CN108786803A - 负载型纳米Pt催化剂及其制备方法 - Google Patents
负载型纳米Pt催化剂及其制备方法 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 91
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- 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
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B01J37/0213—Preparation of the impregnating solution
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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Abstract
本发明属于化工技术领域,公开一种负载型纳米Pt催化剂及其制备方法:以氧化铝为载体,以金属Pt为活性组分,所述活性组分金属Pt以包裹有CeO2的Pt@CeO2核壳结构形式存在,所述载体在催化剂中的质量含量为91%‑99.5%,所述活性组分金属Pt在催化剂中的质量含量为0.01%‑4.0%,制备含有Pt@CeO2纳米核壳结构的纳米溶胶,以含有Pt@CeO2纳米核壳结构的纳米溶胶作为浸渍液浸渍氧化铝载体;本发明催化剂载体具有较大的比表面积,所制得的催化剂活性与稳定性都显著提高,本发明利用独特的Pt@CeO2纳米核壳结构能有效阻止Pt纳米活性组分的聚集,显著提高催化剂的活性、稳定性、抗积炭性能。
Description
技术领域
本发明涉及化工技术领域,本发明涉及一种负载型纳米Pt催化剂及其制备方法,更进一步讲,涉及一种以活性组分金属Pt以包裹有CeO2的Pt@CeO2核壳结构负载在载体上的纳米Pt催化剂及其制备方法。
背景技术
丙烯是一种仅次于乙烯的重要基本有机化工原料,可用于合成聚丙烯、丙烯酸、丙烯醛和环氧丙烷等材料,还可用于生产塑料、有机玻璃和环氧树脂等产品。丙烯的主要来源分3种:石脑油蒸汽裂解、炼厂FCC副产和丙烷脱氢。前两种方法能耗高且须消耗不可再生石油资源。丙烷脱氢制丙烯可以利用较为丰富的丙烷资源,发展潜力巨大。
在丙烷脱氢制丙烯工艺中,脱氢催化剂性能的优劣直接影响丙烯收率及生产成本。催化剂性能主要体现在活性、选择性、稳定性等方面。
CN201510346158.9公开了一种以介孔分子筛为载体的丙烷脱氢催化剂。该催化剂活性组分为VIII族金属,如Pt,助剂包括IIB族金属以及碱土和/或稀土金属。该催化剂用于丙烷脱氢时,具有良好的转化率、选择性及稳定性。
CN201510696918.9公开了一种以多壁碳纳米管为载体丙烷脱氢催化剂,活性组分Pt,助剂P。当应用于丙烷脱氢反应时,具有较高的反应稳定性和丙烯选择性。
CN201510868382.4公开了一种以成型氧化铝为载体的丙烷脱氢催化剂。活性组分为Pt族金属,助剂为IV族-III族双金属。该催化剂用于丙烷脱氢,催化剂选择性稳定性较好。
尽管如此,因上述催化剂制备方法均为传统浸渍法,该法制得的催化剂活性组分分散不均匀,且高温下容易发生Pt聚集。因此会对催化剂性能产生不利影响。
发明内容
本发明的目的在于解决现有技术的不足,本发明的目的是为克服传统浸渍法制备的负载Pt催化剂,活性组分分散不均匀,且高温下容易发生Pt积聚,严重影响催化剂活性及稳定性的问题,提供一种新的活性、选择性及稳定性均得到改善的负载型纳米Pt催化剂及其制备方法,且在丙烷脱氢制丙烯工艺中的应用。
