CN108671935B - 一种表面酸性增强的负载型铜基催化剂的制备方法及应用 - Google Patents
一种表面酸性增强的负载型铜基催化剂的制备方法及应用 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 16
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- 239000002253 acid Substances 0.000 claims abstract description 11
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 25
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
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- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
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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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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明提供了一种表面酸性增强的负载型铜基催化剂的制备方法及应用。本发明通过简单的成核/晶化隔离法并结合氯化钾在制备过程中的结构调控合成催化剂前体,再经过焙烧还原得到表面酸性增强的负载型铜基催化剂,并将其应用于高效糠醛选择性加氢重排制备环戊酮反应,其糠醛的转化率可达到95%~99%,环戊酮的选择性可达到80%~90%。该负载型铜基纳米催化剂,表面酸性位丰富,催化性能好,结构稳定,重复利用率高,具有广泛的应用前景。
Description
技术领域
本发明属于催化剂技术领域,具体来说,涉及一种表面酸性增强的负载型铜基催化剂的制备方法及应用。
背景技术
环戊酮是一种重要的有机分子中间体,在农药、医药、香料、橡胶合成等领域具有重要的应用价值,也可以用于制备生物燃料及燃料添加剂,同时由于其对有机物具有良好的溶解性,也常被用作有机溶剂。目前工业上制备环戊酮的主要方法有己二酸及其衍生物热解法和环戊烯直接氧化法。但这两种方法均存在原料资源不足,价格昂贵,而且原料利用率低,反应所需温度压力较高,副产物对环境污染较大等缺点。因此,开发新的环戊酮合成路线,提高环戊酮产率,降低生产成本极为重要。Hronec等通过研究发现,糠醛在水溶剂中可以通过加氢重排反应直接合成环戊酮[Hronec M,FulajtarováK.Selectivetransformation of furfural to cyclopentanone[J].Catal.Commun.,2012,24:100-104]。该反应以糠醛为原料,来源丰富,而且以水为溶剂绿色环保,因此具有重要的研究意义。近年来,负载型贵金属催化剂用于糠醛加氢生成环戊酮取得了一定成果,但考虑到贵金属资源稀少,价格较贵,因此对于非贵金属催化剂的开发更有意义。目前制备的铜基催化剂虽然表现了较好的催化活性,但是反应温度压力普遍较高,而且催化剂稳定性较差。因此,开发一种更高效、稳定的负载型铜基纳米催化剂具有很大的实用价值。
氧化锆(ZrO2)是一种表面同时拥有酸碱性位及氧化还原性的金属氧化物,由于其独特的物理、化学性质,可作为催化剂、助催化剂和催化剂载体用于催化氧化、催化加氢等多种催化反应中。在ZrO2制备过程中,可以通过调节不同的制备方法以及掺杂其它金属元素控制ZrO2表面结构性能。同时ZrO2还能与金属Cu之间形成相互作用,提高催化性能。
发明内容
本发明提供了一种表面酸性增强的负载型铜基催化剂的制备方法及应用,解决了传统的负载型铜基纳米催化剂易团聚、颗粒大、金属Cu与载体间相互作用小、表面酸性位难以控制、稳定性较差和重复利用率低等问题,并将其应用于高效糠醛选择性加氢重排制备环戊酮反应。
技术方案如下:
本发明所述的表面酸性增强的负载型铜基催化剂的制备方法:将含铜、钼、锆和钾的四种盐的混合水溶液与碳酸钠溶液倒入全返混旋转液膜反应器中,通过高速搅拌使其迅速成核,然后进行水热晶化,最后经焙烧还原得到表面酸性增强的ZrO2负载的铜基纳米催化剂。
进一步的,通过调变Cu的负载量和Mo的掺杂量,调控催化剂表面活性Cu含量,金属Cu粒径及表面酸量,同时通过Mo的掺杂有效稳定四方相ZrO2。以上技术特征可提高载体与金属间的强相互作用,提高催化剂催化性能和稳定性。
进一步的,Cu的负载量为20~40%,Cu平均粒径为8~15nm,催化剂的比表面积为130~180m2/g,表面酸含量为0.4~0.8mmol/g。
进一步的,上述表面酸性增强的负载型铜基催化剂的制备方法的具体步骤如下:
1)称取硝酸铜、硝酸锆、钼酸铵和氯化钾,溶于去离子水中配制盐溶液,其中Cu2+的浓度为0.1~0.2mol/L,MoO4 2-的浓度为0.005~0.02mol/L,Zr4+的浓度为0.05~0.1mol/L,K+浓度为0.01~0.05mmol/L,MoO4 2-和Zr4+的总浓度为0.05~0.15mol/L,MoO4 2-/Zr4+摩尔浓度比为0.05~0.15;称取碳酸钠溶于去离子水中配制碱溶液,控制碳酸钠的摩尔数为金属离子总摩尔数的2~4倍;
2)将以上配好的盐溶液和碱溶液同时置于全返混旋转液膜反应器,在转速3000~6000rpm下充分搅拌3~6min,将得到的悬浊液60~90℃水热晶化48~72h,将所得沉淀使用去离子水洗涤离心至上层清液为中性,干燥;
3)将所得到的固体置于马弗炉中焙烧,升温速率为2~5℃ min-1,从室温升温到400~600℃,之后在恒温温度下保温4~6h,焙烧得到催化剂前体;用氢气和氮气混合气在气氛炉中还原催化剂前体,以2~5℃ min-1的升温速率从室温升温到250~375℃,并在恒温温度下保温3~5h,得到表面酸性增强的ZrO2负载型铜纳米催化剂。
对得到的催化剂前体及催化剂进行结构表征。由X射线衍射(XRD)谱图可以看出四方相ZrO2的特征衍射峰,催化剂前体中CuO的衍射峰,催化剂中金属Cu的衍射峰;由扫描电镜(SEM)图可以发现催化剂粒径一致,分布均匀;由透射电镜(TEM)可以看出催化剂表面金属Cu颗粒大小一致,分布均匀。催化剂的N2吸附脱附曲线属于典型IV型的吸附等温线,滞后环属于H2型,为介孔结构。由X射线光电子能谱(XPS)谱图可以看出,Cu2+物种已被完全还原为Cu0或Cu+物种。该负载型铜基纳米催化剂,表面酸性位丰富,催化性能好,结构稳定,重复利用率高,具有广泛的应用前景。
将上述制备好的表面酸性增强的ZrO2负载型铜纳米催化剂应用于糠醛水相加氢反应的方法为:将糠醛、超纯水、催化剂同时加入到高压反应釜中,氢气气氛下100-200℃下反应3-10h。上述反应完成后,糠醛的转化率达到95~99%,环戊酮选择性可达80~90%。
本发明的优点在于:
(1)通过成核/晶化隔离法结合焙烧还原法,并结合氯化钾在制备过程中的结构调控,简单有效的制备了一种表面酸性增强的负载型铜基催化剂,工艺简单绿色,催化剂稳定性强;
(2)通过调变Cu的负载量和Mo的掺杂量,有效的调控催化剂表面活性Cu含量,金属Cu粒径及表面酸量;
(3)Mo的掺杂能够有效地稳定四方相ZrO2,提高载体与金属间的强相互作用,从而提高催化剂催化性能和稳定性;
(4)基于此方法制备的负载型纳米铜催化剂具有高活性、高稳定的特点,在催化糠醛转化为环戊酮的过程中体现出优异的催化性能,糠醛的转化率达到95~99%,环戊酮选择性可达80~90%,具有重要的实用价值。
附图说明
图1为实施例1制备的催化剂前体及催化剂的XRD谱图,具体是催化剂前体(CuO/Mo-ZrO2)及催化剂(Cu/Mo-ZrO2)的XRD谱图。
图2为实施例1制备的催化剂的SEM和TEM谱图,具体是催化剂(Cu/Mo-ZrO2)的扫描电镜(SEM)(A)及透射电镜(TEM)(B)图。
图3为实施例1制备的催化剂的N2吸附脱附曲线图,具体是:催化剂(Cu/Mo-ZrO2)的低温氮气吸脱附曲线,插图为相应的孔径分布(B)。
图4为实施例1制备的催化剂的Cu 2p XPS和Cu LMM谱图,具体是催化剂(Cu/Mo-ZrO2)的Cu 2p XPS表征,插图为Cu LMM XAES表征。
图5为实施例1糠醛加氢转化率和对环戊酮选择性随时间变化的曲线图。
具体实施方式
下面结合具体的实施例对本发明所述的一种表面酸性增强的负载型铜基催化剂的制备方法及催化剂的使用方法做进一步说明,但是本发明的保护范围并不限于此。
