CN111215061A - 一种抗烧结高分散贵金属催化剂及制备和应用 - Google Patents
一种抗烧结高分散贵金属催化剂及制备和应用 Download PDFInfo
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- CN111215061A CN111215061A CN201811417355.5A CN201811417355A CN111215061A CN 111215061 A CN111215061 A CN 111215061A CN 201811417355 A CN201811417355 A CN 201811417355A CN 111215061 A CN111215061 A CN 111215061A
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- noble metal
- gallate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 66
- 239000006185 dispersion Substances 0.000 title claims abstract description 28
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 26
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 25
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 24
- 239000011029 spinel Substances 0.000 claims abstract description 24
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 21
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- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 66
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
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- 239000007789 gas Substances 0.000 claims description 6
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- 239000011701 zinc Substances 0.000 claims description 6
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052725 zinc Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
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- 239000001307 helium Substances 0.000 claims 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
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- 239000002245 particle Substances 0.000 abstract description 6
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 12
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
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- REFZTFPICLNNPM-UHFFFAOYSA-N 2-sulfanyldodecanoic acid Chemical compound CCCCCCCCCCC(S)C(O)=O REFZTFPICLNNPM-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 2
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- 239000012494 Quartz wool Substances 0.000 description 2
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241001629697 Panicum turgidum Species 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/66—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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Abstract
本发明公开了一种高温抗烧结高分散负载型贵金属催化剂及其制备方法。该催化剂的活性组分为Ru、Rh、Pd、Ag、Ir、Pt六种贵金属中的任何一种或两种以上,载体为尖晶石型纳米镓酸盐、纳米铁酸盐。具体方法为:将尖晶石型纳米镓酸盐或纳米铁酸盐载体加入至贵金属的前驱体溶液中,使前驱体在载体表面吸附,达到前驱体均匀有效的分散,随后经过干燥、焙烧和还原处理得到负载型抗烧结贵金属催化剂。该方法制备得到的一系列贵金属负载型催化剂,经过800℃空气气氛中焙烧24小时之后,贵金属的颗粒尺寸仍保持在3nm以下。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及高温抗烧结、高分散负载型贵金属(Ru、Rh、Pd、Ag、Ir、Pt)催化剂的制备。
背景技术
负载型贵金属催化剂凭借其优异的催化性能被广泛应用于催化重整、烷烃转化以及汽车尾气的吸收处理等重要化工领域。由于贵金属的稀缺性以及贵金属催化剂的催化性能存在着显著的纳米尺寸效应和形貌效应,因而负载型贵金属催化剂的高度分散化成为贵金属催化领域的研究重点,制备和维持特定纳米尺寸及形貌的贵金属催化剂成为其发挥优越催化活性的关键。但贵金属催化剂较低的塔曼温度(Ag:345℃,Pd:640℃,Pt:750℃,Rh:845℃,Ru:990℃,Ir:1085℃),使其在实际使用过程中面临着严峻的挑战。同时催化重整、烷烃转化和汽车尾气的吸收处理等过程往往需要十分苛刻的反应条件,比如甲烷部分氧化制合成气工艺中,催化剂的热点温度甚至会高于1100℃;如此苛刻的反应条件会造成负载型贵金属催化剂中高分散活性组分发生扩散、迁移、聚集以及溶入载体等现象,这一方面引起催化剂可接触活性组分的大大降低,另一方面催化剂的活性结构(尺寸、形貌)得到破坏。因而研制高温抗烧结高分散性的负载型贵金属催化剂具有很重要的实际意义。
目前,提高负载型贵金属催化剂热稳定性的方法主要有1)利用物理的方式形成阻止纳米颗粒迁移长大的障碍。M.Cargnello等(Science,2012,337,713-717.)利用巯基十二烷酸(MUA)作为引导剂,成功制备出了CeO2包裹的Pd纳米颗粒,并将其成功负载在氨基功能化的Al2O3载体表面,该催化剂经过850℃老化之后,仍能保持着原有的Pd@CeO2纳米颗粒,未发生颗粒之间的聚集长大。Joo,S.H.等(Nat.Mater.,2009,8,126-131.)利用TTAB为引导剂制备得到了多孔SiO2包裹的Pt纳米颗粒,该催化剂经过750℃焙烧之后仍保持在20nm左右。2)利用金属载体间的强相互作用而引起的载体对金属颗粒的部分覆盖阻止贵金属颗粒的迁移长大。王军虎等(CN 105080582A)以羟基磷灰石和TiO2的混合物为载体,利用羟基磷灰石与Au之间的SMSI效应对Au纳米颗粒起到稳定效应,利用TiO2作为活性助剂。该催化剂经过800℃焙烧之后,Au颗粒仅由2nm增加到8.5nm;与之对比的Au/TiO2经过相同的热处理之后,由原来的3.5nm增加到30nm以上。3)高温原子捕获的方法制备高分散抗烧结的负载型贵金属催化剂。John Jones等(Science,2016,353,150-154.)将Pt/Al2O3催化剂通过与CeO2机械混合,随后在空气中进行800℃老化处理,Pt通过气相氧化铂的形式扩散至CeO2表面得以捕获,从而在高温条件下形成了单原子分散的Pt催化剂。
