐述本发明。在以下实施例中,使用以下缩写:
GC是气相色谱。
IPA以异丙醇。
MIBK是甲基异丁基酮。
MPa是兆帕。
rpm是每分钟转数。
重量%是重量百分数。
C是摄氏度;ml是毫升;μl是微升;s是秒;min是分钟;kg是千克;mg/mL是毫克/毫升;m是米;cm是厘米。
测试方法
产率,转化率和选择性:将反应制得的产物注入气相色谱。对不同的反应产物进行分析和定量。丙酮转化率是通过反应制得产物的丙酮的比率,产物产率是制得的所需产物的量,选择性是通过GC测得的目标产物与全部产物之比。
双柱GC-FID法描述:
载气:来自高压室氮气的N2
注射器0.2μl体积
入口:前部,模式:分流,温度:250℃,压力:5.4psi(37kPa)
分流比:50.0比1,分流流量73.0毫升/分钟;总流量76.6毫升/分钟
气体节约器:在2.00分钟为20.0毫升/分钟
柱:
柱1:Macherei Nagel 726600.Optima Wax.30m x 250μm x 0.25μm
恒定压力,入口:前部,出口:前部
氮气流:压力5.4psi(37kPa),流量0.7ml/min,平均速度20cm/s
柱2:Varian CP9151 VF1701MS毛细管(Capillary)30.0mx 250μm x 0.25μm
恒定压力,入口:前部,出口:后部
氮气流:压力5.4psi(37kPa),流量0.7ml/min,平均速度20cm/s
加热炉:
设定温度:40℃
保持时间:5分钟
升温1:以5.0℃/分钟的速率升温至115℃
升温2:以15.0℃/分钟的速率升温至240℃
最终时间:在240℃保持6.67分钟
总操作时间:35分钟
检测器:
前部FID:加热器:250℃
流量:H2:30ml/min,空气(Air):350ml/min,补偿N2:30ml/min
信号1:数据速率20Hz,峰宽0.01分钟,起始0,结束35分钟
后部FID:加热器:250℃
流量:H2:30ml/min,空气(Air):350ml/min,补偿N2:30ml/min
信号2:数据速率20Hz,峰宽0.01分钟,起始0,结束35分钟
表1:产率、转化率和选择性的测试标样
化合物名称 | CAS# |
丙酮 | |
苯,1,2,4三甲基- | 95-63-6 |
二丙酮醇 | 123-42-2 |
二异丁基酮(DMH1) | 108-83-8 |
2-庚酮,4,6-二甲基-(DMH2) | 19549-80-5 |
异丙醇 | 67-63-0 |
4-甲基-2-戊醇(MIBC) | 108-11-2 |
甲基异丁基酮(MIBK) | 108-10-1 |
3-戊烯-2-酮,4-甲基-(MSO) | 141-79-7 |
戊烷,2-甲基- | 107-83-5 |
实施例
实施例1在小规模间歇式反应器中的混合床催化剂筛选
在AMBERLYSTTMCH28(Pd-加载的离子交换树脂)和AMBERLYSTTM252H(不含Pd的强酸阳离子型树脂)的混合物中使用不同的重量百分比。在1000rpm的转速下进行搅拌的同时,在200psi(1.38MPa)的氢化条件下,使用间歇式反应器,在110℃进行4小时的树脂混合物测试。通过GC分析测定产率,结果列于表1。
表1:在改变AMBERLYST CH28/252H的条件下的产物产率
如表1所示,在CH28∶252H之比低达20∶80的范围内,MIBK的产率保持恒定。只有当CH28的含量低于20%的时候,MIBK的产率下降。CH28从100%变化到20%使得IPA的形成显著减少,IPA是MIBK合成的一个最主要的问题副产物。因此,在较低Pd浸渍的催化剂含量情况下实现了MIBK相对于IPA的改进的选择性,这也代表了相对于使用纯CH28催化剂,成本显著降低(几乎降至五分之一)。为了最大程度提高MIBK的产率,同时IPA的产量尽可能少,优选CH28的含量接近20%。
实施例2通过间歇式反应器来研究选择性数据
表2:在不同Amberlyst CH28比例下的产率%
实施例3比较结果
表3:产率和选择性
Claims (9)
1.一种混合床聚合物催化剂,其包含:
10-90重量%的第一催化剂,所述第一催化剂包括加载了金属的离子交换树脂,所述金属选自以下的至少一种:钯、铂、铱、铑、钌、铜、金和银;以及
10-90重量%的第二催化剂,所述第二催化剂包括缺少金属的强酸性离子交换树脂,所述强酸性离子交换树脂在水中的pKa小于2,
所述金属均匀分布在混合床中;
以第一催化剂的干重为基准计,所述第一催化剂包含0.1-15%的分布在其中的金属离子。
2.如权利要求1所述的催化剂,其特征在于,所述强酸性离子交换树脂包括苯乙烯类强酸阳离子型树脂,其水份保持容量为10-90%,粒度为100-2000微米,体积容量为0.5-7毫当量/升。
3.如权利要求1所述的催化剂,其特征在于,所述金属包括零价金属。
4.如权利要求1所述的催化剂,其特征在于,所述第一催化剂占所述混合床聚合物催化剂的15-25重量%。
5.如权利要求1所述的催化剂,其特征在于,所述金属包括钯。
6.如权利要求1所述的催化剂,其特征在于,所述第二催化剂包括胶体树脂。
7.如权利要求1所述的催化剂,其特征在于,所述第一催化剂的粒度为100微米至2毫米,所述第二催化剂的粒度为100微米至2毫米。
8.如权利要求1所述的催化剂用于以下至少一种基团的氢化的应用:炔、烯、醛、酮、醇、腈、胺和硝基。
