CN102712559B - 制备具有提高氢化活性的负载型氢化催化剂的方法 - Google Patents
制备具有提高氢化活性的负载型氢化催化剂的方法 Download PDFInfo
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- CN102712559B CN102712559B CN201080061439.5A CN201080061439A CN102712559B CN 102712559 B CN102712559 B CN 102712559B CN 201080061439 A CN201080061439 A CN 201080061439A CN 102712559 B CN102712559 B CN 102712559B
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- Prior art keywords
- acid
- hydrogenation catalyst
- catalyst
- hydrogenation
- catalyzer
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 55
- 230000000694 effects Effects 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 58
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- 239000010949 copper Substances 0.000 claims description 24
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- 238000011068 loading method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
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- 239000004568 cement Substances 0.000 claims description 13
- 150000002894 organic compounds Chemical class 0.000 claims description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 13
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Abstract
本发明涉及一种制备具有提高氢化活性的负载型氢化催化剂的方法,该催化剂包含在含Al2O3载体材料上的氢化金属和/或氢化金属的氧化物,其中煅制负载型氢化催化剂在其最终成型之前或之后及其用于氢化之前用pH>10的碱溶液在20-120℃的温度下处理1-300小时。
Description
本发明涉及一种制备具有提高氢化活性的负载型氢化催化剂的方法,可通过该方法得到的氢化催化剂,其在将具有羰基的有机化合物氢化中的用途和将具有羰基的有机化合物氢化的相应方法。
在负载型氢化催化剂上将具有羰基的有机化合物氢化是本身已知的。例如,WO 2007/006719描述了用于将羰基化合物氢化的催化剂和方法。使用通过硝酸铜溶液、硝酸铝溶液和硝酸镧溶液与碳酸钠的混合物沉淀而制备的催化剂。将沉淀催化剂干燥并煅烧,以及压制。将压制物与铜片和石墨混合并挤压成片。在用于氢化之前,将这些片用水或蒸汽预处理。指定了处理在100-140℃的温度和1-30巴的压力下进行,并可将所用水借助无机酸如硝酸、硫酸或盐酸,或碳酸钠或氢氧化钠溶液调整至4-9,优选6-8.5的pH。