上述方法虽制备得到了具有一定程度抗烧结性能的负载型贵金属催化剂,但其制备过程较为复杂,且适用范围较窄,比如策略1)、2)存在着严重的反应物及产物扩散抑制问题,策略3)的普适性较差;另外,目前的抗烧结催化剂,在大于800℃的高温处理之后,金属颗粒尺寸一般都大于10nm,且老化时间较短(一般低于5h)。一种在更加苛刻条件下(温度大于800℃,老化时间大于10h),且对所有贵金属具有普适稳定性的高分散(小于10nm)负载型贵金属催化剂的制备方法鲜有报道。
发明内容
本发明所解决的技术问题是,提供了一种普适性的抗烧结高分散负载型贵金属催化剂的制备方法,利用纳米镓酸盐、纳米铁酸盐实现了对所有贵金属纳米颗粒的稳定,解决了负载型贵金属催化剂高温易烧结的问题。
为实现上述目的,本发明提供以下技术方案:
本发明提供的一种抗烧结高分散贵金属催化剂,该催化剂由载体和贵金属活性组分构成,载体为具有尖晶石晶体结构的纳米镓酸盐或纳米铁酸盐,贵金属活性组分为Ru、Rh、Pd、Ag、Ir和Pt中的一种或两种以上,贵金属的质量分数为0.01%-20%。
具体操作步骤为:将一定量的镓酸盐或铁酸盐尖晶石载体浸渍于贵金属前驱体溶液中,室温下吸附0.5-30小时后;于60-120℃干燥6-12小时,然后在500-900℃焙烧2-24小时,最后在300-900℃含氢气氛中还原0.5-10小时,得到所述催化剂。
其中,所述尖晶石载体是镓酸盐或铁酸盐的一种或两种以上任意比混合物;镓酸盐尖晶石载体优选为镓酸镁、镓酸镍、镓酸锌和镓酸铜;铁酸盐尖晶石载体优选为铁酸镁、铁酸镍、铁酸锌和铁酸铜。
所述贵金属的前驱体为Ru、Rh、Pd、Ag、Ir和Pt的氯化物、硝酸盐或有机络合物。在催化剂中贵金属的质量分散为0.01%~20%。
所述催化剂制备方法中的优选条件为:室温下吸附3-5小时,80-110℃干燥8-10小时,600-800℃焙烧3-24小时,400-600℃含1-10vol%氢气中还原2-5小时。
本发明具有如下优点:
1、提供了一种制备抗烧结高分散负载型贵金属催化剂的普适性方法和策略。利用同一类载体材料(纳米镓酸盐、纳米铁酸盐)制备得到6种高分散抗烧结的贵金属催化剂。
2、该方法通过简单的浸渍法即可得到高温抗烧结的高分散贵金属催化剂,操作方便、成本较低、绿色环保。
3、该方法制备得到的催化剂具有鲜有报道的抗烧结性能,经过高温(500-900℃)、长时间(2-24小时)的焙烧处理后,贵金属仍保持高分散状态,尺寸范围可保持在单原子至10nm之间。
4、该催化剂对汽车尾气消除反应(如丙烯燃烧反应)具有优异的催化活性和高温抗烧结性能。
附图说明
图1为采用本发明所述方法实施例7-12制备的Ru/MgGa2O4-DR,Rh/MgGa2O4-DR,Pd/MgGa2O4-DR,Ag/MgGa2O4-DR,Ir/MgGa2O4-DR,Pt/MgGa2O4-DR催化剂的XRD谱图。结果表明MgGa2O4尖晶石负载的六种贵金属经高温处理后仅Pd/MgGa2O4-DR样品中出现PdO的衍射峰,而其他样品中均未出现相应贵金属或贵金属氧化物的衍射峰,这说明经高温处理后,相应样品中的贵金属仍保持高分散状态,颗粒尺寸在XRD的检测限以下(<3nm)。
图2为采用本发明所述方法实施例7-12制备的Ru/MgGa2O4-DR(a),Rh/MgGa2O4-DR(b),Pd/MgGa2O4-DR(c),Ag/MgGa2O4-DR(d),Ir/MgGa2O4-DR(e),Pd/MgGa2O4-DR(f)催化剂的电镜照片。结果表明MgGa2O4尖晶石负载的六种贵金属经高温处理后其分散状态主要为单原子和3nm左右的纳米颗粒。说明M/MgGa2O4(M=Ru,Rh,Pd,Ag,Ir,Pt)样品具有优异的高温抗烧结性能。
