CN101631615B - 由中空形状物制成的混合氧化物催化剂 - Google Patents
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- CN101631615B CN101631615B CN200880006754.0A CN200880006754A CN101631615B CN 101631615 B CN101631615 B CN 101631615B CN 200880006754 A CN200880006754 A CN 200880006754A CN 101631615 B CN101631615 B CN 101631615B
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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Abstract
本发明涉及由中空形状物制成的混合氧化物催化剂,所述催化剂用于烯烃的催化气相氧化,并且本发明涉及制备所述催化剂的方法,所述方法通过向由有机材料制成的载体涂布所述催化剂作为一层,并且除去所述有机材料来进行。在各种数量比的惰性气体的存在下,在高温和升压下,在所述催化剂的存在下,通过空气或氧气来发生生成醛和羧酸的反应。
Description
技术领域
本发明涉及由中空形状物制成的混合氧化物催化剂,所述催化剂用于烯烃的催化气相氧化,本发明涉及制备所述催化剂的方法,并且涉及在各种数量比例的惰性气体的存在下,在高温和升压下,采用空气或氧得到醛和羧酸的反应。
特别地,可以采用催化剂来进行丙烯到丙烯醛和丙烯酸或异丁烯到甲基丙烯醛和甲基丙烯酸的强烈放热反应。烯烃与含氧气体在非均相催化剂上的强烈放热反应不仅得到期望的丙烯醛和丙烯酸产品,而且得到一系列的副产物:例如,导致形成CO2、CO、乙醛或乙酸。
已知混合氧化物的化学组成的类型(相形成和反应位点的形成)、和物理结构的类型(例如孔隙率,表面尺寸,催化剂的形状)以及移去热的类型可以极大地影响形成产品的能力(选择性)和生产率(时空收率)。在烯烃氧化的情况下,所用催化剂通常是混合氧化物,这些混合氧化物在其化学和物理组成上具有复杂的结构。许多出版物描述了能够用作从丙烯制备丙烯醛和丙烯酸的催化剂的混合氧化物。这些催化剂通常包括钼、钒和/或钨。通常向这些基本成分中加入元素铋、锑、钒、碲、锡、铁、钴、镍和/或铜中的至少一种。
自从Standard Oil Inc.的第一篇研发成果GB 821999(1958)以来,关于将烯烃非均相催化气相氧化为丙烯醛和丙烯酸的出版物的数量众多。尽管开发时间很长,但是,改善催化剂的性能,例如产品收率、活性和寿命,仍然是需要努力的问题。为此,文献主张了制备和配制催化剂的各种技术。这里,通过举例的方式,介绍了最新的进展:
背景技术
WO 2005/063673涉及通过用惰性材料稀释催化剂来减少在反应区中的热形成,从而增加产品收率。避免过高的温度减少了产品的总体氧化。尽管通过惰性材料来调整反应温度,通过所述方法获得的丙烯醛和丙烯酸的累积收率仅为不超过91.22%。
WO2005035115描述了制备包含金属氧化物组合物和可升华的材料催化剂。金属氧化物用作催化剂;可升华的材料用作生成孔的添加剂。所得的催化剂非常活泼,具有大的表面积,并且能够以高的选择性形成丙烯醛和丙烯酸。
DE 10344149公开了基于Mo12BiaFebX1cX2dX3eX4fOn(1)的未负载的环形催化剂,其长度为2-11mm,外径为2-11mm以及壁厚为0.75-1.75mm,所述催化剂用于将丙烯部分氧化为丙烯醛或甲基丙烯醛。催化剂(I)具有活性和选择性得到改善的优点。
DE 19933450描述了包含镍的金属催化剂,所述金属催化剂包含含有金属合金的中空形状物或球状物,并且,所述金属催化剂用于氢化、脱氢、异构化、还原烷基化以及还原胺化。由此制备的催化剂具有改善的稳定性和寿命。
