CN1031488A - 丙烯醛氧化催化剂及其制备方法 - Google Patents
丙烯醛氧化催化剂及其制备方法 Download PDFInfo
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- CN1031488A CN1031488A CN88104316A CN88104316A CN1031488A CN 1031488 A CN1031488 A CN 1031488A CN 88104316 A CN88104316 A CN 88104316A CN 88104316 A CN88104316 A CN 88104316A CN 1031488 A CN1031488 A CN 1031488A
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Classifications
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Abstract
用于由丙烯醛气相催化氧化制备丙烯酸的催化
剂,含有的活性物质如下式所示:Mo(a)V(b)A(c)B
(d)C(e)D(f)O(x)式中各符号的含意均如说明书所
示。催化剂的比表面为0.50至15.0m2/g,孔隙度为
0.10至0.99cc/g,孔径分布为孔径集中分布在0.1
至小于1.0μm和10.0至100μm的范围内。通过将
未焙烧的催化剂物料粉末组合物加入离心式流动涂
敷装置成型为直径2-10mm的颗粒并焙烧这些颗粒
来制备催化剂,具有良好的再现性。
Description
本发明涉及适用于由丙烯醛生产丙烯酸的催化剂及制备方法,该催化剂含有钼和钒为主要成份。更具体的讲,本发明涉及丙烯醛氧化催化剂,具有较高活性和耐久性,该制备方法的再现性良好。
已有许多文献提出各种丙烯醛的催化剂,用于在高产率下从气相丙烯醛催化氧化生成丙烯酸。这些文献主要涉及催化剂成份的选择和它们的性质。其中有些还论及催化剂性质的选择和生产的再现性。不少文献虽然也涉及催化剂的性质,如比表面积、孔隙度等,但这些催化剂未达到令人满意的程度。
例如,作为公开的表面积,日本特许公开86812/1973和91010/1973认为,0.1至50m2/g的催化表面积是较好的,然而,这里所述的催化剂有反应温度高和生产能力低的缺点。日本特许公开47276/1974和24183/1975描述,比表面以0.1至8m2/g为佳。但是,这些催化剂的缺点是反应温度高达300℃以上。关于孔隙度和表面积的定义,日本特许公开65395/1974,和62409/1974叙述,4至8m2/g的表面积和0.1至0.2ml/g的孔隙度是较好的。可是,这里所述的催化剂含有钴和钼为活性组份,技术水平上是较低的。
日本特许公开47590/1976描述了一种含有磷、钼和铊或周期表ⅠA和Ⅱ族元素的催化剂,该催化剂由轧制成粒法成型,以使得具有4至20m2/g的表面积和0.08至0.5ml/g的孔隙度,在性能上有再现性。然而,这种催化剂也有反应温度高和性能不能令人满意的缺点。日本特许公开9737/1982公开了一种含有钼、钒、铜、铁、锰、碱土金属或锌和氧作为主要成份、还含有磷为任选成份的催化剂,以及用该催化剂氧化丙烯醛来制造丙烯酸的方法。在该催化剂的一个实施例中,用旋转涂糖机使直径3.5mm的刚铝石载上催化成份。在该催化剂中,反应温度比较低,大约200℃,所述催化剂实现较高产率。但是,用这种方法所得催化剂性质难以再现。
发明人认为,催化剂的性质不仅受到催化剂表面积和/或孔隙度的限定,而工业上优良的催化剂的性质兼顾了催化剂表面积、孔隙度和孔径分布三种因素的结合。同时,在用固定床或移动床反应装置进行丙烯醛的氧化反应时,所用的催化剂一般是有合适尺寸的球粒。这些颗粒由制片机、挤压机、制丸机、轧粒机等制成。然而,合成催化剂的物理性质不恒定,也就是说,多数情况表面,催化剂的再现性很低。因此,用这样的成型方法,很难得到催化剂性能不降低的催化剂。
本人经研究后弄清了各种成型机在成型时造成的催化剂性能的改变。结果发现,在含有Mo、V、A、B、C、D和O(其中Mo是钼,V是钒,A是钨或铌中至少一种,B为铁、铜、铋、铬、锑、铊中至少一种,C为碱金属或碱土金属中至少一种,D为硅、铝和钛中至少一种,O为氧)为活性组分的催化材料中,催化剂性能有很大的降低,性能和物理性质的改变取决于成型法,上述现象的主要原因,是成型时限制了催化剂的孔,从而调节了催化剂表面积、孔隙度和孔径。
