CN109312257A - 使用蛋-壳型催化剂选择性氢化植物油的方法 - Google Patents
使用蛋-壳型催化剂选择性氢化植物油的方法 Download PDFInfo
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- CN109312257A CN109312257A CN201780038642.2A CN201780038642A CN109312257A CN 109312257 A CN109312257 A CN 109312257A CN 201780038642 A CN201780038642 A CN 201780038642A CN 109312257 A CN109312257 A CN 109312257A
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- Prior art keywords
- oil
- vegetable oil
- catalyst
- hydrogenation
- metallic catalyst
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- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
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- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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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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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
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Abstract
本发明涉及将多不饱和脂肪酸选择性转化成单不饱和脂肪酸而氢化植物油的方法,和由其获得的产品。通过根据本发明的方法获得的植物油具有特别高的单不饱和脂肪酸含量并适合于用作化学中间体合成的原材料。
Description
描述
本发明涉及选择性氢化植物油的方法。本发明特别涉及能够将多不饱和脂肪酸选择性转化为单不饱和脂肪酸的植物油氢化方法以及由此获得的产品。通过本发明的方法获得的植物油特别具有高的单不饱和脂肪酸含量并尤其适合于用作化学中间体合成的原材料。
由于越来越迫切需要找到替代常规基于石油的来源的可再生来源的原材料,所以植物油现在是化学工业的重要原材料。
例如,WO2008/138892描述了由含有单不饱和脂肪酸甘油三酯的植物油开始的氧化裂解方法,该方法使得可生产对于制备聚酯来说重要的中间体,例如饱和二羧酸、壬二酸或巴西基酸。
众所周知,植物油包含脂肪酸甘油三酯的混合物。这些脂肪酸通常含有16-22个碳原子,并可以是饱和的,例如硬脂酸,单不饱和的,例如油酸,或多不饱和的,例如亚油酸和亚麻酸。
根据获得这些植物油的植物物种的性质,这些植物油具有相当不同的组成,例如单不饱和脂肪酸的不同类型和含量。这极大地限制了植物油作为有机化学工业原材料的应用。
因此,有必要寻找和采用改变植物油组成的方法以促进它们在该领域中的应用。
例如,氢化方法广泛应用于化学领域,特别是应用在油化学领域。存在于不饱和脂肪酸链中的双键事实上可以通过在催化剂如镍、铂、钯或铜存在下的氢加成而加以饱和化。
所述氢化方法是放热的,并且反应速率取决于油的类型、温度、催化剂的活性和浓度、以及氢气压力。尽管被广泛使用,但就选择性而言,这些方法仍然具有显著的局限性。维持多不饱和脂肪酸的高转化率并同时避免形成饱和脂肪酸的可能性尤其受限。