可以根据Andersen,Schneider和Stephanie(参见,″NeueMetallische Werkstoffe″[Novel highly porousmetallic materials ],Ingenieur-Werkstoffe,4,1998,p.36-38)来制备这种中空球状物。在该方法中,均匀地喷洒期望的合金、有机粘合剂以及任选存在的无机粘合剂的混合物,使其通过聚苯乙烯球状物构成的流化床,其中,用所述混合物涂布球状物。然后,在450-1000℃范围内的所选温度下煅烧涂布过的球状物,以烧尽聚苯乙烯,然后采用更高的煅烧温度以将金属烧结在一起,以及使中空形状物稳定。在煅烧之后,通过氢氧化钠溶液使催化剂活化,以制备活化的碱金属催化剂。该催化剂体系的另一个优点是可以通过涂布条件容易地控制中空形状物的壁厚,以及可以通过粒径以及原始粉末混合物的组成容易地控制壁的孔隙率。
要解决的技术问题
通常公认的是,混合氧化物的化学组成的类型(相形成以及反应位点的形成)以及物理结构的类型(例如孔隙率、表面尺寸、催化剂的形状)以及去热的类型可以极大地影响形成产品的能力(选择性)和生产率(时空收率)。本发明的目的是,提供与现有技术相比具有提高的催化活性的催化剂。
本发明基于另一个目的:提供制备醛和酸的改善方法,其中,在高温下和在非均相混合氧化物催化剂的存在下,在惰性气体(包括水蒸汽或来自反应的废气)的存在下,通过用空气或氧气氧化来从丙烯制备丙烯醛和丙烯酸。应该提供混合氧化物催化剂,采用该催化剂,不仅达到大于95%的丙烯转化率,而且得到大于或等于88%的高的产品选择性,从而改善了所述方法的经济可行性。
发明内容
本发明通过如下的技术方案得以实现:
[1].混合氧化物催化剂,所述催化剂由中空形状物构成并且具有以下通式:
(Mo12BiaCb(Co+Ni)cDdEeFfGgHh)Ox (I)
其中
C:铁,
D:选自W和P中的至少一种元素,
E:选自Li、K、Na、Rb、Cs、Mg、Ca、Ba和Sr中的至少一种元素,
F:选自Ce、Mn、Cr和V中的至少一种元素,
G:选自Nb、Se、Te、Sm、Gd、La、Y、Pd、Pt、Ru、Ag和Au中的至少一种元素,
H:选自Si、Al、Ti和Zr中的至少一种元素,
以及下标
a=0.5-5.0
b=0.5-5.0
c=2-15
d=0.01-5.0
e=0.001-2
f=0.001-5
g=0-1.5
h=0-800,
以及
x=由除了氧之外的元素的价态和相应下标决定的数值,
所述混合氧化物催化剂包括直径为0.5-5mm的中空球状物。
[2].根据项1所述的混合氧化物催化剂,其包括不透气的中空形状物。
[3].根据项1所述的混合氧化物催化剂,其包括透气的中空形状物。
[4].根据项1-3所述的混合氧化物催化剂,其包括由多层构成的中空形状物。
[5].一种制备根据项1-4所述的由中空形状物构成的混合氧化物催化剂的方法,包括:将存在于通式I的混合氧化物催化剂中的元素的化合物的溶液混合,制备共沉淀物,将所得的固体分离,任选地将所述固体干燥和煅烧,以及向由有机材料构成的载体以悬浮体的形式涂布所得的细粒状的固体作为一层,任选地与粘合剂一起涂布,以及在将涂布到载体的层的固化过程中或固化之后,除去所述有机材料。
[6].根据项5所述的方法,其中所述载体的形状为球形。
[7].根据项5所述的方法,其中,采用平均粒径分布在0.01-80μm之间的煅烧过的或部分煅烧过的细固体,来制备所述悬浮体。
[8].根据项6所述的方法,其中,采用平均粒径分布在0.01-80μm之间的煅烧过的或部分煅烧过的细固体,来制备所述悬浮体。
[9].根据项5-8所述的方法,其中,通过喷雾-干燥来对所述固体进行干燥,所述喷雾-干燥的粉末的平均粒径分布在0.1-50μm之间,任选地,所述粉末经过研磨。
[10].根据项5和8所述的方法,其中,将所述煅烧过的或部分煅烧过的粉末的平均粒径分布调整至0.01-30μm,任选地,所述粉末经过研磨。
[11].根据项5-8所述的方法,其中,在涂布所述细粒状的固体之后,将催化剂前体干燥,然后,在450-600℃的温度范围内,在氧的存在下进行热处理。
