CN112871189A - 以纳米金刚石为载体的非金属修饰铂系催化剂的制备方法 - Google Patents
以纳米金刚石为载体的非金属修饰铂系催化剂的制备方法 Download PDFInfo
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- 239000002113 nanodiamond Substances 0.000 title claims abstract description 36
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- 238000002360 preparation method Methods 0.000 title abstract description 8
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- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical group [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011591 potassium Substances 0.000 claims description 2
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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Abstract
本发明公开了一种以纳米金刚石为载体的非金属修饰铂系催化剂的制备方法。其是采用非金属前驱体溶液对纳米金刚石进行浸渍,然后在惰性气体下进行高温煅烧,再采用含铂前驱体溶液对其进行铂负载,最后进行还原,得到非金属硼‑氮、硼‑磷双修饰或硼‑氮‑磷三修饰的铂系催化剂。本发明所制备的催化剂在低碳烷烃脱氢催化反应中具有高活性以及高选择性,且相比金属修饰的Pt系催化剂,本发明所制备的非金属修饰的Pt系催化剂合成过程简单易行,并大大降低了制造成本,可为今后开发出高性能低碳烷烃脱氢催化剂提供新的引导方向。
Description
技术领域
本发明属于低碳烷烃脱氢催化剂制备领域,具体涉及一种以纳米金刚石为载体的非金属修饰铂系催化剂的制备方法。
背景技术
随着美国的页岩气革命,丙烷在市场上的价格逐渐降低,相比传统的石脑油裂解和石油催化裂化生产丙烯,丙烷直接脱氢制丙烯具有远大的发展前景。传统的丙烷直接脱氢催化剂为铬系催化剂,但由于铬金属的环境污染问题,使其逐渐被铂系催化剂所替代。丙烷直接脱氢制丙烯为分子数增加、强吸热的可逆反应,因此低压、高温是利于该反应进行的反应条件。往往这种高温反应条件易使铂金属团聚,除此之外,丙烷的深度裂解不仅使丙烯选择性降低还使得产生积炭覆盖活性中心,这些不利因素都导致铂系催化剂的催化性能下降。
铂系催化剂通常以分子筛以及氧化铝作为载体,再添加适量的助剂来提高其催化性能,这些催化剂已经应用于工业生产中。但是分子筛和氧化铝本身具有强酸性,较易导致丙烷深度裂解进而降低催化剂活性。为避免上述问题,碳材料作为铂系催化剂载体逐渐成为研究热点。高度石墨化的碳材料能够改变铂金属的物理化学性质,从而提高其催化活性以及丙烯选择性。
纳米金刚石作为一种碳材料载体,在高温作用下不仅能够产生缺陷位固定铂金属,而且产生的石墨碳能够发生电子转移,进而提高铂金属电子密度,促进丙烯脱附防止深度脱氢。Zhang等人(J. Zhang, X. Cai, K.-H. Wu, et al. Nanodiamond-Core-Reinforced, Graphene-Shell-Immobilized Platinum Nanoparticles as a HighlyActive Catalyst for the Low-Temperature Dehydrogenation of n-Butane,Chemcatchem, 10 (2018) 520-524.)将铂负载在具有sp2/sp3杂化碳的纳米金刚石载体上,在催化正丁烷脱氢上比铂负载在氧化铝上具有更高的催化活性。Wang等人(R. Wang, X.Sun, B. Zhang, et al. Hybrid nanocarbon as a catalyst for directdehydrogenation of propane: formation of an active and selective core-shellsp2/sp3 nanocomposite structure, Chemistry, 20 (2014) 6324-6331.)将未负载任何金属的纳米金刚石在不同高温条件下的惰性气体氛围中处理一定时间,并发现当1100℃处理后能够在丙烷直接脱氢反应上表现出最佳催化活性。
发明内容
本发明的目的在于提供一种以纳米金刚石为载体的非金属掺杂铂系催化剂的制备方法,其采用不同非金属前驱体对纳米金刚石进行修饰,再进行铂负载,将所得催化剂应用于低碳烷烃脱氢催化反应上可表现出高催化活性、高选择性以及良好稳定性,且相比常规的金属修饰铂系催化剂,本发明选用非金属修饰载体制备的铂系催化剂具有价格低廉、操作简单易行的特点,而且为今后铂系催化剂性能提升方案提供了新的参考方向。
为实现上述目的,本发明采用如下技术方案:
一种以纳米金刚石为载体的非金属修饰铂系催化剂的制备方法,其采用非金属前驱体溶液对纳米金刚石进行浸渍,然后在惰性气体下进行高温煅烧,再采用含铂前驱体溶液对其进行铂负载,最后进行还原,即得所述非金属修饰的铂系催化剂;其中,所述非金属选自硼与氮、磷中的至少一种,其中,硼的掺杂量为催化剂重量的0.1~10%、氮和磷的掺杂量均为催化剂重量的0~10%;铂的负载量为催化剂重量的0.1~10%。
所用硼的前驱体为单质硼、硼酸、偏硼酸钠、偏硼酸钾、十水硼砂中的一种或多种;所用氮的前驱体为氨气、氢氧化铵、硝酸铵、氯化铵、三聚氰胺、盐酸多巴胺、尿素中的一种或多种;所用磷的前驱体为植酸、磷酸、磷酸氢二胺、磷酸二氢铵、磷酸三乙酯、磷酸氢二钾、磷酸二氢钾中的一种或多种。
所用纳米金刚石的纯度为93~96.5%,粒径为20~250nm。
所述惰性气体为氩气或氮气。