一种负载型纳米Pt催化剂,以氧化铝为载体,以金属Pt为活性组分,所述活性组分金属Pt以包裹有CeO2的Pt@CeO2核壳结构形式存在,所述载体在催化剂中的质量含量为91%-99.5%,所述活性组分金属Pt在催化剂中的质量含量为0.01%-4.0%,所述CeO2在催化剂中质量含量为0.1%-5%。
本发明还提供一种所述的负载型纳米Pt催化剂的制备方法,包括:制备含有Pt@CeO2纳米核壳结构的纳米溶胶,以含有Pt@CeO2纳米核壳结构的纳米溶胶作为浸渍液浸渍氧化铝载体。
进一步地,还包括以下步骤:经过浸渍后的氧化铝载体再经过干燥、焙烧、还原得到所述负载型纳米Pt催化剂。
进一步地,制备含有Pt@CeO2纳米核壳结构的纳米溶胶包括:
e、向所需量的含Ce化合物中加入去离子水溶解,制得含Ce溶液;
f、将上述含Ce溶液加入到Pt纳米溶胶中,室温搅拌1-2h,制得Pt纳米溶胶和含Ce溶液的混合溶液a;
g、向所需量的还原剂中加入去离子水制得还原剂溶液;
h、在剧烈搅拌下,将步骤g制得的还原剂溶液滴加到Pt纳米溶胶和含Ce溶液的混合溶液a中,室温搅拌4-6h,即制得含有Pt@CeO2核壳结构的纳米溶胶。
进一步地,所述Pt纳米溶胶的制备包括:
a、向所需量的表面稳定剂中加入去离子水溶解,制得表面稳定剂水溶液;
b、取所需量的含Pt化合物溶液加入稳定剂溶液中,室温下搅拌30-60min,制得混合溶液b;
c、向所需量的还原剂中加入去离子水制得还原剂溶液;
d、在剧烈搅拌下将还原剂溶液滴加到混合溶液b中,室温下继续搅拌4-6h,即制得Pt纳米溶胶。
进一步地,具体包括以下步骤:
i、将氧化铝载体迅速加入到步骤h制得的含有Pt@CeO2核壳结构的纳米溶胶中,采用超声波震荡浸渍法浸渍2-6h,浸渍温度20-80℃,至上层溶液变澄清,得催化剂前驱体,
j、移除步骤i浸渍容器内的上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次,
k、将步骤j中得到的洗涤产物,在50-200℃的条件下干燥0.5-12h,
l、将步骤k中得到的干燥产物在300-750℃条件下焙烧0.5-10h,得到氧化态催化剂,
m、将步骤l中得到的氧化态催化剂在80-600℃下,用还原性气体还原0.5-12h得到所述负载型纳米Pt催化剂。
进一步地,步骤a中所述的表面稳定剂为十六烷基三甲基溴化铵、聚乙烯吡咯烷酮中至少一种。
进一步地,步骤b中所述的含Pt化合物为氯铂酸,硝酸铂,氯化铂,醋酸铂,氯铂酸铵中一种或几种。
进一步地,步骤c所述的还原剂为NaBH4。
进一步地,步骤e中所述的含Ce化合物为Ce(NO3)3.mH2O,步骤g中所述的还原剂为NaBH4。
有益效果:
与现有技术相比,本发明制备的负载型纳米Pt催化剂,显著减少Pt聚集,使得活性组分Pt分散均匀,活性组分Pt具有极大的相对比表面积,增加了催化剂活性中心与反应物料的接触机会,且本催化剂载体具有较大的比表面积,所制得的催化剂活性与稳定性都显著提高,本发明利用独特的Pt@CeO2纳米核壳结构能有效阻止Pt纳米活性组分的聚集,显著提高催化剂的活性、稳定性、抗积炭性能,本发明负载型纳米Pt催化剂应用于丙烷脱氢制丙烯反应中,在维持高丙烯选择性的同时,丙烷转化率显著提高,并且本发明催化剂的高温稳定性也明显提高。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当注意的是,此处所描述的具体实施方式仅用于说明本发明,并不用于限制本发明。
本发明提供了一种Pt基脱氢催化剂,该催化剂包括:载体以及负载在载体上的活性组分。其中,所述载体为氧化铝,所述活性组分为Pt,所述活性组分Pt以包裹有CeO2的Pt@CeO2核壳结构形式存在。
