CN1040104C - 饱和烃氨氧化方法 - Google Patents
饱和烃氨氧化方法 Download PDFInfo
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- CN1040104C CN1040104C CN92105412A CN92105412A CN1040104C CN 1040104 C CN1040104 C CN 1040104C CN 92105412 A CN92105412 A CN 92105412A CN 92105412 A CN92105412 A CN 92105412A CN 1040104 C CN1040104 C CN 1040104C
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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Abstract
本发明涉及饱和烃氨氧化,即烷烃转化成α,β-不饱和腈的混合物的方法,更具体地讲涉及烷烃在固化催化剂存在下气相氨氧化法,催化剂活性相含钼和氧,其特征是该活性相还含至少一种选自碱土金属,Mn,Fe,U,La,Co,Ni,Zn,Ag,Cd,W,Zr,Pb,Te,Ga,Al,B,Nb和Ta的元素。本发明特别宜于将丙烷氨氧化成含丙烯腈和丙烯的混合物。
Description
本发明涉及饱和烃氨氧化,即将烷烃转化成含α,β-不饱和腈的混合物的方法。
已知许多烯烃,特别是丙烯氨氧化法,而尽管来源广泛的饱和烃从经济角度看是极有价值的原料,但其反应性(活性)不够,尤其是在形成α,β-不饱和腈的反应中。
饱和烃氨氧化难题之一是寻求饱和烃脱氢催化剂,其中尽管减少或抑制氨燃烧和/或烃燃烧,同时又能保证有足够高的α,β-不饱和腈(目的产物),如用丙烷制成丙烯腈,或有利产物(上述腈和烯烃),如用丙烷制成丙烯腈和丙烯的选择性。
US 3365482已提出异丁烷氨氧化成甲基丙烯腈,其中用β-氨化铝沉积钼并掺锑的催化剂于508℃进行,原料为含异丁烷,空气,氨和水蒸汽的混合物(1.0/4.5/1.0/12.5),甲基丙烯腈选择性49%,异丁烷转化率22%。
原料为丙烷/空气/氨/水蒸汽(1.0/4.7/0.67/12.8)的气相混合物,同一催化剂于550℃进行时,丙烯腈选择性降为15%,丙烷转化率29%。
FR 2027238(部分对应于US 3670009)提出550℃以上气相氨氧化饱和烃的方法,固体催化剂可包括特别是氧化锡,氧化硼,氧化钼和氧化硅,第12-13页的例IX中丙烯腈选择性35%,丙烷转化率32%,但操作条件使丙烷/氨/空气反应混合物(1/1.2/12)处于爆炸范围内。
FR 2072334(对应于GB 1336135)建议500℃以下气相催化氨氧化烷烃,气体混合物中烷烃浓度高,其固体催化剂中可包括特别是氧化锡和氧化钼(90/10重量),但氧化锑和氧化钒催化剂操作性更好。
FR 2072399也提出烷烃气相催化氨氧化方法,在气体混合物进料中烷烃浓度高,所用固体催化剂特别是包括氧化钼的双份混合物。
可特别提出以下配对:
(Mo,Sb)(Mo,Sn)(Mo,V)(Mo,Ti)(Mo,Bi)
但这些配对中没有一对的操作性好于不含钼的配对所达到的操作性。所得丙烯腈收率低;最好情况下,有1.7%丙烷在570℃用锡和钛氧化物催化剂转化成丙烯腈。
FR 2119492(对应于US 3746737和BP 1337759中提出用基于钼和铈氧化物的双份组合物。但配对(Mo,Ce)的操作性似乎在不存在卤素或卤素化合物时不足。
另外还建议向该双份组合物(Mo,Ce)中加第三种元素,选自在和Bi(也可参见US 3833638)。这里,该催化剂体系的操作性在不存在卤素或卤素化合物时也似乎不足。而且应注意到,存在CH3Br时,丙烯腈选择性67%,丙烷转化率98%,但在操作条件下使丙烷/氨/空气反应混合物(1/1.2/12)处于爆炸区域。
FR 2119493也提出用含铋和钼氧化物以及必要时的磷和二氧化硅的固体催化剂气相氨氧化烷烃的办法。
这里,催化剂体系的操作性在不存在卤素或卤素化合物时也不足并且反应混合物处于爆炸区域。
由于有这许多缺陷,所以各种其它或后续研究都着眼于使用基于钒和/或锑的固体催化剂。
在Chemistry Letters 1989(PP 2173-2176)中作者在进行气相氨氧化丙烷时已试验过含钼和铋并显示出白钨矿组织的多成分金属氧化物,其中尽管采用了相当温和的温度,但燃烧产物(CO,CO2)在所有情况下似乎都极高(至少15%),且尽管在处于或接近于爆炸区域的条件下使用,但所试验的某些催化剂组合物对要求反应的活性似乎极低,几乎没有。
而存在卤素化合物不会引起设备腐蚀并因而在工业方法中不希望存在。
而且,很显然同时以工业化规模生产大量CO和CO2是不希望的。
此外,以工业规模应用处于爆炸区域的反应混合物也是完全不希望的,因为该工艺是在固定床中进行的。
因此,似乎很需要可高选择性地得到含α,β-不饱和腈,特别是丙烯腈而同时又可因形成二氧化碳而带来的原料损失的烷烃氨氧化法。
特别希望该方法中,固体催化剂制备起来相当简单,在不存在含卤素助催化剂并且在用气体混合物时该混合物不必处于爆炸区域。
本发明主题因此是在活性相含钼和氧的固体催化剂下气相氨氧化烷烃的方法,其特征是该活性相还含至少一种选自碱土金属,Mn,Fe,U,La,Co,Ni,Zn,Ag,Cd,W,Zr,Pb,Te,Ga,Al,B,Nb和Ta的元素。
根据本发明,在其活性相如上述的催化剂存在下每分子3-12碳无环饱和烃气相与氨和氧反应。