实施例1
称取3.86g硝酸锆Zr(NO3)4·5H2O,0.18g钼酸铵(NH4)6Mo7O24·4H2O,2.03g硝酸铜Cu(NO3)2·3H2O,0.30g氯化钾KCl,溶于100ml的去离子水中配制成盐溶液。称取4.75g碳酸钠Na2CO3溶于100ml去离子水中配制成碱溶液。将以上配制好的盐溶液和碱溶液同时置于全返混旋转液膜反应器,在转速4000rpm下充分搅拌4min,将得到的悬浊液70℃水热晶化48h,将所得沉淀使用去离子水洗涤至上层清液为中性,然后于70℃干燥12h。将所得到的固体置于马弗炉中焙烧,升温速率为5℃ min-1,从室温升温到500℃,之后在恒温温度下保温6h,焙烧得到催化剂前体。用10%H2/N2混合气在气氛炉中还原催化剂前体,以5℃ min-1的升温速率从室温升温到300℃,并在恒温温度下保温3h,得到表面酸性增强的ZrO2负载型铜纳米催化剂。催化剂中,ZrO2为纯四方相,Cu的负载量为31.2%,Cu平均粒径为11.2nm,催化剂的比表面积为163m2/g,表面酸含量为0.67mmol/g。
对得到的催化剂前体及催化剂进行结构表征测试。图1为实施例1催化剂前体及催化剂的X射线衍射(XRD)谱图,由图中可以看出,在2θ=30.2°,35.2°,50.4°和60.2°处的衍射峰对应于四方相ZrO2的(011),(110),(020)和(121)晶面衍射峰,说明该方法能够合成晶型完整、结晶度良好的纯四方相ZrO2。还原后的催化剂在2θ=43.5°处出现了Cu(111)晶面衍射峰,而CuO(111)晶面衍射峰完全消失,证明CuO已被还原。图2(A)为实施例1中所制备催化剂的扫描电镜(SEM)照片,可以看出催化剂的粒径一致,分布均匀;图2(B)的透射电镜(TEM)照片,可以发现催化剂表面金属Cu颗粒大小一致,分布均匀,平均粒径为11.2nm。图3为所制备催化剂的N2吸脱附曲线图,可以看出该曲线属于IV型吸附曲线,滞后环属于H2型,说明材料具有丰富的介孔结构。图4为实施例1的催化剂Cu 2p XPS和Cu LMM谱图,从图中可以看出,在935~945eV处没有Cu2+卫星峰出现,进一步证明Cu2+被还原为了Cu0或Cu+物种。图5为实施例1的催化剂加氢催化过程中糠醛的转化率和环戊酮选择性随时间变化的曲线。
催化剂用于糠醛水相加氢反应。将5mmol糠醛,15ml超纯水,0.2g催化剂同时加入到高压反应釜中,通入3MPa的H2,在160℃反应6h后糠醛的转化率达到99%,环戊酮选择性达到87.3%。
实施例2
称取3.86g硝酸锆Zr(NO3)4·5H2O,0.18g钼酸铵(NH4)6Mo7O24·4H2O,3.14g硝酸铜Cu(NO3)2·3H2O,0.30g氯化钾KCl,溶于100ml的去离子水中配制成盐溶液。称取5.73g碳酸钠溶Na2CO3于100ml去离子水中配制成碱溶液。将以上配制好的盐溶液和碱溶液同时置于全返混旋转液膜反应器,在转速4000rpm下充分搅拌4min,将得到的悬浊液70℃水热晶化60h,将所得沉淀使用去离子水洗涤至上层清液为中性,然后于70℃干燥12h。将所得到的固体置于马弗炉中焙烧,升温速率为5℃ min-1,从室温升温到450℃,之后在恒温温度下保温5h,焙烧得到催化剂前体。用10%H2/N2混合气在气氛炉中还原催化剂前体,以3℃ min-1的升温速率从室温升温到325℃,并在恒温温度下保温4h,得到表面酸性增强的ZrO2负载型铜纳米催化剂。催化剂中,ZrO2为纯四方相,Cu的负载量为38.5%,Cu平均粒径为14.3nm,催化剂的比表面积为147m2/g,表面酸含量为0.58mmol/g。
催化剂用于糠醛水相加氢反应。将5mmol糠醛,15ml超纯水,0.2g催化剂同时加入到高压反应釜中,通入3MPa的H2,在160℃反应6h后糠醛的转化率达到99%,环戊酮选择性达到83.4%。
实施例3