9.一种制备酮的方法,该方法包括:
提供一种混合床聚合物催化剂,其包含10-90重量%的第一催化剂,该第一催化剂包含加载了金属的离子交换树脂,所述金属是选自以下的一种或多种:钯、铂、铱、铑、钌、铜、金和/或银,以第一催化剂的干重为基准计,所述第一催化剂包含0.1-15%的分布在其中的金属离子;以及10-90重量%的第二催化剂,所述第二催化剂包括缺少金属的强酸性离子交换树脂,所述金属均匀地分布在混合床中;所述强酸性离子交换树脂在水中的pKa小于2;
将所述金属均匀分布在所述混合床中;以及
合成所述酮以得到0.1-60%的产率。
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CN201110192501.0A Expired - Fee Related CN102309989B (zh) | 2010-06-30 | 2011-06-28 | 混合床聚合物催化剂 |
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US (1) | US8471069B2 (zh) |
EP (1) | EP2402086B1 (zh) |
KR (1) | KR101283371B1 (zh) |
CN (1) | CN102309989B (zh) |
TW (1) | TWI457175B (zh) |
ZA (1) | ZA201104840B (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI457175B (zh) * | 2010-06-30 | 2014-10-21 | Dow Global Technologies Llc | 混合床聚合物催化劑及其用途 |
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 |
JP6042277B2 (ja) * | 2012-07-10 | 2016-12-14 | オルガノ株式会社 | 白金族金属担持触媒及び反応装置 |
KR101369021B1 (ko) * | 2012-10-25 | 2014-02-28 | 한국화학연구원 | 수분 안정성이 향상된 유독성 가스 제거용 저온산화촉매 |
WO2014163950A1 (en) | 2013-03-13 | 2014-10-09 | Dow Global Technologies Llc | Spliced fiber-reinforced outer shell for cylindrical filtration element |
KR20190046918A (ko) * | 2016-09-20 | 2019-05-07 | 롬 앤드 하스 캄파니 | 페놀의 수소화 방법 |
WO2021066300A1 (ko) | 2019-09-30 | 2021-04-08 | 주식회사 엘지화학 | 수소화 반응용 촉매 및 이의 제조방법 |
EP4188898A1 (en) * | 2020-07-29 | 2023-06-07 | DDP Specialty Electronic Materials US, LLC | Process for preparation of a sugar alcohol |
Citations (2)
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CN1426990A (zh) * | 2001-12-19 | 2003-07-02 | 罗姆和哈斯公司 | 金属掺杂的磺化离子交换树脂催化剂 |
CN1457927A (zh) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | 一种钯/树脂催化剂的制备方法 |
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DE1193931B (de) | 1963-06-29 | 1965-06-03 | Rheinpreussen Ag | Verfahren zur einstufigen Herstellung von Methylisobutylketon |
DE1260454B (de) * | 1966-07-07 | 1968-02-08 | Rheinpreussen Ag | Verfahren zur kontinuierlichen einstufigen Herstellung von gesaettigten Carbonylverbindungen |
US3953517A (en) * | 1967-09-08 | 1976-04-27 | Veba-Chemie Aktiengesellschaft | Process for preparing methyl isobutyl ketone and catalyst |
JPS4833724B1 (zh) * | 1968-06-14 | 1973-10-16 | ||
GB1280368A (en) | 1969-10-08 | 1972-07-05 | Showa Denko Kk | Process for the production of methyl isobutyl ketone |