在本发明中,当然可用反应条件下呈惰性的稀释气体,如氦,氮和氩。同样,水蒸汽可在宽范围内加入气体反应混合物中,因此活性气(饱和烃,氨,氧)可用惰性稀释剂和/或水蒸汽稀释,其中水蒸汽含量可很宽,特别是0-50%,优选3-30%。为了很好利用本发明方法,活性气含量至少3%,优选至少20%。
活性气中饱和烃,氨和氧含量范围也可很宽。
活性气中饱和烃量优选5-70%,氨量优选3-50%,而氧量优选3-45%。
为很好利用本发明方法,反应混合物组成要在爆炸范围之外。就不存在惰性稀释剂时丙烷氨氧化而言,该组成(丙烷,氧,氨)可有利地选在图1中三元图ABC中的ABDE内。
在该三元图中,AB段代表氨量100-0%;BC段代表丙烷量100-0%;而CA段代表氧量100-0%。BC段内的点D对应于在二元(丙烷-O2)线中45%丙烷量;AC段内的点E对应于二元(NH3-O2)线中79%的氨量。
DE段将三元图分成两部分:三角形CDE,为爆炸区域(1巴和25℃测得),四边形ABDE,其中气体反应混合物组成有利。
就惰性稀释气和/或水蒸汽存在下丙烷氨氧化而言,可适当确定三元混合物的组成(丙烷,氧和氨)以使其在稀释气体和/或水蒸汽比例低时处于上述区线内。
在用空气作氧源进行丙烷氨氧化时,可有利地将组成(丙烷,空气和氨)选在图2所示ABC图中的四边形ABFG中。
在该第二图中,AB段为氨量100-0%;BC段为丙烷量100-0%;CA段为空气量100-0%。BC段内的点F对应于二元线丙烷-空气)中丙烷量16%;而AC段内的点G则对应于二元线(氨-空气)中35%的氨量。
FG段将三元图分成两部分:三角形CFG,其中为爆炸区域(1巴和550℃下测定),四边形ABFG,其中可有利选择气体反应混合物的组成。
该第二图应用于氧-稀释气混合物对应于氧量等于空气中氧量(≈21%氧)的情况或该混合物对空气而言是缺氧的情况下。
基本上含丙烯和丙烯腈的混合物可用丙烷制得,丙烯腈为工业上大规模生产的中间产物,而丙烯为常用于生产丙烯腈和本专业人员众所周知的各种其它中间产物的原料。
含甲基丙烯腈和异丁烯或正丁烯的混合物可用异丁烷制得。
本发明方法,特别适用于丙烷氨氧化。
尽管所用饱和烃可为工业段质量,但其中不能含大量的烯属不饱和化合物,因此,所用丙烷仅含微量丙烯。
本发明方法以气相反应形式进行,因此可用任何宜于进行气相氨氧化或氧化的设备。该方法可连续或不连续进行并且可用固定床或流化床。
反应温度一般350-550℃,优选420-510℃。
反应混合物总压可高于或等于大气压,一般1-6巴,优选1-4巴。
气体流速定为时空速100-36000h-1,优选200-20000h-1。
当然本专业人员记住生产产品就能够在温度,气体时空速,催化剂的准确性质以及其它各种反应参数之间找到折衷方案。
在本发明方法中,可用固体催化剂,其活性相含钼和氧,还含至少一种选自碱土金属,Mn,Fe,U,La,Co,Ni,Zn,Ag,Cd,W,Zr,Pb,Te,Ga,Al,B,Nb,和Ta的元素。
作为本发明用催化剂成分之一的活性相基于钼的混合氧化物,其中优选含至少一种上述元素。本发明方法用含至少一种选自碱土金属,锰,铁,钻,铀和镧的元素的活性相可达到很好的结果。
所说活性相优选为钼酸盐,更优选为锰,铀酰,钴或铁的钼酸盐。
尽管上述元素M在活性相中的比例可很宽,但优选由形成相应正钼酸盐的化学计量而求出最低量。在某些情况下并根据M的性质,相应钼酸盐和氧化钼的混合物可通过降低元素M的比例而得到。
例如,钼相对铁大量过量(Mo/Fe=10)就会形成Fe2(MoO4)3和MoO3的混合物,其在所说工艺中的性能似乎不象Fe2(MoO4)3所达到的性能那么好。
所说活性相可以大块形式或粒状形态用于本发明方法,这些相还可以如挤出或粉碎而形成的粉状或珠粒状应用。
这些相可沉积在惰性载体上或将其涂层。载体的性质并不关键,只是在反应条件下对反应物要呈惰性。宜于制造本发明方法所用催化剂的载体例子可举出二氧化硅,氧化铝,二氧化硅/氧化铝,烧结粘土,金刚砂,氧化镁,硅酸镁和硅藻土。该载体优选为非孔隙的,特别是基于粒状形式的耐火氧化物,最常用载体基于粘土。该载体例如粒径为0.5-6mm的惰性,固体,坚硬粗粘土球粒组成。球粒直径的准确值可由本专业人员根据反应器中允许的压降而选的择。还可通过上瓷漆而使该载体成为非孔隙的。
该载体也可为陶瓷基体,优选呈惰性并且刚性的整体结构,其中包括通道或孔沟。这些载体对本专业人员来说是众所周知的并已在文献中广泛报道。陶瓷基体可特别含堇青石,氧化铝,莫来石,瓷料以及硼或硅的碳化物。
当要求用涂层催化剂时,活性相的量可在很宽范围内变化,一般为总量(载体加活性相)的5-35%,优选为10-15wt%。
用于本发明方法的催化剂可用各种已知方法制得,如在水或其它溶剂中混入适宜的单质成分盐,然后蒸发至于,或加碱,如氨水溶液或酸,如盐酸进行沉淀或将混合适宜盐后所得悬浮液进行喷雾干燥。
常用适宜盐可溶于水并含有可后续热分解的阴离子和阳离子。例如在钼的情况下,为碱土金属,锰,铁,钴,铀,镧等的硝酸盐或氯化物。
一旦盐的混合物制成,就可通过所谓蒸发法得到母体,所得悬浮液中的水经20-100℃加热搅拌而蒸发掉,其中时间以得到不流动糊为准。然后停止搅拌和加热。
这样得到的糊铺成约2mm厚层后在空气中于约120℃干燥约15小时,所得母体再研磨并于约200-1000℃,优选400-600℃焙烧至少30min,优选至少1小时。逐渐升高温度,如100-200℃/小时而进行焙烧,其中特别考虑到硝酸铵在约230℃有放热分解的危险。冷却后所得活性相研磨而使其粒径不应超过约400μm。
母体也可通过各种办法得到,其中包括沉淀,例如在盐混合结束时加氨水溶液或盐酸使PH稳定为约7以进行沉淀。优选将悬浮液于20-100℃加热约1小时而结束物质沉淀。
悬浮液过滤后洗涤,滤饼再于上述蒸发有关的条件下铺成层后干燥,研磨并焙烧而得活性相。
