CN102811991B - 用于醛生产的尖晶石结构化催化剂 - Google Patents
用于醛生产的尖晶石结构化催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
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- 238000000034 method Methods 0.000 claims abstract description 19
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及用于通过将链烷醇，尤其是甲醇或乙醇用氧气选择性氧化的醛生产，特别是甲醛或乙醛生产的催化剂，所述催化剂具有尖晶石结构。所述催化剂通常包括Fea q+Vb+Moc+ y+ΔzO4尖晶石结构，其中Δ是任选的阳离子空位和其中z＝3‑q‑x‑y和q×a+x×b+y×c＝8，所含浓度对应于0.6＜q＜3，0＜x＜1.5，0＜y＜1，和0＜z＜1.3和2＜a＜3，3＜b＜5和3＜c＜6。本发明进一步涉及生产所述催化剂的方法和所述催化剂将链烷醇，优选甲醇或乙醇和氧气选择性氧化成醛，优选甲醛或乙醛的用途。
Description
技术领域
本发明涉及用于通过将链烷醇，尤其是甲醇或乙醇与氧气选择性氧化的醛生产，特别是甲醛或乙醛生产的催化剂，所述催化剂具有尖晶石结构。在进一步的方面，本发明涉及生产所述催化剂的方法和所述催化剂将链烷醇，优选甲醇或乙醇和氧气选择性氧化成醛，优选甲醛或乙醛的用途。
背景技术
现在，占主导地位的乙醛的生产的方法是Wacker工艺，其催化乙烯氧化成乙醛。所述催化剂是由氯化钯和氯化铜组成的双组份体系。在Wacker工艺之前，乙醛通过乙炔的水合生产。如今通过催化氧化将乙醇转化为乙醛因为乙醇增加的可获得性而是Wacker工艺潜在的可替代的方法。
如今，由甲醇和氧气商业生产甲醛在银-或金属氧化物催化的工艺中于富含甲醇以及甲醇贫瘠条件操作下分别进行。历史上，由于更低的投资费用，银工艺比氧化物工艺更优选，但作为工艺改进和增加的甲醇价格的结果，更选择性的氧化物工艺赢得了市场份额并且如今是为新产能实现最通常的选择。
在氧化物工艺中，在多管反应器中生产甲醛。通常，一个反应器由10-20000个填充以环状催化剂和通过油作为传热流体(HTF)冷却的管子组成。由于反应是高放热的(ΔH＝-156kJ/mol)，因此很难获得等温条件并且从而在反应区形成热点。为了限制热点温度，在反应器的第一部分，可以用惰性环稀释催化剂。
在氧化物工艺中使用的催化剂是钼酸铁Fe2(MoO4)3和三氧化钼MoO3的混合物，其中Mo∶Fe的原子比率为2和3之间。在大部分方面，催化性能是令人满意的；设备产率高(88-93％)，并且钼和铁均无毒，考虑到环境和人类健康方面其是有利的。
然而，在甲醇氧化中，由于钼从催化剂中挥发，会使催化剂失活。钼从甲醇浓度高的反应器上部升华并且在反应器的下部分解，形成针状MoO3晶体。作为钼升华和浓缩/分解的结果，对甲醛的催化活性和选择性降低并且反应器中的压降升高。因此，大约1-2年后，或甚至小于1年，根据反应条件，在生产液流中的催化剂就要被替换。
发明内容
为了增加现有设备的生产能力并且降低新设备的尺寸和成本，希望增加每反应器管和单位时间甲醛的生产率。实现这样的一种可能性是增加甲醇的入口浓度。然而，作为更高甲醇浓度的结果，热点温度可能增加，因为需要转化更多的甲醇分子。因为更高的温度和甲醇浓度促进了钼从目前的催化剂中挥发，任何通过增加甲醇入口浓度而增加设备生产能力的尝试将有加速钼挥发的风险。
因此，显示出活性元素更低挥发性的替代性的催化剂是令人感兴趣的，只要它们是活性的并显示出对甲醛匹敌的选择性。此外，由于环境和健康方面的考虑，优选限制催化剂中有害物质的量。
根据美国专利No.7193117，大块钒酸金属盐作为甲醇氧化催化剂是活性的和选择性的，其对甲醛的选择性在甲醇高转化率下记录为89.3％至96.6％之间。虽然这些催化剂显示出对甲醛的高选择性，对于该催化剂的稳定性却知之甚少，特别是钒的挥发性。此外，通常催化剂中有毒钒的量高，使它们作为对商业MoO3/Fe2(MoO4)3催化剂的替代品是不合适的。