根据本发明,以所述催化剂的的总质量为基准,所述载体在催化剂中的质量含量为91%-99.5%,所述活性组分Pt在催化剂中的质量含量为0.01%-4%,所述CeO2在催化剂中质量含量为0.1%-5%。
根据本发明,本发明对所述氧化铝没有特殊限定,优选情况下,所述氧化铝可以为伽玛氧化铝。本发明对所述氧化铝的来源没有特殊限定,例如,可以为市售的各种适合用作载体的氧化铝,也可以通过硝酸铝沉淀-焙烧法、拟薄水铝石焙烧法、薄水铝石焙烧法或铝溶胶凝胶法制得的氧化铝。所述伽玛氧化铝纯度应达到95%(质量分数,下同)以上,优选99%以上。
本发明提供了一种负载型纳米Pt催化剂的制备方法,包括:制备含有Pt@CeO2纳米核壳结构的纳米溶胶,以含有Pt@CeO2纳米核壳结构的纳米溶胶作为浸渍液浸渍氧化铝载体。
进一步地,还包括以下步骤:经过浸渍后的氧化铝载体再经过干燥、焙烧、还原得到所述负载型纳米Pt催化剂。
作为本发明的优选方案,所述负载型纳米Pt催化剂经下述制备过程步骤得到,所说的步骤包括:
(一)Pt纳米溶胶制备:
a、向所需量的表面稳定剂中加入去离子水溶解,制得表面稳定剂水溶液1;
b、取所需量的含Pt化合物溶液加入稳定剂溶液中,室温下搅拌30-60min,制得混合溶液b;
c、向所需量的还原剂中加入去离子水制得还原剂溶液;
d、在剧烈搅拌下将还原剂溶液滴加到混合溶液b中,滴加过程伴随大量气泡冒出,室温下继续搅拌4-6h,即制得Pt纳米溶胶。
(二)含有Pt@CeO2纳米核壳结构的纳米溶胶包括:
e、向所需量的含Ce化合物中加入去离子水溶解,制得含Ce溶液;
f、将上述含Ce溶液加入到Pt纳米溶胶中,室温搅拌1-2h,制得Pt纳米溶胶和含Ce溶液的混合溶液a;
g、向所需量的还原剂中加入去离子水制得还原剂溶液;
h、在剧烈搅拌下,将步骤g制得的还原剂溶液滴加到Pt纳米溶胶和含Ce溶液的混合溶液a中,室温搅拌4-6h,即制得含有Pt@CeO2核壳结构的纳米溶胶。
(三)催化剂制备:
i、将氧化铝载体迅速加入到步骤h制得的含有Pt@CeO2核壳结构的纳米溶胶中,采用超声波震荡浸渍法浸渍2-6h,浸渍温度20-80℃,至上层溶液变澄清,得催化剂前驱体,
j、移除步骤i浸渍容器内的上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次,
k、将步骤j中得到的洗涤产物,在50-200℃的条件下干燥0.5-12h,
l、将步骤k中得到的干燥产物在300-750℃条件下焙烧0.5-10h,得到氧化态催化剂,
m、将步骤l中得到的氧化态催化剂在80-600℃下,用还原性气体还原0.5-12h得到所述负载型纳米Pt催化剂。
作为本发明的优选方案,步骤a中所述的表面稳定剂为十六烷基三甲基溴化铵(CATB)、聚乙烯吡咯烷酮(PVP)
作为本发明的优选方案,步骤b中所述的含Pt化合物为氯铂酸,硝酸铂,氯化铂,醋酸铂,氯铂酸铵。
作为本发明的优选方案,步骤c中所述的还原剂为NaBH4。
作为本发明的优选方案,步骤e中所述的含Ce化合物为Ce(NO3)3.mH2O,步骤g中所述的还原剂为NaBH4。
作为本发明的优选方案,步骤m中所述的还原性气体为氢气、一氧化碳或含有二者之一的混合气。
本发明还进一步提供了上述催化剂在丙烷脱氢制丙烯过程中的应用;该应用是在固定床微分反应器中,在还原温度400-600℃,还原时间3-6h;所述还原过程可以在纯氢气氛中进行,也可在纯氢与惰气混合气氛中进行。反应空速为1000-2000h-1,丙烷/氢气进料比1:1-1:5,脱氢反应温度为500-650℃。
以下通过实施例对本发明进行详细描述,但本发明的保护范围并不因此受到限制。