某些可应用于固定床工艺的某些催化剂可经已知方法涂层研细的中间或最终活性相而得到。这种常规方法在于在惰性,但粗珠粒上沉积一层中间或最终的上述活性相。
一旦珠粒涂上了要求量的活性相之后,就用空气于70-150℃下干燥至少30min,然后将其引入烘箱中以于300-600℃,优选450-500℃焙烧至少3小时。
某些可用于本发明固定床或流化床工艺的催化剂可用已知技术,如在优选为非还原性气氛中喷雾干燥而得到。应用这一操作,必要时再于400-1100℃左右焙烧,可得到粒径5-700μm粉,流化床优选用至少80%的粒径为5-100μm的粉。
反应产物在流出气中通过合适的办法回收,例如流出气可通过含稀硫酸的冷凝器而使未回收的氨中和。气体可通过冷冻吸收塔而使丙烯腈,乙腈和氢氰酸,主要含未反应丙烷的未冷凝气,丙烯,轻质烃和必要时的CO2冷凝。丙烯腈和盐酸可从乙腈中蒸馏分离并将回收的丙烯腈-氢氰酸混合物本身蒸馏而将丙烯腈和氢氰酸分开。
下述实施例详述本发明。
例1 制备钼酸镁基催化剂
将52.98g(NH4)5Mo7O24·4H2O(Merck市售)溶于200Cm3去矿物质水中得到七钼酸铵溶液(a)(所得溶液PH5-6),并将79.3g 97%Mg(NO3)2·6H2O(Prolabo市售)溶于200Cm3去矿物质水中而得硝酸镁溶液(b)。溶液(b)加入搅拌反应器中的溶液(a)中(PH=5)。混合物在热板上加热,所得糊120℃干燥约15小时,所得产品在研钵中研磨并在空气中500℃焙烧4小时。
所得产品(I)X-射线衍射分析得组成MgMoO4,比表面BET法测得为5m2/g。
20g产品(I)洒在平均粒径4.8mm的粘土珠粒组成的123g惰性载体上,先放在转动造粒机中并用浓度为10%的葡萄糖水溶液浸湿。一旦珠粒外表干燥,再喷洒少量葡萄糖液。产品(I)再喷到珠粒上。这些操作交替持续到所有产品已涂层为止。干燥在120℃进行2小时并于480℃焙烧6小时。
所得催化剂(A)由沉积到粘土珠粒上的12wt%MgMoO4组成。
例2 制备钼酸锰基催化剂
用U.Ozran,R.C.Gill和M.R.Smith,J.Catal.116,171-183(1989)所述方法制成组成MnMoO4的活性相。
将70.64g(NH4)6Mo7O24·4H2O(Merck市售)溶于200Cm3去矿物质水中制成七钼酸铵溶液(a),将79.16g MnCl2·4H2O(Prolabo市售)溶于400Cm3去矿物质水中制成氯化锰溶液(b)。溶液(a)滴加入供能量搅拌反应器内的溶液(b)中。加热到80℃并加稀盐酸或氨水(均为Prolabo市售)而使PH保持6,历时3小时。物料热过滤到烧结玻璃上并用1l去矿物质水洗涤。所得产物120℃干燥约15小时,研钵中研磨并在空气中于500℃焙烧4小时。
所得产物X-射线衍射分析得组成MnMoO4,而BET法测得比表面积5m2/g。
20g产品(I)慢洒到123g平均粒径4.8mm的粘土珠粒组成的惰性载体上,先放在旋转造粒机中并用浓度10%葡萄糖水溶液浸湿。一旦珠粒外表面变干,就喷少量葡萄糖水溶液。产物(I)然后再洒到珠粒上。这些操作交替持续到所有产物(I)均涂层为止。干燥于120℃进行2小时,并480℃焙烧6小时。
所得催化剂(B)由沉积到粘土珠粒上的11wt%MnMoO4组成。
例3 制备另一钼酸锰基催化剂
制得20g上述例中所述MnMoO4组成的产物(I),然后在20t压力下压成直径3Cm,厚约0.5Cm的片,再破碎成粒径0.3-0.8Cm的粒料,构成催化剂(C)。
例4 制备钼酸铀酰基催化剂
按E.Bordes,State Thesis,Compiegne(1979)所述操作方法制成组成为UO2MoO4的活性相。
将35.32g(NH4)6Mo7O24·4H2O(Merck市售)溶于200Cm3去矿物质水中而得到七钼酸铵溶液(a),并且将100.43g的UO2(NO3)2·6H2O(Prolabo市售)溶于200Cm3的去矿物质水中而得硝酸铀酰溶液(b)。在搅拌反应器中将溶液(b)加入溶液(a)中。再加入100Cm3去矿物质水,混合物在热板上加热,所得糊在120℃干燥约15小时;所得产物然后在研钵中研磨并在空气中于550℃焙烧12小时。
所得产物(I)X-射线衍射分析得组成UO2MoO4,BET法测比表面积2.7m2/g。
20g该产物(I)缓慢洒到123g平均粒径4.8mm的粘土珠粒组成的惰性载体上,先将其放在旋转造粒机中并用浓度为10%的葡萄糖水溶液浸湿。一旦外表面变干,就喷少量葡萄糖溶液。产物(I)然后再洒到珠粒上。这些操作交替持续到所有产物(I)已涂层为止。120℃干燥2小时并480℃焙烧6小时。
所得催化剂由沉积到粘土珠粒上的11wt%UO2MoO4组成。
例5 制备钼酸钙基催化剂
将52.98g(NH4)6Mo7O24·4H2O(Merck市售)溶于200Cm3去矿物质水中而得七钼酸铵溶液(a),并将47.23g Ca(NO3)2·4H2O(Prolabo市售)溶于200Cm3去矿物质水中而得硝酸钙溶液(b)。在搅拌反应器中将溶液(b)加入溶液(a)中。PH初始4.5,再加氨水(Prolabo市售)而升至6.7。热板上加热,所得糊120℃干燥15小时;所得产物再于研钵中研磨并在空气中500℃焙烧7小时。
所得产物(I)经X-射线衍射证实组成为CaMoO4,BET法所测比表面积5m2/g。
20g产物(I)慢加入123g由粒径4.8mm的粘土珠粒组成的惰性载体上,先将其放入旋转造粒机中并用浓度10%的葡萄糖水溶液浸湿。一旦珠粒变干,就喷少量葡萄糖水溶液。产物(I)然后再洒到珠粒上。这些操作交替持续到所有产物(I)均被涂层为止。120℃干燥2小时并480℃焙烧6小时。