图3为采用本发明所述方法实施例43-48制备的Ru/ZnFe2O4-DO,Rh/ZnFe2O4-DO,Pd/ZnFe2O4-DO,Ag/ZnFe2O4-DO,Ir/ZnFe2O4-DO,Pt/ZnFe2O4-DO催化剂的XRD谱图。结果表明ZnFe2O4尖晶石负载的六种贵金属经高温处理后未出现相应贵金属或贵金属氧化物的衍射峰,这说明经高温处理后,6种贵金属均保持高分散状态,颗粒尺寸在XRD的检测限以下(<3nm)。
图4为采用本发明所述方法实施例43-48制备的Ru/ZnFe2O4-DO(a),Rh/ZnFe2O4-DO(b),Pd/ZnFe2O4-DO(c),Ag/ZnFe2O4-DO(d),Ir/ZnFe2O4-DO(e),Pt/ZnFe2O4-DO(f)催化剂的电镜照片。结果表明ZnFe2O4尖晶石负载的六种贵金属经高温处理后未观察到纳米颗粒的存在,说明上述六种贵金属主要以亚纳米甚至单原子状态存在。说明M/ZnFe2O4(M=Ru,Rh,Pd,Ag,Ir,Pt)样品具有优异的高温抗烧结性能。
图5为反应测试例1-4中丙烯燃烧反应的起燃曲线。结果表明实施例4和12得到的Pt/MgGa2O4-FR和Pt/MgGa2O4-DR样品对丙烯燃烧反应具有优异的低温催化活性和高温抗烧结性能。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步说明,但本发明并不仅限于此。
实施例1-4
实施例1-4采用本发明提供的方法,利用镓酸镁为载体制备镓酸镁负载的铑、钯、铱、铂四种高分散负载型催化剂。具体方法如下:称取5.0g MgGa2O4尖晶石载体加入至150mL含0.05g铑、钯、铱和铂的三氯化铑、氯化钯、氯铱酸和氯铂酸的水溶液中,室温搅拌24h,过滤,得到的固体置于60℃干燥12小时,500℃空气中焙烧5小时,再于纯氢中500℃还原2h。得到的催化剂分别记作Rh/MgGa2O4-FR、Pd/MgGa2O4-FR、Ir/MgGa2O4-FR和Pt/MgGa2O4-FR。
实施例5-6
实施例5-6采用本发明提供的方法,采用镓酸镁为载体制备镓酸镁负载的高分散负载型钌和银催化剂。以0.5%的理论质量负载量分别称取一定量的乙酰丙酮钌和硝酸银,分别溶解于一定量的乙醇和浓氨水中,随后加入5.0g MgGa2O4载体进行等体积浸渍,超声震荡均匀后,室温下放置24h,随后置于60℃干燥12小时,500℃空气中焙烧5小时,随后再于纯氢中500℃还原2h。得到镓酸镁负载的高分散钌和银催化剂,分别记作Ru/MgGa2O4-FR和Ag/MgGa2O4-FR。
实施例7-12
实施例7-12说明采用本发明提供的方法制备的镓酸镁尖晶石负载的6种贵金属催化剂经高温长时间老化处理后的热稳定性情况。将实施例1-6中制备得到的Ru/MgGa2O4-FR、Rh/MgGa2O4-FR、Pd/MgGa2O4-FR、Ag/MgGa2O4-FR、Ir/MgGa2O4-FR和Pt/MgGa2O4-FR催化剂置于马弗炉中,5℃/min升温至800℃空气中焙烧24h,随后500℃氢气还原2h,得到的催化剂命名为Ru/MgGa2O4-DR、Rh/MgGa2O4-DR、Pd/MgGa2O4-DR、Ag/MgGa2O4-DR、Ir/MgGa2O4-DR和Pt/MgGa2O4-DR。
利用电感耦合高频等离子体(ICP)定量元素分析得到贵金属的质量分数,如表1所示。
表1.实施例1-12所得催化剂的负载量
实施例13-18
实施例13-18采用本发明提供的方法,采用镓酸镍为载体制备镓酸镍负载的高分散负载型钌、铑、钯、银、铱和铂六种催化剂。具体方法与实施例1-6一致,即称取5.0gNiGa2O4尖晶石载体加入至150ml含0.05g的铑、钯、铱和铂的三氯化铑、氯化钯、氯铱酸和氯铂酸的水溶液中,室温搅拌24h,过滤,得到的固体置于60℃干燥12小时,500℃空气中焙烧5小时,再于纯氢中500℃还原2h。以0.5%的理论质量负载量分别称取一定量的乙酰丙酮钌和硝酸银,分别溶解于一定量的乙醇和浓氨水中,随后加入5.0g NiGa2O4载体进行等体积浸渍,超声震荡均匀后,室温下放置24h,随后置于60℃干燥12小时,500℃空气中焙烧5小时,再于纯氢中500℃还原2h。得到镓酸镍负载的高分散钌、银催化剂。最终得到的催化剂分别标记为Ru/NiGa2O4-FR、Rh/NiGa2O4-FR、Pd/NiGa2O4-FR、Ag/NiGa2O4-FR、Ir/NiGa2O4-FR和Pt/NiGa2O4-FR。