[12].一种制备醛和酸的方法,所述方法在惰性气体、水蒸汽或来自反应的废气的存在下,在高温下通过用空气或氧气氧化烯烃或甲基化芳香族化合物来进行,其特征在于,采用由中空形状物构成并且具有以下通式的催化剂:
(Mo12BiaCb(Co+Ni)cDdEeFfGGHh)Ox (I)
C:铁,
D:选自W和P中的至少一种元素,
E:选自Li、K、Na、Rb、Cs、Mg、Ca、Ba和Sr中的至少一种元素,
F:选自Ce、Mn、Cr和V中的至少一种元素,
G:选自Nb、Se、Te、Sm、Gd、La、Y、Pd、Pt、Ru、Ag和Au中的至少一种元素,
H:选自Si、Al、Ti和Zr中的至少一种元素,
以及下标
a=0-5.0
b=0.5-5.0
c=2-15
d=0.01-5.0
e=0.001-2
f=0.001-5
g=0-1.5
h=0-800,
以及
x=由除了氧之外的元素的价态和相应下标决定的数值,
所述催化剂包括直径为0.5-5mm的中空球状物。
[13].根据项12所述的方法,其中采用根据项1-4所述的催化剂。
[14].根据项12或13所述的方法,其特征在于,从丙烯获得丙烯醛和丙烯酸。
[15].根据项12或13所述的方法,其特征在于,从异丁烯获得甲基丙烯醛和甲基丙烯酸。
[16].根据项12或13所述的方法,其特征在于,从甲苯获得苯甲醛和苯甲酸。
[17].根据项12或13所述的方法,其特征在于,所述催化剂与反应气体混合物接触,所述反应气体混合物包含比例为1∶6-9∶3-18的烯烃或甲基化芳香族化合物、空气和惰性气体。
本发明提供了由中空形状物构成的催化剂,所述催化剂用于对烯烃进行氧化,例如具有以下通式的混合氧化物催化剂:
(Mo12BiaCb(Co+Ni)cDdEeFfGgHh)Ox (I),
其中
C:铁,
D:选自W、P中的至少一种元素,
E:选自Li、K、Na、Rb、Cs、Mg、Ca、Ba和Sr中的至少一种元素,
F:选自Ce、Mn、Cr和V中的至少一种元素,
G:选自Nb、Se、Te、Sm、Gd、La、Y、Pd、Pt、Ru、Ag和Au中的至少一种元素,
H:选自Si、Al、Ti和Zr中的至少一种元素,
以及下标
a=0.5-5.0
b=0.5-5.0
c=2-15
d=0.01-5.0
e=0.001-2
f=0.001-5
g=0-1.5
h=0-800,
以及
x=由除了氧之外的元素的价态和相应下标决定的数值。
采用本发明的催化剂带来显著改善的催化剂活性,可以建立较低的盐浴温度并且得到高的转化率证明了这一点。
由于采用了制备催化剂例如通式I的催化剂的新方法,可以获得特别适合的催化活性固体,例如用于将丙烯转化为丙烯醛和丙烯酸的催化活性固体。在允许将催化剂用作固定床的反应器中,特别有利地进行所述反应。不过,同样可以将催化剂用作流化床催化剂。这里应该指出的是,本发明的催化剂也可以用于将异丁烯转化成甲基丙烯醛和甲基丙烯酸。
通过以下制备步骤获得细粒粉末,可以制备所述组成的催化剂:溶解金属盐,沉淀活性成分,干燥和煅烧,以及使煅烧过的粉末成型。这可以公知方式进行,例如通过压片、挤出或通过涂布载体。对载体形状没有限制。例如,载体可以是锥形、圆柱形或球形。
现在,已经发现了一种新方法来得到中空形状的混合氧化物催化剂。在这种情况下,载体是为活性组合物赋予形状的基质,并且在活性组合物固化之后或在固化过程中被除去,从而形成中空体。通过控制沥滤(leaching-out)来实现所述除去,通过溶剂或优选热方法,例如通过热辐射来控制沥滤。应该优选在450-600℃的温度范围内,在氧的存在下,特别是在空气的存在下,处理涂布过的载体,从而在工业反应器中固化所采用的催化活性组合物,并且载体分解而没有残余物。所用的这些载体是有机材料,例如聚苯乙烯-基聚合物例如ASA(丙烯腈/苯乙烯/丙烯酸酯)、聚苯乙烯(PS、PS-I)、SAN(苯乙烯/丙烯腈)。然而,对这些聚合物没有限制。这些材料通常明显比陶瓷载体便宜,从而降低了催化剂的制备成本。
对载体基质的尺寸没有限制。典型地,采用0.1-20mm,特别是0.1-5mm的载体。也可以想到采用在10-6-0.1mm或大于2mm范围内的载体.