所得催化剂(E)由沉积到粘土珠粒上的11wt%CaMoO4组成。
例6 制备混合钼镧氧化物基催化剂
将35.32g(NH4)6Mo7O24·4H2O(Merck市售)溶于200Cm3去矿物质水而得七钼酸铵溶液(a),并将71.64Cm3的La(NO3)3(含455g/l的La2O3,来源:Rhone-Poulenc factory,La Rochelle)溶于200Cm3去矿物质水中而得硝酸镧溶液。在搅拌反应器中将溶液(a)加入溶液(b)中。再加浓硝酸将混合物酸化至PH=1-2。热板上100-110℃加热并将所得糊于120℃干燥约15h;所得产物在研钵中研磨并500℃在空气中焙烧3小时。
制成的产物(I)由镧钼氧化物组成,这已由X-射线衍射分析证实,并且BET法测定的比表面积6m2/g。
20g产物(I)慢洒到123g平均粒径4.8mm的粘土珠粒组成的惰性载体上,先将其加入旋转粒机中并用浓度为10%的葡萄糖水溶液浸湿。一旦珠粒外表面变干,就喷少量葡萄糖溶液。再将产物(I)洒到珠粒上。这些操作交替持续到所有产物(I)均得以涂层为止。再120℃干燥2小时,并480℃焙烧6小时。
所得催化剂(F)由沉积到粘土珠粒上的9wt%LaMoOX组成。
例7 制备钼酸铁基催化剂
按S.Nasu和S.Shimizu,J.Catal.104,164-175(1987)所述方法制成组成Fe2(MoO4)3的活性相。
将52.98g(NH4)6Mo7O24·4H2O(Merck市售)溶于200Cm3去矿物质水而得七钼酸铵溶液(a),并将80.8g Fe(NO3)3·9H2O(Prolabo市售)溶于200Cm3去矿物质水中而得溶液(b),在搅拌反应器中将溶液(b)加入溶液(a)中。加氨水(Prolabo市售)而将混合物调为PH=7.5。热板上加热,所得糊120℃干燥约15h;所得产物再在研钵中研磨并在空气中于500℃焙烧1小时,再研磨后再于空气中500℃焙烧1小时。
所得产物(I)经X-射线衍射分析表明组成Fe2(MoO4)2,BET法所测比表面积3.9m3/g。
20g产物(I)慢洒到平均粒径4.8mm的粘土珠粒组成的惰性载体上,先将其放入旋转造粒机中并用浓度为10%的葡萄糖水溶液浸湿。一旦珠粒外表面变干,就喷少量葡萄糖溶液。产物再洒到珠粒上。这些操作交替持续到所有产物(I)涂层为止。干燥在120℃进行2小时,焙烧在480℃进行6小时。
所得催化剂(G)由沉积到粘土珠粒上的13wt%Fe2(MoO4)3组成。
例8 制备混合钼锡氧化物基比较催化剂(该催化剂不属于本发
明)
将35.32g(NH4)6Mo7O24·4H2O(Merck市售)溶于200Cm3去矿物质水中得到七钼酸铵溶液,并将45.13gSnCl2·2H2O(Prolabo市售)溶于200Cm3去矿物质水中而得氯化锡溶液(b),再用几滴浓盐酸酸化。在搅拌反应器中将溶液(b)加入溶液(a)中,混合物加热并将氨水(Prolabo市售)加入直至达到中性pH。物料用烧结玻璃过滤并用100Cm3去矿物质水洗涤;所得产物120℃干燥约15小时,研钵中研磨后空气中500℃焙烧3小时。
所得产物经X-射线衍射证实组成为SnO2-2MoO3,BET法测定的比表面积为26m2/g。
20g产物(I)慢洒到123g由平均粒径为4.8mm的粘土珠粒组成的惰性载体上,先将其放入旋转造粒机中并用浓度10%的葡萄糖溶液浸湿。一旦珠粒变干,就喷少量葡萄糖溶液。产物(I)然后再喷到珠粒上。这些操作交替持续到所有产物(I)涂层为止。干燥在120℃进行2小时,而焙烧在480℃进行6小时。
所得催化剂(H)由沉积到粘土珠粒上的11wt%SnO2-2MoO3组成。
例9 制备钼酸锰和氧化铝(30-70%)基催化剂
将26.47g(NH4)6Mo7O24·4H2O溶于120Cm3去矿物质水中制成溶液(a),并将37.65gMn(NO3)2·4H2O溶于60Cm3去矿物质水中制成溶液,将75.2g氧化铝在100Cm3去矿物质水中制成悬浮液(c)。溶液(a)加入溶液(c)后加入溶液(b)。搅拌2小时后将物料蒸发至干。120℃干燥并500℃焙烧4小时,得到产物(I)。
20g产物(I)慢洒到123g平均粒径4.8mm粘土珠粒组成的惰性载体上,先将其放在旋转造粒机中并用浓度为10%的葡萄糖溶液浸湿。一旦珠粒变干,就喷少量葡萄糖溶液。然后将产物(I)再洒到珠粒上。这些操作交替持续到所有产物(I)涂层为止。
120℃干燥2小时,480℃焙烧6小时。所得催化剂(J)由沉积在粘土珠粒上的11wt%MnMoO4-Al2O3(30-70%)组成。
例10 制备钼酸锰和二氧化硅基催化剂
将58.3g(NH4)2Mo2O7和8.2g MoO3溶于150Cm3去矿物质水中得溶液(a),并将100.4gMn(NO3)2·4H2O溶于100Cm3去矿物质水中而得溶液(b)。室温将溶液(b)加入溶液(a)。
31.9Cm3所得溶液稀释成40Cm3溶液后浸渍50g二氧化硅。干燥在120℃进行约15小时,焙烧在500℃进行4小时。
所得催化剂(K)由沉积到二氧化硅上的14.6wt%MnMoO4组成。
氨氧化试验操作总说明
催化剂样品在测定秤上于氮气封内10min内预热到150℃后送入气流中,气流组成对每一样品是特定的,其中含丙烷,氨,氧,水蒸汽和氦。
反应混合物总压1-6巴,对每一样品为特定的。
气流速度定义为时空速(HSV)100-36000h-1,其准确值对每一样品给出。
丙烷氨氧化试验原则如下:
催化剂加热到温度T1,如300℃,该温度下稳定化30min后离开反应器的组合物组成经气相色谱测定。
初始温度T1下催化剂达到的转化率和选择性百分比用以下关系式计算:
丙烷转化率%=%转化丙烷/%引入丙烷
丙烯腈选择性=%转化成丙烯腈的丙烷/%转化丙烷
