CN1411907A - 含氧化铁的催化剂的制备方法 - Google Patents

含氧化铁的催化剂的制备方法 Download PDF

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CN1411907A
CN1411907A CN02147554A CN02147554A CN1411907A CN 1411907 A CN1411907 A CN 1411907A CN 02147554 A CN02147554 A CN 02147554A CN 02147554 A CN02147554 A CN 02147554A CN 1411907 A CN1411907 A CN 1411907A
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K·乔汉森
P·戈德斯
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Abstract

一种用于制备含混合金属氧化物的催化剂的方法，包括下述步骤：－.将金属Me＝Fe，Ni，Al，Cu，Zn，Cr，溶解在硝酸中，提供一种金属混合的硝酸盐产物的酸性溶液，可以将铝以硝酸盐或氢氧化物加入；－.加入糖类，氨基酸和/或羧酸；－.在250－700℃自由空气供料下，通过喷射在一或多个旋转窑的内表面上，喷射到喷射烧结流化床中，喷射到塔式窑中或喷射到钢带传送机加热炉中，使酸性溶液分解为氧化铁和NOx；并且可任选地将生成的NOx再生为硝酸，并将制得的硝酸再循环到第一步中。

Description

含氧化铁的催化剂的制备方法
技术领域
本发明涉及一种用于混合金属氧化物催化剂制备的金属氧化物的制备方法。
背景技术
在本领域中制备混合金属氧化物的方法包括采用沉淀的方法。金属硫化物是一种廉价的纯原料并且通过共沉淀可以获得优良的催化剂，但是含有太高的硫含量。另一方面，金属硝酸盐是一种昂贵的原料，并且将金属溶解在硝酸中需要昂贵的硝酸。
公知的制备混合金属氧化物催化剂的方法在购买酸和碱性原料以及在沉淀、洗涤和废水处理方面费用大。
这方面内容描述在US4482645中，其中Jennings等人制备了一种硝酸铁和硝酸铬的溶液，向其中加入碳酸钠，并且在干燥和分解为氧化物之前将形成的铁和铬的氢氧化物洗去。
发明内容
因此，本发明的总的目的是提供一种以简单且廉价的步骤制备含混合金属氧化物催化剂的改进方法。现在发明和开发了一种基于金属经由硝酸盐和硝酸回收的可供选择的制备路线。
与公知方法相比，本发明的优点在于高质量的催化剂，且进一步在于通过减少生产过程中材料的损失而得到高产率。
本发明的方法包括下述步骤，包括金属Me＝Co，Zn，Fe，Ni，Cr和/或Cu：
(a)通过下述反应(i)将Me溶解在硝酸中，提供一种Me(NO3)3(用三价金属示例说明)的酸性溶液：
(b)可选择与不同的金属硝酸盐溶液混合，例如，Fe(NO3)3溶液与Co(NO3)3溶液。铝以硝酸盐或氢氧化物的方式加入。
(c)可选择地，加入促进剂。如果促进剂(PR)诸如PR＝Na，K，Cs，Rb，Mg，Ca，Ba，Sr是在最终产品中所需的，则将它们以金属硝酸盐、碳酸盐、氢氧化物等形式加入到溶解的Me(III)硝酸盐中。促进剂优选以碱＜PR/Me＜0.2的摩尔比加入。
最终的溶液将为Me(NO3)3溶液，任选地含有PR硝酸盐的促进剂。
如果形成NO2则HNO3的消耗量将增加。
(d)组合的金属硝酸盐溶液和促进剂酸硝酸盐溶液热分解为可任选含有氧化物或硝酸盐形式的促进剂的混合金属氧化物Me2O3或氢氧化物MeOOH，这取决于促进剂的化学特性。在反应过程中还产生NOx气体。Me(NO3)3的纯分解反应如反应(ii)：
(e)根据反应(iii)，在一个吸收塔或串连的吸收塔中从反应(i)和(ii)任选地将NOx气体再生为或多或少浓的硝酸：
或者对于NO而言为反应(iv)
而后，对于铁而言的总反应，即当(i)，(ii)，(iii)和(iv)结合时，为：
总反应：
当仅考虑主组分Me2O3的合成时，我们看到对于总反应而言没有副产物形成并且其它原料氧气通过吸收塔从空气中取出。
当促进剂包含在混合金属硝酸盐溶液中时，总反应会受到某些影响。该影响取决于是否加入了作为硝酸盐、氢氧化物、氧化物等的促进剂PR。如果例如当其以KNO3加入且K/Me的摩尔比＝0.01时总反应方案将为：
这导致生成可用于溶解的少量HNO3。
在上述反应(i)和(ii)中形成的NO和NO2或通常NOx再次在吸收塔中转化为硝酸。反应(iii)和(iv)导致形成用于再循环和溶解Me的硝酸，其为该过程中的主原料。
由于硝酸的少量损失，必须偶尔地将少量的硝酸加入到再生的酸中，以便保持或增强原料的溶解。
在上述步骤(d)中的分解可通过将步骤(a)，(b)或(c)的酸性溶液喷射到一或多个旋转窑的内表面上，喷射到喷射烧结流化床中，喷射到钢带传送机加热炉中，或喷射到在250-700℃下空气自由供料的塔式颗粒下落窑(tower falling particles kiln)中进行的。但是，通过使用这些方法，为了防止产物粘结到回转窑的内表面上，可采取措施，例如借助一个或多个滑动链。
还可通过其它物理或化学方法防止制得的材料从分解的酸性溶液粘附到所述加热炉或窑的内表面。
金属氧化物产物通过加入少量能够还原硝酸盐的有机化合物得以进一步提高。而后，有机化合物与硝酸盐之间的反应将使硝酸盐加速分解。而且，该粉末微弱地聚结并且可以在低能磨碎设备中破碎。
本发明的方法适于在分解前加入不同的添加剂(例如，在催化剂的情况下加入促进剂，或加入为其它目的的其它组分)。使该溶液分解为金属氧化物的一个方法是连续将储液滴入旋转窑中。旋转窑中的温度可以在250-700℃之间变化，优选为350-600℃。本发明一个主要的特征包括利用添加剂，将选自有机化合物的添加剂加入到硝酸盐储液中。通过调整旋转窑中添加剂的用量和/或温度，可以控制粉末的特性(相含量/晶体结构，表面积，粒径，显微结构等)。当加入此种添加剂时，没有这些有机添加剂，粉末将自由地从回转窑中跑出，从而使连续过程成为可能。优选的添加剂选自碳水化合物或糖类(葡萄糖、果糖、乳糖、蔗糖或其它糖类)，甘氨酸和羧酸。另外，粉末聚结成硬而大的块。这些添加剂的低含量或不含这些添加剂通常会导致α-Fe2O3的形成。当热解温度低时，有机添加剂的含量高将导致形成γ-Fe2O3。
具体实施方案
实施例
实施例1
铁与促进剂的硝酸盐一起以所需比例溶解在硝酸中，该促进剂是诸如Cr，Cu，K和Na，并且获得储液。该溶液在350℃下以给定的供料速率滴入旋转窑中。粉末特征用XRD分析方法以及用于比表面积的氮吸收等温线来测量(根据Brunauer，Emmett和Teller理论)。合成粉末的表面积(通过氮吸收测量)为73m2/g。
缺陷：粉末牢固地粘附在旋转窑的壁上并且为非常硬的颗粒。
实施例2
储液按照与实施例1相似的方法制备。而后，溶解一定量的葡萄糖，相当于氧化(硝酸盐)和还原(葡萄糖)反应物之间的“化学计量比”为1/6。该溶液在400℃下以给定的供料速率滴入旋转窑中。
X-射线分析结果显示存在α-Fe2O3，其参数为a＝5.035埃，c＝13.758埃并且微晶尺寸D(024)＝285埃。
合成粉末上的表面积(通过氮吸收测量)为约50m2/g。
SEM研究显示为由空穴高达5μm的大孔隙率组成的独特微结构。采用原子解析(atomic resolution)TEM，发现均匀分布的Fe，Cu和Cr。同时，用TEM检测观察到非常特殊的晶体形态。
实施例3
储液按照与实施例1相似的方法制备。而后，溶解一定量的葡萄糖，相当于氧化(硝酸盐)和还原(葡萄糖)反应物之间的“化学计量比”高于1/2。该溶液在350℃下以给定的供料速率滴入旋转窑中。
X-射线分析结果显示存在立方γ-Fe2O3，其参数为a＝8.333埃并且微晶尺寸D(440)＝97埃。
合成粉末上的表面积(通过氮吸收测量)为70m2/g。
此种粉末用于磁带存储器中。
实施例4
储液按照与实施例1相同的方法制备。而后，溶解一定量的葡萄糖，相当于氧化(硝酸盐)和还原(葡萄糖)反应物之间的“化学计量比”为1/2。该溶液在400℃下以给定的供料速率滴入旋转窑中。
X-射线分析结果显示存在α-Fe2O3和γ-Fe2O3。
实施例5
将摩尔比为1∶1的金属Co与Fe的混合物溶解在浓硝酸中。将氢氧化铝以总摩尔比为Fe∶Co∶Al为1∶1∶2加入。最后，加入KNO3，并使其摩尔百分含量为1％。
该溶液在350℃下以恒定的供料速率滴入旋转窑中。
粉末经破碎，过筛，与石墨混合以及造粒(pelletised)。
小粒(小丸)在传送机加热炉中于550℃下烧结。
该小粒在纯氢下还原，并且可用作合成氨和氨分解的催化剂。
实施例6
金属Cu和氧化锌(ZnO)的混合物溶解在浓HNO3中。其摩尔比为1∶1。氧化铝以总摩尔比为Cu∶Zn∶Al为1∶1∶1加入。浆料在350℃下分解。
粉末经破碎，过筛，与石墨混合，以及造粒。
小粒在稀释的氢中还原，并且可用作合成甲醇或WGS转化的催化剂。