实施例19-24
实施例19-24说明采用本发明提供的方法制备镓酸镍尖晶石负载的6种贵金属纳米催化剂经高温长时间老化处理后的热稳定性情况。处理方法如实施例7-12,即将实施例13-18中制备得到的Ru/NiGa2O4-FR、Rh/NiGa2O4-FR、Pd/NiGa2O4-FR、Ag/NiGa2O4-FR、Ir/NiGa2O4-FR和Pt/NiGa2O4-FR催化剂置于马弗炉中,5℃/min升温至800℃空气中焙烧24h,随后500℃氢气还原2h,得到的催化剂命名为Ru/NiGa2O4-DR、Rh/NiGa2O4-DR、Pd/NiGa2O4-DR、Ag/NiGa2O4-DR、Ir/NiGa2O4-DR和Pt/NiGa2O4-DR。
实施例25-30
实施例25-30采用本发明提供的方法,采用镓酸锌为载体制备镓酸锌负载的高分散负载型钌、铑、钯、银、铱和铂六种催化剂。方法与实施例1-6一致,即称取5.0g ZnGa2O4尖晶石载体加入至150ml含0.05g的铑、钯、铱和铂的三氯化铑、氯化钯、氯铱酸和氯铂酸的水溶液中,室温搅拌24h,过滤,得固体置于60℃干燥12小时,500℃空气中焙烧5小时,再于纯氢中500℃还原2h。以0.5%的理论质量负载量分别称取一定量的乙酰丙酮钌和硝酸银,分别溶解于一定量的乙醇和浓氨水中,随后加入5.0g ZnGa2O4载体进行等体积浸渍,超声震荡均匀后,室温下放置24h,随后置于60℃干燥12小时,500℃空气中焙烧5小时,再于纯氢中500℃还原2h。得到镓酸锌负载的高分散钌、银催化剂。最终得到的催化剂分别标记为Ru/ZnGa2O4-FR、Rh/ZnGa2O4-FR、Pd/ZnGa2O4-FR、Ag/ZnGa2O4-FR、Ir/ZnGa2O4-FR和Pt/ZnGa2O4-FR。
实施例31-36
实施例31-36说明采用本发明提供的方法,制备镓酸锌尖晶石负载的6种贵金属纳米催化剂经高温长时间老化处理后的热稳定性情况。处理方法与实施例7-12一致。即将实施例25-30中制备得到的Ru/ZnGa2O4-FR、Rh/ZnGa2O4-FR、Pd/ZnGa2O4-FR、Ag/ZnGa2O4-FR、Ir/ZnGa2O4-FR和Pt/ZnGa2O4-FR催化剂置于马弗炉中,5℃/min升温至800℃空气中焙烧24h,随后500℃氢气还原2h,得到的催化剂命名为Ru/ZnGa2O4-DR、Rh/ZnGa2O4-DR、Pd/ZnGa2O4-DR、Ag/ZnGa2O4-DR、Ir/ZnGa2O4-DR和Pt/ZnGa2O4-DR。
实施例37-42
实施例37-42说明采用本发明提供的方法,用铁酸锌为载体制备铁酸锌负载的高分散负载型钌、铑、钯、银、铱和铂六种催化剂。即称取5.0g ZnFe2O4尖晶石载体加入至150ml含0.05g的钌、铑、钯、银、铱和铂的氯化钌、三氯化铑、氯化钯、硝酸银、氯铱酸和氯铂酸的水溶液中,室温搅拌24h,过滤,得到的固体置于60℃干燥12小时,500℃空气中焙烧5小时。得到铁酸锌负载的高分散钌、铑、钯、银、铱和铂催化剂。得到的催化剂标记为Ru/ZnFe2O4-FO、Rh/ZnFe2O4-FO、Pd/ZnFe2O4-FO、Ag/ZnFe2O4-FO,Ir/ZnFe2O4-FO和Pt/ZnFe2O4-FO。所得样品的负载量如表2所示:
表2.实施例43-49所得催化剂的负载量
实施例43-48
实施例43-48说明采用本发明提供的方法,制备铁酸锌尖晶石负载的6种贵金属纳米催化剂经高温长时间老化处理后的热稳定性情况。即将实施例37-42中制备得到的Ru/ZnFe2O4-FO、Rh/ZnFe2O4-FO、Pd/ZnFe2O4-FO、Ag/ZnFe2O4-FO,Ir/ZnFe2O4-FO和Pt/ZnFe2O4-FO催化剂置于马弗炉中,5℃/min升温至800℃空气中焙烧24h,得到的催化剂命名为Ru/ZnFe2O4-DO、Rh/ZnFe2O4-DO、Pd/ZnFe2O4-DO、Ag/ZnFe2O4-DO,Ir/ZnFe2O4-DO和Pt/ZnFe2O4-DO。
实施例49-54