所以,为获得含上述成份并具有优良性能的催化剂,进一步研究考虑了表面积、孔隙度和孔径分布。结果发现,这样的催化剂须满足三个条件,即:表面积为0.5至15.0m2/g;孔隙度为0.10至0.90cc/g;孔径分布在0.1至小于1.0μm、1.0至小于10.0μm和10至100μm。孔径为10至100μm的孔所占孔体积不少于总体积的10%,优选15-40%,孔径为1.0至小于10μm的孔和0.1至1.0μm的孔所占体积不小于总体积的10%,优选15~65%。当这些条件满足时,上述催化剂的活性和选择性均有提高。也即,孔径越小,例如小于1.0μm,对表面积和孔体积的贡献就越大。然而,在对活性和选择性有作用以影响反应产物的孔中,仅有大量的小孔是不够的。如果没有孔分布在1.0至小于10.0μm和10.0至100μm二个区间,就不可能提高催化剂的性能。
在上述发现的基础上,发明人继续努力研究,接着发现,用离心式流动涂覆机使未焙烧的不成形催化剂粉末形成颗粒,可以得到有良好再现性和催化性能的催化剂。
在常用的催化剂成型方法中,用轧制造粒法、球形造粒机成型法、流化床造粒化等制备球形,用挤压法、压片法等制备圆柱形。但是,使用这些方法,在很多情况下很难形成催化剂而不降低催化剂性能,性能常常变化很大,再现性也经常很差。与此相反,利用本发明的离心式流动涂覆装置时,装置操作简单并有良好的生产率,可以制备球形或粒状催化剂。而且,用离心式流动涂覆装置成型可以得到较窄颗粒尺寸分布的催化剂,因为这些催化剂是粒状或球形的,其机械强度高、阻力小、耐磨损,并容易从反应装置中取出或装入。
已知离心式流动涂覆装置可用于粉末物料的造粒方法。例如,日本特许公报10878/1971披露了这种应用,即给药物制剂裹糖衣。日本特许公报17292/1977也披露了用涂覆装置给颗粒 芯涂覆催化剂和/或载体的情况。
本发明中,该方法用于制备上述氧化催化剂。按照本发明的方法,可以很容易地得到有上述特定表面积、孔隙度和孔径分布的球形或粒状催化剂,仅仅用水作粘合剂或结合使用一种在焙烧时能通过燃烧或挥发使催化剂带孔的物质,都可使催化剂具有高的物理强度。例如,本发明的催化剂可这样制备:将未经焙烧的催化剂物料粉末成分加入离心式流动涂覆装置,向装置内鼓热风并喷洒象水一样的粘合剂使物料形成颗粒,以间歇或连续操作方式取出增大至所需尺寸的颗粒,必要时使其干燥,然后在200至500℃、最好300至450℃的温度下进行焙烧。
本发明的催化剂可直接使用,也可用惰性载体使之稀释或使催化剂承载于载体中。在颗粒成型过程中,优先选用通过预成型一种粒度比原料粉末大十倍以上的催化剂所得到的芯或颗粒。当然,该芯核也可用惰性载体。惰性载体的例子包括碳化硅、硅石、α-氧化铝和其它已知的耐火材料。关于涂覆催化剂粉末以增加颗粒直径,应先控制粉末不超过100目。为了制备本发明限定表面积、孔隙度和孔径分布并有良好再现性的催化剂,在制备配方或成型时,例如可将聚乙烯醇、硬脂酸等分加入该催化剂物料粉末中。作为粉末粘合剂,可用水、硝酸铵、石墨、淀粉等等,也可用有机溶剂如乙醇、丙酮等。
本发明催化剂的化学组成已知,可用下述通式表示:
Mo(a)V(b)A(c)B(d)C(e)D(f)O(x)
(式中Mo表示钼,V表示钒,A表示选自自钨和铌中的至少一种元素,B表示选自铁、铜、铋、铬、锑和铊一组中的至少一种元素,C表示选自碱金属和碱土金属中至少一种元素,D表示硅、铝和钛中 至少一种元素,O表示氧;另外,a、b、c、d、e、f和x分别表示Mo、V、A、B、C、D和O的原子比率,而且,当a=12时,b=2至14,c=0至12,d=0至6,e=0至6,f=0至30,x是由其它元素的氧化状态确定的一个数值。)
本发明的气相催化氧化反应在下述条件下进行:原料气由1-10%(V)的丙烯醛、1-15%(V)的分子氧、5-60%(V)的水蒸汽和20-80%(V)的惰性气体(如由氮气、碳酸气、饱和烃气等组成的混合气)组成,将原料气在150-400℃下、压力为常压至10atm和空速为500-20,000小时-1(标准温度压力)的条件上导入催化剂上。此外,也可直接用丙烯裂解反应得到的含丙烯醛气体作原料气。
下面用实施例和比较例详细说明本发明。然而,本发明并不限定于这些实施例。在本发明中,转化率和单流产率分别定义如下:
转化率(%)= (反应的丙烯醛分子数)/(加入的丙烯醛分子数) ×100
单流产率(%)= (生成的丙烯酸分子数)/(加入的丙烯醛分子数) ×100
例Ⅰ(催化剂物质悬浮液的制备)
在50升搅动的水中溶入1560克偏钨酸铵、1290克偏钒酸铵、5070克钼酸铵和180克重铬酸铵,制成含水溶液。单独地将1290克硝酸铜溶入3.0升水中制成另一种水溶液。将这两种溶液混合,加热混合液并搅拌,得到一种悬浮液。(该悬浮液称为悬浮液A)。
例Ⅰ-1-1
(用离心式流动涂覆方法制备催化剂)
对一部分悬浮液A加热搅拌,使之蒸发到干硬程度。然后在干燥器中将得到的块状固体在120℃下干燥5小时,磨细至100目得到粉末。先将平均直径为1mm的α-氧化铝加入离心式流动涂覆装置。然后在通入90℃的热风的同时将上述粉末和蒸馏水一起加入,形成平均直径为5mm的球形颗粒。在400℃温度下将如上得到的球形颗粒焙烧5小时。在结果催化剂氧化物中氧以外的组分比例为Mo(12)V(4.6)Cu(2.2)Cr(0.6)W(2.4)。该催化剂称之为催化剂(Ⅰ-1-1)。
