CN112979440B - 一种负载型催化剂在烯烃羰基化合成酮反应中的应用 - Google Patents
一种负载型催化剂在烯烃羰基化合成酮反应中的应用 Download PDFInfo
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
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Abstract
一种负载型金属催化剂，活性组分为Au，Ru，Rh，Ir，Pt，Pd中的任意一种或几种，助剂为Fe，Sn，Ni，Zn，Cu，In，Bi，Se中的任意一种或几种，载体为CeO2，Al2O3，TiO2，ZrO2，MgAl2O4，分子筛，活性炭中的任意一种。其中活性金属的负载量为0.01‑10wt％，助剂的负载量为0.1‑50wt％。催化剂的制备：将活性组分，助剂，载体，以及沉淀剂分散于溶液中，按比例混合。该催化剂用于烯烃羰基化反应，产物中酮类化合物的选择性大于90％。催化剂制备工艺简单，并为酮类化合物的提供了一条高原子经济性的合成方法。
Description
技术领域
本发明涉及一种负载型金属催化剂在烯烃羰基合成酮反应中的应用。
背景技术
酮类化合物(如丙酮，3-戊酮，4-庚酮，5-壬酮)是高档溶剂和重要的精细化工原料，广泛用于染料、农药，医药等精细化工行业。例如3-戊酮是生产农业除草剂二甲戊乐灵和抗禽流感药物达菲的关键中间体。
酮类化合物的合成方法有醇氧化法，酮和醇缩合法，烯烃水合-氧化法等，这些方法存在原料来源受限，目标产物选择性低，以及反应条件苛刻(如以丙酸为原料合成3-戊酮时，反应温度高达300-400℃)等问题。
从乙烯、丙烯、丁烯等廉价原料出发，经烯烃羰基化过程合成酮类化合物是一种绿色、原子经济性高的合成路径。但目前文献报道的催化体系多为均相催化体系，且产物中酮类化合物的选择性不高(主产物是醛或聚酮类化合物)(Applied Catalysis A:General452,155–162(2013)；Journal of Catalysis 159,491–495(1996)；Catalysis Letters,32,55-59(1995))。
发明内容
本发明的目的在于提供一种负载型金属催化剂，该催化剂在烯烃羰基化制酮类化合物的反应中具有良好催化活性和选择性；
本发明的另一目的在于提供一种制备负载型金属催化剂的方法，该方法工艺流程简单，过程易于控制。
为实现上述目的，本发明提供的一种负载型金属催化剂，活性组分为Au，Ru，Rh，Ir，Pt，Pd中的任意一种或几种，优选为Ru，Rh，Ir，Pd中的任意一种。活性金属的负载量为0.01-10wt％，优选为0.01-2wt％。助剂为Fe，Sn，Ni，Zn，Cu，In，Bi，Se中的任意一种或几种；优选为Fe，Sn，Ni，Cu中的任意一种或几种。助剂的负载量为0.1-50wt％，优选为0.1-10wt％。载体为CeO2，Al2O3，TiO2，ZrO2，MgAl2O4，分子筛，活性炭中的任意一种或几种，优选为TiO2，Al2O3，MgAl2O4，分子筛中的任意一种。
本发明提供的一种制备负载型金属催化剂的方法，其制备过程如下：
(1)首先将助剂前躯体，有机胺，以及载体加入分散液中；其浓度分别为：
助剂的质量浓度为0.1-50000mg/mL；优选为1-500mg/mL；
有机胺的浓度为0.1-500mol/L；优选为0.5-10mol/L；
载体悬浊液浓度为50-5000mg/mL；优选为500-3000mg/mL；
助剂与载体的质量比为1×10-3-0.2，优选为5×10-3-0.1；助剂与有机胺的物质的量之比为0.1-20，优选为1-10；
所述分散液是有机溶剂或水中的一种或二种以上，有机溶剂为甲醇、乙醇、乙二醇、甘油中的一种或二种以上；
所述有机胺是乙二胺，三乙胺，三聚氰胺，双氰胺，尿素，六亚甲基四胺中的任意一种或二种以上；
(2)将上述混合液于0-200℃下搅拌0.5-10h，并于60-200℃静置0.5-24h后除去溶剂；
