CN1112243C - 保持含钼金属氧化物催化剂的活性 - Google Patents
保持含钼金属氧化物催化剂的活性 Download PDFInfo
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Abstract
在有机化合物的气相氧化中,使用金属氧化物流化床催化剂,其中含有10%(重量)或以上的钼,铋和选自铁和铈中的至少一种元素,当碲结合入该催化剂中时,其中碲对钼的原子比为(0.05-1.5)∶10,可以延长的时间内保持催化剂的活性,同时,可以防止钼和碲在氧化反应期间损失。
Description
本发明涉及保持含钼金属氧化物催化剂的活性的方法,所述的催化剂用于在高温下,在气相流化床反应中进行的例如有机化合物的氧化作用(包括氨氧化作用和氧化脱氢作用)。
已经知道,含钼的金属氧化物催化剂用于有机氧化物的氧化作用(包括氨氧化作用和氧化脱氢作用),例如,使用这些催化剂通过丙烯氧化生产丙烯醛或丙烯酸、通过丙烯的氨氧化生产丙烯腈、通过异丁烯或叔-丁烯的氧化生产异丁烯醛或甲基丙烯酸、通过异丁烯或叔-丁醇的氨氧化生产甲基丙烯腈、通过丙烷的氨氧化生产丙烯腈、通过异丁烷的氧化生产甲基丙烯腈、通过甲醇、甲醛缩二甲醇或类似物的氧化生产甲醛、通过甲醇的氨氧化生产氢氰化物和通过正-丁烯的氧化脱氢生产丁二烯或类是物。另外,该催化剂还可用于烷基芳基烃或烷基芳香杂环化合物氧化或氨氧化。
作为在上述反应中使用的含钼金属氧化物催化剂,已经公开在下述的文献中,日本专利公告3563/1961(US 2,941,007),日本专利公告27490/1972(US3959384),日本专利公告5870/1971(US2,904,580),日本专利公告33888/1976(US4,503,001),日本专利公开47319/1974(US3,898,267),日本专利公开16887/1973(US4,036,870),日本专利公开257/1990(US5,049,692),日本专利公告35400/1976(US3,911,089),日本专利公告39005/1977(US3,801,670),日本专利公告44249/1985,日本专利公开223812/1995,日本专利公告14659/1981(US3,803,204),日本专利公开111565/1977(US4,055,511)等。建议含有钼和碲的催化剂公开在下列的文献中,日本专利公告41583/1987(US4,446,328),日本专利公告41584/1987(US4,446,328),日本专利公告41585/1987(US4,446,328),日本专利公开70922/1974(GB1,415,766),日本专利公开38330/1980(US4,278,614),日本专利公告38424/1983(US3,969,390),日本专利公告38425/1983(3,928,409),日本专利公开114560/1982,日本专利公开130549/1982(GB2,090,156),日本专利公开228950/1989,日本专利公开118051/1992(US5,132,269),日本专利公告16971/1980等。
虽然这些含钼金属氧化物具有优良的性能,但是,人们已经知道,当反应温度较高时,这些钼组分会从许多催化剂中损失掉,从而引起各种各样的问题,例如催化剂的性能恶化了,并在反应系统的一侧沉积(J.Bulten,催化杂志,10,188-199(1968);G.P.Wing,L.B.Sis,J.S.Wheeler,催化杂志,38,196-205(1975);I.Nicolau,A.Aguilo,P.B.DeGroot,第4届国际化学大会,钼的使用,1982,234-240;等)。
人们认为以下列方式丢失钼组分:在反应中,催化剂中的三氧化钼与水反应,在反应中生成挥发的MoO2(OH)2气体,并从催化剂中损失掉。