Claims (6)

1、一种生产含金属氧化物的催化剂的方法，其中金属选自Fe，Co，A1，Ni，Zn，Cu，Cr及其混合物，包括下述步骤：
(a)将金属溶解在硝酸中，或提供两种或多种不同的金属硝酸盐溶液，随后混合，以获得金属硝酸盐产物的酸性溶液；
(b)加入碳水化合物，氨基酸和/或羧酸；
(c)在250-700℃自由空气供入下使步骤(b)中获得的酸性溶液分解。
2、根据权利要求1的方法，其中碳水化合物选自葡萄糖，果糖乳糖和蔗糖，氨基酸是甘氨酸和/或羧酸是柠檬酸。
3、根据权利要求2的方法，其中分解在300-450℃下进行。
4、根据权利要求2的方法，其中葡萄糖以化学计量比0.1-0.6的量加入。
5、根据权利要求1的方法，还包括一个步骤，即向步骤(a)的酸性溶液中加入一种或多种PR(NO3)x形式的促进剂，其中PR选自Na，Ka，Cs，Mg，Ca，Ba，Sr和Rb。
6、一种由上述任一项权利要求的方法制得的含混合金属氧化物的催化剂。
CNB021475547A 2001-10-15 2002-10-15 含氧化铁的催化剂的制备方法 Expired - Fee Related CN100369670C (zh)

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