(3)将所得固体加入活性金属前驱体溶液中。活性金属前驱体溶液质量浓度为0.01-500mg/mL；优选为0.1-50mg/mL。活性金属与固体的质量比为1×10-4-0.1，优选为5×10-4-0.05。上述混合液于0-200℃下搅拌0.5-10h后除去溶剂；所得固体于200-800℃焙烧，优选为400-600℃；保持时间为0.5-24h；优选为4-12h；
(4)所得固体用H2/N2、H2/CO、H2/CO2混合气中的一种或二种以上(混合气中H2体积浓度5-95％)于100-800℃活化处理，优选为200-500℃。保持时间为0.5-24h；优选为1-12h。
对本发明提供的负载型金属催化剂，其催化活性测试方法如下：
于反应釜中，加入催化剂、烯烃和溶剂，在0.1-15MPa CO气氛下于50-200℃下搅拌0.5-24h得产物。
所述烯烃为C2-C16烯烃中的一种或几种；所述溶剂为甲醇，叔丁醇，甲苯、环己烷、正己烷中的一种或几种；加入液态烯烃的浓度为0.05-10mol/L，充入气态烯烃的浓度为0.1-15MPa；烯烃与活性金属的物质的量之比为100-105。
本发明具有如下效果：
1.负载型贵金属催化剂的制备方法流程简单，易于控制。所制备的催化剂中活性金属的分散度高，其粒径小于0.7纳米；
2.所制备的催化剂用于烯烃羰基化反应，产物中酮类化合物的选择性大于90％。；
具体实施方式
实施例1：1mL水中，加入1mmol四氯化锡，1mmol硝酸锌，1g Al2O3，8mmol尿素，室温下搅拌0.5h后于120℃静置24h。所得产物于80℃烘干后，加入1mL 0.4wt％RhCl3溶液，室温下搅拌2h。所得固体于500℃焙烧2h后，于350℃用H2/N2(80/20,v/v)还原4h，流速为300mL/min。通过电镜可以看出所得催化剂中Rh粒径均小于0.7nm；
实施例2：1mL水中，加入1mmol四氯化锡，1mmol硝酸钴，1g Al2O3，8mmol尿素，室温下搅拌0.5h后于120℃静置24h。所得产物于80℃烘干后，加入1mL 0.4wt％RhCl3溶液，室温下搅拌2h。所得固体于500℃焙烧2h后，于350℃用H2/N2(80/20,v/v)还原4h，流速为300mL/min。通过电镜可以看出所得催化剂中Rh粒径均小于0.7nm；
实施例3：1mL水中，加入1mmol四氯化锡，1mmol硝酸钴，1g Al2O3，8mmol三聚氰胺，室温下搅拌0.5h后于120℃静置24h。所得产物于80℃烘干后，加入1mL 0.4wt％RhCl3溶液，室温下搅拌2h。所得固体于500℃焙烧2h后，于350℃用H2/N2(80/20,v/v)还原4h，流速为300mL/min。通过电镜可以看出所得催化剂中Rh粒径均小于0.7nm；
实施例4：1mL水中，加入1mmol四氯化锡，1mmol硝酸钴，1g Al2O3，8mmol乌洛托品，室温下搅拌0.5h后于120℃静置24h。所得产物于80℃烘干后，加入1mL 0.4wt％RhCl3溶液，室温下搅拌2h。所得固体于500℃焙烧2h后，于350℃用H2/N2(80/20,v/v)还原4h，流速为300mL/min。通过电镜可以看出所得催化剂中Rh粒径均小于0.7nm；
应用例1：
5mL甲醇中充入0.5MPa乙烯，2MPa CO，加入20mg对应实施例1的催化剂，在140℃下反应12h。经气相色谱-质谱分析，产物中3-戊酮的选择性为90％；反应物转化率大于20％。
应用例2：
5mL甲醇中充入0.5MPa乙烯，2MPa CO，加入20mg对应实施例2的催化剂，在140℃下反应12h。经气相色谱-质谱分析，产物中3-戊酮的选择性为90％；反应物转化率大于30％。
应用例3：
5mL甲醇中充入0.5MPa乙烯，2MPa CO，加入20mg对应实施例3的催化剂，在140℃下反应12h。经气相色谱-质谱分析，产物中3-戊酮的选择性为90％；反应物转化率大于30％。
应用例4：
5mL甲醇中充入0.5MPa乙烯，2MPa CO，加入20mg对应实施例4的催化剂，在140℃下反应12h。经气相色谱-质谱分析，产物中3-戊酮的选择性为90％；反应物转化率大于30％。
Claims (9)
1.一种负载型金属催化剂在乙烯羰基化合成3-戊酮反应中的应用，其特征在于：催化剂的活性组分为Rh，助剂为Sn和 Zn；载体为Al2O3；其中活性金属的负载量为0.01-10wt%，助剂的负载量为0.1-50wt%；
