CN1964783A - 基于氧化铜的催化剂挤出物及其用于氢化羰基化合物的用途 - Google Patents
基于氧化铜的催化剂挤出物及其用于氢化羰基化合物的用途 Download PDFInfo
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- CN1964783A CN1964783A CNA2004800368200A CN200480036820A CN1964783A CN 1964783 A CN1964783 A CN 1964783A CN A2004800368200 A CNA2004800368200 A CN A2004800368200A CN 200480036820 A CN200480036820 A CN 200480036820A CN 1964783 A CN1964783 A CN 1964783A
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- Prior art keywords
- catalyst
- oxide
- acid
- weight
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- 150000001728 carbonyl compounds Chemical class 0.000 title abstract description 5
- 239000005751 Copper oxide Substances 0.000 title abstract 2
- 229910000431 copper oxide Inorganic materials 0.000 title abstract 2
- 239000012876 carrier material Substances 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 38
- 239000000853 adhesive Substances 0.000 claims description 26
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- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
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Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- 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
- C07C29/136—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 of >C=O containing groups, e.g. —COOH
- C07C29/147—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 of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
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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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Abstract
本发明涉及一种挤出物形式的催化剂,其包含5-85重量%氧化铜并且包含在活性组合物中的并作为粘合剂的相同氧化物载体材料。本发明还涉及该催化剂用于氢化羰基化合物的用途。
Description
本发明涉及催化剂成型体,优选是挤出物的形式,该催化剂成型体是基于包含氧化铜和同时作为粘合剂的氧化物载体的活性组合物,并且本发明涉及它们用于氢化羰基化合物的用途。
铜催化剂在化学工业上具有广泛的用途。负载的铜催化剂是对于羰基化合物如羧酸酯和酸酐的氢化、醛或硝基化合物的氢化而言的合适选择。这些催化剂一般以丸状成型体生产和应用。
改善这些催化剂、例如它们在后续反应的选择性方面的一种可能方式是优化成型体的几何形态和针对具体应用的孔隙率。但是,这种优化对催化剂丸存在着局限性,因为小的多孔丸不再具有满意的机械强度或者生产成本变得不合比例的昂贵。
