CN111875506B - 一种混合金属氧化物非均相催化剂催化伯二醇胺化的方法 - Google Patents
一种混合金属氧化物非均相催化剂催化伯二醇胺化的方法 Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明涉及一种混合金属氧化物非均相催化剂催化伯二醇胺化的方法，包括：将非均相催化剂装入反应器中，将伯二醇和液氨持续不断通过反应器，连续通入氢气，胺化反应。该方法在非均相催化剂下利用氨气将原料丰富、廉价易得的伯二醇通过一步法直接进行胺化，在原料转化率和目标产物选择性方面均有所提高，催化效果较好。
Description
技术领域
本发明属于羟胺化的方法领域，特别涉及一种混合金属氧化物非均相催化剂催化伯二醇胺化的方法。
背景技术
伯二胺是具有两个伯氨基(-NH2)的化合物，在生产和生活中具有诸多用途。例如可以用作溶剂、稳定剂用于合成螯合剂；作为原料用于生产合成树脂、药物、抑制剂、防腐剂、聚氨酯；作为硬化剂用于环氧树脂或作为界面活性物质使用。总之，伯二胺是胺化反应中非常有价值的产物之一。
目前，伯二胺可以通过伯二醇与氨之间的非均相催化的羟胺化反应来制备。WO2008006752A1公开了一种制备胺的方法，其中伯醇与氨在含有二氧化锆和镍的非均相催化剂的存在下反应，但是采用该方法转化率和选择性相对较低。中国专利CN 100358628C公开了一种使用特定的非均相Cu/Ni/Zr/Sn催化剂将醇胺化的方法(反应方程式如下所示)。在此方法中，目标产物二氨基二甘醇的产率最高为5％，同时形成22％吗啉和36％单氨基二甘醇作为副产物，目标产物选择性差。EP0696572A1公开了用含有氧化镍、氧化铜、氧化锆和氧化钼的非均相催化剂进行氨和二甘醇的醇胺化反应方案，催化效果相比之前有所提高，这让我们看到了金属氧化物非均相催化剂催化醇胺化反应的潜力。虽然高温高压的条件有利于羟胺化反应得进行，但是上述专利所使用的非均相催化剂在温度为200℃±、氨气压力200bar±的苛刻条件下仍没有显示出较好的催化效果，并且产生了大量副产物，例如单胺化产物和环状胺(哌嗪、吡咯烷和吗啉等)，这导致目标产物伯二胺的产率极低。
同样的情况在二乙醇胺与氨的胺化反应中出现，哌嗪是作为主产物获得的(反应方程式如下)。即使在原料二乙醇胺转化率很高时，二亚乙基三胺也仅以痕量获得，目标产物选择性较差。
在采用同样的方法由聚醚醇制备聚醚胺时(反应方程式如下所示)，基本观察不到目标产物二聚伯胺，但是生成聚合偶联产物的副反应占据主要。在聚醚醇胺化过程中，聚醚需要在反应条件下分解，这就需要较高的温度和氢气压力。而在如此苛刻的条件下，生成的副产物难以从目标产物伯二胺中分离出来。上述所有醇与氨的非均相催化胺化反应都存在共同的缺点，即目标产物伯二胺产率低，副产物多，反应选择性差。这些缺陷大大限制了伯二醇胺化反应在大规模工业化生产中的应用。
发明内容
本发明所要解决的技术问题是提供一种混合金属氧化物非均相催化剂催化伯二醇胺化的方法，以克服现有技术中非均相催化剂催化伯二醇胺化制备伯二胺原料转化率低和目标产物选择性差的缺陷。
本发明提供一种混合金属氧化物非均相催化剂催化伯二醇胺化的方法，包括：
将非均相催化剂装入反应器中，将伯二醇和液氨持续不断通过反应器，通过连续通入氢气控制反应器压力，胺化反应，得到伯二胺，其中非均相催化剂组分按照质量百分比包括：氧化镍、氧化铜、氧化亚铜中一种或几种30～90wt.％，氧化铬、氧化锆、氧化钴、氧化铝、氧化锰、氧化锡中一种或几种0～51wt.％且不为0，以及氧化铂、氧化钯中一种或两种0～20wt.％且不为0；非均相催化剂与伯二醇的摩尔比为1:100～1:500；伯二醇与液氨的流速比为5:4～5:2。