由此制得的催化剂在具有高选择性和寿命的同时,具有优异的活性,并且带来非常好的产品收率。
通过以期望的浓度组合溶解了的通式I的催化活性元素的化合物,获得在所述方法中用于气相氧化的催化剂。理想地,所述成分以选自铵或胺化合物、草酸盐、碳酸盐、磷酸盐、乙酸盐、羰基化合物和/或硝酸盐的化合物的形式,单独地或以它们的组合使用。特别优选碳酸盐、硝酸盐以及磷酸盐或它们的组合物。也可以采用所述盐的酸,例如硝酸、磷酸或碳酸。
如前面已经提及的,催化剂制备的第一阶段形成沉淀物。根据沉淀阶段中采用的金属盐的类型,向沉淀混合物中加入溶液混合物的形式的成分可以是有必要的。理想地,这里采用氨或铵盐,例如碳酸铵、七钼酸铵,或金属硝酸盐,例如硝酸铁、硝酸钴;也可以采用相应的酸,例如硝酸,用量为建立离子比例所需要的量。沉淀过程中的pH为<8,特别是<7。
可以在一个沉淀阶段进行共沉淀物的制备。特别优选通过逐步添加各组分或通过添加它们的组合物,来在几个阶段进行沉淀。原则上对沉淀阶段的数目没有限制。然而,优选一个至三个沉淀阶段。
进一步可以直接加工所得的悬浮体,或使其熟化>0至24小时,优选>0至12小时,更优选>0至6小时。明显的是,在进一步加工之前,使沉淀的悬浮体均匀化,例如通过搅拌进行均匀化。
在熟化之后,可以通过蒸发、离心或过滤,从悬浮体中除去液体。也可以蒸发液体并且同时干燥固体,例如,这可以通过喷雾干燥来实现。应该在80-130℃的温度下蒸发液体。可以用空气、含氧惰性气体或惰性气体,例如氮气,来干燥固体。当在烘箱中进行干燥时,温度应该在100-200℃之间。在喷雾干燥器中,干燥介质的起始温度应该为200-500℃,以及应该提供80-200℃的干燥粉末的沉积温度。所得的颗粒应该优选其粒径分布为15-160μm,并且平均粒径在15-80μm之间。
原则上,随后可以在各种不同类型的烘箱中煅烧干燥的粉末,例如在强制热风烘箱(forced-air oven)、旋转烘箱(rotary oven)、盘炉(trayoven)、立筒烘箱(shaft oven)或带式烘箱(belt oven)中煅烧。烘箱的控制质量和检测质量应该为最大限度。根据烘箱的类型,粉末在烘箱中的停留时间应该在0.25-13h之间。
也可以进行盐,例如硝酸盐或碳酸盐的煅烧和热分解,这在一个或多个阶段同时发生。可以采用200-600℃,特别是300-600℃的温度。可以加入惰性气体进行热分解,所述惰性气体是由氧与惰性气体构成的混合物。
可以采用的惰性气体是,例如,氮气、氦气、水蒸汽或这些气体的混合物。
由此得到的粉末可以直接用作催化剂。粉末的平均粒径分布应该在0.01-50μm的范围内。
为了将混合氧化物粉末转化成本发明的形式,将所述粉末涂布于载体上,在催化活性组合物固化之后,将载体除去从而形成中空体。通过溶剂或优选热方法,例如通过热辐射来控制沥滤,从而进行所述除去。本发明的催化剂的前体由载体和催化活性层构成的,优选在490-600℃,特别是490-580℃的温度范围内处理催化剂前体,从而,使用于工业反应器中的催化活性组合物固化,并且可以同时或随后除去载体而没有残余物残留。所用的载体是有机材料,例如,聚苯乙烯-基聚合物例如ASA(丙烯腈/苯乙烯/丙烯酸酯)、聚苯乙烯(PS,PS-I)、SAN(苯乙烯/丙烯腈)、但是对这些聚合物没有限制;也可以,例如,采用纤维素或糖类。