因此,本发明的目的是寻找一种优化的催化剂系统,其弱化了现有技术催化剂丸的上述缺陷。已经令人惊奇地发现,利用合适的挤出方法和合适的粘合剂与粘合剂量能够生产出具有期望性能的催化剂成型体。
基于挤出的含铜材料的催化剂成型体原则上可由文献获知。
因而,Müller等人在Journal of Catalysis,218,2003,第419-426页描述了氧化铜/氧化锌催化剂挤出物的生产,其具有氧化铝水合物作为粘合剂材料,其中所述的氧化铝作为γ-氧化铝存在于成品催化剂中。其中没有描述有利于本文所述应用的无锌催化剂。这些挤出物的缺点在于与没有被挤出的相应系统相比,它们的活性表面积被显著降低。另外,所描述的挤出物形式的催化剂(CuO/ZnO)活性组合物被粘合剂(Al2O3)稀释,这进一步降低了活性。
在WO 97/34694的实施例22中,描述了由其中无任何其它添加剂的共沉淀CuO/Al2O3粉末生产催化剂挤出物。但是,成型体所达到的机械稳定性和孔隙率不能完全令人满意。所述实施例中达到的孔隙率仅与压片材料的孔隙率相当。
因此,本发明的目的是提供一种催化剂,该催化剂易于生产并且具有高机械稳定性和良好的催化活性,尤其是对羰基化合物的氢化具有良好的催化活性。
现在已经发现,包含氧化铜和氧化物载体材料作为活性组分以及另外与所述载体材料匹配的氧化物粘合剂的催化剂成型体,优选是挤出物的形式,易于在工业上生产并且也导致高的活性和选择性以及高稳定性。
本发明提供了一种催化剂成型体,优选是挤出物形式,其包含5-85重量%的氧化铜,以及在活性组合物中的且作为粘合剂的相同氧化物载体材料。
本发明的催化剂包含氧化铜和氧化物载体材料作为活性组分,所述氧化铜在合适时是还原形式,和所述氧化物载体材料是选自氧化铝、氧化钛、氧化锆、二氧化硅、氧化锰和它们的混合物。作为载体材料,优选使用氧化铝,其尤其以X射线无定形氧化物的形式存在于催化剂中。所述催化剂可任选地以最高20重量%、优选最高10重量%的比例包含来自元素周期表1-14族(旧IUPAC命名法的IA-VIIIA和IB-IVB族)元素的一种或多种其它金属或它们的化合物,优选氧化物。如果氧化锌作为可选的其它金属存在于所述催化剂中,则氧化锌的比例优选<5重量%,特别优选<1重量%,并且尤其<500ppm。
代替氧化物本身,所述活性组分还可以部分或全部地包含氧化铜和氧化物载体材料的合适的前体化合物,例如以氧化物的水合物、氢氧化物和/或碳酸盐的形式。氧化铜优选作为与氧化物载体材料的紧密混合物的形式存在于所述活性组分中。
氧化铜或氧化铜的前体化合物在活性组分中的比例是从>10重量%到98重量%,优选30-95重量%,特别优选50-95重量%并且尤其80-90重量%(按激发态计算,即基于作为金属氧化物存在的100%活性组分)。
本发明催化剂进一步包含至少一种粘合剂。所述粘合剂包含也可以存在于活性组分中的相同氧化物载体材料,或优选这种载体材料的前体。如果活性组分包含氧化铜以及例如主要氧化铝或其前体,那么粘合剂同样包含氧化铝和/或其前体,尤其氧化铝水合物,特别优选勃姆石或假勃姆石。如果活性组分包含氧化铜以及例如主要的氧化硅或其前体,那么粘合剂同样包含氧化硅和/或其前体,尤其硅酸、硅酸酯或烷基化硅酸的酯。其中氧化铝和/或氧化铝前体作为存在于活性组分和粘合剂两者中的组分的本发明催化剂实施方式是优选的。
基于催化剂的总质量,氧化铜的比例为5-85重量%,优选10-70重量%,特别优选40-65重量%。
本发明催化剂是挤出物的形式。除了上述组分之外,其它组分和助剂一般加入要挤出的混合物中。通常使用水和,如果合适的话,酸或碱。另外,有助于在挤出期间改善加工性能和/或进一步提高催化剂成型体的机械强度和/或期望的孔隙率的有机和无机物质可另外作为助剂使用。这样的助剂是本领域熟练技术人员公知的,实例包括石墨、硬脂酸、硅胶、硅氧烷、纤维素化合物、淀粉、聚烯烃、碳水化合物(糖类)、蜡和藻酸盐。
可任选存在于催化剂中的、来自元素周期表1-14族(旧IUPAC命名法的IA-VIIIA和IB-IVB族)元素的其它金属或其化合物,优选氧化物,可存在于活性组合物和/或粘合剂中,和/或作为其它组分加入要挤出的混合物中。
在优选使用勃姆石作为粘合剂的情况下,含水的酸,特别是甲酸或硝酸,被混入正在被挤出的混合物中,除此之外,如果合适的话,混入羧甲基纤维素、马铃薯淀粉或硬脂酸。
在存在于催化剂挤出物中的氧化物载体材料中,即选自氧化铝、氧化钛、氧化锆、二氧化硅、氧化锰和其混合物的材料中,10-98重量%、优选15-95重量%、尤其20-50重量%是来自所用的粘合剂。相应地,存在于挤出物中的载体材料的2-90重量%、优选5-85重量%和特别优选50-80重量%是来自活性组分(各种情况下都按氧化物载体材料计算)。
