CN107999061B - 一种烯烃氢甲酰化制醛高效催化剂的制备方法及其应用 - Google Patents
一种烯烃氢甲酰化制醛高效催化剂的制备方法及其应用 Download PDFInfo
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical group [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 17
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Abstract
本发明提供一种烯烃氢甲酰化制醛高效催化剂的制备方法,该催化剂为负载型催化剂由载体和活性中心组成,载体为比表面积巨大的硅酸镁纳米管,活性中心为纳米金属铑;该催化剂的制备方法如下:采用浸渍法将活性中心前驱体浸渍在载体上,再进行烘干、还原,从而得到所述多相催化剂。本发明中活性中心Rh0的获得区别于传统还原方法,直接在保护气体下低温煅烧得到。本发明所提供的催化剂在烯烃氢甲酰化制备醛的液相反应中与传统均相催化剂相比具有催化性能良好,分离容易,使用寿命延长,可循环使用的特点,具有广阔的工业应用价值。
Description
技术领域
本发明的技术方案涉及负载型催化剂制备方法领域,具体为一种烯烃氢甲酰化制醛高效催化剂的制备方法。
背景技术
氢甲酰化反应也称OXO反应,是目前化学均相催化工业中最重要的反应之一,化学反应过程是由烯烃在一定催化剂、温度和压力条件下与一氧化碳和氢气加成生成多一个碳原子的醛。氢甲酰化醛类产物是制备各类溶剂、增塑剂、表面活性剂等化工产品的关键原料和重要的有机合成中间体。另外,由不对称烯烃的氢甲酰化反应可合成手性产物,这在药物、农药和天然产物等合成方面很有价值。功能化烯烃氢甲酰化反应的高区域选择性控制是该研究领域的热点之一,调变配体的电子效应和立体效应以实现对产物醛的正、异构比和手性进行调控。
对于氢甲酰化催化反应体系,一个重要的技术问题是催化剂与产物的分离和防止活性组分流失。目前,工业上烯烃氢甲酰化反应主要以均相催化体系为主。虽然烯烃氢甲酰化均相催化体系具有催化活性高,选择性好,反应条件温和等优点;但是催化反应中所使用的过渡金属配合物催化剂溶于氢甲酰化产物和反应所使用的有机溶剂,造成产物与过渡金属配合物催化剂分离困难,尤其是金属配合物催化剂与高沸点产物的分离,这可造成产能400kt/a使用Rh基催化剂的氢甲酰化工厂年损失几百万欧元,尽管每公斤产物只带走1 ppmRh。如联碳(UCC)公司及三菱化成公司的铑一叔膦法(US Pat.3527809,US Pat. 4247486,US Pat.5105018)等,该催化剂具有更高的活性、选择性和更温和的反应条件,但产物醛与催化剂是处在均一的液相中,产物与催化剂的分离以及催化剂的回收通常采用蒸馏或减压蒸馏的方法(如美国专利4528403号),这种方法对受热易分解的催化剂是不合适的,尤其是对于高碳烯烃氢甲酰化,产物醛的沸点较高,采取蒸馏产物分离催化剂的方法常会导致产物聚合、催化剂分解失活等问题。水溶性铑膦复合物催化剂,催化剂与产物容易分离,工艺流程简单,但由于两相反应传质效率较低,如US Pat.4248802,相转移剂的加入会带来分离的问题,甚至可能会导致乳化而增加相分离难度。
多相催化剂将金属纳米粒子固载到载体上具有易分离和易回收的优点,但在氢甲酰化反应中的活性和选择性较低,因而大大阻碍了其在工业上的应用。CN10144475A公开的技术方案采用卤烷基三甲基硅烷与二苯基膦锂作为偶联剂,将铑络合物固载到介孔分子筛或者纳米二氧化硅上,此法制备的催化剂活性组固载牢固,不易流失,并且催化剂与产物能很好地分离,但是催化剂活性较低,导致烯烃转化率低。
因此需要开发新的高活性及高选择性的氢甲酰化催化剂,同时兼具稳定性好,适于工业化应用的催化剂。硅酸镁纳米管(MgSNTs)具有较高的比表面积(SSA)和一维管状结构,它可以有效地分散和固载金属活性组分,提高催化剂的反应活性和稳定性,并能克服均相体系中催化剂与产物难分离的缺点。