为了解决这个问题,研究者们已采用了通过改进催化剂组分以降低游离的三氧化钼的量,使游离的三氧化钼转变成为钼酸盐。然而,这不是必需满足的,因为这使反应结果和催化剂的寿命或性能彼此相容变得非常困难。
进而,研究者们还以降低反应温度,寻找有关固定床反应即使在低温下仍具有活性的催化剂,以及尝试防止热点的发生。从而,解决这种问题以得到一些烯烃氧化值。然而,在高温下进行这些反应,例如,在烯烃的氨氧化反应中,钼组分丢失的问题常常趋向于比较多。
人们认为丢失一些量的钼成分是不可避免的。通常采用这样的方法,通过在反应中补充钼组分以保持含钼催化剂的活性。当反应是固定床反应时,使用这种类型的方法公开在下述的文献中,日本专利公告1848/1966,英国专利公告814075日本专利公开193136/1984和10779/1995(US5,602,280)等;当反应是流化床反应时,使用这种类型的方法公开在下述的文献中,日本专利公告57422/1983,德国专利公告3311521,日本专利公开301051/1993等,所有这些方法都是这样,在惰性载体上载有氧化钼或钼化合物,或者将富钼组分的催化剂加入到反应系统中,以补充使用的催化剂流失的钼组分。虽然,通过这些方法可以保留催化活性达到某一值,但是它们仍存在一些问题,因为它们必需在一短的时间周期内,连续的和重复补充钼组分。另外,特别在固定床反应中,补充钼组分以使按照需要的在催化剂上沉积的钼组分的分布变得非常困难。然而有这种可能,在低温区域,挥发的钼组分被沉积在或积聚在反应系统内会引起各种各样的问题,并且补充钼组分会促使这种趋向。
然而,在本技术领域,应使研制的含钼金属氧化物催化剂满足一些要求,即该催化剂在反应期间不会迅速丢失钼组分,并长时间周期保持优良的催化活性而不用补充钼组分,或者即使需要补充一些钼组分也是极少量的。
本发明的实现可以克服上述传统含钼金属氧化物催化剂的缺陷,本发明的目的是提供一种防止含钼金属氧化物催化剂丢失它的钼组分、同时当在高温下用气相流化床反应进行有机化合物的反应(包括氨氧化和氧化脱氢反应)而充分地保持优良的催化剂活性的方法。
在我们研究的过程中,我们发现如下:在下列情况下,用气相流化床反应进行烯烃氨氧化使用催化剂是含有钼、铋和一种或二种选自铁和铈组成基团的元素的金属氧化物,如果将少量的碲加入到金属氧化物中,人们认为在反应期间可以防止催化剂中钼组分的损失,同时可以延长催化剂的寿命。本发明的实现是基于这种发现。
本发明的一个方面是保持含钼氧化物催化剂活性的方法,本发明的另一方面是含有的钼组分不低于10%(重量)的含钼氧化物催化剂,将其用于在300-500℃的范围内用气相流化床反应进行有机化合物的氧化,它包括(i)铋、(ii)铁和/或铈和(iii)碲,碲对钼的原子比=(0.05-1.5)∶10。〔催化剂〕
本发用于保持含钼氧化物催化剂的活性的方法中,重要的一点是将碲混入含有钼、铋和铁和/或铈的金属氧化物中。按照此,可以防止含钼金属氧化物催化剂丢失钼组分并可保持优良的催化活性。
在不含铋、铁或铈的催化剂的情况下,即使向其加入碲组分催化剂仍会迅速还原,其结果,在催化剂表面分离出金属碲,或在反应期间,从催化剂中丢失碲组分,这种类型的催化剂在用作工业催化剂的性能方面是不充分的。
在保持催化活性上有所改善的本发明的含钼氧化物催化剂与上述现有的含钼氧化催化剂的区别在于它们的钼含量为10%(重量)或更多并且它们含有(i)铋,(ii)铁和/或铈,和(iii)碲,其碲对钼的原子比=(0.05-1.5)∶10。
本发明催化剂的钼含量是10%(重量)或更多,优选在10-70%(重量)的范围内。
将碲加入到这种含钼氧化物催化剂中,以便碲∶钼的原子比为(0.05-1.5)∶10,优选(0.1-1.0)∶10。
本发明的含钼金属氧化物组分催化剂的优选实施例由下式表示:
MoaBibMecTedQeRfXgYhOz
