CN101402039B - 一种负载型金属钯催化剂的制备方法 - Google Patents
一种负载型金属钯催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 11
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- 238000002360 preparation method Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
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- 150000002940 palladium Chemical class 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 claims 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 13
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- 230000000694 effects Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
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- 230000002708 enhancing effect Effects 0.000 abstract 1
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 17
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- 230000000052 comparative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
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Abstract
一种负载型金属钯催化剂的制备方法,属于催化剂技术领域。该催化剂首先由层状前体法在Al2O3载体表面引入助催化剂的金属组分,再将主催化剂活性组分金属钯通过浸渍法负载在载体表面。首先在Al2O3微球表面合成含催化剂助剂金属元素和铝元素的水滑石前体。由于水滑石晶体的晶格定位效应,助剂金属原子和铝原子相互高度分散并与载体牢固结合;在后续的干燥和焙烧过程中,上述得到的水滑石前体转变为助剂金属氧化物与氧化铝并相互高度分散,并且能够对接下来负载的催化剂主活性金属钯元素起到隔离和分散作用。优点在于:提高催化剂的催化性能,增强催化剂的稳定性,同时达到减少贵金属钯消耗量的目的。
Description
技术领域
本发明属于催化剂技术领域,特别是提供了一种负载型金属钯催化剂的制备方法。
背景技术
负载型催化剂以其优良的传热传质性能,以及容易实现连续化反应等特点,在石油化工过程,特别是在烃类转化、烯烃选择性氧化、以及选择性加氢等重要反应过程中获得了广泛使用,其使用量占催化剂总量的70%以上。
而常见的重要石油化工过程中负载型催化剂对于助剂金属多采用浸渍法、喷淋法或者涂覆法等方法添加到催化剂中,对于用这些方法负载的助剂金属,在制备过程受溶剂化效应和金属组分的团簇效应影响,而且在后续高温焙烧过程中易产生金属组分微晶凝并现象,从而导致助剂金属组分分散性差,催化剂结构不稳定,活性金属分散度较低,制备过程能耗高和贵重金属消耗量大的结果。
水滑石类化合物包括水滑石(Hydrotalcite)和类水滑石(Hydrotalcite-likecompound),其主体一般由两种金属的氢氧化物构成,因此又称为层状双羟基复合金属氧化物(Layered Double Hydroxide,简写为LDH)。LDH的插层化合物称为插层水滑石。水滑石、类水滑石和插层水滑石统称为水滑石类插层材料(LDHs)。该材料为六方片层结构,片层本身具有极强的刚性,极难制备出形貌可控的片状结构。该类材料是一种具有独特结构特性的无机材料:如元素组成在较宽范围内的可调变性、孔结构的可调变性以及层间插层阴离子种类的可设计性等奠定了这类材料有可能成为具有潜在应用前景的工业催化剂或催化剂前驱体的基础。
在专利CN 1269260A中提到,在Al2O3载体表面及内孔组装含有二价金属的水滑石前体,再经过焙烧成为的催化剂在生成醇醚醋酸脂的反应中有很好的活性;在Journalof catalysis 231(2005)92-104中提到过在镁铝复合氧化物表面负载Ni作为催化剂,对提高Ni的活性起到了良好的效果,另外由于水滑石层板金属离子间的相互作用对金属原子有很好的隔离作用,本方法在提高催化剂的催化性能,增强催化剂的稳定性和减少贵重金属消耗量方面将有较好的效果。