发明内容
本发明所要解决的技术问题是:提供一种烯烃氢甲酰化制醛高效催化剂的制备方法。该方法以硅酸镁纳米管为载体,采用浸渍-还原法制备具有高反应活性和稳定性的烯烃氢甲酰化催化剂。以克服传统均相体系中催化剂与产物难分离的缺点;以克服催化剂活性较低等缺点。
本发明解决该问题所采取的技术方案是:
一种烯烃氢甲酰化制醛高效催化剂的制备方法,其步骤是:
(1)取3.5份浓度为0.002克/毫升水的三氯化铑水溶液,待用;
(2)取1g硅酸镁纳米管放入烧瓶中加入20~50ml去离子水水,待用;
(3)在搅拌条件下,将步骤(1)中配制的溶液加入到步骤(2)中的烧瓶中,常温搅拌6~24个小时;
(4)然后将步骤(3)中所得的混合物离心、在333~353K温度下的空气气氛中干燥12~36小时;
(5)将得到粉体转移到管式炉中,在保护气氛下煅烧,锻烧所用的温度为573K,升温速率速为10K/min,煅烧时间为2~4小时,得到产物为硅酸镁纳米管负载铑催化剂;
(6)催化反应完毕后,将反应溶液离心,乙醇洗3次后,烘干得到可循环催化剂;
本技术方案步骤(5)中的保护气氛可以是氮气、氩气、CO2。
本发明具有以下优点:
1.本发明方法所得的硅酸镁纳米管负载铑催化剂。硅酸镁纳米管具有较高的比表面积和孔容,有利于催化活性位的暴露和底物的扩散。如图3所示,铑纳米粒子均匀的分布在硅酸镁纳米管的表面和内部,金属活性中心的尺寸均一,约为1-3nm。
2.本发明采用的方法简单有效,过程步骤少,Rh0直接通过低温煅烧的方法获得,绿色环保,成本低。
3.本发明采用的原料硝酸镁、硅酸钠、氢氧化钠、三氯化铑均为普通化学试剂,廉价易得。
4.本发明所制备的催化剂适合量产,可用于工业大规模生产。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1为实施例1中所述载体材料氮气吸附和孔径分布表征;
图2为实施例1中硅酸镁纳米管负载铑催化剂的XRD谱图,其中(A)为负载前的产物,(B)为负载后的产物。
图3为实施例1中硅酸镁纳米管负载铑催化剂的TEM谱图,其中(A)为负载前的产物,(B)为负载后的产物。
图4为实施例1中所得催化剂金属活性中心纳米铑粒子的XPS测试。
具体实施方式
实施例1
(1)将0.0009mol三氯化铑溶于盛有100ml水的烧瓶中,配制成三氯化铑水溶液,待用;
(2)将1g硅酸镁纳米管分散于盛有10ml水的烧瓶中,待用;
(3)在搅拌条件下,将取6.5ml步骤(1)中配制的溶液加入到步骤(2)中的烧瓶中,浸渍搅拌反应6个小时;
(4)然后将步骤(3)中得到的混合物离心分离,在333K温度下的空气气氛中干燥12小时;
(5)将得到粉体转移到管式炉中,在氮气气氛下煅烧,锻烧所用的温度为573K,升温速率速为10K/min,煅烧时间为2小时,得到产物约为1g硅酸镁纳米管负载铑催化剂;
(6)称取一定量所得催化剂与反应底物醋酸乙烯酯和溶剂甲苯一起加入到高压反应釜进行催化实验,通过气相数据计算催化剂催化活性。
经TEM测试,产物为硅酸镁纳米管结构表面和内部分散着尺寸均一的铑纳米粒子。
实施例2
将实施例1中步骤(5)中的573K温度下改为523K。其他步骤同实施例1。得到的产物同实施例1。
实施例3
将实施例1中步骤(5)中的573K温度下改为623K。其他步骤同实施例1。得到的产物同实施例1。
实施例4
将实施例1中步骤(3)中的浸渍搅拌6个小时改为浸渍搅拌反应24个小时,其他步骤同实施例1。得到的产物同实施例1。
实施例5
将实施例1中步骤(4)中的333K温度下改为353K。其他步骤同实施例1。得到产物同实施例1。
实施例6
将实施例1中的步骤(4)中的干燥12小时改为36小时,其他步骤同实施例1。得到的产物同实施例1。
实施例7
将实施例1中的步骤(5)中的煅烧时间定为4个小时,其他步骤同实施例1。得到的产物同实施例1。