实施例中,所用到的CATB、H2PtCl6.6H2O、NaBH4、GaCl3、KNO3、Mg(NO3)2、SnCl2、Ce(NO3)3.6H2O均为国药试剂,分析纯。硝酸厂商为北京化工厂,分析纯。硅溶胶厂商为青岛海洋化工有限公司,40wt%。田菁粉厂商为中西远大,总糖含量85.9%。
拟薄水铝石粉末为SB粉(德国Condea公司进口),相关数据如下:
SB粉物理性质
堆密度 | g/L | 680-800 |
比表面积 | m2/g | 230min |
孔体积 | mL/g | 0.5min |
SB粉粒径分布
<25μm | % | 40.0max |
<45μm | % | 55.0max |
>90μm | % | 18.0max |
实施例1
(1)含有Pt@CeO2纳米核壳结构的纳米溶胶制备
取0.6g(由摩尔比计算CATB/Pt=8:1)十六烷基三甲基溴化铵(CATB),用50.0mL去离子水溶解,然后用移液枪移取一定量(3mL0.10mol/L)的H2PtCl6溶液加入到上述CATB溶液中,室温下搅拌30-40min。称取一定量的0.12gNaBH4溶于10mL去离子水制得NaBH4溶液,在剧烈搅拌下将NaBH4溶液滴加到H2PtCl6和CATB的混合溶液中,滴加速度60滴/min(约3ml/min),滴加过程伴随大量气泡冒,室温下继续搅拌5h,可得Pt纳米溶胶。取0.26gCe(NO3)3.6H2O溶5mL去离子水,并将其缓慢加入到上述Pt纳米溶胶中,室温搅拌1h。称取0.18gNaBH4溶于10mL去离子水制得NaBH4溶液。在剧烈搅拌下将NaBH4溶液滴加到Pt纳米溶胶和硝酸铈的混合溶液中,滴加速度60滴/min(约3ml/min),室温下继续搅拌5h,可得含有Pt@CeO2纳米核壳结构的纳米溶胶。
(2)Al2O3载体制备
向200gSB粉中加入10g田菁粉,150mL浓度为20wt%HNO3溶液,将其加入捏合机中捏合30min,随后挤成2mm条状,干燥后,600℃焙烧4h得到载体Z1.
(3)催化剂制备
将15g制得的Z1载体(条形2mm)迅速加入到Pt@CeO2纳米溶胶中,采用超声波震荡浸渍法浸渍5h,至上层溶液变澄清。移除上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次。120℃干燥过夜,500℃焙烧2h,焙烧升温度率5℃/min。得到负载型纳米Pt@CeO2/Al2O3催化剂C1。
实施例2
(1)含有Pt@CeO2纳米核壳结构的纳米溶胶制备
取0.6g(由摩尔比计算CATB/Pt=8:1)十六烷基三甲基溴化铵(CATB),用50.0mL去离子水溶解,然后用移液枪移取一定量(1.5mL0.10mol/L)的H2PtCl6溶液加入到上述CATB溶液中,室温下搅拌30-40min。称取一定量的0.12gNaBH4溶于10mL去离子水制得NaBH4溶液,在剧烈搅拌下将NaBH4溶液滴加到H2PtCl6和CATB的混合溶液中,滴加速度60滴/min(约3ml/min),滴加过程伴随大量气泡冒,室温下继续搅拌5h,可得Pt纳米溶胶。取0.26gCe(NO3)3.6H2O溶5mL去离子水,并将其缓慢加入到上述Pt纳米溶胶中,室温搅拌1h。称取0.18gNaBH4溶于10mL去离子水制得NaBH4溶液。在剧烈搅拌下将NaBH4溶液滴加到Pt纳米溶胶和硝酸铈的混合溶液中,滴加速度60滴/min(约3ml/min),室温下继续搅拌5h,可得含有Pt@CeO2纳米核壳结构的纳米溶胶。
(2)Al2O3载体制备
向200gSB粉中加入10g田菁粉,300mL浓度为20wt%HNO3溶液,将其加入捏合机中捏合30min,随后挤条2mm条状,干燥后,600℃焙烧4h得到载体Z1.