例Ⅰ-1-2
(用离心式流动涂覆方法制备催化剂)
重复例Ⅰ-1-1,但用40%(W)的硝酸铵溶液代替水作粘合剂,得到催化剂(Ⅰ-1-2)。
例Ⅰ-2-1和Ⅰ-2-2
(用制片方法制备催化剂)
加热搅拌使一部分悬浮液A蒸发到干硬程度。在干燥器中用120℃的气流将得到的块状固体干燥5小时,然后将干块磨成不超过100目的粉末。向粉末加入2%(W)的碳粉,并将该混合物制成直径5mm和高5mm的片剂。在400℃下焙烧该片剂5小时制成催化剂(Ⅰ-2-1)。重复同样的程序制得另一催化剂(Ⅰ-2-2)。
例Ⅰ-3-1和Ⅰ-3-2
(用挤压方法制备催化剂)
蒸发浓缩一部分悬浮液A直到能挤压为止,挤压以形成直径5mm和长5mm的压出物。将压出物在400℃下焙烧5小时制得催化剂(Ⅰ-3-1)。重复同样的程序制得另一种催化剂(Ⅰ-3-2)。
例Ⅰ-4
(用球形造粒机成型方法制备催化剂)
用外部热源对一部分悬浮液A进行浓缩热处理,直到其能挤压为止。将浓缩物挤压造型以形成直径6mm和长4至7mm的压出物。然后使压出物经过一个球形造粒机以形成3mm×5mm的球体。在400℃下将球体焙烧5小时制成催化剂(Ⅰ-4)。
例Ⅰ-5
(用轧制造粒方法制备催化剂)
加热搅拌使一部分悬浮液A蒸发至干硬程度。然后在一个干燥器中使得到的块状固体在120℃下干燥5小时,将干块磨成约100目的粉末。先将平均直径为1mm的α-氧化铝颗粒加入扎制造粒机。然后将上述粉末加入,用80℃的热风和作为粘合剂的蒸馏水,制得平均直径为5mm的球。将球在400℃焙烧5小时制得催化剂(Ⅰ-5)。
例Ⅰ-6
(用制丸方法制备催化剂)
用外部热源对一部分悬浮液A进行浓缩热处理,得到一种似固物质,该物质在400℃下焙烧时要减小50%的重量。用制丸机将该似固物质制成平均直径为5mm的小球。在400℃下焙烧小球5小时,即制成催化剂(Ⅰ-6)
〔反应试验〕
按下述步骤进行了上述每种催化剂Ⅰ-1至Ⅰ-6的活性试验。
将1000ml催化剂装入内径为25.4mm的钢制反应器中,将工业用丙烯(纯度不低于95%)在钼/钴/钨氧化物催化剂存在下进行气相流催化氧化所得到的一种气体混合物导入反应器,使其在200至250℃的反应温度和3000小时-1的空速条件下进行反应。反应混合气的平均组成如下:
丙烯醛 5.64%(V)
丙烯+丙烷 0.65%(V)
丙烯酸+乙酸 0.74%(V)
氮气 70.03%(V)
水蒸汽 17.22%(V)
氧气 4.75%(V)
其它 0.97%(V)
例Ⅰ-1-3
用例Ⅰ-1-1的催化剂进行一种8000小时连续反应试验。反应试验的步骤与例Ⅰ相同。反应的起始温度是200℃,在8000小时期间升高5℃温度就足够了。在205℃的反应温度下的反应结果是丙烯醛转化率为99.6%和丙烯酸单流产率为97.0%。
例Ⅰ-7
(制备载体上的催化剂)
将一部分悬浮液A倒入位于热水浴中的蒸发器中,并向其加入比表面为1m2/g,空隙度为42%和直径为3至5mm的颗粒状α-氧化铝载体,其中孔的分布是直径75至250μ的孔占92%。使混合物搅拌蒸发到干硬程度,然后在400℃下,焙烧5小时制得催化剂(Ⅰ-7)。以与例Ⅰ-1至Ⅰ-6相同的方式进行反应试验。
表1列出了由催化剂Ⅰ-1至Ⅰ-7测出的物理性质和活性。
例Ⅱ
(制备催化剂并进行其再现性试验)
用与例1相同的方式制备悬浮液并分为四等份作四批用。由这四批制备适用于各种成型法的粉末成类似粘土材料。用与例Ⅰ-1至Ⅰ-7相同的方式将该材料制成催化剂,通过比较性能检验同种成形方法的再现性。用同一种成形方法,在同样的条件下用同样的程序制备四批催化剂。按照例Ⅰ-1至Ⅰ-7的程序进行性能测验,唯一例外的是按例Ⅰ-1-1进行例Ⅱ-1的测验。
表2列出了所得的结果。
由表2可明显得知,用离心式流动涂覆法成型的催化剂的物理性能和活性仅有较小的变化。在较小变化的基础上,可知能够制备具有良好再现性的催化剂。另一方面,还可看出,用其它成型法和某些批料制成的催化剂不具有本发明特定的表面积、孔隙度和孔径分布,尽管催化剂是在同样条件下制备的。作为可获得优良性能和再现性的方法,其它的成型方法不如离心式流动涂覆法好。
例Ⅲ
(制备催化剂材料悬浮液)
在搅拌加热6.0升水的同时,向水中溶入234.0克偏钒酸铵和1059.4克钼酸铵,制得含水溶液。另外,将241.6克硝酸铜和40.4克硝酸铁溶入水中制得另一水溶液。将两种水溶液混合。接着,向得到的溶液中加入134ml含20%(W)SiO2的硅溶胶作为载体,形成悬浮液。(该悬浮液称为悬浮液B。)
例Ⅲ-1
(用离心式流动涂覆法制备催化剂)