实施例8-9
将实施例1中的步骤(5)中的氮气改为氩气、CO2,其他步骤同实施例1。得到的产物同实施例1。
实施例10
将实施例1中得到的催化剂反应后离心分离回收,乙醇洗3次后50℃真空干燥2h。得到实施例10。
实施例11
将实施例10中得到的催化剂反应后离心分离回收,乙醇洗3次后50℃真空干燥2h。得到实施例11。
实施例12
将实施例11中得到的催化剂反应后离心分离回收,乙醇洗3次后50℃真空干燥2h。得到实施例12。
实施例13
将实施例1中的步骤(6)中的反应底物改为环己烯,溶剂改为四氢呋喃,其他步骤同实施例1。得到的实施例13。
实施例14
将实施例1中的步骤(6)中的反应底物改为丙烯酰胺,溶剂改为35ml甲苯和35ml四氢呋喃,其他步骤同实施例1。得到的实施例14。
评价上述催化剂催化烯烃氢甲酰化反应在GS-0.25型高压釜中进行。具体实验步骤为:将5ml的反应底物、0.4g催化剂、65ml反应溶剂放入高压釜中,然后封闭高压釜。先通入一定量CO气体置换釜中空气,充放气两次。置换完毕后,充入总压力为6体积比1∶1 的CO和H2。压力稳定后,开启加热装置和搅拌装置。待接近反应温度100℃时,降低加热电压,在设定的恒温条件下反应。到达预设的反应时间后,停止反应,冷却反应釜至室温。先将反应釜内气体放出后,于通风橱中开启高压釜,取出反应混合液(离心处理分离催化剂与反应液后),用6C-MS定性、岛津GC-2014定量分析反应样品。具体的色谱分析条件如下:进样器温度为255℃,检测器温度为260℃,SE-30毛细管色谱柱。程序升温条为:初温100℃,保持3min后,以10℃/min升温至150℃,再以25℃/min升温至250℃,并保持5min。
表1 新型硅酸镁纳米管负载铑催化剂的烯烃氢甲酰化反应性能
催化剂编号 | 转化率% | 生成醛总选择性% | 支∶直 |
实施例1 | 100 | 80.02 | 100∶0 |
实施例10(第一次循环) | 95 | 73.20 | 100∶0 |
实施例11(第二次循环) | 88.4 | 70.68 | 100∶0 |
实施例12(第三次循环) | 70.36 | 72.12 | 100∶0 |
实施例13 | 100 | 82.81 | - |
实施例14 | 30.26 | 26.54 | 25∶75 |
由上表的结果可知,本发明提供的用于烯烃氢甲酰化反应的新型负载型催化剂制备方法简单,反应工艺及装置简单,可以在常规高压釜反应器中进行反应,反应性能稳定,收率高,催化剂循环使用结果良好,有效解决现有技术中存在的金属组分流失或者配体流失,或者催化剂难以回收循环利用等问题,具有广阔的工业应用前景。
以上已对本发明进行了详细描述,但本发明并不局限于本文所描述具体实施方式。本领域技术人员理解,在不背离本发明范围的情况下,可以做出其他更改和变形。本发明的范围由所附权利要求限定。
Claims (1)
1.一种烯烃氢甲酰化制醛催化剂的制备方法,其步骤是:
(1)取3.5份浓度为0.002克/毫升水的三氯化铑水溶液,待用;
(2)取1g 硅酸镁纳米管放入烧瓶中加入20~50 ml去离子水,待用;
(3)在搅拌条件下,将步骤(1)中配制的溶液加入到步骤(2)中的烧瓶中,常温搅拌6~24个小时;
(4)然后将步骤(3)中所得的混合物离心、在333~353K温度下的空气气氛中干燥12~36小时;
(5)将得到粉体转移到管式炉中,在保护气氛下煅烧,锻烧所用的温度为573K,升温速率为10K/min,煅烧时间为2~4 小时,得到产物为硅酸镁纳米管负载铑催化剂,其中,铑纳米粒子均匀地分布在硅酸镁纳米管的表面和内部,铑纳米粒子的尺寸为1~3纳米;
(6)催化反应完毕后,将反应溶液离心,乙醇洗3次后,烘干得到可循环催化剂;
所述步骤(5)中的保护气氛为氮气、氩气、CO2。
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