活性组合物与准备用于挤出过程的粘合剂的比例是由活性组合物和粘合剂的组成、催化剂的目标组成或来自粘合剂的载体材料的期望比例确定。
选择具有优选高比例的氧化铜的活性组分并使用最少量的包含与活性成分中相同的载体材料的粘合剂,使得同时获得非常活泼且力学极其稳定的挤出物成为可能。根据本发明的生产方法避免了本身在反应中呈惰性的粘合剂组分对催化剂的不利稀释作用,并且也利用合适的粘合剂组分达到了高强度。
所述活性组合物可利用本领域熟练技术人员公知的方法生产。优选其中氧化铜是以与活性组合物的其它组分和酸性氧化物紧密混合的细分解形式获得的方法。特别优选的是由水溶液沉淀合适的金属盐和/或氢氧化物,洗涤沉淀物,并干燥和烧结该沉淀物。可能的金属盐是例如硝酸盐、硫酸盐、碳酸盐、氯化物、乙酸盐或草酸盐。这些起始材料然后通过公知方法处理以通过挤出生产成型体,如果合适的话添加助剂。
所述挤出物通过例如捏合或碾磨起始化合物与粘合剂如勃姆石或假勃姆石(AIOOH)获得,然后煅烧。粘合剂可以在挤出前预处理。优选使用酸例如甲酸或硝酸进行预处理。其它的助剂,例如成孔剂如羧甲基纤维素、马铃薯淀粉或硬脂酸,可以在挤出之前或期间另外加入。
本发明催化剂可以各种挤出物形状生产,可以提及的实例为圆柱形挤出物、星状或肋状挤出物、三叶状物、空心挤出物和蜂窝状物。这些挤出物的典型直径为0.5-10mm,优选1-6mm,特别优选1.5-3mm。长度与直径的平均比例为0.2∶1-20∶1,优选0.7∶1-10∶1,特别优选1∶1-5∶1。
在成型后,催化剂进行干燥并且如果合适的话煅烧。在基于氧化铜和氧化铝的优选催化剂的情况下,优选选择能导致氧化铝主要以X射线无定形的形式存在并且氧化铜作为精细晶体黑铜矿存在的煅烧条件。优选的是,在粉末衍射图谱中检测到仅<30重量%、特别优选<20重量%且尤其<10重量%的氧化铝作为晶体相。对于这些优选催化剂而言,常规煅烧温度为300-800℃,优选500-700℃并且特别优选550-650℃,煅烧时间为5分钟到5小时,优选10分钟到2小时。
所述铜催化剂在氧化状态下的BET表面积为10-400m2/g,优选15-200m2/g,尤其20-150m2/g。安装状态下还原催化剂的铜表面积(N2O分解)是>1m2/g铜,优选>3m2/g铜,尤其>6m2/g铜。
本发明催化剂具有宏观均匀的结构。其组分,即氧化铜、氧化物载体材料和粘合剂,作为彼此紧密的混合物存在,这是由于该催化剂中没有如例如涂层催化剂情况下具有不同结构的组分的大区域(mm范围的区域)。
另一方面,在微观水平上,在本发明的优选实施方式中,载体材料既以作为活性组合物中的精细分散体形式存在、又以由加入的粘合剂形成的颗粒形式存在。在该具体实施方式中,催化剂成型体体积的1-95%、优选3-80%且尤其5-50%由载体颗粒组成,即直径大于约2μm或体积大于约4μm3的颗粒。
在本发明的优选方案中,使用具有在大的中孔或小的大孔范围内的规定孔隙率的催化剂成型体。对于10nm-100nm孔隙直径,这些催化剂具有的孔隙体积>0.15ml/g,优选>0.20ml/g,特别优选>0.30ml/g。
因此,本发明的一种具体实施方式提供一种包含5-85重量%氧化铜和氧化物载体材料的催化剂成型体,其中
a)在10nm-100nm的孔隙直径范围内,该成型体具有的孔隙体积>0.15ml/g,和/或
b)该成型体中的氧化物载体材料既以精细分散形式存在、又以颗粒形式按占成型体体积的1-95%的体积比例存在。
本发明催化剂优选具有根据上述特征a)的孔隙体积和根据特征b)的载体材料结构。
特定的孔隙率依照DIN 66133通过压汞法确定。评价孔隙直径在4nm-300nm范围内的数据。本发明的孔隙率可通过本领域熟练技术人员公知的方法确定,例如通过选择活性组分的粒径分布和尤其是粘合剂的粒径分布,通过成型方法的参数和/或通过所用添加剂和助剂的类型和量。
当用作羰基化合物的氢化催化剂时,催化剂以还原的活化形式使用。在催化剂安装于进行本发明方法的反应器中之前或之后,利用还原气体、优选氢气或氢气/惰性气体混合物进行活化。如果催化剂以氧化形式安装于反应器内,则活化可以在用于根据本发明氢化的设备启动之前或启动期间、即原位进行。在设备启动之前的单独活化一般使用还原气体,优选氢气或氢气/惰性气体混合物,在升高温度下进行,优选在100-350℃温度下。在原位活化的情况下,活化作为在设备运行期间在升高温度下与氢气接触的结果而出现。