用与例Ⅰ-1-1相同的方法处理一部分悬浮液B制备催化剂。但在400℃下焙烧6小时。产品催化剂氧化物中除氧以外的元素成分比为:Mo(12)V(4)Cu(2)Fe(0.2)Si(1.0)。
例Ⅲ-2-1和Ⅲ-2-2
(用制片法制备催化剂)
用与例Ⅰ-2相同的方法处理一部分悬浮液B制备催化剂。但在400℃下焙烧6小时。
〔反应试验〕
用例Ⅲ-1到Ⅲ-2的催化剂,以和例Ⅰ相同的方式进行反应,但反应温度是230℃。
例Ⅳ
(制备用于催化剂的悬浮液)
在12升水中加热溶解钼酸铵(1596克)。在充分搅拌下向该溶液中加入220.8克偏钒酸铵、1126.5克氢氧化铌、162克草酸亚铁、88.5克氯化亚铜和45克硝酸钾。搅拌加热该混合物后,加入678克SiO2粉末制得悬浮液。(该悬浮液称之为悬浮液C)。
例Ⅳ-1
(用离心式流动涂覆法制备催化剂)
用和例Ⅰ-1-1相同的方式处理部分悬浮液C制备催化剂,但在420℃下焙烧5小时。结果催化剂氧化物中除氧之外的元素组成比为:
Mo(12)V(2.5)Nb(8.4)Cu(1.2)Fe(1.2)K(0.6)Si(15)。
例Ⅳ-2-1和Ⅳ-2-2
(用挤压法制备催化剂)
用和例Ⅰ-3相同的方式处理部分悬浮液C制备催化剂。但在420℃下进行5小时焙烧。
〔反应试验〕
用例Ⅳ-1至Ⅳ-2的催化剂,以和例Ⅰ相同的方式进行反应,但反应温度为240℃。
例Ⅴ
(制备催化剂物料悬浮液)
用和例Ⅰ相同的方式得到悬浮液。用五氧化二锑作锑源,用硝酸盐作镁源,用氧化物作铝源。(该悬浮液称为悬浮液D)。
例Ⅴ-1
(用离心式流动涂覆法制备催化剂)
用和例Ⅰ-1-1相同的方法处理一部分悬浮液D制备催化剂。结果催化剂氧化物中氧以外的元素组成比为:
Mo(12)V(4.0)Sb(0.5)Mg(2.0)Al(5.0)。
例Ⅴ-2-1和Ⅴ-2-2
(用球形造粒机成形法制备催化剂)
用与例Ⅰ-4相同的方法处理一部分悬浮液D制备催化剂。
〔反应试验〕
用例Ⅴ-1至Ⅴ-2的催化剂,以和例Ⅰ相同的方式进行反应,不同的是反应温度为240℃。
例Ⅵ
(制备催化剂物料悬浮液)
用和例Ⅰ同样的方法得到悬浮液。用硝酸盐作铯源和锶源,用氧化物作钛源。(该悬浮液称之为悬浮液E。)
例Ⅵ-1
(用离心式流动涂覆方法制备催化剂)
以和例Ⅰ-1-1同样的方式处理一部分悬浮液E制备催化剂。结果催化剂氧化物中氧以外元素的组分比为:
Mo(12)V(4)W(2.0)Cu(2.0)Sr(2.0)Ti(10)
例Ⅵ-2-1和Ⅵ-2-2
按照例Ⅰ-5使一部分悬浮液E成形为催化剂。
〔反应试验〕
用例Ⅵ-1至Ⅵ-2的催化剂,以和例Ⅰ相同的方式进行反应,不同的是反应温度为220℃。
例Ⅶ
(制备催化剂物料悬浮液)
用和例Ⅰ相同的方式得到一种悬浮液。另外用硝酸铁作铁源,用硝酸钠作钠源,用氧化物作铝源。(该悬浮液称之为悬浮液F。)
例Ⅶ-1
以例Ⅰ-1-1的同样方式处理一部分悬浮液F制备催化剂。结果催化剂氧化物中氧之外元素的组成比为:
Mo(12)V(8.0)W(4.0)Cu(1.0)Fe(1.0)Na(0.5)Al(5.0)。
例Ⅶ-2-1和Ⅶ-2-2
(用制丸方法制备催化剂)
按照例Ⅰ-6使一部分悬浮液F形成为催化剂。
〔反应试验〕
用例Ⅶ-1至Ⅶ-2的催化剂,以例Ⅰ的同样方式进行反应,不同的是反应温度为210℃。
例Ⅷ
(制备催化剂物料悬浮液)
用和例Ⅰ相同的方法得到一种悬浮液。另外,用硝酸盐作铋和铷源,用硅胶作硅源。(该悬浮液称之为悬浮液G。)
例Ⅷ-1
(用离心式流动涂覆方法制备催化剂)
以例Ⅰ-1-1同样的方式处理一部分悬浮液G制备催化剂。结果催化剂氧化物中氧以外元素的组成比为:
Mo(12)V(8.0)W(4.0)Cu(1.0)Bi(1.0)Rb(0.05)Si(5.0)
例Ⅷ-2-1和Ⅷ-2-2
(用加载体成形法制备催化剂)
按照例Ⅰ-7使部分悬浮液G成形为催化剂。
〔反应试验〕
用例Ⅷ-1至Ⅷ-2的催化剂,以例Ⅰ的同样方式进行反应。
例Ⅸ
(制备催化剂物料悬浮液)
用与例Ⅰ相同的方法得到一种悬浮液。另外,用硝酸盐作铋和铯源,用硅胶作硅源。(该悬浮液称之为悬浮液H)。
例Ⅸ-1
(用离心式流动涂覆方法制备催化剂)
用与例Ⅰ-1-1相同的方式处理部分悬浮液H制备催化剂。结果催化剂氧化物中氧以外元素的组成比:
Mo(12)V(8.0)W(1.0)Bi(1.0)Cs(0.05)Si(5.0)
例Ⅸ-2-1和Ⅸ-2-2
(用制片法制备催化剂)
按照例Ⅰ-2使部分悬浮液H成形为催化剂。
〔反应试验〕
用例Ⅸ-1至Ⅸ-2的催化剂,以例Ⅰ的同样方式进行反应。
表3合并列出上述例Ⅲ至例Ⅸ的结果。
例Ⅹ-1
(用离心式流动涂覆方法制备催化剂)
重复例Ⅰ-1-1,不同的是先将平均直径为3mm的α-氧化铝加入离心式流动涂覆装置作芯体,而不用平均直径1mm的氧化铝。
例Ⅹ-2
重复例Ⅹ-1,不同的是用平均直径为5mm的α-氧化铝为芯体。
