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CN1792444B - 用于将甲醇氧化为甲醛的催化剂的制备方法 - Google Patents

用于将甲醇氧化为甲醛的催化剂的制备方法 Download PDF

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CN1792444B
CN1792444B CN2005101338868A CN200510133886A CN1792444B CN 1792444 B CN1792444 B CN 1792444B CN 2005101338868 A CN2005101338868 A CN 2005101338868A CN 200510133886 A CN200510133886 A CN 200510133886A CN 1792444 B CN1792444 B CN 1792444B
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E·康卡
C·鲁比尼
M·马尔基
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Abstract

一种用于将甲醇氧化为甲醛的催化剂的制备方法，包括在温度为20至100℃的水悬浮液中，使Mo/Fe比处于1.5至5之间的铁粉与三氧化钼反应，接着，任选同时用氧化剂氧化该混合物，氧化剂的用量等于或大于将二价铁离子氧化成三价铁离子并将钼氧化成6价态所需的量。

Description

用于将甲醇氧化为甲醛的催化剂的制备方法
本发明涉及一种用于将甲醇氧化为甲醛的催化剂的制备方法及其在甲醛制备过程中的用途。
用于将甲醇氧化为甲醛的催化剂(通常称为“钼酸铁”，因为Fe2(MoO4)3是主要活性组分之一)包括Mo/Fe比在1.5和5之间的Fe2(MoO4)3/MoO3混合物，通常根据包括下述步骤的方法制备：使可溶性铁盐，如FeCl3、Fe(NO3)3等的水溶液与碱性钼酸盐或者铵盐的水溶液混合，从中沉淀出上述催化剂混合物，接着稀释该悬浮液，过滤并洗涤沉淀物，通过搅拌将其转变为浆态物，干燥该浆态物，接着将干燥粉末或其糊状物成型，从而得到具有特定几何形状的颗粒，并且通常在温度450至550℃之间煅烧该颗粒。
沉淀在pH值相对较低的溶液(在从氯化铁溶液沉淀的情况下为1-2)中进行，钼酸铁在其中溶解度很大。
排放含有钼酸根离子以及铵、铁、硝酸根和氯离子的母液和洗涤水很成问题，由于这些离子是污染物，目前在很多国家实行的法律法规禁止其排放或者允许其以远远低于所述母液和/或洗涤水浓度的浓度排放。
现在已经出人意料地发现了一种包括Mo/Fe比在1.5和5之间的Fe2(MoO4)3/MoO3混合物的催化剂的制备方法，该方法可以避免排放母液和/或洗涤水，因而不存在现有技术方法中的问题。
根据本发明方法的另一个优点在于得到的催化剂不含铁盐的阴离子，如氯离子，而根据现有技术的方法制得的催化剂中它的量虽然很小，但却是一直存在的。在根据新方法制得的催化剂中，实际上没有来自碱金属离子的杂质，即使有的话，它们的量也低于40ppm。
根据本发明的方法包括以粉末形式悬浮在水中的铁与三氧化钼反应，接着用过氧化氢或其它氧化剂进行氧化处理，其用量等于或大于将二价铁离子氧化成三价铁离子并将钼氧化成六价态所需的量。作为另一种方案，可以在铁和氧化钼反应期间加入氧化剂。
反应中Mo/Fe的原子比在1.5至5之间，优选2.5-3；该方法在从约20℃至体系沸点(100℃)，优选60-80℃的温度下进行。一旦反应完成，将沉淀物的悬浮液稀释，并将母液分离并重复利用；将沉淀物干燥，并将其粉末或糊状物成型，得到具有特定几何形状的颗粒，特别是具有通孔的圆柱状颗粒，或者具有三叶状截面的颗粒，在叶上具有平行于颗粒轴线的通孔。
通过在450至600℃，优选480至580℃的温度下焙烧来活化颗粒。
以粉末状存在的铁优选以平均直径40至150微米的微球形颗粒形式使用。
以重量计，铁中的碳含量通常低于0.15％。诸如镍、铜、硅和锰的元素可以以优选低于1％的含量存在。通常总是有锰存在，因而可以作为新方法的标记物。相对于将二价铁离子氧化成三价铁离子并将钼氧化成六价态所需的量来说，过氧化氢或者等效的氧化剂，如氧气，有机过氧化物或者氢过氧化物优选过量使用。
由于不存在现有技术制备方法中使用的试剂带来的杂质，得到的催化剂具有可显著长时间使用的恒定性能。