以20℃速度逐渐将催化剂从300℃加热到550℃并且每40min测定转化率和选择性百分比。
在例子中用了以下符号:
DCC3H8 =丙烷转化率
SACN =丙烯腈选择性
SACN+C3H6 =丙烯腈和丙烯选择性
SCOX=一氧化碳和二氧化碳选择性
T=温度
EXAMPLES=实施例
CATALYST=催化剂
例11-13
催化剂(A),(B)和(D)性能测定操作条件如下:时空速(HSV)=100h-1总压=1.3巴反应混合物组成:C3H8=11%NH3=7.5%O2=10%H2O=25%He=46.5%结果和特定条件列在表I中:
表I
例14-16比较试验a:催化剂(E)-(H)性能测定所用操作条件如下:HSV=1000h-1总压=1.3巴反应混合物组成:C3H8=30%NH3=15%O2=15%H2O=20%He=20%结果和特定条件列在下表II中:
EXAMPLES | CATALYST | T℃ | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
11 | (A) | 470 | 6 | 10 | 73 | 0 |
12 | (B) | 470510 | 25.5 | 119 | 9877 | 00 |
13 | (D) | 470510 | 35 | 1514 | 4471 | 00 |
表II
例17-19催化剂(A)在不同丙烷分压下性能测定操作条件如下:温度=510℃HSV=1000h-1总压=1.3巴反应混合物组成:C3H8=11%,19%,26%NH3=7.5%O2=10%H2O=25%He=31.5%,38.5%,46.5%结果和特定操作条件如下表III:
EXAMPLES | CATALYST | T℃ | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
14 | (E) | 475490 | 24 | 09.5 | 7869 | 00 |
15 | (F) | 460490510 | 177.5 | 31910 | 835560 | 006 |
16 | (G) | 460475490 | 576 | 202319 | 595658 | 0013 |
a | (H) | 440460475 | 91111 | 62024 | 324347 | 191613 |
表III
例20-23催化剂(B)在不同温度下性能测定操作条件如下:HSV=1000h-1总压=1.3巴反应混合物组成:C3H8=19%NH3=7.5%O2=10%H2O=25%He=38.5%结果和特定条件如表IV:
EXAMPLES | C3H8(%) | DCC3H6(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
17 | 11 | 17 | 3 | 50 | 21 |
18 | 19 | 16 | 16 | 69 | 5 |
19 | 26 | 16 | 13 | 72 | 5.5 |
表IV
例24-26催化剂(B)在不同HSV下性能测定操作条件如下:温度=510℃总压=1.3巴反应混合物组成:
EXAMPLES | T℃ | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
20 | 420 | 0.4 | 16 | 81 | 0 |
21 | 470 | 2 | 17 | 72 | 0 |
22 | 485 | 3 | 17 | 71 | 0 |
23 | 510 | 8 | 30 | 67 | 0 |
C3H5=19%
NH3=7.5%
O2=10%
H2O=25%
He=38.5%特定条件和结果如表V:
表V
例27-31催化剂(B)在不同温度下性能测定操作条件如下:HSV=500h-1总压=1.3巴反应混合物组成:C3H8=19%NH3=7.5%O2=10%H2O=25%He=38.5%结果和特定条件如表VI:
EX-AMPLES | HSV(h-1) | 催化剂体积(ml) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
24 | 200 | 100 | 13 | 21 | 77 | 2 |
25 | 500 | 40 | 13 | 27 | 65 | 0 |
26 | 1000 | 20 | 8 | 30 | 67 | 0 |
表VI
例32-36催化剂(C)在不同温度下的性能测定操作条件如下:HSV=1000h-1总压=1.3巴反应混合物组成:
EXAMPLES | T℃ | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
27 | 420 | 1 | 3 | 87 | 0 |
28 | 450 | 3 | 15 | 58 | 0 |
29 | 470 | 5 | 20 | 62 | 0 |
30 | 490 | 9 | 27 | 62 | 0 |
31 | 510 | 13 | 27 | 65 | 0 |
C3H6=19%
NH3=7.5%
O2=10%
H2O=25%
He=38.5%特定条件和结果如表VII:
表VII
例37-39催化剂(B)在不同丙烷分压下的性能测定操作条件如下:温度=510℃HSV=1000h-1总压=1.3巴反应混合物组成
EXAMPLES | T℃ | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
32 | 410 | 3 | 9 | 64 | 0 |
33 | 430 | 6 | 13 | 74 | 0 |
34 | 470 | 11 | 16 | 76 | 4 |