发现催化剂的增强氢化活性和选择性,同时保持成型体的高稳定性。
然而,催化剂的起始活性对一些应用而言仍需改进。
因此,本发明的目的是提供一种制备具有提高氢化活性的负载型氢化催化剂而不降低负载型催化剂的选择性或机械稳定性的方法。
根据本发明,本发明的目的通过一种制备具有提高氢化活性的负载型氢化催化剂的方法实现,所述催化剂包含在含Al2O3载体材料上的氢化金属和/或氢化金属的氧化物,其中所述煅制负载型氢化催化剂在其最终成型之前或之后并且在其用于氢化之前在20-120℃的温度下用pH>10的碱溶液处理1-300小时。
根据本发明已发现,具体载体材料中包含氧化铝的负载型氢化催化剂的情况下,催化剂的活性可通过在>10的pH下碱处理而显著增强,而不会不利地影响选择性和机械稳定性。这涉及用pH>10的碱溶液或在>10的pH下处理。
术语“负载型氢化催化剂”包括除一种或多种氢化金属外还包含载体材料的催化剂。例如催化剂可以为其中将催化剂载体通过用氢化金属浸渍而处理的那些。还包括通过共沉淀,即其中氢化金属或其盐或氧化物与载体材料一起从前体溶液中沉淀而制备的催化剂。一般而言,催化剂可通过任何合适的方法得到,条件是氢化金属和含Al2O3载体材料彼此并排存在。催化剂可以为无载体催化剂、浸渍催化剂、蛋壳型催化剂或沉淀催化剂。合适的催化剂例如描述于WO 2007/006719、US 2008/0299390、US 2008/0071120和US 7,510,591中。
根据本发明制备的负载型氢化催化剂包含含Al2O3载体材料。载体材料优选包含大于50重量%,更优选大于75重量%Al2O3。它可以为纯Al2O3载体或还包含例如其它金属氧化物如氧化铈、二氧化钛、氧化锆、二氧化硅和/或氧化镧的含Al2O3载体材料。另外,载体除铝外还可包含其它金属。任何其余部分优选还包含金属氧化物。
所用氢化金属可以为用于氢化催化剂中的所有常规活性金属。氢化金属优选选自化学元素周期表第8-11族,更优选选自化学元素周期表第10和11族。氢化金属更优选包含铜、铁、镍、铑、钌、钯或铂,或选自这些或其混合物。
尤其对于将羰基化合物氢化成相应的醇,负载型铜催化剂在工业上大规模使用。也可根据本发明使用的这种催化剂包含载体材料上载的活性材料。可通过任何所需方法将活性材料应用于现存的载体材料上或与载体材料共沉淀。
在本发明制备方法中,将煅制负载型氢化催化剂碱处理。通常将例如通过共沉淀制备的催化剂在沉淀之后洗涤,干燥并煅烧。这之后可以为压片或挤出步骤和另外的煅烧。在通过浸渍制备的催化剂的情况下,浸渍和干燥之后也是煅烧,其后又可以为另一成型步骤。
用于本发明方法中的催化剂材料已经受先前制备中所提到的至少一个煅烧步骤。催化剂材料可包含已经受最终成型的催化剂,或在第一煅烧之后得到的催化剂粉末。
在本发明方法中,处理用pH>10,优选>11,更优选>12,尤其是>13的碱溶液进行。用于处理的碱溶液优选具有所述pH,或所述pH存在于用碱处理催化剂的过程中。
根据本发明,可使用任何合适的碱溶液。优选使用碱的水、醇或混合水/醇溶液。有用的醇的实例为链烷醇,优选C1-4链烷醇,例如甲醇、乙醇、丙醇、异丙醇或丁醇。在水/醇溶液中,醇组分优选不大于30重量%,更优选不大于20重量%,尤其是不大于10重量%。特别优选用水溶液操作。
所用碱可在宽范围内自由选择。碱溶液优选包含碱金属氢氧化物或碱土金属氢氧化物或其混合物。特别合适的碱金属氢氧化物为氢氧化钠溶液或氢氧化钾溶液。特别合适的碱土金属氢氧化物为氢氧化镁、氢氧化钙和氢氧化钡。
碱溶液更优选包含氢氧化钠或氢氧化钾,尤其是氢氧化钠。
特别优选用氢氧化钠水溶液处理。