〔反应试验〕
用例Ⅹ-1至Ⅹ-2的催化剂,以如例Ⅰ同样的方式进行反应。在210℃的反应温度下的反应结果是:例Ⅹ-1的丙烯醛转化率为99.6%,丙烯醛单流产率为97.2%;例Ⅹ-2的丙烯醛转化率99.4%,丙烯酸单流产率为97.3%。
对例Ⅹ-1,比表面积4.0m2/g,孔隙度0.237cc/g,孔体积比:10-100μm,1-10μm,0.1-1μm分别占总孔体积的22%,20%和48%。
对于例Ⅹ-2,比表面积为2.5m2/g,孔隙度为0.185cc/g,直径10-100μm,1-10μm和0.1-1μm的孔体积占总孔体积比率分别为22%,21%和55%。
Claims (6)
1、一种用于由丙烯醛气相催化氧化制备丙烯酸的催化剂,含有下式所表示的活性物质:
Mo(a)V(b)A(c)B(d)C(e)D(f)O(x)
式中Mo表示钼、V代表钒、A表示选自钨和铌中的至少一种元素,B表示选自铁、铜、铋、铬、锑和铊一组中的至少一种元素,C表示选自碱金属和碱土金属中至少一种元素,D表示选自硅、铝和钛中至少一种元素,O表示氧;另外,a、b、c、d、e、f和x分别表示Mo、V、A、B、C、D和O的原子比率,而且,当a=12时,b=2至14,c=0至12,d=0至6,e=0至6,f=0至30,x是由其它元素的氧化状态确定的一个数值,本发明的特征在于,催化剂的比表面为0.50至15.0m2/g,孔隙度为0.10至0.90cc/g,孔径分布为孔径集中分布在0.1至小于1.0μm、1.0至小于10.0μm和10.0至100μm的范围内。
2、按照权利要求1的催化剂,其特征是,孔径为0.1至小于1.0μm的孔占有的孔体积,孔径为1.0至小于10.0μm的孔占有的孔体积和孔径为10至100μm的孔占有的孔体积分别至少为总孔体积的10%。
3、按照权利要求1的催化剂,其特征是,孔径为0.1至小于1.0μm的孔占有的孔体积、孔径为1.0至小于10.0μm的孔占有的孔体积和孔径为10至100μm的孔占有的孔体积分别为总孔体积的15至65%、15至65%和15至40%。
4、具有良好再现性的催化剂制备方法,该催化剂用于由丙烯醛气相催化氧化制备丙烯酸,其活性组分由下式表示:
Mo(a)V(b)A(c)B(d)C(e)D(f)O(x)
式中Mo表示钼、V表示钒、A表示选自钨和铌中的至少一种元素,B表示选自铁、铜、铋、铬、锑和铊一组中的至少一种元素,C表示选自碱金属和碱土金属中的至少一种元素,D表示选自硅、铝和钛中的至少一种元素,O表示氧;另外,a、b、c、d、e、f和x分别表示Mo、V、A、B、C、D和O的原子比率,而且,当a=12时,b=2至14,c=0至12,d=0至6,e=0至6,f=0至30,x是一个由其它元素氧化状态确定的数值;本方法的特征在于,将未焙烧的催化剂物料粉末组合物加进一个离心式流动涂覆装置,使之成型为平均直径为2至10mm的颗粒,然后焙烧这些颗粒,得到比表面为0.50至15.0m2/g,孔隙度为0.10至0.90cc/g和如下孔径分布的催化剂,其中孔径集中分布在0.1至小于1.0μm、1.0至小于10.0μm和10.0至100μm的范围内。
5、按照权利要求4的催化剂制备方法,其特征是,孔径为0.1至小于1.0μm的孔占有的孔体积,孔径为1.0至小于10.0μm的孔占有的孔体积和孔径为10至100μm的孔占有的孔体积分别为总孔体积的至少10%。
6、按照权利要求4的催化剂制备方法,其特征是,孔径是0.1至小于1.0μm的孔占有的孔体积、孔径为1.0至小于10.0μm的孔占有的孔体积和孔径为10至100μm的孔占有的孔体积分别为总孔体积的15至65%,15至65%和15-40%。
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Cited By (7)
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---|---|---|---|---|
CN1087658C (zh) * | 1995-03-03 | 2002-07-17 | 日本化药株式会社 | 催化剂和其制备方法 |
CN100333831C (zh) * | 2000-12-22 | 2007-08-29 | 日本化药株式会社 | 烷烃氧化催化剂及其制备方法和生产不饱和含氧化合物的方法 |
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Families Citing this family (71)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ228084A (en) * | 1988-02-24 | 1990-11-27 | Kawasaki Steel Co | Catalysts and their use in catalytic production of pyromellitic dianhydride |