35 | 490 | 20 | 23 | 73 | 9 |
36 | 510 | 24 | 24 | 73 | 6 |
C3H8=11%,19.26%
NH3=7.5%
O2=10%
H2O=25%
He=31.5%,38.5,46.5%特定条件和结果如表VIII:
表VIII
例40-42催化剂(B)在不同氨分压下的性能测定操作条件如下:温度=510℃HSV=1000h-1总压=1.3巴反应混合物组成:
EXAMPLES | C3H8(%) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
37 | 11 | 5 | 19 | 77 | 0 |
38 | 19 | 8 | 30 | 67 | 0 |
39 | 26 | 5 | 13 | 80 | 0 |
C3H8=19%
NH3=4%,7.5,11%
O2=10%
H2O=25%
He=35%,38.5,42%特定条件和结果如表IX:
表IX
例43-45催化剂(D)在不同丙烷分压下的性能测定操作条件如下:温度=510℃HSV=1000h-1总压=1.3巴反应混合物组成:
EXAMPLES | NH3(%) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
40 | 4 | 4 | 0 | 82 | 17 |
41 | 7.5 | 8 | 30 | 67 | 0 |
42 | 11 | 10 | 30 | 60 | 0 |
C3H6=11%,19.26%
NH3=7.5%
O2=10%
H2O=25%
He=31.5%,38.5,46.5%特定条件和结果如表X:
表X
例46-48催化剂(D)在不同氨分压下的性能测定操作条件如下:温度=510℃HSV=1000h-1总压=1.3巴反应混合物组成:C3H8=19%
EXAMPLES | C3H8(%) | DCC3H6(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
43 | 11 | 5 | 14 | 71 | 0 |
44 | 19 | 4 | 11 | 73 | 0 |
45 | 26 | 7 | 22 | 54 | 0 |
NH3=4%,7.5,11%
O2=10%
H2O=25%
He=35%,38.5,42%特定条件和结果如表XI:
表XI
例49-51催化剂(F)在不同氧分压下的性能测定操作条件如下:温度=490℃HSV=1000h-1总压=1.3巴反应混合物组成:C3H8=20%
EXAMPLES | NH3(%) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
46 | 4 | 6 | 24 | 62 | 0 |
47 | 7.5 | 4 | 11 | 73 | 0 |
48 | 11 | 4 | 13 | 70 | 0 |
NH3=15%
O2=5%,15,25%
H2O=20%
He=20%,30,40%特定条件和结果如表XII:
表XII
例52-53催化剂(G)在不同氨分压下的性能测定操作条件如下:温度=490℃HSV=1000h-1总压=1.3巴反应混合物组成:C3H6=20%NH3=5%,25%O2=5%H2O=20%He=20%,40%特定条件和结果如表XIII:
EXAMPLES | O2(%) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
49 | 5 | 4 | 15 | 63 | 0 |
50 | 15 | 6 | 14 | 59 | 0 |
51 | 25 | 8 | 18 | 58 | 4 |
表XIII
例54-55催化剂(G)在不同氧分压下的性能测定操作条件如下:温度=475℃HSV=1000h-1总压=1.3巴反应混合物组成:
EXAMPLES | NH3(%) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
52 | 5 | 12 | 17 | 45 | 28 |
53 | 25 | 14 | 7 | 42 | 4 |
C3H8=20%
NH3=15%
O2=5%,25%
H2O=20%
He=20%,40%特定条件和所得结果如表XIV:
表XIV
例56-57催化剂(J)和(K)性能测定操作条件如下:HSV=1000h-1总压=1.3巴反应混合物组成:C3H8=48%NH3=95%O2=18%H2O=20%He=5%特定条件和结果如表XV:
EXAMPLES | O2(%) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
54 | 5 | 8 | 15 | 58 | 4 |
55 | 25 | 11 | 17 | 60 | 14 |
表XV
比较试验b,c,d:催化剂H在不同温度下性能测定操作条件如下:HSV=1000h-1总压=1.3巴反应混合物组成:
EXAMPLES | CATALYST | T℃ | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
56 | (J) | 500 | 15 | 15 | 62 | 0 |
57 | (K) | 460 | 12 | 14 | 37 | 0.2 |
C3H8=20%
NH3=5%
O2=15%
H2O=20%
He=40%特定条件和结果如表XVI:
表XVI
EXAMPLES | T℃(%) | DCC3H8(%) | SACN(%) | SACN+C3H6(%) | SCOX(%) |
b | 460 | 19 | 13 | 25 | 38 |