本发明的目的不仅仅是提供适用于通过将链烷醇氧化，尤其是甲醇或乙醇氧化的醛生产，特别是甲醛或乙醛生产的催化剂。所述目的还是要提供对醛，优选甲醛或乙醛显示出高选择性，具有活性元素低挥发性的稳定的和具有限制量有害物质的催化剂。
这一目的可以通过根据本发明的催化剂得以实现，其中催化剂具有尖晶石结构，通常包括铁、氧、钒和/或钼。所述催化剂优选包括Fea+ qVb+ xMoc+ yΔzO4尖晶石结构，其中Δ是任选的阳离子空位和其中z＝3-q-x-y和q×a+x×b+y×c＝8在浓度上对应于0.6＜q＜3，0≤x＜1.5，0≤y≤1，和0≤z＜1.3和2≤a≤3，3≤b≤5和3≤c≤6。q、x、y和z的浓度可以进一步为1.4≤q＜3，0≤x≤1，0≤y≤0.3，0≤z≤0.9或更具体地0.57＜q＜3，0＜x＜1.5，0≤y≤1和0≤z＜1.29，1.33＜q＜3，0＜x＜1.5，0≤y≤1和0≤z＜1，0.57＜q＜3，0＜x＜1，0≤y≤1和0≤z＜1.29，1.33＜q＜3，0＜x＜1，0≤y≤1和0≤z＜1，0.75＜q＜3，0＜x＜1.5，0≤y≤0.3和0≤z＜1.14，1.42＜q＜3，0＜x＜1.5，0≤y≤0.3和0≤z＜0.88，1.14＜q＜3，0＜x＜1，0≤y≤0.3和0≤z＜0.98，1.42＜q＜3，0＜x＜1，0≤y≤0.3和0≤z＜0.88，0.57＜q＜3，0≤x＜1.5，0＜y≤1和0≤z＜1.29，1.33＜q＜3，0≤x＜1.5，0＜y≤1和0≤z＜1，0.57 ＜q＜3，0≤x＜1，0＜y≤1和0≤z＜1.29，1.33＜q＜3，0≤x＜1，0＜y≤1和0≤z＜1，0.75＜q＜3，0≤x＜1.5，0＜y≤0.3和0≤z＜1.14，1.42＜q＜3，0≤x＜1.5，0＜y≤0.3和0≤z＜0.88，1.14＜q＜3，0≤x＜1，0＜y≤0.3和0≤z＜0.98或1.42＜q＜3，0≤x＜1，0＜y≤0.3和0≤z＜0.88。所述催化剂可以在结构中具有阳离子空位，如通过尖晶石化学计量的偏差所确定，所述偏差通过构成金属的化合价和因此反应条件，即反应温度和反应气体的组成所确定。例如Al、Ca、Co、Cr、Cu、Mg、Mn、Ni、Zn和Ti的阳离子也能够与Fe形成尖晶石结构并且因此也可以成功地用在适于链烷醇氧化至醛的催化剂中。
附图说明：
图1是对于制备的样品3的X射线衍射图。
图2是对于制备的样品9的X射线衍射图。
具体实施方式
由一定量的铁阳离子、钒和/或钼的结合组成具有尖晶石结构的催化剂具有这些所希望的性能的这一发现是相当预料不到的技术效果。除了对由惰性介质中甲醇和氧气得到甲醛显示出高的选择性(>90％)之外，在300℃,氮气中10％甲醇和10％氧气的流动气体的气流作用5天后，均未能检测到钒或钼从本发明催化剂中的挥发。本发明的另一个优势是相对于例如在美国专利No.7193117中公开的催化剂，高选择性催化剂可以以低钒含量制备，使之对于环境和人方面更加适合。
Fea+ qVb+ xMoc+ yΔzO4催化剂通过从含有所希望量的Fe、V和Mo的均相水溶液中沉淀制备。所述均相溶液由一个、两个或三个独立的含有分别以合适的浓度溶解的Fe(NO3)3.9H2O、NH4VO3和(NH4)6Mo7O24·4H2O水溶液制备。
如果在催化剂中需要多于一个的元素，则在均匀化之前将两个或三个良好搅拌的溶液一起混合。如果必要，为了获得元素的均匀混合，可以加热溶液和/或通过添加如HNO3、H2SO4和/或HCl等的酸降低PH值。
当PH值通过加入碱例如NH3和/或NaOH等充分提升时，则获得了固体沉淀。如果必要，为了通过增加沉淀物的尺寸而简化固体从液相的分离，则将含有该沉淀物的液体的温度升至35-100℃，通常40-70℃。
通过离心分离颗粒并随后用水和丙酮洗涤。作为替代方法，通过过滤分离颗粒并随后用水和丙酮洗涤。通过离心或过滤获得的洗涤后的颗粒随后在烘箱中干燥。