用碱溶液处理通过将催化剂用碱溶液喷雾或将催化剂浸入碱溶液中而进行,在这种情况下催化剂可同时机械移动。优选用足以完全覆盖催化剂的碱溶液的量作业。处理过程中的温度为20-120℃,优选35-105℃,尤其是50-100℃。处理时间可根据碱浓度或pH和温度选择。它一般为1-300小时,优选5-200小时,尤其是10-150小时。
特别优选用0.3-3.0摩尔氢氧化钠水溶液处理,特别优选用0.5-2.0摩尔氢氧化钠水溶液的那些。pH尤其为13.5以上或14以上。
用碱溶液处理可浸出小部分存在于载体中的氧化铝。尤其是在处理的成型体的边缘区域,可发生氧化铝的贫化。由于用碱溶液处理,一部分以无定形或X射线无定形形式存在的氧化铝同样可转化成细晶勃姆石(AlOOH)。载体材料中这些结构变化可以为增强活性的成因。
用碱溶液处理可使氢化催化剂中和/或煅制催化剂粉末中的铝含量作为元素铝计算降低0-6重量%,优选0.1-6重量%,尤其是0.1-3重量%。
活性的上升,不像在常规阮内(Raney)金属体系的情况下可归因于金属铝的完全浸出和伴随的金属表面积提高。在根据本发明处理的催化剂中,仅显著更小部分的氧化铝,此时为氧化铝、羟基氧化铝和/或氢氧化铝从负载型催化剂如片中浸出。这一般不会显著改变氢化金属的表面积。
根据本发明特别优选处理如WO 2007/006719所述制备的催化剂。
这类催化剂以一种如下方法制备,其中:
-提供包含氧化铜和氧化铝和至少一种铁、镧、钨、钼、钛、锆、锡或锰的氧化物的氧化材料,
-将粉状金属铜、铜片、粉状水泥、石墨或其混合物加入氧化材料中,
-并使所得混合物成型为成型体,和
-通过本发明方法处理成型体。
氧化材料更优选包含基于煅烧之后的氧化材料的总重量,
-比例为50≤x≤80重量%,优选55≤x≤75重量%的氧化铜,
-比例为15≤y≤35重量%,优选20≤y≤30重量%的氧化铝
-比例为1≤z≤30重量%,优选2≤z≤25重量%的至少一种铁、镧、钨、钼、钛、锆、锡或锰的氧化物,
其中80≤x+y+z≤100,尤其是95≤x+y+z≤100,在以上意义上的氧化材料中不包含水泥。
加入的金属铜的比例基于氧化材料的总重量优选为1-40重量%。
石墨优选以基于氧化材料的总重量0.5-5重量%的量加入。
制备起始催化剂的本发明优选方法详细描述于下文中。
本发明方法中所用催化剂的特征是铜活性组分、铝组分和至少一种铁、镧、钨、钼、钛、锆、锡或锰的氧化物组分优选用碳酸钠溶液同时或依次沉淀,然后干燥,煅烧,压片或挤出,并再一次煅烧。
特别地,以下沉淀方法是有用的:
A)将铜盐溶液、铝盐溶液和铁、镧、钨、钼、钛、锆、锡或锰盐的溶液,或包含铜盐、铝盐和铁、镧、钨、钼、钛、锆、锡或锰盐的溶液用碳酸钠溶液并行或依次沉淀。随后将沉淀材料干燥并任选煅烧。
B)将铜盐溶液和铁、镧、钨、钼、钛、锆、锡或锰的溶液,或包含铜盐和至少一种铁盐的溶液沉淀于预制氧化铝载体上。在特别优选的实施方案中,这以粉末形式存在于水悬浮液中。然而,载体材料也可以以球、挤出物、碎片或片的形式存在。
B1)在一个实施方案(I)中,铜盐溶液和铁、镧、钨、钼、钛、锆、锡或锰盐的溶液,或包含铜盐和铁、镧、钨、钼、钛、锆、锡或锰盐的溶液优选用碳酸钠溶液一起沉淀。所用初始进料为氧化铝载体材料的水悬浮液。
将由A)或B)产生的沉淀固体以常规方式过滤并优选洗涤以使它们不含碱,例如如DE 19809418.3所述。
将来自A)和B)的最终产物在50-150℃,优选120℃的温度下干燥,随后合适的话在一般200-600℃下,尤其是在300-500℃下煅烧优选两小时。
用于A)和/或B)的起始物质原则上可以为所有可溶于应用中所用溶剂中的Cu(I)和/或Cu(II)盐,例如硝酸盐、碳酸盐、乙酸盐、草酸盐或铵配合物,类似的铝盐,和铁、镧、钨、钼、钛、锆、锡或锰盐。对于根据A)和B)的方法,特别优选使用硝酸铜。