c | 475 | 20 | 19 | 32 | 43 |
d | 490 | 21 | 26 | 41 | 28 |
例58 制备钼酸铀酰基催化剂
组成UMo10Ox的活性相按以下操作制成。
将176.56g(NH4)6Mo7O24·4H2O(Merck市售)溶于400Cm3去矿物质水中制成七钼酸铵溶液(a),并将50.2g UO2(NO3)2·6H2O(Prolabo市售)溶于50Cm3去矿物质水中制成硝酸铀酰溶液(b)。在搅拌反应器中将溶液(b)加入溶液(a)并加热到约80℃。物料保持在80-100℃达约2小时,所得糊120℃干燥约15小时;所得产物在空气中于500℃焙烧4小时。
所得产物BET法测比表面积2.4m2/g。
10g该产物慢洒到65g平均粒径4.8mm的粘土珠粒组成的惰性载体中,先放入旋转造粒机中并用浓度为10%的葡萄糖溶液浸湿。一旦珠粒外表变干,就喷少量葡萄糖溶液。该产物再洒到珠粒上,这些操作交替持续到所有产物均涂层为止,干燥在120℃进行2小时,焙烧在480℃进行6小时。
所得催化剂(L)由沉积在粘土珠粒上的11.2wt%UMo10Ox组成。
例59 制备钼酸钴基催化剂
组成CoMoO4的活性相用以下方法制成。
将70.6g(NH4)6Mo7O24·4H2O(Merck市售)溶于400Cm3去矿物质水中制成七钼酸铵溶液(a),并将116.4g Co(NO3)2·6H2O溶于150Cm3去矿物质水中而制成硝酸钴溶液(b)。在搅拌反应器中将溶液(b)加入溶液(a)并加热沸腾。所得糊120℃干燥约15小时并且在空气中500℃焙烧4小时。
所得产物BET法测比表面积7.7m2/g。
10g该产物慢洒到50g由平均粒径4.8mm的粘土珠粒组成的惰性载体上,先将其放入旋转造粒机中并用10%浓度的葡萄糖溶液浸湿。一旦珠粒外表面变干,就喷少量葡萄糖溶液。该产物然后再洒到珠粒上。这些操作交替持续到所有产物均涂层为止。再120℃干燥2小时并480℃焙烧6小时。
所得催化剂(M)由沉积在粘土珠粒上的11.7wt%CoMoO4组成。
例60 制备钼酸钴基催化剂
组成CoMoO4的活性相用以下办法制得:
将70.6g(NH4)6Mo7O24·4H2O(Merck市售)溶于400Cm3去矿物质水中制成七钼酸铵溶液(a),并将116.4g Co(NO3)2·6H2O溶于150Cm3去矿物质水中而制成硝酸钴溶液(b)。在搅拌反应器中将溶液(b)加入溶液(a)并加热沸腾。所得糊120℃干燥约15小时并且在空气中500℃焙烧4小时。
所得产物BET法测比表面积13m2/g。
10g该产物慢洒到67g由平均粒径4.8mm的粘土珠粒组成的惰性载体上,先将其放入旋转造粒机中并用10%浓度的葡萄糖溶液浸湿。一旦珠粒外表面变干,就喷少量葡萄糖溶液。该产物然后再洒到珠粒上。这些操作交替持续到所有产物均涂层为止。再120℃干燥2小时并480℃焙烧6小时。
所得催化剂(N)由沉积在粘土珠粒上的10wt%CoMoO4组成。
例61-65
催化剂(L)在不同温度和不同反应混合物组成下的性能测定
操作条件如下:
HSV=1000h-1
总压=1.3巴
反应混合物组成,温度和结果如表XVII:
表XVII
例66-69催化剂(M)在不同温度和不同反应混合物组成下的性能测定操作条件如下:HSV=1000h-1总压=1.3巴反应混合物组成,温度和所得结果列在表XVIII中。
EXAMPLES | 61 | 62 | 63 | 64 | 65 |
C3H8(%vol) | 7.5 | 25 | 25 | 40 | 48 |
NH3(%vol) | 15 | 25 | 10 | 15 | 9 |
O2(%vol) | 15 | 10 | 25 | 15 | 18 |
He(%vol) | 42.5 | 20 | 20 | 10 | 5 |
T(℃) | 460 | 430 | 460 | 460 | 480 |
DCC3H8(%) | 4 | 2 | 5 | 3 | 6 |
SACN(%) | 19 | 15 | 13 | 13 | 18 |
SACN+C3H6(%) | 48 | 59 | 32 | 78 | 44 |
SCOx(%) | 0 | 0 | 0 | 1 | 0 |
表XVIII
例70-73催化剂(N)在不同温度和不同反应混合物组成下的性能测定操作条件如下:HSV=1000h-1总压=1.3巴反应混合物组成,温度和结果如表XIX。
EXAMPLES | 66 | 67 | 68 | 69 | |||||
C3H8(%vol) | 7.5 | 25 | 40 | 48 | |||||
NH3(%vol) | 15 | 25 | 15 | 9 | |||||
O2(%vol) | 15 | 10 | 15 | 18 | |||||
He(%vol) | 42.5 | 20 | 10 | 5 | |||||
T (℃) | 460 | 480 | 460 | 480 | 460 | 480 | 440 | 460 | 480 |
DCC3H8(%) | 8 | 17 | 6 | 6 | 7 | 11 | 6 | 10 | 16 |
SACN(%) | 20 | 31 | 14 | 12 | 13 | 17 | 16 | 18 | 17 |
SACN+C3H6(%) | 76 | 75 | 59 | 67 | 83 | 84 | 73 | 79 | 75 |
SCOx(%) | 0 | 0 | 0 | 0 | 0 | 1 | 0 | 1 | 5 |
表XIX
EXAMPLES | 70 | 71 | 72 | 73 | ||
C3H8(%vol) | 7.5 | 25 | 40 | 48 | ||
NH3(%vol) | 15 | 10 | 15 | 9 | ||