式中:Me表示一个或二个选自Fe和Ce中的元素;
Q表示至少一种选自Be,Mg,Ca,Sr,Ba,Ni和Co中的元素,优选一种选自Mg,Ca,Ba,Ni和Co中的元素。
R表示至少一种选自P,B,As,Se,Li,Na,K,Rb,Cs和Tl中的元素,优选至少一种选自P,B,Li,Na,K,Rb和Cs中的元素。
X表示至少一种选自V,W,Y,La,Zr,Hf,Nb,Ta,Zn,Cd,Al,Ga,In,Ge,Sn,Sb和Pb中的元素,优选至少一种选自V,W,La,Zr,Nb,Ta,Zn,Al,Ga,In,Ge,Sn和Sb中的元素;
Y表示至少一种选自Pr,Nd,Sm,Eu,Gd,Th,U,Cr,Mn,Re,Ru,Rh,Pd,Os,Ir,Pt,Cu,Ag和Au中的元素,优选至少一种选自Pr,Nd,Sm,U,Cr,Mn,Re,Ru,Rh,Pd,Os,Ir,Pt,Cu和Ag中的元素;和
符号a,b,c,d,e,f,g,h和z表示原子比,当a=10时,b,c,d,e,f,g和h分别如下:0.1≤b≤3,优选0.2≤b≤2.5;
0.1≤c≤10,优选0.2≤c≤8;
0.05≤d≤1.5,优选0.1≤d≤1.25
0≤e≤6.75,优选0≤e≤6.5
0≤f≤3,优选0.2≤f≤2
0≤g≤8,优选0≤g≤5
0≤h≤0.8,优选0≤h≤0.7,和
z表示上述组分化合时,在形成的氧化物中的氧原子数;
人们知道,碲成分会很快的还原并且比钼成分更容易损失掉〔T.Ohara,M.Hirai,N.Shimizu,烃加工,11月,1972,85-88〕。在含有钼和碲的催化系统中,由于碲的损失引起催化活性的降低不会带来一系列问题。
然而,当将碲加入到含有钼,铋,铁和/或铈的催化系统中时,所提供的加入的碲的量与上述钼的量比较是很少的,一方面可防止碲组分自身的损失,同时可防止钼组分的损失。这从传统知识来说是一种意外的发现。
对于这种现象的原因还不太清楚,但是一般认为如下:在钼氧化物中或在钼酸盐中含有的钼用离子半径大致相等于这些钼的碲部分代替以形成固溶体并促使晶格氧的运动,从而提高了氧化还原的稳定性,还强化了结构的稳定性。
当将碲加入到催化剂中,没有检测到新结晶相的形成,通过X-射线粉末绕射法难于发现清晰的变化。
在加入碲的量为碲:钼的原子比小于0.05-10时,防止钼组分损失作用较小。另一方面,当加入碲的量为碲∶钼的原子比大于1.5-10时,可促进催化剂的烧结。其结果,可以降低反应比,并可降低所希望产品的收率。而在氨氧化反应的情况下,虽然可以确认防止钼成分损失的作用,但是氨的氧化趋向升高,或者碲组分的损失趋向于增多。
在本发明中,将碲成分的规定量加入到含有钼,铋,和铁和/或铈的金属氧化物中,传统认为上述碲成分的量在反应中将容易还原并容易损失掉。按照上述进行,能够显著的防止钼组分的损失,同时,也防止碲组分的损失。从而,可以防止催化剂急剧恶化,可以延长保持优良的催化活性时间周期。另外,例如在反应系统沉积或积累钼组分等问题也减少了。在工业生产中,本发明具有极大经济价值的优越性。
本发明的催化剂表明,即使没有载体支持,也具有优良的活性。然而,可以使用下述的载体支持,例如硅石,氧化铝,硅石-氧化铝,二氧化钛或氧化锆或其混合物。在这种情况下,载体量优选催化剂总重量的10-70%。
虽然本发明的催化剂可用于固定床反应和流化床反应,但是,将其用于流化床反应可以强化它的优点。即在流化床反应中,本发明催化剂的流化大大地改善了,从而使在反应期间催化剂性能的降低比较小,使催化剂微粒的气动力学传输的操作性,在旋风分离器的斜腿中催化剂的向下流动等也得到显著的改善。而当使用含钼催化剂时,常常引起在反应器或热交换器中钼组分的沉积或积累,而按照本发明,上述的现象显著的减少了,或者在这些设备中没有观察到。从工业观点认为,也是有利的。
作为流化床催化剂,优选的微粒直径为10-500微米。