(3)催化剂制备
将15g制得的Z1载体(条形2mm)迅速加入到Pt@CeO2纳米溶胶中,采用超声波震荡浸渍法浸渍5h,至上层溶液变澄清。移除上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次。120℃干燥过夜,500℃焙烧2h,焙烧升温度率5℃/min。得到负载型纳米Pt@CeO2/Al2O3催化剂C2。
实施例3
(1)含有Pt@CeO2纳米核壳结构的纳米溶胶制备
取0.6g十六烷基三甲基溴化铵(CATB),用50.0mL去离子水溶解,然后用移液枪移取一定量(3mL0.10mol/L)的H2PtCl6溶液加入到上述CATB溶液中,室温下搅拌30-40min。称取一定量的0.12gNaBH4溶于10mL去离子水制得NaBH4溶液,在剧烈搅拌下将NaBH4溶液滴加到H2PtCl6和CATB的混合溶液中,滴加速度60滴/min(约3ml/min),滴加过程伴随大量气泡冒,室温下继续搅拌5h,可得Pt纳米溶胶。
取0.13gCe(NO3)3.6H2O溶5mL去离子水,并将其缓慢加入到上述Pt纳米溶胶中,室温搅拌1h。称取0.18gNaBH4溶于10mL去离子水制得NaBH4溶液。在剧烈搅拌下将NaBH4溶液滴加到Pt纳米溶胶和硝酸铈的混合溶液中,滴加速度60滴/min(约3ml/min),室温下继续搅拌5h,可得含有Pt@CeO2纳米核壳结构的纳米溶胶。
(2)Al2O3载体制备
向200gSB粉中加入10g田菁粉,300mL浓度为20wt%HNO3溶液,将其加入捏合机中捏合30min,随后挤条2mm条状,干燥后,600℃焙烧4h得到载体Z1.
(3)催化剂制备
将15g制得的Z1载体(条形2mm)迅速加入到Pt@CeO2纳米溶胶中,采用超声波震荡浸渍法浸渍5h,至上层溶液变澄清。移除上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次。120℃干燥过夜,500℃焙烧2h,焙烧升温度率5℃/min。得到负载型纳米Pt@CeO2/Al2O3催化剂C3。
对比例1
(1)浸渍液制备
用移液枪移取一定量(3mL0.10mol/L)的H2PtCl6溶液,用去离子水稀释至50ml
(2)Al2O3载体制备
向200gSB粉中加入10g田菁粉(助挤剂),300mL浓度为20wt%HNO3溶液,将其加入捏合机中捏合30min,随后挤条2mm条状,干燥后,600℃焙烧4h得到载体Z1.
(3)催化剂制备
将15g制得的Z1载体(条形2mm)迅速加入到H2PtCl6浸渍液中,采用超声波震荡浸渍法浸渍5h,至上层溶液变澄清。移除上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次。120℃干燥过夜,500℃焙烧2h,焙烧升温度率5℃/min。得到普通负载型Pt/Al2O3催化剂D1。
对比例2
(1)Pt纳米溶胶制备
取0.6g十六烷基三甲基溴化铵(CATB),用50.0mL去离子水溶解,然后用移液枪移取一定量(3mL0.10mol/L)的H2PtCl6溶液加入到上述CATB溶液中,室温下搅拌30-40min。称取一定量的0.12gNaBH4溶于10mL去离子水制得NaBH4溶液,在剧烈搅拌下将NaBH4溶液滴加到H2PtCl6和CATB的混合溶液中,滴加速度60滴/min(约3ml/min),滴加过程伴随大量气泡冒,室温下继续搅拌5h,可得Pt纳米溶胶。
(2)Al2O3载体制备
向200gSB粉中加入10g田菁粉(助挤剂),300mL浓度为20wt%HNO3溶液,将其加入捏合机中捏合30min,随后挤条2mm条状,干燥后,600℃焙烧4h得到载体Z1.