最后，将干燥的颗粒在300-650℃，优选400-550℃的温度下在还原剂，例如H2和/或CO与氧化剂，例如H2O和/或CO2一起在一种或多种惰性剂，例如He、 Ne、N2、Ar和/或Kr中的气氛下烧结。还原、氧化和惰性剂的气体成分分别可以在0-50vol.％、0-50vol.％和99.99-0vol.％之间变化。还原通常持续至少3小时。最终催化剂具有2-25m2/g的比表面积(BET)，更优选3-10m2/g，最优选4-7m2/g。
本发明进一步涉及所述催化剂在冷却的用于选择氧化甲醇和氧气至甲醛的多管反应器中的用途。在反应器进口处的气体混合物中，甲醇的存在浓度为6-13％和氧气的浓度为8-15％，与惰性气体，最通常为氮气一起。本发明催化剂可以单独使用或与其它催化剂在反应器任何位置一起使用。
本发明进一步参考所附实施例解释说明，所述实施例作为示例进行解释并不以任何方式限制本发明。
实施例1阐明了尖晶石相催化剂的制备。
实施例2是说明FeVO4催化剂制备的对比实施例。
实施例3阐明了尖晶石相催化剂的催化性能
实施例4阐明了通过在用于甲醇氧化之前和之后在比活性和元素组成的变化显示的尖晶石相催化剂的老化。
实施例5是阐明通过在用于甲醇氧化之前和之后在比活性和元素组成的变化显示的三斜相FeVO4催化剂(实施例2制备)的老化的对比实施例。
实施例1
尖晶石相催化剂的制备
根据表1中定义的组成，通过从含有单独溶解的Fe(样品1)或与V一起(样品2-5)或与Mo一起(样品6-7)或与V和Mo一起(样品8)的均相水溶液中沉淀制备了8个样品。所述均相溶液由一种(样品1)，两种(样品2-7)或三种(样品8)独立的水溶液，0.5M的Fe(NO3)3·9H2O溶液(Merck)，0.04M的NH4VO3溶液(Merck)和0.5M的(NH4)6Mo7O24·4H2O(Riedel-de Haen)制备。为了制备样品2-8，将两种或三种良好搅拌的溶液一起混合并且通过加入3M HNO3将PH值降低至1.0。也为了样品1的制备将PH值降低至1.0。将PH降低至1.0之后，所有的溶液是均相的。随后当通过添加3M NH3将PH迅速升高至4.0时，获得了固体沉淀。通过维持搅拌在50℃加热浑浊的溶液2小时，进行颗粒粗化以刺激颗粒的回收。通过离心(3000rpm，3分钟)将颗粒分离并且随后分别用水、丙酮和再次用水洗三次。最后，将样品在80℃下干燥16小时，随后在 H2/H2O/Ar混合气氛中450℃还原15小时。
通过使用Ni-过滤的CuKα辐射和旋转样品架在Seifert XRD3000TT衍射仪上的X射线粉末衍射(XRD)分析测定催化剂的相组成。以0.1°每步(2.0秒/步)在5-80度的2θ之间收集数据。如表1所示，制备的所有样品1-8(标识为新鲜)为Fea+ qVb+ xMoc+ yΔzO4尖晶石类型结构的单相，与Fe3O4相似。新鲜样品3的衍射图在图1中显示。
实施例2
FeVO4催化剂的制备
为了将实施例1中描述的样品1-8与已知钒酸盐催化剂相比较，制备了US专利No.7193117中公开的钒酸铁(FeVO4)并且标示为样品9。制备步骤与上述实施例1中描述的相同，除了不同的最终烧结。代替在还原性气氛中进行烧结，所述烧结在空气中580℃下进行6小时。如通过X射线衍射测定和在图2显示的，获得的催化剂是三斜FeVO4。
实施例3
尖晶石相催化剂的催化性能
实施例1的制备样品1-8的甲醇氧化中的性能在300℃和大气压下不锈钢栓塞流反应器中测量。为了保证等温条件，将反应器包埋入置于管式炉的铝缸体(aluminum block)中。在测量之前，将催化剂仔细研磨至精细的粉末并且压制成片，其被粉碎筛成直径范围为0.250-0.425mm的颗粒。将反应器装载需要量的催化剂。在80ml/分钟的N2流中，将催化剂加热至反应温度。当达到反应温度300℃时，将10ml/分钟的O2和10ml/分钟的气体甲醇流加入到氮气流中。所有催化剂运行过夜，显示16小时后由液流获得的活性和选择性。
催化活性在低甲醇转化率(＜10％)下测定以保证差别的条件，然而显示的选择性数据在甲醇高转化率(90％)下收集。在装备有Haysep C柱和FID和TCD探测器的气相色谱中在线分析甲醇、甲醛(FA)、二甲基醚(DME)、甲酸甲酯(MF)、二甲氧基甲烷(DMM)和CO2。在IR仪器上(Rosemount Binos100)在线分析CO。
结果在表2中显示。
实施例4