增加选择性的体系是增加反应温度的体系。然而,这可能导致在植物油内存在的不饱和脂肪酸的异构化反应的发生。
因此需要开发一种选择性氢化植物油的新方法,它能将多不饱和脂肪酸选择性转化成单不饱和脂肪酸。
从这一问题开始,现已令人惊奇地发现,经由在具有蛋-壳型活性相分布的负载型金属催化剂存在下操作,甚至在低温下,可以达到在所述油内存在的甘油三酯的多不饱和脂肪酸的显著转化,同时增加或至少维持对单不饱和脂肪酸的选择性。即使当用少量催化剂,在大气压或者略高于大气压的压力下操作时,也能达到这些有利的效果。当水存在和不存在时,也可以有效地进行所述方法。
本发明尤其涉及催化氢化植物油的方法,其中使所述油与分子氢在蛋-壳型负载型金属催化剂,即其中活性相主要分布在所述载体外表面上的催化剂存在下,在有利地小于或等于50℃,优选小于或等于25℃,更优选小于或等于20℃的温度下接触。
事实上已经令人惊奇地发现,通过在这些条件下操作,就将所述油内存在的甘油三酯的多不饱和脂肪酸氢化来说,可改进金属催化剂的催化活性和选择性。
包含钯金属(优选负载在碳或氧化铝上)的蛋-壳型催化剂尤其适合于这一目的。
由于根据本发明的方法,事实上可以实现多不饱和脂肪酸选择性转化成单不饱和脂肪酸,并获得具有高的单不饱和脂肪酸含量的油,它随后尤其适合于用作合成化学中间体的起始材料。
这一组成的结果是,由根据本发明的方法获得的植物油尤其适合于还与其它植物油混合用作起始材料,用于其中无机和有机过氧化物,过酸,硝酸,高锰酸盐,高碘酸盐,O2,O3或其气态混合物用作氧化剂的氧化裂解方法。
使用过氧化物如过氧化氢、以及O2或含有O2的混合物作为氧化剂的氧化裂解方法是优选的。具体实例是申请WO 2008/138892、WO 2011/080296或WO 2013/079849A1中描述的氧化裂解方法。
通过本发明方法获得的油的尤其有利的特征是单不饱和脂肪酸的各种位置异构体的含量。它们可用于例如从可再生资源开始制备各种链长度的双官能分子。例如,根据这种方法的催化氢化富含多不饱和C18脂肪酸的植物油允许获得大量12-十八碳烯羧酸(C18:1(n-6)),其又可以经历上述氧化裂解方法之一而获得可再生C12二羧酸。
从根据本发明的方法获得的植物油尤其可用作氧化裂解方法的起始材料,所述氧化裂解方法包括以下步骤:
a)优选在能够催化烯属双键的氧化反应的催化剂存在下,使不饱和羧酸的甘油三酯与氧化性化合物反应,而获得含有邻位二醇的中间体化合物;
b)优选在能够催化将所述邻位二醇氧化成羧基的反应的催化剂存在下,使所述中间体化合物与氧气、或含有氧气的气态混合物反应,而获得饱和单羧酸和含有饱和二羧酸的甘油三酯。
当获自根据本发明的方法的植物油与其它植物油混合用作氧化裂解方法的原材料时,所述混合物优选含有超过10%的获自本发明方法的植物油。
当存在时,在反应过程中的水量可以变化,相对于金属催化剂的重量,优选保持在400:1或更低,更优选200:1或更低,甚至更优选100:1或更低。水可以在反应开始时存在或在反应过程期间逐步引入,例如通过使特定量氢气饱和。
有利地,除了在催化剂内存在的水以外,不添加水。
根据本发明的一个方面,在反应过程中不存在水。
根据本发明的方法可以氢化植物油,例如豆油,橄榄油,蓖麻油,向日葵油,花生油,玉米油,棕榈油,麻疯果油(jatropha oil),蓟油(thistle oil),如来自刺苞菜蓟(Cynara cardunculus)、乳蓟(Sylibum marianum)的蓟油,红花油,萼距花油(cupheaoil),十字花科油(Brass icaceae oil)如来自海甘蓝(Crambe abyssinica,)、埃塞俄比亚芥(Brassica carinata)、甘蓝型油菜(Brassica napus(colza)),雷斯克勒(Lesquerella)的那些,或它们的混合物。也可以根据本发明氢化废弃的煎炸油或其它废植物油。
使用向日葵油、十字花科油或蓟油如来自刺苞菜蓟(Cynara cardunculus)和乳蓟(Silybum marianum)的蓟油是尤其优选的。