在本发明方法中,优选将上述干燥和任选煅烧粉末加工成片、环、环形片、挤出物、蜂巢或类似成型体。为此,现有技术的所有合适方法是可能的。特别优选使用直径d和高度h<5mm的催化剂成型体或催化剂挤出物、直径d<6mm的催化剂球或泡孔直径rz<5mm的催化剂蜂巢。氧化材料的组成一般使得氧化铜的比例为40-90重量%,铁、镧、钨、钼、钛、锆、锡或锰的氧化物的比例为0-50重量%,且氧化铝的比例为至多50重量%,每种情况下基于上述氧化组分之和的总重量,这三种氧化物一起构成煅烧之后的氧化材料的至少80重量%,以上意义上的氧化材料中不包含水泥。
在本发明用碱溶液处理之后,优选将催化剂再次洗涤,干燥和任选再一次煅烧。
可甚至更详细地描述如上所述优选的催化剂:
一般而言,将粉状铜、铜片或粉状水泥或石墨或其混合物以每种情况下基于氧化材料的总重量0.5-40重量%,优选2-20重量%,更优选3-18重量%加入氧化材料中。
所用水泥优选为高铝水泥。高铝水泥更优选基本由氧化铝和氧化钙组成,更优选由约75-85重量%氧化铝和约15-25重量%氧化钙组成。另外,也可使用基于氧化镁/氧化铝、氧化钙/氧化硅和氧化钙/氧化铝/氧化铁的水泥。
特别地,氧化材料可具有基于氧化材料的总重量至多10重量%,优选至多5重量%比例的至少一种选自元素Re、Fe、Ru、Co、Rh、Ir、Ni、Pd和Pt的其它组分。
在本发明方法的另一优选实施方案中,除铜粉、铜片或水泥粉或其混合物外,将石墨在成型为成型体之前加入氧化材料中。优选加入足够的石墨使得可更好地进行成型为成型体。在优选实施方案中,加入基于氧化材料的总重量0.5-5重量%石墨。石墨在铜粉、铜片或水泥粉或其混合物之前还是之后,还是同时加入氧化材料中是不重要的。
在将铜粉、铜片或水泥粉或其混合物,和如果合适的话石墨加入氧化材料中之后,任选将成型之后得到的成型体经一般0.5-10小时,优选0.5-2小时的期间煅烧至少一次。该至少一个煅烧步骤中的温度一般为200-600℃,优选250-500℃,更优选270-400℃。
在用水泥粉成型的情况下,可有利地将所得成型体在煅烧之前用水润湿,随后将它干燥。
在用作氧化形式的催化剂的情况下,将成型体在与氢化溶液接触之前用还原气体如氢气,优选氢气/惰性气体混合物,尤其是氢气/氮气混合物,在20-500℃,优选150-350℃,尤其是180-200℃的温度下预还原。优选使用氢气含量为1-100体积%,更优选1-50体积%的混合物。
在优选实施方案中,将本发明成型体在用作催化剂之前以本身已知的方式通过用还原介质处理而活化。活化预先在还原烘箱中或在放置于反应器中之后进行。当将催化剂预先在还原烘箱中活化时,将它放入反应器中并在氢气压力下直接与氢化溶液接触。根据氢化金属,例如如在Cu或Ni的情况下,活化催化剂是高度自燃的。干活化催化剂与空气的直接接触因此容易导致对催化剂的损害和严重的安全危害。如果催化剂预先在还原烘箱中活化,则因此可明智地将活化催化剂用惰性溶剂覆盖以运输,然后将它们以溶剂-润湿的形式放入反应器中。为此合适的实例为水、醇或适度挥发性或非挥发性链烷烃。特别有利地,输送至反应器中可以在对后续工艺而言固有的物质如反应物(通常羰基化合物)或产物(通常醇)中进行。作为选择,也可将活化催化剂输送并放入在惰性气体如氮气或氩气下的反应器中。
通过本发明方法制备的成型体的优选使用领域为具有羰基的有机化合物在固定床中的氢化。然而,其它实施方案,例如与向上和向下运动的催化剂材料的流化反应同样是可能的。氢化可在气相或液相中进行。优选在液相中,例如以滴流模式或以液相模式进行氢化。当以滴流模式作业时,使待氢化的包含羰基化合物的液体反应物流过在氢气压力下的置于反应器中的催化剂床,其在催化剂上形成液体薄膜。相反,当以液相模式作业时,将氢气引入充满液体反应混合物的反应器中,在此过程中氢气以上升气泡通过催化剂床。