EP0383636A1 (en) * | 1989-02-17 | 1990-08-22 | Nippon Shokubai Co., Ltd. | Carrier for catalyst and method for production thereof |
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US5210293A (en) * | 1989-07-05 | 1993-05-11 | Bp Chemicals Limited | Process and catalyst for the production of ethylene and acetic acid |
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JPH04159243A (ja) * | 1990-10-19 | 1992-06-02 | Mitsubishi Rayon Co Ltd | アクリル酸の製造法 |
DE4132263A1 (de) * | 1991-09-27 | 1993-04-01 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von acrolein zu acrylsaeure |
JP3108511B2 (ja) * | 1992-02-27 | 2000-11-13 | 三菱レイヨン株式会社 | 不飽和アルデヒド及び不飽和カルボン酸合成用触媒の製造法 |
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US6432870B1 (en) * | 1999-05-25 | 2002-08-13 | Toagosei Co., Ltd. | Process for preparing metal oxide catalyst for acrylic acid production |
JP3943291B2 (ja) * | 1999-08-04 | 2007-07-11 | 株式会社日本触媒 | アクロレインおよびアクリル酸の製造方法 |
TWI268806B (en) * | 1999-09-15 | 2006-12-21 | Rohm & Haas | A catalyst useful for oxidation of alkanes |
US6762148B2 (en) | 1999-09-17 | 2004-07-13 | Nippon Kayaku Kabushiki Kaisha | Catalyst process of making |
JP3744750B2 (ja) | 1999-12-08 | 2006-02-15 | 株式会社日本触媒 | 複合酸化物触媒およびアクリル酸の製造方法 |
US6444845B1 (en) | 2000-04-28 | 2002-09-03 | Saudia Basic Industries Corporation | Process for the oxidation of unsaturated aldehydes to produce carboxylic acids using Mo-V based catalysts |
US6531631B1 (en) | 2000-04-28 | 2003-03-11 | Saudi Basic Industries Corporation | Oxidation of ethane to acetic acid and ethylene using molybdenum and vanadium based catalysts |
JP4530595B2 (ja) * | 2000-12-13 | 2010-08-25 | 旭化成ケミカルズ株式会社 | 酸化またはアンモ酸化用酸化物触媒 |
WO2002051539A1 (en) * | 2000-12-22 | 2002-07-04 | Uop Llc | Crystalline multinary metal oxide compositions, process for preparing and processes for using the composition |
CN100390147C (zh) * | 2001-09-07 | 2008-05-28 | 喜洋洋有机合成有限公司 | 杂芳腈的制备方法,其改良的催化剂及所述改良催化剂的制备方法 |