发明内容
本发明的目的在于提供一种负载型金属钯催化剂的制备方法,由层状前体法在Al2O3载体表面引入助催化剂的金属组分,再将主催化剂活性组分金属钯通过浸渍法负载在载体表面的催化剂。与传统共浸渍或者分步浸渍引入助剂的金属钯催化剂相比,该方法制备的钯催化剂具有更高的催化加氢反应活性和选择性。本方法能够达到提高催化剂的催化性能,增强催化剂的稳定性,同时达到减少贵金属钯消耗量的目的。
本发明首先在Al2O3微球表面合成含催化剂助剂金属元素和铝元素的水滑石前体。由于水滑石晶体的晶格定位效应,助剂金属原子和铝原子相互高度分散并与载体牢固结合;在后续的干燥和焙烧过程中,上述得到的水滑石前体转变为助剂金属氧化物并与氧化铝相互高度分散,并且能够对接下来负载的催化剂主活性金属钯元素起到隔离和分散作用。具体制备步骤如下:
1、M2+Al-LDHs/Al2O3的制备
称取一定量的尿素溶于去离子水配置成溶液,其中尿素的浓度为0.2~2mol/L;将粒度为26~100目具有一定几何形状的Al2O3载体加入上述溶液中,其加入量为每100ml混合溶液加入1~6g Al2O3,在80~150℃条件下搅拌3~15小时。称取一定量的可溶性M2+盐溶于去离子水配置成溶液,按照一定比例加入到上述混合物,使其中M2+离子的浓度保持在0.001~1mol/L,80~160℃温度下搅拌3~15小时,冷却过滤,用去离子水洗涤,于80~120℃下干燥,得到M2+Al-LDHs/Al2O3。
其中Al2O3载体的形状可以是球型,三叶草型,片状等形状的一种或者是几种的混合物,其晶形可以是δ、β、γ、θ、η中的任意一种或其多种的混合物。
其中M2+可以是Mg2+,Ni2+,Ca2+,Pt2+,Cu2+中的任意一种或者是几种的混合物。
X射线衍射(XRD)、傅立叶变换红外(FT-IR)、X光电子能谱(XPS)等表征手段说明,M2+Al-LDHs/Al2O3前体中M2+Al-LDHs位于Al2O3载体的表层及内孔表面。
2、负载型催化剂的制备
称取一定质量的可溶性钯盐配置成水溶液,使其浓度保持在0.03~0.3mol/L,将步骤1中得到的M2+Al-LDHs/Al2O3前体置于氯化钯水溶液中,于50~90℃的水浴摇床中放置1~24小时,过滤,将得到的固体用去离子水洗涤,于80~120℃下干燥,然后在300~900℃的温度下焙烧2~24小时,将焙烧过的样品放置于固定床还原装置中,用H2在200~600℃的温度下还原处理2~24小时,得到负载型催化剂。
通过电感耦合等离子发射光谱可测得该催化剂中Pd的为0.1%~5%之间。
本发明的特点在于,该种方法能够将M2+Al-LDHs层状前体生长在Al2O3在体表面及内孔表面,由于LDHs的特殊性质,助剂金属元素和铝元素会受到晶格的束缚定向隔离且均匀分布,在随后的焙烧过程中不容易发生离子的迁移,并且能够对接下来负载的Pd元素起到隔离和分散作用,使得助剂金属元素和主活性金属能均匀稳定的分布在载体的表面,提高了催化剂整体的稳定性和催化性能,并且起到减少贵金属催化剂用量的作用。
将本发明制备的催化剂通过固定床催化加氢微反应装置,进行对苯二甲酸二甲酯催化加氢生成1,4-环己烷二甲酸二甲酯反应评价,反应物转化率为90%~97%,产物选择性在90%~98%。以传统浸渍法制备的Pd/Al2O3作为参照,在相同条件下进行对苯二甲酸二甲酯催化加氢生成1,4-环己烷二甲酸二甲酯反应评价,反应物转化率为85%~95%,产物选择性在75%~88%。因此本发明制备的催化剂具有更高的催化活性和选择性。
附图说明
图1是实施例1、2、3所用到的固定床催化加氢微反应装置图示。
图2是实施例1所制得的MgAl-LDHs/Al2O3的XRD谱图。
图3是实施例2所获得的样品的低温氮气吸脱附等温线图。
具体实施方式:
实施例1:
称取4g尿素溶于去离子水配置成80ml溶液,将2g粒度为60目球形η-Al2O3加入上述溶液中,在130℃条件下搅拌12小时。称取12gMg(NO3)2·6H2O溶于去离子水配置成20ml溶液,加入到上述混合物,130℃温度下搅拌12小时,冷却过滤,用去离子水洗涤,于80℃下干燥,得到MgAl-LDHs/Al2O3。称取0.04g氯化钯配置成水溶液,将得到的MgAl-LDHs/Al2O3置于氯化钯水溶液中,于50℃的水浴摇床中放置24小时,过滤,将得到的固体用去离子水洗涤,于80℃下干燥,然后在450℃的温度下焙烧8小时,将焙烧过的样品放置于固定床还原装置中,用H2在300℃的温度下还原处理3小时,得到负载型催化剂。