活性组分金属的粒径尺寸小于0.7纳米；
负载型金属催化剂制备过程如下：
（1）首先将助剂前躯体，有机胺，以及载体加入分散液中；其浓度分别为：
助剂前躯体的质量浓度为0.1-50000 mg/mL；
有机胺的浓度为0.1-500 mol/L；
载体悬浊液浓度为50-5000 mg/mL；
所述分散液是有机溶剂或水中的一种或二种以上，有机溶剂为甲醇、乙醇、乙二醇、甘油中的一种或二种以上；
所述有机胺是乙二胺，三乙胺，三聚氰胺，双氰胺，尿素，六亚甲基四胺中的任意一种或二种以上；
（2）将上述混合液于0-200 oC下搅拌0.5-10 h，并于60-200 oC静置0.5-24 h后除去溶剂；
（3）将所得固体加入活性金属前驱体溶液中，活性金属前驱体溶液质量浓度为0.01-500 mg/mL；上述混合液于0-200 oC下搅拌0.5-10 h后除去溶剂；所得固体于200-800 oC焙烧；保持时间为0.5-24 h；
（4）所得固体用H2/N2、H2/CO、H2/CO2混合气中的一种或二种以上于100-800 oC活化处理，保持时间为0.5-24 h；混合气中H2体积浓度5-95%。
2.如权利要求1所述的应用，其特征在于，活性组分的负载量为0.01-2wt%；，助剂的负载量为0.1-10wt%。
3.如权利要求1所述的应用，其特征在于，步骤（1）中，助剂前躯体与载体的质量比为1×10-3-0.2；助剂前躯体与有机胺的物质的量之比为0.1-20。
4.如权利要求1所述的应用，其特征在于，步骤（1）中，助剂前躯体的质量浓度为1-500mg/mL；
有机胺的浓度为0.5-10 mol/L；
载体悬浊液浓度为500-3000 mg/mL；
助剂前躯体与载体的质量比为5×10-3-0. 1；助剂前躯体与有机胺的物质的量之比为1-10。
5.如权利要求1所述的应用，其特征在于，步骤（3）中，活性金属与固体的质量比为1×10-4-0.1。
6.如权利要求1所述的应用，其特征在于，步骤（3）中，活性金属前驱体溶液质量浓度为0.1-50 mg/mL，固体焙烧温度为400-600oC；保持时间为4-12 h；
活性金属与固体的质量比为5×10-4-0. 05。
7.如权利要求1所述的应用，其特征在于，步骤（4）中，活化处理温度为200-500oC，保持时间为1-12。
8.根据权利要求1-7任一所述的应用，其特征在于：
于反应釜中，加入催化剂、乙烯和溶剂，在0.1-15 MPa CO气氛下于50-200 oC下搅拌0.5-24 h得产物。
9.根据权利要求8所述的应用，其特征在于：
所述溶剂为甲醇，叔丁醇，甲苯、环己烷、正己烷中的一种或几种；加入液态乙烯的浓度为0.05-10 mol/L，充入气态乙烯的浓度为0.1-15 MPa；乙烯与活性金属的物质的量之比为100-105。
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| DE2445193A1 (de) * | 1974-09-21 | 1976-04-01 | Basf Ag | Verfahren zur herstellung von diaethylketon |
| CN103084192A (zh) * | 2011-10-28 | 2013-05-08 | 中国科学院大连化学物理研究所 | 由氢、一氧化碳和乙烯制备3-戊酮和丙醛的钴磷化物催化剂 |
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| DE2445193A1 (de) * | 1974-09-21 | 1976-04-01 | Basf Ag | Verfahren zur herstellung von diaethylketon |
| CN103084192A (zh) * | 2011-10-28 | 2013-05-08 | 中国科学院大连化学物理研究所 | 由氢、一氧化碳和乙烯制备3-戊酮和丙醛的钴磷化物催化剂 |
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