在一个实施方案中,将待氢化的溶液以直程泵送通过催化剂床。在本发明方法的另一实施方案中,在通过反应器之后一部分产物作为产物流连续地取出并任选通过如上定义的第二反应器。将另一部分产物与包含羰基化合物的新鲜反应物一起返回供入反应器中。该程序在下文中称为循环模式。
当选择滴流模式作为本发明方法的实施方案时,此处优选循环模式。进一步优选使用主反应器和后反应器以循环模式作业。
本发明方法适于将羰基化合物如醛和酮、羧酸、羧酸酯、羧酸酐或内酯氢化成相应的醇,优选脂族和脂环族、饱和和不饱和羰基化合物。在芳族羰基化合物的情况下,不想要的副产物可通过芳环的氢化而形成。羰基化合物可带有其它官能团如羟基或氨基。不饱和羰基化合物一般被氢化成相应的饱和醇。如本发明上下文中所用,术语“羰基化合物”包括具有C=O基团的所有化合物,包括羧酸及其衍生物。应当理解也可将两种或多于两种羰基化合物的混合物一起氢化。也可将单独羰基化合物氢化以包含大于一个羰基。
优选使用本发明方法将脂族醛、羟基醛、酮、酸、酯、酐、内酯和糖氢化。
优选的脂族醛为支化和非支化、饱和和/或不饱和脂族C2-C30醛,例如如可通过具有内或末端双键的线性或支化烯烃羰基合成得到的。也可将还包含大于30个羰基的低聚化合物氢化。
脂族醛的实例包括:甲醛、丙醛、正丁醛、异丁醛、戊醛、2-甲基丁醛、3-甲基丁醛(异戊醛)、2,2-二甲基丙醛(新戊醛)、己醛、2-甲基戊醛、3-甲基戊醛、4-甲基戊醛、2-乙基丁醛、2,2-二甲基丁醛、3,3-二甲基丁醛、辛醛、癸醛、戊二醛。
除所述短链醛外,长链脂族醛也尤其合适,如例如通过线性α-烯烃羰基合成得到的。
特别优选烯醇化产物,例如2-乙基己烯醛、2-甲基戊烯醛、2,4-二乙基辛烯醛或2,4-二甲基庚烯醛。
优选的羟基醛为C3-C12羟基醛,例如如可通过脂族和脂环族醛和酮本身或与甲醛醇醛缩合反应而得到的。实例为3-羟基丙醛、二羟甲基乙醛、三羟甲基乙醛、3-羟基丁醛、3-羟基-2-乙基己醛、3-羟基-2-甲基戊醛、2-羟甲基丙醛、2,2-二羟甲基丙醛、3-羟基-2-甲基丁醛、3-羟基戊醛、2-羟甲基丁醛、2,2-二羟甲基丁醛(DMB)、羟基新戊醛。特别优选羟基新戊醛(HPA)和二羟甲基丁醛(DMB)。
优选的酮为丙酮、丁酮、2-戊酮、3-戊酮、2-己酮、3-己酮、环己酮、异佛尔酮、甲基异丁基酮、一缩二丙酮、苯乙酮、苯丙酮、二苯甲酮、亚苄基丙酮、二亚苄基丙酮、亚苄基苯乙酮、2,3-丁二酮、2,4-戊二酮、2,5-己二酮和甲基乙烯基酮。
也可转化羧酸及其衍生物,优选具有1-20个碳原子的那些。应特别提到以下:
羧酸,例如甲酸、乙酸、丙酸、丁酸、异丁酸、正戊酸、三甲基乙酸(“新戊酸”)、己酸、庚酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、丙烯酸、甲基丙烯酸、油酸、反油酸、亚油酸、亚麻酸、环己烷羧酸、苯甲酸、苯乙酸、邻-甲苯酸、间-甲苯酸、对-甲苯酸、邻-氯苯甲酸、对-氯苯甲酸、邻-硝基苯甲酸、对-硝基苯甲酸、水杨酸、对-羟基苯甲酸、邻氨基苯甲酸、对-氨基苯甲酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸;
羧酸酯,例如上述羧酸的C1-C12烷基酯,尤其是甲酸甲酯、乙酸乙酯、丁酸丁酯、邻苯二甲酸二烷基酯、间苯二甲酸二烷基酯、对苯二甲酸二烷基酯、己二酸二烷基酯、马来酸二烷基酯,例如这些酸的二甲基酯,(甲基)丙烯酸甲酯、丁内酯、己内酯和聚羧酸酯如聚丙烯酸和聚甲基丙烯酸酯和它们的共聚物和聚酯,例如聚甲基丙烯酸甲酯,对苯二甲酸酯和其它工业塑料,在这种情况下氢解,即特别进行将酯转化成相应酸和醇;
脂肪;
羧酸酐,例如上述羧酸的酐,尤其是乙酸酐、丙酸酐、苯甲酸酐和马来酸酐;
羧酰胺,例如甲酰胺、乙酰胺、丙酰胺、硬脂酰胺、对苯二甲酰胺。
也可转化羟基羧酸,例如乳酸、苹果酸、酒石酸或柠檬酸,或氨基酸如甘氨酸、丙氨酸、脯氨酸和精氨酸,和肽。