本发明催化剂适合于将羰基化合物例如醛和酮氢化以形成相应的醇,其中优选脂族和脂环族的饱和和不饱和的羰基化合物。在芳族羰基化合物的情况下,由于芳环的氢化,可形成不期望的副产物。羰基化合物可携带其它官能团如羟基或氨基。不饱和羰基化合物一般被氢化为相应的饱和醇。用于本发明目的的术语“羰基化合物”包含所有具有C=O基的化合物,包括羧酸和它们的衍生物。当然,两种或更多的羰基化合物的混合物也可以共同氢化。此外,要氢化的各种羰基化合物可包含多于1个的羰基。
本发明催化剂优选用于氢化脂族醛、羟基醛、酮、酸、酯、酸酐、内酯和糖类。
优选的脂族醛是支化和未支化的、饱和和/或不饱和的脂族C2-C30-醛,可例如通过由线性或支化的、具有内部或端部双键的烯烃的羰基合成反应获得。而且,包含超过30个羰基的低聚化合物也可以被氢化。
脂族醛的实例为:
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。
除了上述短链醛之外,其它合适的醛还特别包括长链脂族醛,可通过例如由线性α-烯烃的羰基合成获得。
特别优选的是烯醇化产物(enalization products),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。
优选的羟基醛是可通过例如脂族和脂环族的醛和酮与其本身或与甲醛的醇醛缩合反应获得的C3-C12-羟基醛。实例为3-羟基丙醛、二羟甲基乙醛、三羟甲基乙醛(季戊四醛)、3-羟基丁醛(丁间醇醛)、3-羟基-2-乙基己醛(丁基羟醛)、3-羟基-2-甲基戊醛(丙基羟醛)、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、羟基戊醛。特别优选的是羟基新戊醛(HPA)和二羟甲基丁醛(DMB)。
优选的酮是丙酮、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、异亚丙基丙酮、乙酰苯、丙酰苯、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5-甲基乙烯基酮。
此外,羧酸和它们的衍生物,优选具有1-20个碳原子的那些,可以反应。可以特别提及的如下:
羧酸,例如甲酸、乙酸、丙酸、丁酸、异丁酸、正戊酸、三甲基乙酸(特戊酸)、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、苯基乙酸、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、马来酸、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-C10-烷基酯,特别是甲酸甲酯、乙酸乙酯、丁酸丁酯、对苯二甲酸二甲酯、己二酸二甲酯、马来酸二甲酯、(甲基)丙烯酸甲酯、丁内酯、己内酯,和聚羧酸酯如聚丙烯酸酯和和聚甲基丙烯酸酯和它们的共聚物,以及聚酯如聚甲基丙烯酸甲酯、对苯二甲酸酯和其它工业塑料;
脂肪;
羧酸酐,例如上述羧酸的酸酐,特别是乙酸酐、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。
还可以使氢羧酸如乳酸、苹果酸、酒石酸或柠檬酸,或氨基酸如甘氨酸、丙氨酸、脯氨酸和精氨酸和缩氨酸反应。
本发明方法特别优选用于酯、酸酐、醛和羟基醛的氢化。
要氢化的羰基化合物可单独或作为与氢化反应产物的混合物送入氢化反应器,这样能够以未稀释形式出现或使用另外的溶剂。合适的其它溶剂特别是水,醇如甲醇、乙醇和在反应条件下形成的醇。优选的溶剂是水、THF、NMP以及醚如二甲醚、二乙醚、MTBE,特别优选水。
在反应条件下为液体的起始材料的氢化反应可以以向上流动模式或者以向下流动模式进行,各种情况下都优选具有循环流动,一般在温度50-250℃、优选70-200℃、特别优选100-140℃和压力15-250巴、优选20-200巴、特别优选25-100巴进行。气相氢化一般在温度120-350℃、优选180-300℃和压力1-100巴、优选1-60巴、尤其2-20巴下进行。
根据本发明使用的催化剂一般具有令人满意的工作寿命。虽然催化剂的活性和/或选择性在其操作期间下降,但是可以利用本领域熟练技术人员公知的方法再生。其中,优选在升高温度下在氢气流中还原处理所述催化剂。如果合适的话,还原处理可在氧化处理之前。在这种情况下,包含分子氧的气体混合物,例如空气,在升高温度下从催化剂床中通过。另一种可能性是用合适的溶剂清洗催化剂。