所述高温煅烧的温度为600~1500℃,时间为0.1~10h。
所述含铂前驱体为硝酸铂、氯铂酸、氯铂酸钾、二氯四氨合铂或乙酰丙酮铂。
所述非金属前驱体溶液或含铂前驱体溶液均采用水、甲醇、乙醇、甲醛、丙酮中的一种或多种为溶剂配制而成。
所述铂负载是先在常温下采用超声波处理0.5-10h,再搅拌0.5-10h进行浸渍。
所述还原是采用还原剂或还原性气氛氢气进行处理;所用还原剂选自乙二醇、C1~C3的羧酸、C1~C3的羧酸钠中的任意一种。
上述方法制备的非金属掺杂铂系催化剂可用于低碳烷烃的脱氢反应中,所述脱氢反应的温度为500~650℃,压力为0.1~0.5MPa,反应时间为0.1~20 h。
本发明显著优点在于:
本发明采用纳米金刚石碳材料为载体,能够有效克服分子筛以及氧化铝载体强酸性导致的丙烷深度裂解的问题,提高产物丙烯的选择性,并且该类载体能够明显改变铂金属的物理化学性质,进而提升其催化性能。
相比较金属助剂,本发明所用非金属助剂能够降低催化剂制造成本、解决金属污染问题,且其操作简单易行,并具有高活性与高选择性,能够为低碳烷烃脱氢催化剂提供新的参考方向。
附图说明
图1为实施例1-3及对比例4所得催化剂的X射线衍射谱图。
具体实施方式
本发明采用20~250nm粒径范围、93~96.5wt%的纳米金刚石碳材料作为铂系催化剂载体,经过非金属修饰应用于低碳烷烃脱氢催化反应中。非金属修饰纳米金刚石的方法是:先采用对应的非金属前驱体溶液浸渍纳米金刚石、然后在惰性气体下高温煅烧,再经铂负载、还原。所述非金属修饰是采用硼-氮和硼-磷双修饰以及硼-氮-磷三修饰。
下面通过实施例进一步详细说明本发明,但本发明并不限于此。
所用硼、氮、磷前驱体溶液的配制方法为:以硼酸为硼前驱体、无水乙醇为溶剂配制含硼溶液,其中硼的浓度为5mg/mL;以三聚氰胺为氮前驱体、甲醛为溶剂配制含氮溶液,其中氮的浓度为5mg/mL;以磷酸二氢铵为磷前驱体、去离子水为溶剂配制含磷溶液,其中磷的浓度为5mg/mL。
所用铂的前驱体溶液配制方法为:以六水氯铂酸为铂前驱体、无水乙醇为溶剂配制含铂溶液,其中铂的浓度为5mg/mL。
实施例1:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL含硼溶液、5mL含氮溶液和5mL水,磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入3mL氯铂酸的无水乙醇溶液和7mL无水乙醇,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中硼的负载量为5 wt%、氮的负载量为5 wt%、铂的负载量为5 wt%,记为A。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应10h内的性能数据见表1。
表1 实施例1所制备催化剂在丙烷脱氢反应中的性能数据
实施例2:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL含硼溶液、5mL含磷溶液和5mL甲醛;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入3mL氯铂酸的无水乙醇溶液和7mL无水乙醇,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中硼的负载量为5 wt%、磷的负载量为5 wt%、铂的负载量为5 wt%,记为B。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应10h内的性能数据见表2。
表2 实施例2所制备催化剂在丙烷脱氢反应中的性能数据
实施例3:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL含硼溶液、5mL含氮溶液和5mL含磷溶液;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入3mL氯铂酸的无水乙醇溶液和7mL无水乙醇,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中硼的负载量为5 wt%、氮的负载量为5 wt%、磷的负载量为5 wt%、铂的负载量为5wt%,记为C。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应10h内的性能数据见表3。
表3 实施例3所制备催化剂在丙烷脱氢反应中的性能数据
对比例1:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL含硼溶液、5mL甲醛和5mL水;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入3mL氯铂酸的无水乙醇溶液和7mL无水乙醇,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中硼的负载量为5 wt%、铂的负载量为5 wt%,记为D。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应0.1h的丙烷转化率为23.32%、丙烯选择性为89.05%。
对比例2:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL无水乙醇、5mL含氮溶液和5mL水;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入3mL氯铂酸的无水乙醇溶液和7mL无水乙醇,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中氮的负载量为5 wt%、铂的负载量为5 wt%,记为E。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应0.1h的丙烷转化率为16.52%、丙烯选择性为77.86%。