〔催化剂的应用〕
优选本发明的催化剂用于有机化合物的氧化反应。在本文中使用的氧化反应指的不仅是简单的氧化,而且还指氨氧化和氧化脱氢。特别是,优选使用本发明的催化剂用于生产不饱和醛,不饱和腈,氢氰化物,芳烃醛,芳烃腈,或者通过有机化合物氧化,氨氧化或氧化脱氢生产的类似物。一般,这些反应是在300-500℃下进行的,特别是,在生产腈的氨氧化反应中,最佳的反应温度常常高于400℃,从而连成由于催化剂中的钼组分的损失会带来各种各样的问题。据此,特别优选本发明的催化剂用于用烯烃,石蜡或醇的氨氧化生产腈。优选本发明的催化剂反应,例如烯烃氨氧化成为相应的腈,特别是丙烯或异丁烯的氨氧化成丙烯腈或甲基丙烯腈,以及醇氨氧化反应成相应的腈,特别是甲醇氨氧化成氢氰化物。
〔催化剂的制备方法〕
本发明的催化剂可用任何已知的方法制备。例如可使用的这些方法公开在下列出版物中:日本专利公告8568/1962,49253/1982(US3,746,657),12913/1979和1674/1976(DE1,542,330),日本专利公开59046/1990和214543/1990(US5,059,573)等。〔催化剂的原料〕
本发明的催化剂的每种成分的原料选自大量的各种各样的材料,例如金属,氧化物,氢氧化物,氯化物和每种金属成分的硝酸盐。而,当催化剂要进行化学处理或烧结时,这些可转变成为氧化物的化合物也可被使用。
用作钼组分的原料可是氧化钼例如:三氧化钼,钼酸,仲钼酸铵,偏钼酸铵,和杂多酸例如磷钼酸,和硅钼酸及其盐。
用作铋组分的原料可是铋盐例如:硝酸铋,硫酸铋,三氧化铋,和金属铋和硝酸的氧化产品。
用作铁组分的原料可是氧化铁例如:氧化亚铁,氧化铁,和四氧化三铁,铁的无机酸盐例如氯化亚铁,氯化铁,硝酸铁和碳酸铁,金属铁与硝酸的氧化产品,以及铁的有机酸盐例如草酸铁和柠檬酸铁。
用作铈组分的原料可是例如:氧化铈,氢氧化铈,硫酸铈,乙酸铈,硝酸铈和硝酸铈铵。
用作碲组分的原料可是例如:金属碲,二氧化碲,三氧化碲,碲酸和硝酸碲。
用作钴组分的原料可是例如:氧化钴,氢氧化钴和金属钴和硝酸的氧化产品。
用作镍组分的原料可是例如:氧化镍,氢氧化镍,硝酸镍和金属镍和硝酸的氧化产品。
用作钒组分的原料可是例如:偏钒酸铵,硫酸氧钒,草酸氧钒,五氧化钒和过氧化钒化合物。
用作钨组分的原料可是例如:三氧化钨,钨酸,钨盐例如仲钨酸铵,偏钨酸铵和杂多酸例如磷钨酸和其盐。
用作其它Q,R,X和Y组分的原料,可以使用每种成分的氧化物,氢氧化物,氯化物,和硝酸盐。
用作载体的原料可是硅石溶胶,硅石水凝胶,烟化硅石,氧化铝溶胶,氧化铅粉末,二氧化钛溶胶,二氧化钛粉末等。
〔催化剂的制备〕
通过将上述用于催化剂的材料混合制备本发明的催化剂使催化剂具有所需要的组分,然后干燥,焙烧该混合物。关于流化床催化剂的制备,优选通过混合催化剂组分喷雾干燥制得的浆料以获得球形微粒。在200-800℃优选400-750℃加热这些微粒0.5-10小时。焙烧优选是在没有还原的气氛下进行,这种气氛或是在含有分子氧的氧化气氛下,或是在惰性气体例如氮气的气氛下进行,从经济原因方面考虑,优选在空气气氛下进行焙烧。用作焙烧的设备可使用管式炉,旋转炉,流化床焙烧炉等。
〔实施例〕
现在参照下列的实施例详细描述本发明的实施例和优点,然而这些实施例不限制本发明。〔催化活性的试验方法〕
装填有催化剂的流化床反应器内径为25mm,外径为400mm,在下列条件下,将丙烯或甲醇,氨,氧和氮输入反应器;
(试验条件)
(1)丙烯/氨/氧/氮(摩尔比)=1/1.2/1.9/7.9;反应温度:420-450℃;
气体线速:4.5cm/秒;压力:202.6kpa。
(2)甲醇/氨/氧/氮(摩尔比)=1/1.0/1.2/4.5;反应温度420℃;
气体线速:4.5cm/秒;压力:101.3kpa。
丙烯或甲醇的转化率,丙烯腈或氢氰化物的收率如下:
丙烯或甲醇的转化率(%)=〔(通过反应丙烯或甲醇消耗的摩尔数)/(输入丙烯或甲醇的摩尔数)〕×100;
丙烯腈或氢氰化物的收率(%)=〔(生产的丙烯腈或氢氰化物的摩尔数)/(输入的丙烯或甲醇的摩尔数)〕×100;
(催化剂1)
一种氧化物组分具有下列经验式:
Mo10Bi0.8Te0.5Fe1.7Ni2.1Co3.75Mn0.8Cr0.4K0.08O42.84(SiO2)40
通过下列方法制备上述组分,将溶解在400g纯水中的368g钼酸铵加热,加入2,511g20%硅石溶胶,搅拌。向该溶液加入127.6g硝酸镍、228g硝酸钴、33.4g硝酸铬、48g 50%硝酸锰和1.7g硝酸钾250g纯水溶液。搅拌该混合物,向该混合物加入81g硝酸铋、143.5g硝酸铁、24g碲酸、30g柠檬酸和100g10%硝酸溶液,搅拌。通过加入15%的氨水将生成的浆液的PH最后调节到8。在100℃加热该浆液1小时,通过旋转盘式喷雾干燥器喷雾干燥,上述的喷雾干燥器的进口和出口温度分别调节到320℃和160℃。在250℃热处理得到的微粒,然后在400℃第1次焙烧上述微粒2.5小时,最后在600℃焙烧上述微粒3小时。
(催化剂2)
一种氧化物组分具有如下的经验式:
Mo10W0.4Bi0.8Te0.25Fe1.6Ni2.0Co3.5Cr0.25Mn0.9
Smo.09Na0.25K0.4Rb0.04Cs0.09O43.5(SiO2)40
以生产催化剂1的相同方法制备上述组分,要注意的是,在670℃焙烧催化剂3小时。
(催化剂3)
一种氧化物组分具有如下的经验式:
P0.25Mo10Bi2.0Te1.0Fe5.5Ce0.5K0.06O44.65(SiO2)40
以生产催化剂1的相同方法制备上述组分,要注意的是,在690℃焙烧催化剂3小时。
(催化剂4)
一种氧化物组分具有如下的经验式:
P0.3Mo10Bi1.0Te0.25Fe2.0Mg6.0K0.2O42.15(SiO2)60
以生产催化剂1的相同方法制备上述组分,要注意的是,在600℃焙烧催化剂3小时。
(催化剂5)
一种氧化物组分具有如下的经验式:
P0.3Mo10Wo0.1Bi1.0Te1.5Fe2.0Mg6.0K0.2O44.65(SiO2)60
以生产催化剂1的相同方法制备上述组分,要注意的是,在600℃焙烧催化剂3小时。
(催化剂6)
一种氧化物组分具有如下的经验式:
Mo10Bi1.0Te0.25Fe7.5Mg6.0K0.2O42.5(SiO2)60
以下列方法制备上述组分:将77g65%硝酸与423g纯水混合,在该混合物中溶解432.8g硝酸铁和34.6g硝酸铋。然后向该溶液加入3,433g硅石溶胶,和8.2g碲酸,搅拌,向生成的混合物加入252.2g仲钼酸铵1000g纯水溶液。在100℃热处理该混合物3小时,用生产催化剂1的相同方法喷雾干燥得到的浆液,在750℃焙烧3小时。(催化剂7)
一种氧化物组分具有如下的经验式:
Mo10Bi0.8Fe1.7Ni2.1Co3.75Mn0.8Cr0.4K0.08O41.84(SiO2)40
以生产催化剂1的相同方法制备上述组分,要注意的是,在600℃焙烧催化剂3小时。
(催化剂8)
一种氧化物组分具有如下的经验式:
Mo10W0.4Bi0.8Fe1.6Ni2.0Co3.5Cr0.25Mn0.9Sm0.09Na0.25K0.4Rb0.04Cs0.09O43(SiO2)40
以生产催化剂1的相同方法制备上述组分,要注意的是,在670℃焙烧催化剂3小时。
(催化剂9)
一种氧化物组分具有如下的经验式:
P0.25Mo10Bi2.0Fe3.5Ce0.5K0.06O44.15(SiO2)40
以生产催化剂1的相同方法制备上述组分,要注意的是,在690℃焙烧催化剂3小时。
(催化剂10)
一种氧化物组分具有如下的经验式:
P0.3Mo10W0.1Bi1.0Te0.01Fe2.0Mg6.0K0.2O41.67(SiO2)60