特别地,后者获自属于菜蓟属(Cardueae tribe)的植物物种并且是非常强健的一年生或多年生草本植物,该植物还有的进一步优点在于它们可以在气候不佳的干旱地区种植。
用于根据本发明的方法的催化剂(包括负载型金属催化剂)可呈典型地具有2至4毫米尺寸的片材、颗粒、圆柱粒料或球体形式使用。
可使用的金属催化剂的实例是镍、铂、钯、铜、铁、铑、钌、铱、锇、钼、钨和它们的混合物。
根据本发明的一个优选的方面,所使用的金属催化剂按通常20mg/kg-500mg/kg,优选30-100mg/kg,更优选40-50mg/kg的量包含钯,相对于必须氢化的植物油的量。催化剂的用量可以在这一范围内变化,这取决于催化剂的形式、其表面积和金属催化剂相对于任何载体的浓度。典型地,催化剂包含0.1-10重量%的钯金属;优选催化剂包含0.1-5重量%,更优选0.1-0.5重量%的钯金属。
催化剂中存在的金属负载在本领域中已知的任何载体上,例如在氧化铝,各种形式的碳,包括纳米管,金属氧化物例如CeO2、ZrO2、CrO2、TiO2、MgO、二氧化硅,无机/有机溶胶-凝胶基质,多晶氧化物基底,无定形碳,沸石,硅铝酸盐,碱土金属碳酸盐如碳酸镁、碳酸钙或碳酸钡、硫酸钡,蒙脱石,聚合物基质,多官能树脂,离子交换树脂,陶瓷载体或它们中两种或更多种的混合物。在方法的一个优选形式中,催化剂包含负载在氧化铝或碳上的钯金属。
可以使用本领域技术人员已知的任何技术制备负载型催化剂,例如通过在载体上细分散金属盐,随后将该金属盐还原为金属状态。例如可以通过浸渍、从溶液中吸附、共沉淀或沉积(例如利用化学气相沉积)来进行金属盐的分散阶段。典型地通过在分子氢的气氛存在下加热负载型金属盐来进行所述金属盐的还原阶段。催化剂制备阶段可以独立于根据本发明的氢化方法来进行,或可在其初始阶段中进行。例如,可以将负载型金属盐置于氢化反应器内并在添加植物油之前在氢气气氛中原位还原。对于在根据本发明的方法中使用尤其适合的催化剂是例如在碳上的含5重量%钯(例如作为由Johnson Matthey制造),或0.3重量%钯的蛋-壳型钯。
在本申请中,“蛋-壳”型催化剂规定为这样的催化剂,即其活性金属组分或其前体中的一种或多种主要(例如至少50%)作为外层位于载体的表面上并不分散在载体内。
蛋-壳型的催化剂可以包含大约0.1重量%-大约10重量%,有利地大约0.2重量%-5重量%金属组分,如果还没有全部呈金属状态则表示为转化成金属状态的金属组分的标称重量百分率,基于所述蛋-壳催化剂的重量。
有利地,金属组分的大于50%,例如大于60%或更多,有利地大于80%位于载体的周边外层中。有利地使用负载在碳或γ-氧化铝上的蛋-壳基于钯的催化剂。
有利地,在反应结束时回收催化剂并再循环到随后的氢化反应。
在根据本发明方法的优点当中,存在下述事实:可尤其在基于钯的催化剂存在下进行该方法,且不需要添加用于改进选择性的催化剂促进剂如铜、银、锌、锡、铅、钛、锆、铪、钒、铌、钽、铬、钼、钨或锰。
一般而言,根据本发明的方法可以在一个或多个适合的能够确保适合的物质/液体/固体混合的设备项中进行,如搅拌式反应器、固定床反应器、移动床反应器、流化床或气升式反应器。
在反应结束时,可以利用已知的技术容易地回收催化剂并再使用若干次。在一个优选的实施方案中,根据本发明的催化氢化植物油的方法包括在其期间使催化剂与植物油分离(例如利用过滤或滗析)的步骤。
在搅拌反应器的情况下,特别地,装置的搅拌帮助测定氢气的扩散速度和植物油与氢气之间的接触程度。取决于反应器的体积和构型,可以使用例如为100-1200rpm,更尤其是200-1000rpm的搅拌速度。体系的搅拌速度优选为500-1000rpm。
氢化反应在50℃或更小,优选30℃-0℃,甚至更优选25℃-0℃,甚至更优选小于20℃且大于0℃,例如3℃-18℃的温度下进行。在更高的温度下,已经观察到不饱和酸的更大的顺-反异构化程度,这导致相当大量的反式异构体形成。
一般而言,反式异构体具有比顺式异构体更高的熔点并超过特定的转化水平,这可能导致固相的形成,所述固相例如含有反式9-十八碳烯酸。当与天然存在的植物油(主要含顺式异构体)相比时,含反式异构体的植物油还对由过氧化物引起的氧化反应不太敏感。当所述油经历氧化裂解反应时,这决定更长的反应时间。