对比例3:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL无水乙醇、5mL含磷溶液和5mL甲醛;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入3mL氯铂酸的无水乙醇溶液和7mL无水乙醇,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中磷的负载量为5 wt%、铂的负载量为5 wt%,记为F。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应0.1h的丙烷转化率为16.50%、丙烯选择性为87.34%。
对比例4:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL无水乙醇、5mL去离子水和5mL甲醛;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入3mL氯铂酸的无水乙醇溶液和7mL无水乙醇,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中铂的负载量为5 wt%,记为G。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应0.1h的丙烷转化率为12.90%、丙烯选择性为89.88%。
对比例5:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL含硼溶液、5mL甲醛和5mL水;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入10mL无水乙醇溶液,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中硼的负载量为5wt%,记为H。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应0.1h的丙烷转化率为8.08%、丙烯选择性为86.91%。
对比例6:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL含氮溶液、5mL乙醇和5mL水;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入10mL无水乙醇溶液,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中氮的负载量为5wt%,记为I。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应0.1h的丙烷转化率为5.32%、丙烯选择性为84.21%。
对比例7:
取粒径大小约50nm的纳米金刚石0.5g,加入5mL含磷溶液、5mL乙醇和5mL甲醛;磁力搅拌1h后,将温度升至110℃,搅拌至干,再在110℃干燥过夜;将干燥好的样品转移至管式炉中,在氮气氛围下1100℃高温煅烧4h,煅烧后的样品充分研磨;然后取研磨好的样品0.3g,加入10mL无水乙醇溶液,磁力搅拌1h,超声处理3h后再搅拌3h,然后将温度调至110℃,搅拌至干后80℃干燥过夜,再在氢气氛围下580℃还原1h,所得催化剂中磷的负载量为5wt%,记为J。
取0.2g上述制备的催化剂,装填于微反装置中,以丙烷体积分数为5%的丙烷和氮气的混合物为反应原料,在600℃、0.1MPa、丙烷进料质量空速为1.8h-1的条件下进行脱氢反应,反应0.1h的丙烷转化率为7.56%、丙烯选择性为90.21%。
对比实施例和对比例所得催化剂直接脱氢制丙烯的催化性能可以发现,采用硼-氮和硼-磷双修饰以及硼-氮-磷三修饰的纳米金刚石再负载铂,要比硼、氮、磷单修饰纳米金刚石再负载铂的效果要好。
对比实施例和对比例4所得催化剂的XRD谱图可以发现,与未修饰直接负载铂相比,硼-氮和硼-磷双修饰以及硼-氮-磷三修饰纳米金刚石再负载铂引入了新的活性物种以及一些特殊结构,例如P=O基团、BN结构以及PtP2物种等,这些特殊的变化可能是催化剂性能发生巨大提升的主要原因。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (10)
1.一种以纳米金刚石为载体的非金属修饰铂系催化剂的制备方法,其特征在于:采用非金属前驱体溶液对纳米金刚石进行浸渍,然后在惰性气体下进行高温煅烧,再采用含铂前驱体溶液对其进行铂负载,最后进行还原,即得所述非金属修饰的铂系催化剂;
所述非金属选自硼与氮、磷中的至少一种,其中,硼的掺杂量为催化剂重量的0.1~10%、氮和磷的掺杂量均为催化剂重量的0~10%;铂的负载量为催化剂重量的0.1~10%。
2.根据权利要求1所述的制备方法,其特征在于:所用硼的前驱体为单质硼、硼酸、偏硼酸钠、偏硼酸钾、十水硼砂中的一种或多种;
所用氮的前驱体为氨气、氢氧化铵、硝酸铵、氯化铵、三聚氰胺、盐酸多巴胺、尿素中的一种或多种;
所用磷的前驱体为植酸、磷酸、磷酸氢二胺、磷酸二氢铵、磷酸三乙酯、磷酸氢二钾、磷酸二氢钾中的一种或多种。
3.根据权利要求1所述的制备方法,其特征在于:所用纳米金刚石的纯度为93~96.5%,粒径为20~250nm。
4.根据权利要求1所述的制备方法,其特征在于:所述惰性气体为氩气或氮气。
5.根据权利要求1所述的制备方法,其特征在于:所述高温煅烧的温度为600~1500℃,时间为0.1~10h。
6.根据权利要求1所述的制备方法,其特征在于:所述含铂前驱体为硝酸铂、氯铂酸、氯铂酸钾、二氯四氨合铂或乙酰丙酮铂。
7.根据权利要求1所述的制备方法,其特征在于:所述非金属前驱体溶液或含铂前驱体溶液均采用水、甲醇、乙醇、甲醛、丙酮中的一种或多种为溶剂配制而成。
8.根据权利要求1所述的制备方法,其特征在于:所述铂负载是先采用超声波处理,再搅拌浸渍。
9.根据权利要求1所述的制备方法,其特征在于:所述还原是采用还原剂或还原性气氛氢气进行处理;所用还原剂选自乙二醇、C1~C3的羧酸、C1~C3的羧酸钠中的任意一种。
10. 一种如权利要求1所述方法制备的非金属掺杂铂系催化剂在低碳烷烃脱氢反应中的应用,其特征在于:所述脱氢反应的温度为500~650℃,压力为0.1~0.5MPa,反应时间为0.1~20 h。
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