WO2004007071A1 (en) * | 2002-07-12 | 2004-01-22 | Lg Chem, Ltd. | Method for preparing a catalyst for partial oxidation of acrolene |
US7115776B2 (en) | 2002-07-18 | 2006-10-03 | Basf Aktiengesellschaft | Heterogeneously catalyzed gas-phase partial oxidation of at least one organic compound |
US20040038820A1 (en) * | 2002-08-20 | 2004-02-26 | Nippon Shokubai Co., Ltd. | Production process for catalyst |
US7022643B2 (en) | 2002-08-20 | 2006-04-04 | Nippon Shokubai Co., Ltd. | Production process for catalyst |
JP4253176B2 (ja) * | 2002-11-12 | 2009-04-08 | 株式会社日本触媒 | アクリル酸製造用触媒およびアクリル酸の製造方法 |
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JPWO2004078344A1 (ja) * | 2003-03-05 | 2006-06-08 | 旭化成ケミカルズ株式会社 | 粒状多孔性アンモ酸化触媒 |
KR100497175B1 (ko) | 2003-03-26 | 2005-06-23 | 주식회사 엘지화학 | 프로필렌 및 이소부틸렌 부분산화 반응용 촉매의 제조방법 |
US7642214B2 (en) * | 2003-06-10 | 2010-01-05 | Nippon Kayaku Kabushiki Kaisha | Catalyst for oxidation of alkane, process for preparing thereof and process for producing unsaturated oxygen-containing compound |
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Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4014927A (en) * | 1972-09-07 | 1977-03-29 | Mitsubishi Petrochemical Company Limited | Process for production of unsaturated acids from corresponding unsaturated aldehydes |
US4138366A (en) * | 1976-05-05 | 1979-02-06 | The Standard Oil Company | Process for producing unsaturated aliphatic acids and catalysts therefore |
DE2626887B2 (de) * | 1976-06-16 | 1978-06-29 | Basf Ag, 6700 Ludwigshafen | Katalysator für die Oxadation von (Methacrolein zu (Meth)Acrylsäure |
IT1160321B (it) * | 1978-12-12 | 1987-03-11 | Euteco Spa | Catalizzatori per l'ossidazione di acroleina ad acido acrilico |
US4278566A (en) * | 1979-03-19 | 1981-07-14 | Standard Oil Company (Indiana) | Hydrotreating process |
AU547464B2 (en) * | 1981-06-17 | 1985-10-24 | Amoco Corporation | Catalyst for hydrotreating hydrocarbon feed |
-
1988
- 1988-06-01 EP EP88108780A patent/EP0293859B1/en not_active Expired - Lifetime
- 1988-06-01 DE DE8888108780T patent/DE3867912D1/de not_active Revoked