以生产催化剂1的相同方法制备上述组分,要注意的是,在600℃焙烧催化剂3小时。
(催化剂11)
一种氧化物组分具有如下的经验式:
P0.3Mo10W0.1Bi1.0Te2.0Fe2.0Mg6.0K0.2O45.65(SiO2)60
以生产催化剂1的相同方法制备上述组分,要注意的是,在600℃焙烧催化剂3小时。
(催化剂12)
一种氧化物组分具有如下的经验式:
Mo10Bi0.5Te0.25Fe7.5O42.0(SiO2)80
以生产催化剂6的相同方法制备上述组分,要注意的是,在750℃焙烧催化剂3小时。
实施例1-5与比较例1-5
使用上述催化剂1-5(实施例1-5)和催化剂7-11(比较例1-5),在上述的试验条件下进行丙烯的氨氧化,结果见表1;
表1
注:“PP”是丙烯的缩写;
试验实施例 | 催化剂 | 接触时间秒 | 在50小时反应后 | 在500小时反应后 | ||
PP转化率% | AN收率% | PP转化率% | AN收率% | |||
实施例12345 | 催化剂12345 | 4.504.254.752.753.00 | 9696.295.596.296.0 | 76.779.275.978.878.5 | 93.594.394.995.395.8 | 75.277.675.377.978.2 |
比较例12345 | 催化剂7891011 | 4.54.254.752.753.00 | 96.296.595.996.395.8 | 77.079.076.378.578.0 | 92.593.293.594.195.5 | 74.176.274.0.76.377.7 |
“AN”是丙烯腈的缩写;
实施例6和比较例6
在上述试验条件下用上述的催化剂6(实施例6)或催化剂12(比较例6)进行甲醇的氨氧化反应,结果示于表2:
表2
注:“ME”是甲醇缩写;
试验例 | 催化剂 | 接触时间(秒) | 50小时反应后 | 500小时反应后 | ||
ME转化率% | HCN收率% | ME转化率% | HCN收率% | |||
实施例6 | 催化剂6 | 0.3 | 98.4 | 88.5 | 98.5 | 88.3 |
比较例6 | 催化剂12 | 0.3 | 98.8 | 89.1 | 97.8 | 87.1 |
〔讨论〕
与在比较例1,2,3和6使用的不含碲的催化剂的活性比较,当用于氧化反应时例如丙烯或甲醇的氨氧化反应本发明的催化剂的活性可以稳定的长时间周期内保持比较高。而在用本发明的催化剂进行反应后,确认几乎没有钼组分沉积在反应器的上部。在反应之后从反应器中落下呈现优良的流动性,分析这些催化剂的组分的结果显示钼和碲的含量几乎没有变化。
相反,在比较例1,2,3或6中用不含碲组分的催化剂进行反应后,或比较例4中用仅含少量碲组分的催化剂进行反应后,发现白色的氧化钼沉积在反应器的上部。收集氧化钼并称重,结果在比较例1中氧化钼的重量为0.12g,在比较例4中氧化钼的重量为0.1g。而在比较例1,2,3和6中用的催化剂,发现在反应后,上述催化剂从反应器中落下流动性较差。而在比较例5中用含有高碲含量催化剂11的催化剂进行反应之后,发现在反应器的上部沉积有金属碲。
Claims (2)
1,一种钼含量不低于10%(重量)的含钼氧化物催化剂,用于在300-500℃的范围内由气相流化床反应进行丙烯氨氧化和甲醇氨氧化,用下列通式表示含有的组分:
MoaBibMecTedQeRfXgYhOz
式中:Me表示一个或二个选自Fe和Ce中的元素;
Q表示至少一种选自Be,Mg,Ca,Sr,Ba,Ni和Co中的元素;
R表示至少一种选自P,B,As,Se,Li,Na,K,Rb,Cs和Tl中的元素;
X表示至少一种选自V,W,Y,La,Zr,Hf,Nb,Ta,Zn,Cd,Al,Ga,In,Ge,Sn,Sb和Pb中的元素;