可以例如通过在反应开始之前加热反应混合物调节温度。因为氢化反应是放热的,所以反应的进展导致反应混合物内温度的逐渐升高。典型地经由阻止过热的冷却系统控制所述升高,所述过热可能对反应过程具有不利影响。
就分子氢而言,氢化反应典型地在1至15巴的分子氢压力,优选1至10巴,更优选1至6巴下进行,同时维持总的压力小于20巴,优选小于15巴,更优选小于10巴。取决于要求,氢气可以连续地导入到反应器中,调节流量,或以一个或多个等分试样进料,例如3、5或7个等分试样,同时仍维持氢气压力在上述范围内。
该方法有利地在有机溶剂存在下进行,所述有机溶剂优选选自烃,优选具有高于C5的链长度的烃,酯,酮,例如C3-C8酮,C3-C6醇或醚,例如THF,以便降低体系的粘度并增加反应速率。本领域技术人员将容易地能够基于必须氢化的油的溶解性和水在反应混合物中的存在从这些中选择最适合的溶剂。优选的有机溶剂是可以容易回收(例如通过蒸馏)的那些。适合的有机溶剂的具体实例是石油醚、己烷、庚烷、辛烷、丙酮、乙酸乙酯、甲苯、异丁醇、甲基乙基酮、甲基异丁基酮。
有机溶剂和油之间的重量比优选为0.25:1-3:1,更优选0.5:1-2:1。
如本领域中已知的那样,可以添加添加剂例如碱以便进一步改进氢化反应的选择性。所述碱的实例是胺,碱金属、碱土金属的氧化物、氢氧化物或碳酸盐、或铵。碱的具体实例是N-乙基二异丙基胺、三乙胺,二胺类如亚乙基二胺,其同系物和/或衍生物如四甲基乙二胺,四烷基胺,其中该烷基链是例如C2至C6烷基链,环胺如二氮杂双环辛烷或二氮杂双环十一碳烯,氢氧化铵盐例如胆碱或氢氧化四丁基铵。当石油醚用作植物油的溶剂时,胆碱或氢氧化四丁基铵有利地在助溶剂例如甲醇的存在下使用。在这种情况下,甲醇溶解所述氢氧化四丁基铵并形成独立相,其中所述催化剂在反应结束时将分层(partition),从而促进回收。
可以按本领域技术人员已知的方式控制该方法,例如通过测量反应器中的压力并在已经吸收特定量的氢气时中断该反应。
作为替代方案,可以通过取样和分析反应混合物的组成监测反应的过程。可以基于起始植物油的组成例如通过分析不饱和部分的量容易地测定反应完成所要求的氢气的理论量。
根据本发明的方法的持续时间取决于植物油的性质、操作条件、所需转化率和所使用的反应器的尺寸,并典型地为5分钟-6小时,例如60-300分钟。
根据一个优选的方面,根据本发明的氢化反应在0℃至30℃,更优选0℃至25℃,甚至更优选0℃至20℃的温度下进行,优选维持分子氢压力为1至2巴,更优选1至1.5巴。
根据一个尤其优选的方面,反应在18℃至3℃的温度下进行。在这些条件下操作事实上可以达到多不饱和酸的甘油三酯的尤其高的转化率和对于单不饱和酸甘油三酯的选择性,而对于添加剂例如胺没有任何需求。
如果在18℃或以下的温度下进行所述方法,则有利地使用有机溶剂,原因在于粘度增加。尽管如此,这种方法仍要求受限量的有机溶剂以达到令人满意的转化率;例如在这些温度下有利地使用相对于所述油按1:1至2:1的重量比例的溶剂。
现在将用多个实施例来说明本发明,这些实施例在范围方面旨在仅为说明性的,而不限制本发明。
实施例
在下述实施例中,在油样品(140μl)在140μl甲醇化KOH(2N)中酯交换后测定油的羧酸组成。从所述甲醇化溶液中萃取羧酸甲酯到3ml己烷中,然后在配备有火焰离子化检测器(FID)和SLB-IL111 100m×0.25mm×0.2微米毛细管柱(SUPELCO)的气相色谱仪中,在275kPa的恒压下分析。
烘箱的温度程控:100℃(35分钟)-2.5℃/分钟-140℃(30分钟)-5.0℃/分钟-260℃(25分钟),总时间130分钟。
注射器温度:250℃;分流比=250:1;载气:氦气。
如下测定二不饱和酸的转化率(C18:2):
其中∑起始C18:2和∑最终C18:2分别对应于氢化反应之前和之后,相对于总的羧酸组成,C18二不饱和酸的各种异构体的重量%的总和。
如下测定对于单不饱和酸(C18:1)的选择性:
其中Σ最终C18:1和Σ起始C18:1分别对应于氢化反应之后和之前,相对于总的羧酸组成,C18单不饱和酸的各种异构体的重量%的总和,并且Σ起始C18:2和Σ最终C18:2分别对应于氢化反应之前和之后,相对于总的羧酸组成,C18二不饱和酸的各种异构体的重量%的总和。
实施例1
在装有电磁搅拌器和温度计并经由质量流量计与氢气瓶连接的500ml圆筒形反应器中进行氢化反应。
向反应器中加入50g向日葵油,大约110ml己烷和0.05g包含蛋-壳型的5%Pd/C的粉末催化剂(Alfa&Aesar;干燥)。
将反应器与泵连接以除去空气,然后进料H2流。
以700rpm剧烈地搅拌反应器144分钟,在低温保持器中在15℃下保持温度。在反应器的出口处利用计数器测量所吸收的氢气量,该值等于2.1L。
过滤该催化剂,并蒸发有机溶剂,而获得氢化的向日葵油。表1中示出了相对于起始油的组成,在144分钟反应时间之后,通过GC分析测量的相对于总的羧酸组成,氢化油中C18羧酸的重量百分比组成。
亚油酸的转化率是80.5%,对于油酸的选择性是93.3%。
表1
实施例2(对比)
如实施例1中那样进行氢化反应,但是使用0.05g包含5%非蛋-壳Pd/C的粉末催化剂(Aldrich;干燥载体)。
在129分钟后停止反应器;吸收的氢气的量是2.1L。
滤出该催化剂,并蒸发有机溶剂,以便获得氢化的向日葵油。
如表1所示,对亚油酸的转化率仅是75.8%,同时对油酸的选择性是82.2%,即比在相同条件下使用实施例1中的蛋-壳型催化剂获得的选择性小超过10%。
实施例3
在与实施例1相同的反应器中进行氢化反应,装入85g向日葵油,大约100ml异丁醇,300mg水和90mg包含蛋-壳型的5%Pd/C的催化剂(Johnson&Matthey;50%湿度)。
以700rpm剧烈地搅拌反应器214分钟,维持16-17℃的温度。吸收的氢气的量是2.15L。
滤出该催化剂,并蒸发有机溶剂,以便获得氢化的向日葵油。在214分钟的反应时间后在氢化油中的C18羧酸的重量百分率组成示于表1中。
亚油酸的转化率超过89%,对油酸的选择性是94.7%。
Claims (15)
1.植物油的催化氢化方法,其中使所述油与分子氢在负载型金属催化剂存在下接触,其特征在于所述催化剂具有蛋-壳型和所述方法在小于或等于50℃的温度下进行。
2.根据权利要求1的方法,其中所述金属催化剂选自镍、铂、钯、铜、铁、铑、钌、钼、锇、铱、钨和它们的混合物。
3.根据权利要求2的方法,其中所述金属催化剂包含金属钯。
4.根据权利要求3的方法,其中相对于植物油的量,在20mg/kg-500mg/kg金属钯存在下进行所述氢化。
5.根据权利要求3和4中每一项的方法,其中所述金属催化剂包含0.1-10重量%钯金属。
6.根据权利要求1-5中任一项的方法,其中用于所述金属催化剂的载体选自氧化铝,碳,混合氧化物例如CeO2、ZrO2、CrO2、TiO2、MgO、二氧化硅,无机/有机溶胶-凝胶基质,多晶氧化物基底,无定形碳,沸石,硅铝酸盐,碱土金属碳酸盐如碳酸镁、碳酸钙或碳酸钡、硫酸钡,蒙脱石,聚合物基质,多官能树脂,离子交换树脂,陶瓷载体或它们中两种或更多种的混合物。
7.根据权利要求6的方法,其中所述催化剂包含负载在氧化铝或碳上的金属钯。
8.根据权利要求1-7中任一项的方法,其中所述方法在1至15巴的分子氢压力下进行。
9.根据权利要求1-8中任一项的方法,其中所述温度为0℃至30℃。
10.根据权利要求9的方法,其中所述温度为0℃至25℃。
11.根据权利要求1-10中任一项的方法,在选自烃、酯、酮、C3-C6醇、醚的有机溶剂存在下进行。
12.根据权利要求11的方法,其中相对于所述植物油,所述有机溶剂按0.25:1至3:1的重量比例。
13.根据权利要求1-12中任一项的方法,相对于金属催化剂的重量,在400:1或更低的水量存在下进行。
14.根据权利要求1-13中任一项的方法,其中所述植物油选自向日葵油、十字花科油或蓟油。
15.通过根据权利要求1-14中任一项的方法获得的油作为起始材料用于通过氧化裂解反应制备C12二羧酸的用途。
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