特别优选的待氢化有机化合物为饱和或不饱和羧酸、羧酸酯、羧酸酐、醛或内酯或其两种或更多种的混合物。
因此,本发明还涉及一种如上所述方法,其中有机化合物为羧酸、羧酸酯、羧酸酐、醛或内酯。
这些化合物的实例包括马来酸、马来酸酐、琥珀酸、琥珀酸酐、己二酸、6-羟基己酸、2-环十二烷基丙酸,上述酸的酯如甲基、乙基、丙基或丁基酯。其它实例为羟基新戊醛(HPA)、二羟甲基丁醛(DMB)、γ-丁内酯和己内酯。
在非常特别优选的实施方案中,本发明涉及一种如上所述方法,其中有机化合物为己二酸或己二酸酯或其混合物。
可将待氢化的羰基化合物单独或作为与氢化反应的产物的混合物供入氢化反应器中,在这种情况下,这可以以未稀释的形式或使用另外溶剂进行。合适的另外溶剂特别是水、醇如甲醇、乙醇和在反应条件下形成的醇。优选的溶剂为水、THF和NMP;特别优选水。
各自优选以循环模式进行的滴流和液相模式的氢化一般在50-350℃,优选70-300℃,更优选100-270℃的温度和3-350巴,优选5-330巴,更优选10-300巴的压力下进行。
在非常特别优选的实施方案中,本发明催化剂用于制备己二醇和/或己内酯的方法中,如DE 196 07 954、DE 196 07 955、DE 196 47 348和DE 196 47 349所述。
本发明方法使用本发明催化剂实现高转化率和选择性。同时本发明催化剂具有高化学和机械稳定性。
本发明还涉及可通过上述方法得到的负载型氢化催化剂。
本发明还涉及如可根据本发明得到的负载型氢化催化剂在将具有羰基的有机化合物氢化中的用途。有机化合物优选为羧酸、羧酸酯、羧酸酐、醛或内酯。
本发明还涉及一种在氢化催化剂上将具有羰基的有机化合物氢化的方法,其中使用可如上所述得到的负载型氢化催化剂。
优选在固定床反应器中在约200巴的氢气压力和约200℃的温度下进行本方法。通常,以不大于0.1-0.6kg/(l*h)的催化剂时空速实现大于99.5%的转化率。本发明催化剂的使用在一些情况下容许催化剂时空速成三倍至1.8kg/(l*h),而没有观察到转化率的下降(至小于99.5%)。这不会不利地影响选择性或成型体的机械稳定性。
通过实施例详细地说明本发明。
实施例
在实施例中,根据WO 2007/006719,实施例1的Cu/Al2O3/La2O3催化剂以尺寸为1.5×1.5mm或3×3mm的片的形式使用。所选择的实例反应为己二酸二甲酯氢化成1,6-己二醇。另外,还检查二羟甲基丁醛(DMB)氢化成三羟甲基丙烷。
固态催化剂的机械稳定性借助侧压强度测定。侧压强度用来自Zwick的Z 2.5/T 919仪器测定。
I.催化剂的制备:
对比例:
制备相当于WO 2007/006719 A1的实施例1。压片随着加入3重量%石墨和15重量%铜片进行以得到1.5×1.5mm片。
因此制备的催化剂包含56重量%Cu元素、11.3重量%Al元素和3.2重量%La元素。氧化和未使用状态的侧压强度平均为67N。
实施例1:
将685g根据对比例的催化剂片在室温下用1000ml 0.5M NaOH处理48小时。随后将取出的催化剂片用蒸馏水洗涤至中性并在120℃下干燥16小时。因此制备的催化剂包含53重量%Cu元素、10.3重量%Al元素和3.1重量%La元素。氧化和未使用状态的侧压强度平均为69N。
实施例2:
将1500g根据对比例(相同方法,不再压缩和压片)的催化剂粉末在50℃下经126小时搅入具有6000ml 2.0M NaOH的悬浮液中。将热悬浮液不经稀释而过滤并用冷蒸馏水洗涤至中性。将滤饼在120℃下干燥16小时。使干滤饼通过0.8mm筛并与3%石墨和15%铜片压制成1.5×15mm片。将片在350℃下后煅烧两小时。因此制备的催化剂包含59重量%Cu元素、6.9重量%Al元素和3.6重量%La元素。氧化和未使用状态的侧压强度平均为46N。
活化:
将所有催化剂以本领域技术人员熟悉的程序在1巴和180℃的温度下用N2/H2混合物还原。
II.己二酸二甲酯氢化成1,6-己二醇
对比例
将200ml根据对比例制备的催化剂以活化形式装入夹套油热管式反应器(直径14mm)中。在200℃、200巴氢气压力和200L(STP)/h氢气进料下以不同的进料速率连续地计量加入己二酸二甲酯。反应器以单程操作。反应器可在至多0.6g/(ml*h)的WHSV范围内以>99.5%的酯转化率和>99.7%的1,6-己二醇选择性操作。
实施例1
将160ml根据实施例1制备的催化剂以活化形式引入夹套油热管式反应器(直径14mm)中。在200℃、200巴氢气压力和200L(STP)/h氢气进料下以不同的进料速率连续地计量加入己二酸二甲酯。反应器以单程操作。反应器可在至多1.8g/(ml*h)的WHSV范围内以>99.7%的酯转化率和>99.5的1,6-己二醇选择性操作。
实施例2
将200ml根据实施例2制备的催化剂以活化形式引入夹套油热管式反应器(直径14mm)中。在200℃、200巴氢气压力和200L(STP)/h氢气进料下以不同的进料速率连续地计量加入己二酸二甲酯。反应器以单程操作。反应器可在至多1.5g/(ml*h)的WHSV范围内以>99.8%的酯转化率和>99.8的1,6-己二醇选择性操作。
III.二羟甲基丁醛(DMB)氢化成三羟甲基丙烷(TMP)
对比例
将150ml根据对比例制备的催化剂活化并引入油热套管式反应器中。在100℃和90巴氢气压力下以不同的进料速率连续地计量加入70%DMB水溶液。反应器以6:1的循环:进料比操作。系统可在至多0.2ml/(ml*h)的LHSV范围内以>99.6%的醛转化率和>96%的TMP选择性操作。
实施例1
将150ml根据实施例1制备的催化剂活化并引入油热套管式反应器中。在100℃和90巴氢气压力下以不同的进料速率连续地计量加入70%DMB水溶液。反应器以6:1的循环:进料比操作。反应器可在至多0.5ml/(ml*h)的LHSV范围内以>99.9%的酯转化率和>95%的TMP选择性操作。
Claims (9)
1.一种制备具有提高氢化活性的负载型氢化催化剂的方法,所述催化剂包含在含Al2O3载体材料上的氢化金属和氢化金属的氧化物,其中所述煅制负载型氢化催化剂在其最终成型之前或之后及在其用于氢化之前在20-100℃的温度下用pH>10的碱溶液处理10-200小时,且其中提供包含氧化铜和氧化铝和至少一种铁、镧、钨、钼、钛、锆、锡或锰的氧化物的氧化材料,将粉状金属铜、铜片、粉状水泥、石墨或其混合物加入氧化材料中并使所得混合物成型为成型体。
2.根据权利要求1的方法,其中所述碱溶液包含碱金属氢氧化物或碱土金属氢氧化物或其混合物。
3.根据权利要求2的方法,其中所述碱溶液包含氢氧化钠。
4.根据权利要求1-3中任一项的方法,其中用碱的水溶液进行处理。
5.根据权利要求1-3中任一项的方法,其中所述氢化金属包含铜。
6.可通过根据权利要求1-3中任一项的方法得到的负载型氢化催化剂。
7.根据权利要求6的负载型氢化催化剂在将具有羰基的有机化合物氢化中的用途。
8.根据权利要求7的用途,其中所述有机化合物为羧酸、羧酸酯、羧酸酐、醛或内酯。
9.一种在氢化催化剂上将具有羰基的有机化合物氢化的方法,其包括使用可通过根据权利要求1-3中任一项的方法得到的负载型氢化催化剂。
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EP3024572A1 (en) * | 2013-06-27 | 2016-06-01 | Clariant Corporation | Manganese oxide-stabilized zirconia catalyst support materials |