还可以加入钼酸铈来进一步提高催化剂的性能，其中铈是三价或者四价的，以铈的重量计其用量为0.05至10％，优选0.1-5％。实际上钼酸铈具有显著降低催化剂床中热点温度的效果，因而可以增加催化剂床的稳定性并因而增加其寿命。
可以通过在倾析母液之后，使根据本发明的方法得到的沉淀与钼酸铈沉淀混合来加入钼酸铈，其中钼酸铈沉淀可以由三价和/或四价可溶性铈盐，如碳酸铈的溶液与碱金属或铵钼酸盐溶液混合而得到(随后按洗涤以除去杂质离子)；或者由水悬浮液中的碳酸铈和三氧化钼加热至不再产生CO2而得到；或者采用与前面方法类似的方法，通过在铁和氧化钼反应过程中将三氧化钼和碳酸铈直接加入混合物中而得到。
含钼酸铈的催化剂在高分辨条件下记录的X-射线衍射(XRD)谱表明较低铈浓度(3000ppm)处的线出现在晶格间距d＝8.44
Figure S051D3886820060112D000021
；d＝6.69以及d＝4.79
Figure S051D3886820060112D000023
处，而对于较高铈浓度(17000ppm)，则具有出现在晶格间距d＝8.53
Figure S051D3886820060112D000024
；d＝6.74；d＝4.82处的线和出现在晶格间距d＝4.29
Figure S051D3886820060112D000027
；d＝3.37
Figure S051D3886820060112D000028
以及d＝2.75
Figure S051D3886820060112D000029
处的线。
使用具有Bragg-Brentano几何形状的Panalytical X’Pert θ/2θ自动粉末衍射仪，用λ＝1.54184
Figure S051D3886820060112D000031
和1.6kW功率的CuKaX射线来进行高分辨XRD分析。使用步长为0.01°、每步收集时间为15秒的5°至125°2θ角度区间。对测角计的进一步描述包括两个0.04-弧度的Soller狭缝，1°发散和抗散射狭缝，以及0.4-mm接收狭缝。使用次级石墨单色仪来进一步收集衍射射束。
无论含钼酸铈的催化剂还是不含钼酸盐的催化剂都具有1至7m2/g，优选2-6m2/g的表面积。
根据已知的方法进行甲醇氧化。
气体混合物含有6至10％体积浓度的甲醇和9至13％体积浓度的氧气，其余是惰性气体，如氮气。反应器是束管型的，通过在管外循环的冷却剂液体移出反应热。
气体线速为1-2Nm/秒；浴槽温度在250至320℃之间。
优选地，气体混合物以120至160℃之间的温度加入反应器中。
给出如下的实施例来阐述本发明，但并不限制本发明。
实施例
用于将甲醇氧化成甲醛催化实验的中试装置由浸没在熔融盐浴中的管式反应器组成。反应器长1950mm，内径20.4mm。催化剂位于反应器的中间部分以确保最大的等温性。通过浸没式电热器加热熔融盐浴，温度由调节器来控制。
气体由反应器的上部区域进料。
空气和氮气按质量流量进料，甲醇通过恒流泵进料，并且首先送到蒸发器中。
用气相色谱分析反应器出口处的流体以及净化塔之后的气体。
实施例1
将11升水加入容积为20升、设有搅拌器和温度控制系统的反应器中。搅拌液体，并将128克以粉末状存在的金属铁和825克MoO3加入所述反应器中。将其加热至75℃并在该条件下保持20小时。最后形成深蓝色的悬浮液。将悬浮液冷却至65℃，并通过蠕动泵用35％过氧化氢(大约1.4升)处理，直到其变成黄色为止。氧化持续大约3小时。
将沉淀物过滤、干燥、造粒(润滑之后)成有孔圆柱体的形式，并在500℃在空气中活化4 小时。
实施例2
重复实施例1的制备过程，向反应物中加入7.1g碳酸铈(42％Ce)和4.6g MoO3；测试条件与实施例1相同。
实施例3
催化试验条件
催化剂床由两层组成：上层为400mm的陶瓷环，下层是700mm的催化剂。
入口气体的总流速为1.5Nm/秒(1765NI/小时)。
入口混合物中的O2含量约9.5％。
表1列出了使用实施例1的催化剂得到的结果；表2列出了使用实施例2的催化剂得到的结果。
表1
 浴槽温度℃  入口甲醇浓度％  甲醇转化率％  甲醛收率％
 250  6.03  94.74  87.79
 255  6.01  96.75  89.92
 260  6.03  98.06  91.43
 265  6.03  98.67  91.85
表2
 浴槽温度℃  入口甲醇浓度％  甲醇转化率％  甲醛收率％
 250  6.02  94.35  87.69
 255  6.03  96.49  90.10
 260  6.01  97.73  91.34
 265  6.04  98.62  92.12