在本文的上下文中,对载体的几何形状没有限制,而是通过对反应器和反应区域的要求(例如管直径、催化剂床的长度)来进行控制。例如,载体可以是锥形、圆柱形、鞍状、球形或多边形。同样地,对载体的尺寸没有限制。典型地,采用0.1-5mm的载体。然而,也可以想得到采用10-6-0.1mm或大于2mm的范围内的载体。根据载体尺寸,混合氧化物层的厚度通常在10-6-1.5mm之间;特别优选涂层厚度为0.1-1.5mm。通过喷洒包含催化剂粉末和粘合剂的含水悬浮体,来进行载体的涂布,从而制备催化剂前体。优选以在470℃-600℃煅烧的形式来使用催化剂粉末。为了随后形成孔,也可以向悬浮体中添加已知成孔剂中的一种。
所用的粘合剂可以是各种油、纤维素、聚乙烯醇、糖类、丙烯酸酯以及它们的烷基衍生物、它们的混合物或缩合物。优选丙烯酸酯、聚乙烯醇、以及纤维素或糖。特别优选丙烯酸酯和/或纤维素和/或糖类的衍生物和缩合物,以及它们的混合物。
在优选不超过110℃的温度下将涂布过的载体干燥之后,将载体除去。通过合适的溶剂或热方法,例如在高温在氧存在下通过热辐射控制沥滤从而进行所述除去。应该优选在490-600℃的温度范围内处理涂布过的载体,从而使活性组合物形成固体壳,同时载体溶解或分解而没有残余物残留。
本发明同样提供了在本发明的催化剂的存在下将烯烃氧化成不饱和醛以及相应的酸。
通常在250-450℃的温度和1.0-2.2bara的压力下,进行制备丙烯醛以及丙烯酸的反应。优选以1∶6-9∶3-18的比例,在2-10mol烯烃/dm3催化剂床/h的载荷下,向催化剂床供给烯烃、空气以及惰性气体反应物。
可以采用来自反应的废气代替惰性气体,已经从所述废气中除去了可凝结的组分。当采用管束反应器(bundle reactor)或流化床反应器时,获得特别好的结果。
当将本发明的催化剂用在所提及的氧化过程中时,带来改善的活性,即使在高的单位负载的情况下也如此。
以下,将结合实施例来说明本发明。所用的定义有:
产品收率(%)为(mol/h所形成的产品)/(mol/h所供给的反应物)*100
烯烃转化率(%)为[1-(mol/h离开反应管的烯烃)/(mol/h进入反应管的烯烃)]*100
选择性(%)为(产品收率/转化率)*100。
通过后面的实施例详细说明本发明是为了帮助理解,但是本发明不限于这些实施例。
具体实施方式
实施例
实施例1
通过如下来制备溶液I:以23.2∶47.26∶29.28∶0.0646∶0.2067的质量比将铁、钴、镍、锰、钾的硝酸盐溶解在3.5升的水中,并且在搅拌下将它们加热到40℃,以及加入0.1mol的Sm3+和2mol的HNO3的硝酸溶液。
对于溶液II,在40℃制备2118.6g七钼酸铵在2.7升水中的溶液;最后,将4.4g磷酸和0.42g Aerosil 200(Degussa)、14g氧化铝加入到1升的水中.