- 1988-06-01 US US07/201,026 patent/US4892856A/en not_active Expired - Lifetime
- 1988-06-01 ES ES198888108780T patent/ES2028180T3/es not_active Expired - Lifetime
- 1988-06-03 CS CS386588A patent/CS274469B2/cs not_active IP Right Cessation
- 1988-06-03 JP JP63135627A patent/JPS6485139A/ja active Granted
- 1988-06-03 RU SU884355922A patent/RU1833201C/ru active
- 1988-06-03 BR BR8802702A patent/BR8802702A/pt not_active IP Right Cessation
- 1988-06-04 CN CN88104316A patent/CN1020861C/zh not_active Expired - Lifetime
- 1988-06-04 KR KR1019880006752A patent/KR930007409B1/ko not_active IP Right Cessation
- 1988-07-01 AU AU18627/88A patent/AU611693B2/en not_active Ceased
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1087658C (zh) * | 1995-03-03 | 2002-07-17 | 日本化药株式会社 | 催化剂和其制备方法 |
CN100333831C (zh) * | 2000-12-22 | 2007-08-29 | 日本化药株式会社 | 烷烃氧化催化剂及其制备方法和生产不饱和含氧化合物的方法 |
CN101274279B (zh) * | 2007-03-29 | 2013-07-17 | 株式会社日本触媒 | 氧化物催化剂、制备丙烯醛或丙烯酸的方法和制备吸水性树脂的方法 |
CN102040505A (zh) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | 由不饱和醛氧化制不饱和酸的方法 |
CN102039141B (zh) * | 2009-10-13 | 2012-11-14 | 中国石油化工股份有限公司 | 由不饱和醛氧化制不饱和酸的催化剂及其制备方法 |
CN104271236A (zh) * | 2012-03-13 | 2015-01-07 | 国际人造丝公司 | 用于产生丙烯酸和丙烯酸类的包含钒、铋和钨的催化剂 |
CN108290143A (zh) * | 2015-12-01 | 2018-07-17 | 三菱化学株式会社 | (甲基)丙烯酸制造用催化剂的制造方法和(甲基)丙烯酸的制造方法 |
CN108290143B (zh) * | 2015-12-01 | 2020-12-11 | 三菱化学株式会社 | (甲基)丙烯酸制造用催化剂的制造方法和(甲基)丙烯酸的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR890000151A (ko) | 1989-03-11 |
AU611693B2 (en) | 1991-06-20 |
CS386588A2 (en) | 1990-09-12 |
RU1833201C (en) | 1993-08-07 |
CS274469B2 (en) | 1991-04-11 |
DE3867912D1 (de) | 1992-03-05 |
BR8802702A (pt) | 1988-12-27 |
ES2028180T3 (es) | 1992-07-01 |
EP0293859A1 (en) | 1988-12-07 |
EP0293859B1 (en) | 1992-01-22 |
JPH0570502B2 (zh) | 1993-10-05 |
US4892856A (en) | 1990-01-09 |
KR930007409B1 (ko) | 1993-08-10 |
JPS6485139A (en) | 1989-03-30 |
AU1862788A (en) | 1990-01-04 |
CN1020861C (zh) | 1993-05-26 |
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