通过在甲醇氧化中使用之前和之后在比活性和元素组成中的变化显示的尖 晶石相催化剂的老化
对于制备的每一样品1-8，将0.02g的催化剂在300℃带有10％甲醇和10％氧气的氮气流中处理5天。选择催化剂的量以保证对应于反应器入口条件的差别的甲醇转化率(＜10％)。先前，已经报道了在催化床入口部分钼的损失最为严重[A.Andersson，M.Hernelind，O.Augustsson，Catal.Today112(2006)40]。处理之前(新鲜催化剂)和处理之后(使用过的催化剂)，用ICP-AES对催化剂进行元素分析。使用的样品1-8的比活性也如实施例3中描述的测定。
样品选择的结果在表3中显示。
实施例5
通过在甲醇氧化中使用之前和之后比活性和元素组成中变化显示的三斜相FeVO4催化剂的老化
将样品9如对于样品1-8在以上实施例4中所述处理并且作为新鲜和使用过的使用ICP-AES进行元素分析。使用的样品9的比活性也如在实施例3中描述的测量。
结果在表3中显示。
表1.制备催化剂的元素组成(摩尔比)和通过制备催化剂和在甲醇氧化中(在300℃，甲醇/O2/N2＝10/10/80vol.-％)5天后的X射线衍射确定的相组成。样品1-8为Fe-V-Mo-氧化物尖晶石催化剂和样品9是三斜FeVO4催化剂。
a)在通式Fea+ qVb+ xMoc+ yΔzO4中，阳离子空位数z通过电荷平衡根据z＝3-q-x-y和q×a+x×b+y×c＝8给出。
表2.新鲜样品1-8对于产物的比活性和选择性，如在300℃由氮气中10％甲醇和10％氧气组成的进料测定。
a)在区别的条件下测定(甲醇转化率＜10％)。
b)对产物甲醛(FA)，二甲基醚(DME)，甲酸甲酯(MF)和碳氧化物(COx)的选择性在90％甲醇转化率下测定。
c)对产物的比活性和选择性在10-25％甲醇转化率下测定。
表3.通过ICP-AES测量的在甲醇氧化之前和之后所制备的催化剂的选择的组成(摩尔比)和相应的比活性(活性比率)的变化
a)在合成中设计的催化剂的组成。
b)在300℃，甲醇/O2/N2＝10/10/80vol.-％甲醇氧化中使用5天之后催化剂的组成。
c)使用过的催化剂的比活性除以新鲜催化剂的比活性。
Claims (16)
1.用于通过用氧气选择性氧化链烷醇的醛生产的催化剂，其特征在于所述催化剂具有Fea+ qVb+ xMoc+ yΔzO4尖晶石结构，其中Δ是任选的阳离子空位和其中z＝3-q-x-y和q×a+x×b+y×c＝8，所含浓度对应于0.6<q<3，0≤x<1.5，0≤y≤1，和0≤z<1.3和2≤a≤3，3≤b≤5和3≤c≤6。
2.根据权利要求1的催化剂，其特征在于所述催化剂包括钒。
3.根据权利要求1-2任一项的催化剂，其特征在于所述催化剂包括钼。
4.根据权利要求1的催化剂，其特征在于1.4≤q<3。
5.根据权利要求1或2的催化剂，其特征在于0≤x≤1。
6.根据权利要求1或2的催化剂，其特征在于0≤y≤0.3。
7.根据权利要求1或2的催化剂，其特征在于0≤z≤0.9。
8.根据权利要求1的催化剂，其特征在于所述醛为甲醛和所述链烷醇为甲醇。
9.根据权利要求1的催化剂，其特征在于所述醛为乙醛和所述链烷醇为乙醇。
10.根据权利要求1的催化剂，其特征在于所述催化剂具有2-25m2/g的比表面积(BET)。
11.根据权利要求10的催化剂，其特征在于所述催化剂具有3-10m2/g的比表面积(BET)。
12.根据权利要求11的催化剂，其特征在于所述催化剂具有4-7m2/g的比表面积(BET)。
13.用于生产根据权利要求1-12任一项的催化剂的方法，其特征在于所述催化剂通过从包括理想量的Fe、V和Mo的均相水溶液中沉淀制备，其中所述均相溶液首先由一种、两种或三种单独的分别含有溶解的Fe(N03)3·9H2O、NH4VO3和(NH4)6Mo7O24·4H2O的水溶液制备，其中在通过添加碱到所述均相溶液中获得所述沉淀之后，随后将形成的沉淀从所述溶液中分离、洗涤、干燥并且在300-650℃的温度下在一种或多种惰性剂中还原剂连同氧化剂一起的气氛下烧结。
14.根据权利要求1-12任一项的催化剂在冷却的多管反应器中用于将链烷醇，采用氧气进行选择性氧化成醛的用途。