依照本发明使用的氢化方法实现了高的转化率和选择性,并且催化剂在反应混合物存在下显示出高的化学稳定性。依照本发明生产的催化剂在氧化状态和还原状态都具有显著提高的机械稳定性,结果,本发明方法是特别经济的。
本发明将通过下述实施例阐述。
BET表面积的测量
BET表面积的测定依照DIN 66131通过N2吸附进行。
切切削硬度的测量
切削硬度的测量按照下述进行:
随机选取25个目测无裂纹的挤出物,将厚度0.3mm的刀具以逐渐增加的力量压在各个挤出物上连续进行试验,直到挤出物被切穿。这样所需要的力即为切削硬度,单位是牛顿。
实施例1
生产本发明的活性组合物
将1.5L水加入装配有搅拌器的可加热式沉淀容器内并加热到80℃。在搅拌下,于1小时内同时计量加入一种在2000ml水中包含877gCu(NO3)2*2.5H2O和551gAl(NO3)3*9H2O的金属盐溶液和一种碳酸钠溶液(浓度20重量%)。计量加入的碳酸钠的量应该使该沉淀容器内的pH为6。在加入所有金属盐溶液后,计量加入其它的碳酸钠溶液直到沉淀容器内的pH为8,并且在该pH下再搅拌该混合物15分钟。碳酸钠溶液的总消耗量为3.7kg。所形成的悬浮液进行过滤,并用水洗涤固体直到不再包含硝酸盐(<25ppm)。该产物在大约120℃下干燥。按照该方法制备的活性组合物包含按氧化物计算的约80重量%CuO和20重量%Al2O3。
生产挤出物
将133g勃姆石(Versai 250,来自Sasol)在混合碾压机(Mix-Muller)中用甲酸(浓度30重量%)处理,与干燥的活性组合物混合,并且在加入233ml水之后强烈混合。混合后的物质然后挤出,形成直径为2mm且平均长度为8mm的挤出物。挤出物随后在约120℃下干燥并在600℃下煅烧。该催化剂挤出物包含按氧化物计算的约65重量%CuO和35重量%Al2O3。催化剂中约54%的氧化物载体材料Al2O3是来自粘合剂。
最重要的催化剂性能总结在表2中。
在本发明催化剂上将马来酸酐(MA)氢化为四氢呋喃(THF)和γ-丁内酯(GBL)的混合物。
在反应开始之前,催化剂用氢气处理。为此,将反应器加热到180℃,并且在所有情况下均在大气压力下用氢气和氮气混合物还原所述催化剂,还原时间如表1所示。
表1
时间(分钟) | 氢气(标准L/h) | 氮气(标准L/h) |
120 | 50 | 950 |
30 | 100 | 900 |
30 | 500 | 500 |
该催化剂然后在280℃下用200标准L/h的氢气处理1小时。
为了进行氢化,将熔融的MA反向泵送到在245℃下操作且氢气流从中通过的蒸发器内。将氢气流和MA送入被加热的装有70ml催化剂和70ml玻璃环的混合物的反应器(直径:27mm)内,利用气相色谱对该反应器的输出气体进行定量分析。操作参数和实验结果示于表3。
实施例2
生产本发明的活性组合物
将1.5L水加入装配有搅拌器的可加热式沉淀容器内并加热到80℃。在搅拌下,于1小时内同时计量加入一种在2000ml水中包含877gCu(NO3)2*2.5H2O和1410g Al(NO3)3*9H2O的金属盐溶液和一种碳酸钠溶液(浓度20重量%)。计量加入的碳酸钠的量应使该沉淀容器内的pH为6。在加入所有金属盐溶液后,计量加入其它的碳酸钠溶液直到沉淀容器内的pH为8,并且在该pH下再搅拌该混合物15分钟。碳酸钠溶液的总消耗量为4.4kg。所形成的悬浮液进行过滤,并用水洗涤固体直到不再包含硝酸盐(<25ppm)。该产物在大约120℃下干燥。按照该方法制备的活性组合物包含按氧化物计算的约61重量%CuO和39重量%Al2O3。
生产挤出物
将160g勃姆石(Versal 250,来自Sasol)在混合碾压机(Mix-Muller)中用甲酸(浓度30重量%)处理,与干燥的活性组合物混合,并且在加入327ml水之后强烈混合。混合后的物质然后挤出,形成直径为2mm且平均长度为8mm的挤出物。挤出物随后在约120℃下干燥并在600℃下煅烧。该催化剂挤出物包含按氧化物计算的约50重量%CuO和50重量%Al2O3。催化剂中约36%氧化物载体材料Al2O3是来自粘合剂。
最重要的催化剂性能总结在表2中。与实施例1相对应的氢化实验结果示于表3,该催化剂挤出物在还原和再氧化后的电子显微照片示于图1。
对比例1
生产挤出物
将88.7g勃姆石(Versal 250,来自Sasol)在混合碾压机(Mix-Muller)中用甲酸(浓度30重量%)处理,与83.4g碱式碳酸铜(孔雀石:CuCO3*Cu(OH)2;来自Aldrich)混合,并且在加入80ml水之后强烈混合。混合后的物质然后挤出,形成直径为2mm且平均长度为8mm的挤出物。挤出物随后在约120℃下干燥并在600℃下煅烧。该催化剂挤出物包含约50重量%CuO和50重量%Al2O3。在该实施例中,活性组合物中不包含载体组分,因此载体是完全来自所用的粘合剂。