在强烈的搅拌下,将溶液II缓慢加入到溶液I中。在一个单独的容器中,制备由790g硝酸铋和0.72mol的HNO3构成的另一种溶液III。将该溶液加入到另一种活性成分,得到用于制备活性催化剂相的共沉淀物。
将共沉淀物强烈搅拌12小时。在350℃的气体入口温度下,在喷雾干燥器中,用旋转盘将所得的悬浮体干燥。调整气流从而获得110+/-10℃的出口温度。
在强制热风烘箱中,在445℃的温度下,将该粉末处理1小时直到形成混合氧化物。通过喷洒两种物质的喷嘴(two-substance nozzle)将混合氧化物作为含水悬浮体喷洒到球形Styropor载体上,并且在60℃在空气流中干燥。为了将颗粒均匀化,用辊筒将颗粒进行循环。为了将涂布的活性组合物固化,在氧的存在下,在520℃将所得的材料加热5小时。
实施例2
将实施例1的催化剂与组成为7.3体积%的丙烯(化学级)、60体积%的空气和惰性气体的混合物接触。浴温为318℃和接触时间为2.0秒,获得丙烯醛和丙烯酸,选择性为95%,转化率为92%。
对比例3
根据实施例1制备催化剂。代替Styropor球形,所用的载体是氧化铝载体,氧化铝载体不能除去。所得的催化剂具有相同的几何形状。在高出12℃的浴温下,需要将反应时间延长到1.35倍,以获得可比较的转化率。丙烯醛和丙烯酸的选择性为94%。
Claims (17)
1.混合氧化物催化剂,所述催化剂由中空形状物构成并且具有以下通式:
(Mo12BiaCb(Co+Ni)cDdEeFfGgHh)Ox (I)
其中
C:铁,
D:选自W和P中的至少一种元素,
E:选自Li、K、Na、Rb、Cs、Mg、Ca、Ba和Sr中的至少一种元素,
F:选自Ce、Mn、Cr和V中的至少一种元素,
G:选自Nb、Se、Te、Sm、Gd、La、Y、Pd、Pt、Ru、Ag和Au中的至少一种元素,
H:选自Si、Al、Ti和Zr中的至少一种元素,
以及下标
a=0.5-5.0
b=0.5-5.0
c=2-15
d=0.01-5.0
e=0.001-2
f=0.001-5
g=0-1.5
h=0-800,
以及
x=由除了氧之外的元素的价态和相应下标决定的数值,
所述混合氧化物催化剂包括直径为0.5-5mm的中空球状物。
2.根据权利要求1所述的混合氧化物催化剂,其包括不透气的中空形状物。
3.根据权利要求1所述的混合氧化物催化剂,其包括透气的中空形状物。
4.根据权利要求1-3所述的混合氧化物催化剂,其包括由多层构成的中空形状物。
5.一种制备根据权利要求1-4所述的由中空形状物构成的混合氧化物催化剂的方法,包括:将存在于通式I的混合氧化物催化剂中的元素的化合物的溶液混合,制备共沉淀物,将所得的固体分离,任选地将所述固体干燥和煅烧,以及向由有机材料构成的载体以悬浮体的形式涂布所得的细粒状的固体作为一层,任选地与粘合剂一起涂布,以及在将涂布到载体的层的固化过程中或固化之后,除去所述有机材料。
6.根据权利要求5所述的方法,其中所述载体的形状为球形。
7.根据权利要求5所述的方法,其中,采用平均粒径分布在0.01-80μm之间的煅烧过的或部分煅烧过的细固体,来制备所述悬浮体。
8.根据权利要求6所述的方法,其中,采用平均粒径分布在0.01-80μm之间的煅烧过的或部分煅烧过的细固体,来制备所述悬浮体。
9.根据权利要求5-8所述的方法,其中,通过喷雾-干燥来对所述固体进行干燥,所述喷雾-干燥的粉末的平均粒径分布在0.1-50μm之间,任选地,所述粉末经过研磨。
10.根据权利要求5和8所述的方法,其中,将所述煅烧过的或部分煅烧过的粉末的平均粒径分布调整至0.01-30μm,任选地,所述粉末经过研磨。
11.根据权利要求5-8所述的方法,其中,在涂布所述细粒状的固体之后,将催化剂前体干燥,然后,在450-600℃的温度范围内,在氧的存在下进行热处理。
12.一种制备醛和酸的方法,所述方法在惰性气体、水蒸汽或来自反应的废气的存在下,在高温下通过用空气或氧气氧化烯烃或甲基化芳香族化合物来进行,其特征在于,采用由中空形状物构成并且具有以下通式的催化剂:
(Mo12BiaCb(Co+Ni)cDdEeFfGGHh)Ox (I)
C:铁,
D:选自W和P中的至少一种元素,
E:选自Li、K、Na、Rb、Cs、Mg、Ca、Ba和Sr中的至少一种元素,
F:选自Ce、Mn、Cr和V中的至少一种元素,
G:选自Nb、Se、Te、Sm、Gd、La、Y、Pd、Pt、Ru、Ag和Au中的至少一种元素,
H:选自Si、Al、Ti和Zr中的至少一种元素,
以及下标
a=0-5.0
b=0.5-5.0
c=2-15
d=0.01-5.0
e=0.001-2
f=0.001-5
g=0-1.5
h=0-800,
以及
x=由除了氧之外的元素的价态和相应下标决定的数值,
所述催化剂包括直径为0.5-5mm的中空球状物。
13.根据权利要求12所述的方法,其中采用根据权利要求1-4所述的催化剂。
14.根据权利要求12或13所述的方法,其特征在于,从丙烯获得丙烯醛和丙烯酸。
15.根据权利要求12或13所述的方法,其特征在于,从异丁烯获得甲基丙烯醛和甲基丙烯酸。
16.根据权利要求12或13所述的方法,其特征在于,从甲苯获得苯甲醛和苯甲酸。
17.根据权利要求12或13所述的方法,其特征在于,所述催化剂与反应气体混合物接触,所述反应气体混合物包含比例为1∶6-9∶3-18的烯烃或甲基化芳香族化合物、空气和惰性气体。
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GB2055787B (en) * | 1979-08-01 | 1983-02-16 | Ass Cement Co | Closed cellular hollow refractory spheres |
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JP2988660B2 (ja) * | 1996-12-12 | 1999-12-13 | 株式会社日本触媒 | メタクロレインおよびメタクリル酸の製造方法 |