O2(%vol) | 15 | 25 | 15 | 18 | ||
He(%vol) | 42.5 | 20 | 10 | 5 | ||
T (℃) | 480 | 460 | 480 | 440 | 460 | 440 |
DCC3H6(%) | 11 | 8 | 15 | 6 | 11 | 5 |
SACN(%) | 14 | 17 | 20 | 11 | 17 | 12 |
SACN+C3H6(%) | 84 | 82 | 76 | 83 | 83 | 82 |
SCOx(%) | 2 | 0 | 4 | 0 | 1 | 0 |
Claims (14)
1.在固体催化剂存在下烷烃气相氨氧化方法,催化剂活性相含钼和氧,其特征是该活性相还含至少一种选自碱土金属,Mn,Fe,U,La,Co,Ni,Zn,Ag,Cd,W,Zr,Pb,Te,Ga,Al,B,Nb和Ta的元素。
2.权利要求1的方法,其特征是该活性相含至少2种选自上述的元素。
3.权利要求1的方法,其特征是该活性相含至少一种选自碱土金属,锰,铁,钴,铀和镧的元素。
4.以上任一项权利要求的方法,其特征是该活性相为以钼为基础的混合氧化物。
5.权利要求1-3中任一项的方法,其特征是该活性相为正钼酸盐。
6.权利要求5的方法,其特征是该活性相为锰,铀酰,钴或铁的钼酸盐。
7.权利要求1~3中任一项的方法,其特征是烷烃为丙烷。
8。权利要求1~3中任一项的方法,其特征是反应在水蒸汽存在下进行。
9.权利要求1~3中任一项的方法,其特征是反应温度为350-550℃。
10.权利要求1~3中任一项的方法,其特征是总压为1-6巴。
11.权利要求1~3中任一项的方法,其特征是时空速为100-36000h-1。
12.权利要求1~3中任一项的方法,其特征是由饱和烃、氨和氧的混合物构成的活性气含有饱和烃5-70%,氨3-50%和氧3-45%。
13.权利要求1~3中任一项的方法,其特征是气体混合物组成在爆炸范围之外。
14.权利要求1~3中任一项的方法,其特征是除活性相而外,该催化剂还含载体。
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FR2678610A1 (fr) * | 1991-07-04 | 1993-01-08 | Rhone Poulenc Chimie | Procede d'ammoxydation d'hydrocarbures satures. |
AU3950493A (en) * | 1992-04-03 | 1993-11-08 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | A method of controlling the oxidation of chemicals during storage using noble gases |
US5840648A (en) * | 1997-09-02 | 1998-11-24 | The Standard Oil Company | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
KR20020095527A (ko) * | 2001-06-14 | 2002-12-27 | 엘지전자 주식회사 | 소프트 키의 속성 표시방법 |
GB0217274D0 (en) * | 2002-07-25 | 2002-09-04 | Boreas Consultants Ltd | Pipe liner connector |
US20070042903A1 (en) * | 2005-08-18 | 2007-02-22 | Dehuan Huang | Lanthanum doping catalyst for preparing carbon nanotubes having uniform diameter and producing method thereof |
CN111013620A (zh) * | 2019-12-18 | 2020-04-17 | 夏丽丹 | 一种耐磨的混合金属氧化物催化剂及其制备方法 |
CN111203251A (zh) * | 2020-02-26 | 2020-05-29 | 递铂国际贸易(大连)有限公司 | 一种低碳烃氨氧化合成不饱和腈的耐磨混合金属氧化物催化剂及其制备方法 |
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TW218007B (zh) | 1993-12-21 |
EP0524895A1 (fr) | 1993-01-27 |
JPH0692354B2 (ja) | 1994-11-16 |
CA2073073C (fr) | 1998-08-11 |
DE69221561D1 (de) | 1997-09-18 |
JPH05194347A (ja) | 1993-08-03 |
US5556984A (en) | 1996-09-17 |
CN1068325A (zh) | 1993-01-27 |
KR950006897B1 (ko) | 1995-06-26 |
FR2678610B1 (zh) | 1994-08-19 |
SG75767A1 (en) | 2000-10-24 |
MX9203877A (es) | 1994-03-31 |
DE69221561T2 (de) | 1998-02-26 |
EP0524895B1 (fr) | 1997-08-13 |
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