15.根据权利要求14的用途，其中所述链烷醇是甲醇或乙醇和所述醛是甲醛或乙醛。
16.根据权利要求14的用途，其特征在于所述链烷醇为甲醇并且在反应器进口处在与惰性气体一起的气体混合物中以6-13％的浓度存在，氧气以8-15％的浓度存在。
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2011
- 2011-01-19 EP EP11737352.2A patent/EP2528883B1/en active Active
- 2011-01-19 PL PL11737352T patent/PL2528883T3/pl unknown
- 2011-01-19 US US13/520,083 patent/US9056304B2/en active Active
- 2011-01-19 CN CN201180007361.3A patent/CN102811991B/zh active Active
- 2011-01-19 PT PT117373522T patent/PT2528883T/pt unknown
- 2011-01-19 WO PCT/SE2011/000007 patent/WO2011093763A1/en active Application Filing
- 2011-01-19 ES ES11737352T patent/ES2859484T3/es active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852361A (en) * | 1969-06-28 | 1974-12-03 | Basf Ag | Production of formaldehyde |
| US4220560A (en) * | 1977-12-12 | 1980-09-02 | Shell Oil Company | Spinel dehydrogenation catalyst |
| US5106811A (en) * | 1990-10-01 | 1992-04-21 | Texaco Inc. | Composition involving V2 O3 -FeO-SiO2 and process for making composition |
| CN101096013A (zh) * | 2006-06-28 | 2008-01-02 | 住友化学株式会社 | 用于制备不饱和醛和/或不饱和羧酸的催化剂的再生方法和制备不饱和醛和/或不饱和羧酸的方法 |
| CN101500989A (zh) * | 2006-06-28 | 2009-08-05 | 哈佛学院院长等 | 四脒基金属(iv)化合物及其在气相沉积中的用途 |
| CN101564692A (zh) * | 2009-06-01 | 2009-10-28 | 西北大学 | 苯甲醇选择性氧化催化剂及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130006019A1 (en) | 2013-01-03 |
| CN102811991A (zh) | 2012-12-05 |
| SE534233C2 (sv) | 2011-06-07 |
| EP2528883A4 (en) | 2013-11-06 |
| EP2528883B1 (en) | 2021-01-13 |
| PL2528883T3 (pl) | 2021-07-05 |
| EP2528883A1 (en) | 2012-12-05 |
| SE1000070A1 (sv) | 2011-06-07 |
| US9056304B2 (en) | 2015-06-16 |
| WO2011093763A1 (en) | 2011-08-04 |
| PT2528883T (pt) | 2021-03-15 |
| ES2859484T3 (es) | 2021-10-04 |
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