JPS5126769B2 (zh) | 1972-07-25 | 1976-08-09 | ||
AU7839498A (en) * | 1997-06-18 | 2000-01-05 | Catalytic Distillation Technologies | Production of mibk using catalytic distillation technology |
EP0996740B1 (en) | 1997-08-01 | 2005-09-21 | Martek Biosciences Corporation | Dha-containing nutritional compositions and methods for their production |
CN1114585C (zh) * | 1998-04-16 | 2003-07-16 | 中国石化金陵石油化工公司 | 双金属树脂型催化剂及其制备方法 |
CN1101269C (zh) * | 1999-09-17 | 2003-02-12 | 中国石油化工集团公司 | 丙酮合成甲基异丁基酮的催化剂及其制备方法 |
ZA200107297B (en) | 2000-09-15 | 2002-03-11 | Catalytic Distillation Tech | Production of methyl isobutyl ketone. |
US20060135793A1 (en) | 2004-11-26 | 2006-06-22 | Blessing Robert W | Process for the dimerisation of levulinic acid, dimers obtainable by such process and esters of such dimers |
KR100834963B1 (ko) | 2006-10-18 | 2008-06-19 | 금호피앤비화학 주식회사 | 금속이 도핑된 술폰화 양이온교환 수지 촉매 및 이를 이용한 메틸이소부틸케톤의 제조방법 |
TWI457175B (zh) * | 2010-06-30 | 2014-10-21 | Dow Global Technologies Llc | 混合床聚合物催化劑及其用途 |
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2011
- 2011-06-20 TW TW100121362A patent/TWI457175B/zh not_active IP Right Cessation
- 2011-06-21 EP EP11170642.0A patent/EP2402086B1/en not_active Not-in-force
- 2011-06-28 CN CN201110192501.0A patent/CN102309989B/zh not_active Expired - Fee Related
- 2011-06-29 US US13/172,528 patent/US8471069B2/en not_active Expired - Fee Related
- 2011-06-29 KR KR1020110063356A patent/KR101283371B1/ko not_active IP Right Cessation
- 2011-06-30 ZA ZA2011/04840A patent/ZA201104840B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1426990A (zh) * | 2001-12-19 | 2003-07-02 | 罗姆和哈斯公司 | 金属掺杂的磺化离子交换树脂催化剂 |
CN1457927A (zh) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | 一种钯/树脂催化剂的制备方法 |
Also Published As
Publication number | Publication date |
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EP2402086A1 (en) | 2012-01-04 |
US8471069B2 (en) | 2013-06-25 |
EP2402086B1 (en) | 2016-11-02 |
KR20120002464A (ko) | 2012-01-05 |
ZA201104840B (en) | 2012-03-28 |
KR101283371B1 (ko) | 2013-07-08 |
CN102309989A (zh) | 2012-01-11 |
US20120004467A1 (en) | 2012-01-05 |
TW201204462A (en) | 2012-02-01 |
TWI457175B (zh) | 2014-10-21 |
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