Claims (9)

1.一种用于将甲醇氧化为甲醛的催化剂的制备方法，包括
在温度为20至100℃的水悬浮液中，使Mo/Fe比处于1.5至5之间的铁粉与三氧化钼反应，然后用氧化剂氧化该铁粉与三氧化钼的混合物，或者
在温度为20至100℃的水悬浮液中，使Mo/Fe比处于1.5至5之间的铁粉与三氧化钼反应，同时用氧化剂氧化该铁粉与三氧化钼的混合物，
氧化剂的用量等于或大于将二价铁离子氧化成三价铁离子并将钼氧化成6价态所需的量。
2.根据权利要求1所述的方法，其中氧化剂是过氧化氢，相对于将二价铁离子氧化成三价铁离子并将钼氧化成六价态所需的量来说，过氧化氢过量使用。
3.根据权利要求1或2所述的方法，其中铁粉和三氧化钼之间的反应在60至80℃的温度下进行。
4.根据权利要求1所述的方法，其中将反应的母液分离并重复利用，将反应的沉淀物干燥成粉末或糊状物，并将所得粉末或糊状物成型，得到具有特定几何形状的颗粒，并在450至600℃的温度下焙烧所述颗粒，所述具有特定几何形状的颗粒为具有通孔的圆柱状颗粒，或者具有三叶状截面的颗粒，在叶上具有平行于颗粒轴线的通孔。
5.根据权利要求4所述的方法，其中在480至580℃的温度下焙烧所述颗粒。
6.根据权利要求1所述的方法，其中将钼酸铈按照以铈的重量计0.05至10％的量加入催化剂中，其中铈是三价或四价的。
7.一种通过权利要求1-6任一项所述的方法制备的催化剂，包括Mo/Fe比在1.5和5之间的Fe2(MoO4)3/MoO3混合物，不含来自铁盐的阴离子，来自碱金属离子和/或铵离子的杂质含量低于40ppm。
8.根据权利要求7所述的催化剂，包括以铈的重量计0.05至10％的钼酸铈，其中铈是三价或四价的。
9.一种通过氧化甲醇制备甲醛的方法，其中使用根据权利要求1至6中任一项所述的方法得到的催化剂或者所述催化剂具有权利要求7和8中任一项所列出的性质，并且其中甲醇和氧气分别按照6-10％和9-13％的体积浓度加入束管式反应器中，其余是惰性气体，气体线速度为1-2Nm/秒，在管外循环的冷却浴的温度为250至320℃。
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