称取3.86g硝酸锆Zr(NO3)4·5H2O,0.18g钼酸铵(NH4)6Mo7O24·4H2O,1.20g硝酸铜Cu(NO3)2·3H2O,0.30g氯化钾KCl,溶于100ml的去离子水中配制成盐溶液。称取4.03g碳酸钠Na2CO3溶于100ml去离子水中配制成碱溶液。将以上配制好的盐溶液和碱溶液同时置于全返混旋转液膜反应器,在转速5000rpm下充分搅拌3min,将得到的悬浊液70℃水热晶化72h,将所得沉淀使用去离子水洗涤至上层清液为中性,然后于70℃干燥12h。将所得到的固体置于马弗炉中焙烧,升温速率为3℃ min-1,从室温升温到600℃,之后在恒温温度下保温5h,焙烧得到催化剂前体。用10%H2/N2混合气在气氛炉中还原催化剂前体,以5℃ min-1的升温速率从室温升温到350℃,并在恒温温度下保温4h,得到表面酸性增强的ZrO2负载型铜纳米催化剂。催化剂中,ZrO2为纯四方相,Cu的负载量为20.7%,Cu平均粒径为9.6nm,催化剂的比表面积为155m2/g,表面酸含量为0.61mmol/g。
催化剂用于糠醛水相加氢反应。将5mmol糠醛,15ml超纯水,0.2g催化剂同时加入到高压反应釜中,通入3MPa的H2,在160℃反应6h后糠醛的转化率达到99%,环戊酮选择性达到85.5%。
实施例4
称取3.86g硝酸锆Zr(NO3)4·5H2O,0.09g钼酸铵(NH4)6Mo7O24·4H2O,1.91g硝酸铜Cu(NO3)2·3H2O,0.30g氯化钾KCl,溶于100ml的去离子水中配制成盐溶液。称取4.67g碳酸钠Na2CO3溶于100ml去离子水中配制成碱溶液。将以上配制好的盐溶液和碱溶液同时置于全返混旋转液膜反应器,在转速6000rpm下充分搅拌3min,将得到的悬浊液70℃水热晶化64h,将所得沉淀使用去离子水洗涤至上层清液为中性,然后于70℃干燥12h。将所得到的固体置于马弗炉中焙烧,升温速率为5℃ min-1,从室温升温到550℃,之后在恒温温度下保温5h,焙烧得到催化剂前体。用10%H2/N2混合气在气氛炉中还原催化剂前体,以5℃ min-1的升温速率从室温升温到290℃,并在恒温温度下保温5h,得到表面酸性增强的ZrO2负载型铜纳米催化剂。催化剂中,ZrO2为纯四方相,Cu的负载量为29.6%,Cu平均粒径为12.5nm,催化剂的比表面积为143m2/g,表面酸含量为0.48mmol/g。
催化剂用于糠醛水相加氢反应。将5mmol糠醛,15ml超纯水,0.2g催化剂同时加入到高压反应釜中,通入3MPa的H2,在160℃反应6h后糠醛的转化率达到97%,环戊酮选择性达到81.7%。
Claims (1)
1.一种表面酸性增强的负载型铜基催化剂催化糠醛水相加氢反应的方法,其特征在于,所述方法的具体操作为:将表面酸性增强的负载型铜基催化剂、糠醛、超纯水同时加入到高压反应釜中,氢气气氛下100-200℃反应3-10h;
所述表面酸性增强的负载型铜基催化剂的制备方法为:将含铜、钼、锆和钾的四种盐的混合水溶液与碳酸钠溶液倒入全返混旋转液膜反应器中,通过高速搅拌使其迅速成核,然后进行水热晶化,最后经焙烧还原得到表面酸性增强的ZrO2负载的铜基纳米催化剂;Cu的负载量为20~40%,Cu平均粒径为8~15nm,催化剂的比表面积为130~180m2/g,表面酸含量为0.4~0.8mmol/g;通过调变Cu的负载量和Mo的掺杂量,调控催化剂表面活性Cu含量,金属Cu粒径及表面酸量,同时通过Mo的掺杂有效稳定四方相ZrO2;
所述表面酸性增强的负载型铜基催化剂的制备方法的具体步骤如下:
1)称取硝酸铜、硝酸锆、钼酸铵和氯化钾,溶于去离子水中配制盐溶液,其中Cu2+的浓度为0.1~0.2mol/L,MoO4 2-的浓度为0.005~0.02mol/L,Zr4+的浓度为0.05~0.1mol/L,K+浓度为0.01~0.05mmol/L,MoO4 2-和Zr4+的总浓度为0.05~0.15mol/L,MoO4 2-/Zr4+摩尔浓度比为0.05~0.15;称取碳酸钠溶于去离子水中配制碱溶液,控制碳酸钠的摩尔数为金属离子总摩尔数的2~4倍;
2)将以上配好的盐溶液和碱溶液同时置于全返混旋转液膜反应器,在转速3000~6000rpm下充分搅拌3~6min,将得到的悬浊液60~90℃水热晶化48~72h,将所得沉淀使用去离子水洗涤离心至上层清液为中性,干燥;
3)将所得到的固体置于马弗炉中焙烧,升温速率为2~5℃ min-1,从室温升温到400~600℃,之后在恒温温度下保温4~6h,焙烧得到催化剂前体;用氢气和氮气混合气在气氛炉中还原催化剂前体,以2~5℃ min-1的升温速率从室温升温到250~375℃,并在恒温温度下保温3~5h,得到表面酸性增强的ZrO2负载型铜纳米催化剂。
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