所述非均相催化剂组分按照质量百分比为：氧化镍、氧化铜、氧化亚铜中一种或几种45～85wt.％，氧化铬、氧化锆、氧化钴、氧化铝、氧化锰、氧化锡中一种或几种14.5～51wt.％，以及氧化铂、氧化钯中一种或两种0.5～5wt.％。
所述非均相催化剂组分按照质量百分比为：45wt.％NiO、21wt.％ZrO2、15wt.％Al2O3、15wt.％Cr2O3，以及4wt.％PtO2；或者49wt.％CuO、16wt.％Cr2O3、15wt.％Co3O4、16wt.％SnO2，以及4wt.％PdO；或者62wt.％NiO、20wt.％Co3O4、16wt.％Al2O3，以及2wt.％PtO2；或者63wt.％CuO、17wt.％ZrO2、15wt.％MnO2，以及5wt.％PtO2。
所述反应器为高压管式反应器。
所述伯二醇为二甘醇、二乙醇胺或者聚醚醇。
所述非均相催化剂的制备方法包括：将不同的金属盐与水混合，缓慢加入碳酸钠溶液(15％)中，静置沉淀并分离，经干燥、烘焙、压片，即得。
所述金属盐为金属硝酸盐。
所述伯二醇通过反应器的速率为250mL/h；液氨通过反应器的速率为150mL/h。
所述胺化反应的工艺参数为：反应温度为200～250℃，反应器中绝对压力为180～220bar，反应时间为48～240h。
有益效果
本发明在混合金属氧化物非均相催化剂的催化下，利用氨气将原料丰富、廉价易得的伯二醇(例如二甘醇)通过一步法直接进行胺化，成功制取目标产物伯二胺(例如2,2-氧代双乙胺)。原料伯二醇的转化率为65.8％，伯二胺的选择性为19.7％。实验证明，与同类型非均相催化剂催化胺化体系相比，本发明在原料转化率和目标产物选择性方面均有所提高，催化效果较好。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明实施例中，二甘醇、液氨、硝酸镍、硝酸铜、硝酸铝、硝酸铬、硝酸铂以及碳酸钠均购置于梯希爱(上海)化成工业发展有限公司。
实施例1
(1)混合金属氧化物非均相催化剂的制备
室温下，将含有1500g硝酸镍、800g硝酸锆、350g硝酸铝、400g硝酸铬和150g硝酸铂溶于5L去离子水中，将此金属混合液缓慢加入1L碳酸钠溶液(浓度15％)中，滴加完毕后搅拌5min使其沉淀完全，静置沉淀并分离，经干燥、烘焙、压片后得到混合金属氧化物非均相催化剂，其组成成分详见表1。催化剂各项物理性能测试结果如下：密度为2.1g/mL；径向强度为4.5kg；比表面积为30m2/g。
表1
(2)非均相催化剂催化二甘醇与氨的胺化反应
在一高压管式反应器中装填250mL上述催化剂，将二甘醇和液氨分别以250mL/h和150mL/h的速率持续不断通过反应器，反应器温度始终控制在200℃，通过连续通入氢气将反应器内的压力控制在200bar，经过液相氨化反应120h后，将得到800g粗制产品混合物转移至1L的四口烧瓶中，并与装有50cm拉西环填料的精馏柱相连接，精馏步骤具体实施方案及结果详见表2。
表2
注：理论产量为675g，总收率为96.3％，原料转化率65.8％。
实施例2～5
不同反应温度下非均相催化剂催化效果对比，改变实施例1中的反应温度，其余步骤与实施例1相同，所得产品组成如下表3。综合表3中目标产物选择性和原料转化率两个数据分析可得，其余条件不变时，在实验温度范围200～250℃内，随着温度的升高，催化剂催化效果越来越好；而低于此温度范围时催化剂催化效果较差，目标产物选择性和原料转化率都显著下降。
表3
实施例6～8
为了探究催化剂组成成分对催化效果的影响，依据本发明提供的方案，按照表4的投料比制备一系列不同的非均相催化剂，并分别对二甘醇进行催化胺化。其余具体操作步骤和实验参数设置均与实施例1相同。所制备非均相催化剂组成成分见表4，所得产品组成见表5。