通过固定床催化加氢微反应装置,用该催化剂进行对苯二甲酸二甲酯催化加氢生成1,4-环己烷二甲酸二甲酯,反应条件为:反应温度220℃,H2压为80atm,氢油比为80,采用乙酸乙酯做溶剂,溶剂用量100ml/3g对苯二甲酸二甲酯,反应时间6h,结果对苯二甲酸二甲酯转化率为91%,1,4-环己烷二甲酸二甲酯选择性98%。
为了比较样品的催化性能,我们称取12g Mg(NO3)2·6H2O和0.04g氯化钯利用共浸渍法制备在Al2O3载体表面,在相同评价条件下,得到结果为对苯二甲酸二甲酯转化率为88%,1,4-环己烷二甲酸二甲酯选择性80%。
实施例2:
称取8g尿素溶于去离子水配置成70ml溶液,将3g粒度为100目球形θ-Al2O3加入上述溶液中,在100℃条件下搅拌15小时。称取16g Ni(NO3)2·6H2O溶于去离子水配置成30ml溶液,加入到上述混合物,110℃温度下搅拌14小时,冷却过滤,用去离子水洗涤,于100℃下干燥,得到NiAl-LDHs/Al2O3。称取0.3g氯化钯配置成水溶液,将得到的NiAl-LDHs/Al2O3置于氯化钯水溶液中,于80℃的水浴摇床中放置12小时,过滤,将得到的固体用去离子水洗涤,于120℃下干燥,然后在500℃的温度下焙烧6小时,将焙烧过的样品放置于固定床还原装置中,用H2在400℃的温度下还原处理2.5小时,得到负载型催化剂。
用同实施例1的条件对该催化剂进行应用性能测试,结果对苯二甲酸二甲酯转化率为90%,1,4-环己烷二甲酸二甲酯选择性94%。
为了比较样品的催化性能,我们称取16g Ni(NO3)2·6H2O和0.3g氯化钯利用共浸渍法制备在Al2O3载体表面,在相同评价条件下,得到结果为对苯二甲酸二甲酯转化率为92%,1,4-环己烷二甲酸二甲酯选择性88%。
实施例3:
称取6g尿素溶于去离子水配置成60ml溶液,将3g粒度为40目球形γ-Al2O3加入上述溶液中,在100℃条件下搅拌15小时。称取9g氯化钙溶于去离子水配置成60ml溶液,加入到上述混合物,120℃温度下搅拌10小时,冷却过滤,用去离子水洗涤,于90℃下干燥,得到CaAl-LDHs/Al2O3。称取0.3g氯化钯配置成水溶液,将得到的CaAl-LDHs/Al2O3置于氯化钯水溶液中,于90℃的水浴摇床中放置14小时,过滤,将得到的固体用去离子水洗涤,于100℃下干燥,然后在400℃的温度下焙烧9小时,将焙烧过的样品放置于固定床还原装置中,用H2在300℃的温度下还原处理4小时,得到负载型催化剂。
用同实施例1的条件对该催化剂进行应用性能测试,结果对苯二甲酸二甲酯转化率为92%,1,4-环己烷二甲酸二甲酯选择性90%。
为了比较样品的催化性能,我们称取18g氯化钙和0.3g氯化钯利用共浸渍法制备在Al2O3载体表面,在相同评价条件下,得到结果为对苯二甲酸二甲酯转化率为85%,1,4-环己烷二甲酸二甲酯选择性78%。
Claims (2)
1.一种负载型金属钯催化剂的制备方法,其特征在于,制备步骤如下:
(1)M2+Al-LDHs/Al2O3的制备
称取一定量的尿素溶于去离子水配制成溶液,其中尿素的浓度为0.2~2mol/L;将粒度为26~100目具有一定几何形状的Al2O3载体加入上述溶液中,其加入量为每100ml混合溶液加入1~6g Al2O3,在80~150℃条件下搅拌3~15小时;称取一定量的可溶性M2+盐溶于去离子水配制成溶液,按照比例加入到上述混合溶液中,使其中M2+离子的浓度保持在0.001~1mol/L,80~160℃温度下搅拌3~15小时,冷却过滤,用去离子水洗涤,于80~120℃下干燥,得到M2+Al-LDHs/Al2O3;
(2)负载型催化剂的制备
称取一定质量的可溶性钯盐配制成水溶液,使其浓度保持在0.03~0.3mol/L,将步骤1中得到的M2+Al-LDHs/Al2O3前体置于氯化钯水溶液中,于50~90℃的水浴摇床中放置1~24小时,过滤,将得到的固体用去离子水洗涤,于80~120℃下干燥,然后在300~900℃的温度下焙烧2~24小时,将焙烧过的样品放置于固定床还原装置中,用H2在200~600℃的温度下还原处理2~24小时,得到负载型催化剂;
所述的M2+为Mg2+,Ni2+,Ca2+,Pt2+,Cu2+中的任意一种或者是几种的混合物。
2.按照权利要求1所述的方法,其特征在于,Al2O3载体的形状为球型,三叶草型,片状形状的一种或者是几种的混合物,其晶型为δ、β、γ、θ、η中的任意一种或几种的混合物。
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