(3)催化剂制备
将15g制得的Z1载体(条形2mm)迅速加入到Pt@CeO2纳米溶胶中,采用超声波震荡浸渍法浸渍5h,至上层溶液变澄清。移除上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次。120℃干燥过夜,500℃焙烧2h,焙烧升温度率5℃/min。得到负载型纳米Pt/Al2O3催化剂D2。
实施例4
评价方法:催化剂评价装置为固定床微型反应装置,原料及产物均为在线分析,分析仪器为SP-2100气相色谱。固定床反应器内径10mm,恒温区10cm。
评价条件:催化剂用量4.0g反应压力常压反应温度600-630℃氢气流量80ml/min,丙烷流量50ml/min,催化剂还原温度500℃,还原时间4h,空速2300h-1取样开始时间5min。
产物分析及计算方法:丙烷脱氢反应后产物主要有丙烷、丙烯、乙烷、乙烯、甲烷及微量C4以上组分,脱氢反应中各产物的色谱峰根据标准物在色谱中的停留时间不同而进行定性分析。反应产物的含量由气相色谱分析仪进行定量测量测定过程中,取样时间间隔为30min。本方法所用的色谱工作站采用面积归一法。
根据色谱所得的各组分的量,分别计算丙烷转化率X、丙烯选择性S和丙烯收率Y,数据记录到表1中。
表1
从上表1数据可以看出,本发明样品C1-C3应用于丙烷脱氢反应时,初始丙烷转化率在31-35%之间,初始丙烯选择性在89-94%之间。在8h内丙烷转化率与选择性分别稳定在29%与87%以上。特别是C1样品,初始丙烷转化率与丙烯选择性分别为34.9%与93.7%,8h内丙烷转化率与丙烯选择性分别稳定在33.6%与92.3%以上,均显著高于对比例D1-D2。说明本发明提供的负载型纳米Pt催化剂,以氧化铝为载体,以Pt@CeO2核壳型纳米粒子为活性组分,当其应用于丙烷脱氢制丙烯时,丙烷转化率和丙烯选择性显著提高,并且该催化剂的稳定性良好。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
Claims (10)
1.一种负载型纳米Pt催化剂,其特征在于,以氧化铝为载体,以金属Pt为活性组分,所述活性组分金属Pt以包裹有CeO2的Pt@CeO2核壳结构形式存在,所述载体在催化剂中的质量含量为91%-99.5%,所述活性组分金属Pt在催化剂中的质量含量为0.01%-4.0%,所述CeO2在催化剂中质量含量为0.1%-5%。
2.一种根据权利要求1所述的负载型纳米Pt催化剂的制备方法,其特征在于,包括:制备含有Pt@CeO2纳米核壳结构的纳米溶胶,以含有Pt@CeO2纳米核壳结构的纳米溶胶作为浸渍液浸渍氧化铝载体。
3.根据权利要求2所述的负载型纳米Pt催化剂的制备方法,其特征在于,还包括以下步骤:经过浸渍后的氧化铝载体再经过干燥、焙烧、还原得到所述负载型纳米Pt催化剂。
4.根据权利要求2所述的负载型纳米Pt催化剂的制备方法,其特征在于,制备含有Pt@CeO2纳米核壳结构的纳米溶胶包括:
e、向所需量的含Ce化合物中加入去离子水溶解,制得含Ce溶液;
f、将上述含Ce溶液加入到Pt纳米溶胶中,室温搅拌1-2h,制得Pt纳米溶胶和含Ce溶液的混合溶液a;
g、向所需量的还原剂中加入去离子水制得还原剂溶液;
h、在剧烈搅拌下,将步骤g制得的还原剂溶液滴加到Pt纳米溶胶和含Ce溶液的混合溶液a中,室温搅拌4-6h,即制得含有Pt@CeO2核壳结构的纳米溶胶。
5.根据权利要求2所述的负载型纳米Pt催化剂的制备方法,其特征在于,
所述Pt纳米溶胶的制备包括:
a、向所需量的表面稳定剂中加入去离子水溶解,制得表面稳定剂水溶液;
b、取所需量的含Pt化合物溶液加入稳定剂溶液中,室温下搅拌30-60min,制得混合溶液b;
c、向所需量的还原剂中加入去离子水制得还原剂溶液;
d、在剧烈搅拌下将还原剂溶液滴加到混合溶液b中,室温下继续搅拌4-6h,即制得Pt纳米溶胶。
6.根据权利要求3所述的负载型纳米Pt催化剂的制备方法,其特征在于,
具体包括以下步骤:
i、将氧化铝载体迅速加入到步骤h制得的含有Pt@CeO2核壳结构的纳米溶胶中,采用超声波震荡浸渍法浸渍2-6h,浸渍温度20-80℃,至上层溶液变澄清,得催化剂前驱体,
j、移除步骤i浸渍容器内的上层清液,然后对底部催化剂前驱体进行真空抽滤,随后分别用去离子水和乙醇各洗涤2次,
k、将步骤j中得到的洗涤产物,在50-200℃的条件下干燥0.5-12h,
l、将步骤k中得到的干燥产物在300-750℃条件下焙烧0.5-10h,得到氧化态催化剂,
m、将步骤l中得到的氧化态催化剂在80-600℃下,用还原性气体还原0.5-12h得到所述负载型纳米Pt催化剂。
7.根据权利要求5所述的负载型纳米Pt催化剂的制备方法,其特征在于,步骤a中所述的表面稳定剂为十六烷基三甲基溴化铵、聚乙烯吡咯烷酮中至少一种。
8.根据权利要求5所述的负载型纳米Pt催化剂的制备方法,其特征在于,步骤b中所述的含Pt化合物为氯铂酸,硝酸铂,氯化铂,醋酸铂,氯铂酸铵中一种或几种。
9.根据权利要求5所述的负载型纳米Pt催化剂的制备方法,其特征在于,步骤c所述的还原剂为NaBH4。