综合表5中目标产物选择性和原料转化率两个数据分析可得，其余条件不变时，非均相催化剂中活性组分氧化钯、氧化铂用量越接近用量范围的上限，胺化反应催化效果越好。实验证明，活性组分的用量对催化效果起着至关重要的作用。
表4
表5
对比例1
以实施例1作为对照，依据本发明提供的方案，将非均相催化剂的原料投料比变为：1500g硝酸镍、800g硝酸锆、650g硝酸铝、400g硝酸铬，其余催化剂制备步骤同实施例1。所制备的催化剂组成部分如下：48wt.％NiO、22wt.％ZrO2、17wt.％Al2O3、13wt.％Cr2O3。用该非均相催化剂对二甘醇进行催化胺化，其余具体操作步骤和实验参数设置均与实施例1相同，实验结果见表6。综合目标产物选择性和原料转化率两个数据分析可得，其余条件不变时，当不添加活性组分氧化钯、氧化铂时，二甘醇胺为主产物，目标产物选择性和原料转化率均降低，催化效果明显下降。
表6
对比例2
以实施例1作为对照，依据本发明提供的方案，将非均相催化剂的原料投料比变为：1000g硝酸镍、500g硝酸锆、350g硝酸铝、400g硝酸铬、900g硝酸铂，其余催化剂制备步骤同实施例1。所制备的催化剂组成部分如下：36wt.％NiO、16wt.％ZrO2、15wt.％Al2O3、11wt.％Cr2O3、22wt.％PtO2。用该非均相催化剂对二甘醇进行催化胺化，其余具体操作步骤和实验参数设置均与实施例1相同，实验结果见表6。综合目标产物选择性和原料转化率两个数据分析可得，其余条件不变时，当添加的活性组分氧化钯、氧化铂不在所述范围0.5～5wt.％内时，原料转化率虽没有明显变化，但目标产物选择性显著下降，此时不利于产物伯二胺的生成，利于吗啉的生成。
Claims (4)
1.一种混合金属氧化物非均相催化剂催化伯二醇胺化的方法，包括：
将非均相催化剂装入反应器中，将伯二醇和液氨持续不断通过反应器，连续通入氢气，胺化反应，得到伯二胺，其中非均相催化剂组分按照质量百分比为：45wt.％NiO、21wt.％ZrO2、15wt.％Al2O3、15wt.％Cr2O3，以及4wt.％PtO2；或者49wt.％CuO、16wt.％Cr2O3、15wt.％Co3O4、16wt.％SnO2，以及4wt.％PdO；或者62wt.％NiO、20wt.％Co3O4、16wt.％Al2O3，以及2wt.％PtO2；或者63wt.％CuO、17wt.％ZrO2、15wt.％MnO2，以及5wt.％PtO2；非均相催化剂与伯二醇的摩尔比为1:100～1:500；伯二醇与液氨的流速比为5:4～5:2。
2.根据权利要求1所述方法，其特征在于，所述伯二醇为二甘醇、二乙醇胺或者聚醚醇。
3.根据权利要求1所述方法，其特征在于，所述非均相催化剂的制备方法包括：将不同的金属盐与水混合，缓慢加入碳酸钠溶液中，静置沉淀并分离，经干燥、烘焙、压片，即得。
4.根据权利要求1所述方法，其特征在于，所述胺化反应的工艺参数为：反应温度为200～250℃，反应器中绝对压力为180～220bar，反应时间为48～240h。
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| US5002922A (en) * | 1989-02-04 | 1991-03-26 | Basf Aktiengesellschaft | Catalyst for the amination of alcohols under hydrogenating conditions |
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