KR100569632B1 (ko) * | 1999-05-13 | 2006-04-10 | 가부시키가이샤 닛폰 쇼쿠바이 | 불포화 알데히드 및 불포화 카르복실산을 제조하기 위한촉매 및 이 촉매를 사용하여 불포화 알데히드 및 불포화카르복실산을 제조하기 위한 방법 |
DE19933450A1 (de) | 1999-07-16 | 2001-01-18 | Degussa | Metallkatalysatoren |
RU2285690C2 (ru) * | 2000-06-20 | 2006-10-20 | Басф Акциенгезельшафт | Способ получения акролеина и/или акриловой кислоты |
JP2004526686A (ja) * | 2000-12-23 | 2004-09-02 | デグサ アクチエンゲゼルシャフト | カルボニル化合物の水素化によるアルコールの製法 |
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TW200400851A (en) * | 2002-06-25 | 2004-01-16 | Rohm & Haas | PVD supported mixed metal oxide catalyst |
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TWI342877B (en) * | 2003-12-26 | 2011-06-01 | Lg Chemical Ltd | Method of producing unsaturated aldehyde and/or unsaturated acid |
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2007
- 2007-03-01 DE DE102007009981A patent/DE102007009981A1/de not_active Withdrawn
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2008
- 2008-01-28 US US12/528,407 patent/US20100324331A1/en not_active Abandoned
- 2008-01-28 MX MX2009007862A patent/MX2009007862A/es active IP Right Grant
- 2008-01-28 SG SG201101399-2A patent/SG170046A1/en unknown
- 2008-01-28 RU RU2009135860/04A patent/RU2491122C2/ru not_active IP Right Cessation
- 2008-01-28 CN CN200880006754.0A patent/CN101631615B/zh not_active Expired - Fee Related
- 2008-01-28 EP EP08708303.6A patent/EP2125213B1/de active Active
- 2008-01-28 JP JP2009551149A patent/JP5610771B2/ja not_active Expired - Fee Related
- 2008-01-28 WO PCT/EP2008/050985 patent/WO2008104432A1/de active Application Filing
- 2008-01-28 BR BRPI0808026-7A2A patent/BRPI0808026A2/pt not_active Application Discontinuation
- 2008-01-28 MY MYPI20093589A patent/MY162690A/en unknown
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US4537874A (en) * | 1982-10-22 | 1985-08-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for production of unsaturated aldehydes |
CN1856364A (zh) * | 2003-09-22 | 2006-11-01 | 巴斯福股份公司 | 制备环状超催化剂的方法 |
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WO2008104432A1 (de) | 2008-09-04 |
DE102007009981A1 (de) | 2008-09-04 |
SG170046A1 (en) | 2011-04-29 |
RU2009135860A (ru) | 2011-05-27 |
JP5610771B2 (ja) | 2014-10-22 |
BRPI0808026A2 (pt) | 2014-06-17 |
EP2125213B1 (de) | 2019-03-20 |
US20100324331A1 (en) | 2010-12-23 |
JP2010520040A (ja) | 2010-06-10 |
CN101631615A (zh) | 2010-01-20 |
RU2491122C2 (ru) | 2013-08-27 |
US20120283088A1 (en) | 2012-11-08 |
MX2009007862A (es) | 2009-07-31 |
EP2125213A1 (de) | 2009-12-02 |
MY162690A (en) | 2017-07-14 |
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