10.根据权利要求4所述的负载型纳米Pt催化剂的制备方法,其特征在于,步骤e中所述的含Ce化合物为Ce(NO3)3.mH2O,步骤g中所述的还原剂为NaBH4。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113428892A (zh) * | 2021-07-27 | 2021-09-24 | 王伟建 | 一种简单可控制备超长羟卤铅矿纳米线的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102247843A (zh) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | 一种用于环烷烃脱氢铂基催化剂稳定性的改进方法 |
CN102335628A (zh) * | 2011-07-21 | 2012-02-01 | 南京大学 | 一种负载型纳米双金属复合催化剂及其制备方法 |
EP2430112A2 (en) * | 2009-04-23 | 2012-03-21 | The University of Chicago | Materials and methods for the preparation of nanocomposites |
CN103599776A (zh) * | 2013-11-21 | 2014-02-26 | 福州大学 | 一种Pd/CeO2可见光光催化剂及其制备方法和应用 |
CN104226310A (zh) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | 一种具有核壳结构的选择加氢催化剂及制备方法 |
CN105774171A (zh) * | 2014-12-24 | 2016-07-20 | 北京有色金属研究总院 | 一种多孔载体表面钯或钯合金复合膜及其制备方法 |
-
2018
- 2018-04-28 CN CN201810400639.7A patent/CN108786803B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2430112A2 (en) * | 2009-04-23 | 2012-03-21 | The University of Chicago | Materials and methods for the preparation of nanocomposites |
CN102247843A (zh) * | 2010-05-19 | 2011-11-23 | 中国科学院大连化学物理研究所 | 一种用于环烷烃脱氢铂基催化剂稳定性的改进方法 |
CN102335628A (zh) * | 2011-07-21 | 2012-02-01 | 南京大学 | 一种负载型纳米双金属复合催化剂及其制备方法 |
CN102335628B (zh) * | 2011-07-21 | 2013-04-10 | 南京大学 | 一种负载型纳米双金属复合催化剂及其制备方法 |
CN104226310A (zh) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | 一种具有核壳结构的选择加氢催化剂及制备方法 |
CN103599776A (zh) * | 2013-11-21 | 2014-02-26 | 福州大学 | 一种Pd/CeO2可见光光催化剂及其制备方法和应用 |
CN105774171A (zh) * | 2014-12-24 | 2016-07-20 | 北京有色金属研究总院 | 一种多孔载体表面钯或钯合金复合膜及其制备方法 |
Non-Patent Citations (2)
Title |
---|
SHUYAN SONG ETAL.: "Achieving the Trade-Off between Selectivity and Activity in Semihydrogenation of Alkynes by Fabrication of (Asymmetrical Pd@Ag Core)@(CeO2 Shell) Nanocatalysts via Autoredox Reaction", 《ADVANCED MATERIALS》 * |
XIAO WANG ETAL.: "γ-Al2O3 supported Pd@CeO2 core@shell nanospheres: salting-out assisted growth and self-assembly, and their catalytic performance in CO oxidation", 《CHEMICAL SCIENCE》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113428892A (zh) * | 2021-07-27 | 2021-09-24 | 王伟建 | 一种简单可控制备超长羟卤铅矿纳米线的制备方法 |
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