TW201536734A (zh) | 2014-03-12 | 2015-10-01 | Basf Se | 甲酸鹽的分解 |
US11673125B2 (en) | 2016-08-18 | 2023-06-13 | The University Of Chicago | Metal oxide-supported earth-abundant metal catalysts for highly efficient organic transformations |
CN108014802A (zh) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | 制备醇的催化剂及使用方法 |
CN108014805A (zh) * | 2016-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | 制备醇的催化剂及其方法 |
KR102245932B1 (ko) * | 2017-10-23 | 2021-04-28 | 주식회사 엘지화학 | 트리메틸올프로판의 제조방법 |
CN111215079B (zh) * | 2018-11-26 | 2023-02-03 | 中国科学院大连化学物理研究所 | 一种采用镍基多相催化剂用于醛类加氢制醇类反应的方法 |
CN110639513A (zh) * | 2019-10-21 | 2020-01-03 | 大连理工大学 | 一种己二酸直接加氢制1,6-己二醇催化剂的制备方法及应用 |
KR102293261B1 (ko) * | 2019-11-15 | 2021-08-23 | 한양대학교 산학협력단 | 구리 담지 촉매 및 이를 이용한 퓨란계 화합물의 선택적 수소화 방법 |
CN111715238B (zh) * | 2020-07-01 | 2022-08-05 | 万华化学集团股份有限公司 | 一种加氢催化剂及其制备方法和应用 |
CN112517018B (zh) * | 2020-11-30 | 2022-08-05 | 万华化学集团股份有限公司 | 一种2,2-二羟甲基丁醛加氢制备三羟甲基丙烷的催化剂及其制备方法和应用 |
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CN102712559A (zh) | 2012-10-03 |
PL2501667T3 (pl) | 2017-04-28 |
WO2011061185A2 (de) | 2011-05-26 |
WO2011061185A3 (de) | 2011-10-13 |
MY160585A (en) | 2017-03-15 |
US9132417B2 (en) | 2015-09-15 |
TWI490034B (zh) | 2015-07-01 |
JP5536226B2 (ja) | 2014-07-02 |
BR112012011816A2 (pt) | 2016-03-08 |
KR20120084795A (ko) | 2012-07-30 |
US20120245394A1 (en) | 2012-09-27 |
EP2501667A2 (de) | 2012-09-26 |
MX2012005666A (es) | 2012-06-19 |
CA2780686A1 (en) | 2011-05-26 |
TW201134548A (en) | 2011-10-16 |
JP2013510714A (ja) | 2013-03-28 |
EP2501667B1 (de) | 2016-11-02 |
ES2612957T3 (es) | 2017-05-19 |
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