最重要的催化剂性能总结在表2中。使用非本发明催化剂C1且按与实施例1相似的方式进行的氢化实验的结果示于表3。
表2:催化剂数据
实施例 | 体积密度[g/l] | 切削硬度[N] | 直径[mm] | BET[m2/g] | 孔隙体积[cm3/g] | |
总计 | 对于D=10-100nm | |||||
1 | 906 | 25 | 1.7 | 104 | 0.31 | 0.24 |
2 | 790 | 20 | 1.7 | 121 | 0.48 | 0.36 |
C1 | 620 | 11 | 1.8 | 155 | 0.59 | 0.13 |
表3:氢化结果
实施例 | 压力[巴] | 热点温度[℃] | WHSV[kg MA/L催化剂*h] | GHSV[L/h] | 进料中的浓度(MA)[体积%] | C(MA)[mol%] | S(SA)[mol%] | S(THF)[mol%] | S(GBL)[mol%] | S(BuOH)[mol%] |
1 | 10 | 250 | 0.15 | 2800 | 1.25 | 100 | 0.7 | 51.6 | 45.8 | 0.3 |
2 | 10 | 250 | 0.17 | 3200 | 1.25 | 100 | 1.5 | 49.3 | 47.6 | 0.1 |
V1 | 10 | 250 | 0.03 | 700 | 1.15 | 100 | 60.6 | 1.0 | 32.4 | 0 |
GHSV表示气体空时速率=反应气体在STP下基于催化剂体积的体积流量
C表示转化率
S表示选择性
从中可以清楚地看出,对于期望的产物THF和GBL,本发明催化剂显示出优异的选择性。除WHSV显著降低之外,对比催化剂还产生大量的琥珀酸酐(SA),即其活性显著降低。
图1显示如实施例2所述的催化剂挤出物的扫描电子显微照片(图像由来自抛光断面的反向散射电子产生;以大约170×170μm2的图形摘录示出)。在暗的区域中,实质上只有铝通过EPMA探测到(在该扫描电子图像中,密度较高的区域,例如由于铜含量较高,表现得较明亮);在其它区域,铝和铜都存在。暗颗粒的面积表明氧化铝颗粒在该试样中的比例为约18%;假定该抛光断面代表该试样,则这与全部催化剂挤出物中的约18体积%的颗粒Al2O3相对应。
Claims (12)
1.一种催化剂成型体,其包含5-85重量%的氧化铜以及在活性组合物中的且作为粘合剂的相同氧化物载体材料。
2.如权利要求1所述的包含5-85重量%氧化铜和氧化物载体材料的催化剂成型体,其中
a)在10nm-100nm的孔隙直径范围内,该成型体具有的孔隙体积>0.15ml/g,和/或
b)该成型体中的氧化物载体材料既以精细分散形式存在、又以颗粒形式按占成型体体积的1-95体积%的体积比例存在。
3.如权利要求1所述的催化剂,其具有所述特性a)和b)。
4.如权利要求1-3中任一项所述的催化剂,其中使用的氧化物载体材料是氧化铝、氧化钛、氧化锆、氧化硅、氧化锰或它们的混合物。
5.如权利要求1-4中任一项所述的催化剂,其中氧化物载体材料是Al2O3。
6.如权利要求5所述的催化剂,其中Al2O3主要作为X射线无定形的材料存在。
7.如权利要求1-6中任一项所述的催化剂,其是挤出物。
8.一种制备如权利要求1-7中任一项所述催化剂的方法,其中将包含10-98重量%氧化铜和氧化物载体的活性组分与包含相同载体材料或其前体的粘合剂混合,并成型以形成成型体。
9.如权利要求8所述的方法,其中催化剂中的10-98重量%的氧化物载体材料是来自所用的粘合剂。
10.如权利要求1-9中任一项所述的催化剂用于羰基化合物的氢化反应的用途。
11.如权利要求1-10中任一项所述的催化剂用于马来酸酐的气相氢化反应的用途。
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DE10111197A1 (de) * | 2001-03-08 | 2002-09-19 | Basf Ag | Verfahren zur Herstellung von Katalysatoren mit geringem Volumenschwund |
US6664207B2 (en) * | 2001-09-26 | 2003-12-16 | Conocophillips Company | Catalyst for converting carbon dioxide to oxygenates and processes therefor and therewith |