Y表示至少一种选自Pr,Nd,Sm,Eu,Gd,Th,U,Cr,Mn,Re,Ru,Rh,Pd,Os,Ir,Pt,Cu,Ag和Au中的元素;和
符号a,b,c,d,e,f,g,h和z表示原子比,当a=10时,b,c,d,e,f,g和h分别如下:0.1≤b≤3,0.1≤c≤10,0.05≤d≤1.5,0≤e≤6.75,0≤f≤3,0≤g≤8,0≤h≤0.8,和z表示上述组分结合时在形成的氧化物中的氧原子数,其中所述组合物不含钛。
2,按照权利要求1的含钼氧化物催化剂,其通式中的符号a-h分别为下列值:
a:10;
b:0.2-2.5;
c:0.2-8;
d:0.1-1.25;
e:0-6.5;
f:0-2;
g:0-5;
h:0-0.7。
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KR100807972B1 (ko) | 2005-08-10 | 2008-02-28 | 주식회사 엘지화학 | 아크릴산 선택성이 높은 복합 금속 산화물 촉매 |
CN101678334A (zh) * | 2007-05-03 | 2010-03-24 | 国际壳牌研究有限公司 | 催化剂及其制备和用途 |
US7763225B2 (en) * | 2007-06-25 | 2010-07-27 | Ascend Performance Materials Llc | Process of catalytic ammoxidation for hydrogen cyanide production |
US8455388B2 (en) * | 2010-03-23 | 2013-06-04 | Ineos Usa Llc | Attrition resistant mixed metal oxide ammoxidation catalysts |
WO2012033048A1 (ja) * | 2010-09-07 | 2012-03-15 | 三菱レイヨン株式会社 | 固体触媒の抜取り方法 |
CN104203908B (zh) * | 2012-02-29 | 2016-12-07 | 三菱丽阳株式会社 | 丙烯腈的制造方法 |
KR101495478B1 (ko) * | 2013-05-06 | 2015-02-23 | 주식회사 엘지화학 | 부타디엔 제조를 위한 산화촉매 및 그 제조방법 |
CN105905924B (zh) * | 2016-05-12 | 2018-11-09 | 安徽省安庆市曙光化工股份有限公司 | 制备氢氰酸的方法 |
US10479759B2 (en) | 2017-02-08 | 2019-11-19 | Clariant Corporation | Synthetic methods for the preparation of propylene ammoxidation catalysts |
CN110893344B (zh) * | 2018-09-13 | 2021-04-27 | 中国科学院大连化学物理研究所 | 一种甲醇氧化制甲醛铁钼催化剂及制备和应用 |
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US6136998A (en) | 2000-10-24 |
EP0836881A1 (en) | 1998-04-22 |
EP0836881B1 (en) | 2003-07-30 |
NL1007287C2 (nl) | 1998-05-11 |
CN1179359A (zh) | 1998-04-22 |
ES2203759T3 (es) | 2004-04-16 |
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