US6800586B2 (en) * | 2001-11-23 | 2004-10-05 | Engelhard Corporation | NOx reduction composition for use in FCC processes |
-
2003
- 2003-12-09 DE DE10357717A patent/DE10357717A1/de not_active Withdrawn
-
2004
- 2004-12-04 KR KR1020067013749A patent/KR101084825B1/ko active IP Right Grant
- 2004-12-04 US US10/580,950 patent/US7807603B2/en not_active Expired - Fee Related
- 2004-12-04 WO PCT/EP2004/013809 patent/WO2005058491A1/de active Application Filing
- 2004-12-04 DE DE502004011938T patent/DE502004011938D1/de active Active
- 2004-12-04 AT AT04803522T patent/ATE489166T1/de not_active IP Right Cessation
- 2004-12-04 JP JP2006543446A patent/JP4625470B2/ja not_active Expired - Fee Related
- 2004-12-04 CN CNB2004800368200A patent/CN100496718C/zh active Active
- 2004-12-04 EP EP04803522A patent/EP1694438B1/de not_active Revoked
- 2004-12-08 MY MYPI20045072A patent/MY144948A/en unknown
-
2007
- 2007-11-02 US US11/934,266 patent/US7459571B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102464636A (zh) * | 2010-11-13 | 2012-05-23 | 华中药业股份有限公司 | 一种dl-泛内酯的合成方法 |
CN116060025A (zh) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | 一种加氢催化剂及其制备方法和应用 |
WO2023246892A1 (en) * | 2022-06-22 | 2023-12-28 | Basf Corporation | Shaped catalyst body |
Also Published As
Publication number | Publication date |
---|---|
US7459571B2 (en) | 2008-12-02 |
EP1694438A1 (de) | 2006-08-30 |
KR20060132861A (ko) | 2006-12-22 |
CN100496718C (zh) | 2009-06-10 |
US7807603B2 (en) | 2010-10-05 |
WO2005058491A1 (de) | 2005-06-30 |
DE10357717A1 (de) | 2005-07-14 |
DE502004011938D1 (de) | 2011-01-05 |
JP2007516824A (ja) | 2007-06-28 |
MY144948A (en) | 2011-11-30 |
JP4625470B2 (ja) | 2011-02-02 |
ATE489166T1 (de) | 2010-12-15 |
US20080064883A1 (en) | 2008-03-13 |
US20070117719A1 (en) | 2007-05-24 |
EP1694438B1 (de) | 2010-11-24 |
KR101084825B1 (ko) | 2011-11-21 |
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