实施例49-54说明采用本发明提供的方法,用铁酸钴为载体制备铁酸钴负载的高分散负载型钌、铑、钯、银、铱和铂六种催化剂。即称取5.0g CoFe2O4尖晶石载体加入至150ml含0.05g的钌、铑、钯、银、铱和铂的氯化钌、三氯化铑、氯化钯、硝酸银、氯铱酸和氯铂酸的水溶液中,室温搅拌24h,过滤,得到的固体置于60℃干燥12小时,500℃空气中焙烧5小时。得到铁酸钴负载的高分散钌、铑、钯、银、铱和铂催化剂。得到的催化剂标记为Ru/CoFe2O4-FO、Rh/CoFe2O4-FO、Pd/CoFe2O4-FO、Ag/CoFe2O4-FO、Ir/CoFe2O4-FO和Pt/CoFe2O4-FO。
实施例55-60
实施例55-60说明采用本发明提供的方法,制备铁酸钴尖晶石负载的6种贵金属纳米催化剂经高温长时间老化后的热稳定性情况。即将实施例49-54中制备得到的Ru/CoFe2O4-FO、Rh/CoFe2O4-FO、Pd/CoFe2O4-FO、Ag/CoFe2O4-FO、Ir/CoFe2O4-FO和Pt/CoFe2O4-FO催化剂置于马弗炉中,5℃/min升温至800℃空气中焙烧24h,得到的催化剂命名为Ru/CoFe2O4-DO、Rh/CoFe2O4-DO、Pd/CoFe2O4-DO、Ag/CoFe2O4-DO、Ir/CoFe2O4-DO和Pt/CoFe2O4-DO。
催化剂测试例1-2
利用丙烯燃烧反应对催化剂的催化活性和高温抗烧结性能进行评价,以实施例4和12制备的Pt/MgGa2O4-FR和Pt/MgGa2O4-DR催化剂为例。称取~50mg的Pt/MgGa2O4-FR和Pt/MgGa2O4-DR催化剂粉末置于内径为~5mm的石英反应管中部,两端封有石英棉。将套有石英管的外径约为1mm的k型热电偶插入催化剂粉末中进行控温和测温。反应原料气为:0.1vol.%C3H6+20vol.%O2(N2),反应空速为12,000mL/(gcat·h)。反应产物使用FGA 10烟气分析仪进行测定。
催化剂测试例3-4
利用丙烯燃烧反应对催化剂在含水汽原料中的催化活性和高温抗烧结性能进行评价,以实施例4和12制备的Pt/MgGa2O4-FR和Pt/MgGa2O4-DR催化剂为例。称取~50mg的Pt/MgGa2O4-FR和Pt/MgGa2O4-DR催化剂粉末置于内径为~5mm的石英反应管中部,两端封有石英棉。将套有石英管的外径约为1mm的k型热电偶插入催化剂粉末中进行控温和测温。反应原料气为:0.1vol.%C3H6+20vol.%O2+H2O(N2),反应过程中水汽的引入通过使用原料气带入饱和水蒸汽的方式进行,反应空速为12,000mL/(gcat·h)。反应产物使用FGA 10烟气分析仪进行测定。
Claims (7)
1.一种抗烧结高分散贵金属催化剂,其特征在于:由载体和贵金属活性组分构成,载体为具有尖晶石晶体结构的纳米镓酸盐和/或纳米铁酸盐,贵金属活性组分为Ru、Rh、Pd、Ag、Ir和Pt中的一种或两种以上,贵金属的质量分数为0.01%-20%。
2.根据权利要求1所述的抗烧结高分散贵金属催化剂,其特征在于:贵金属经高温处理后仍保持高分散状态,尺寸范围保持在单原子至10nm之间。
3.一种权利要求1或2所述抗烧结高分散贵金属催化剂的制备方法,其特征在于:将一定量的镓酸盐和/或铁酸盐尖晶石载体浸渍于贵金属前驱体溶液中,室温下吸附0.5-30小时后,于60-120℃干燥6-12小时,然后在500-900℃焙烧2-24小时,最后在300-900℃含氢气氛中还原0.5-10小时,得到所述催化剂。
4.根据权利要求3所述的抗烧结高分散贵金属催化剂的制备方法,其特征在于:尖晶石载体是镓酸盐或铁酸盐中的一种或两种以上任意比混合物;镓酸盐尖晶石载体优选为镓酸镁、镓酸镍、镓酸锌和镓酸铜中的一种或两种以上;铁酸盐尖晶石载体优选为铁酸镁、铁酸镍、铁酸锌和铁酸铜中的一种或两种以上;所述贵金属的前驱体为Ru、Rh、Pd、Ag、Ir和Pt的氯化物、硝酸盐或有机络合物中的一种或两种以上。
5.根据权利要求3或4所述的抗烧结高分散贵金属催化剂的制备方法,其特征在于:优选条件为:室温下吸附3-5小时后,80-110℃干燥8-10小时,600-800℃焙烧3-24小时,最后在400-600℃含1vol%-50vol%氢气中还原2-5小时。
6.根据权利要求3或5所述的抗烧结高分散贵金属催化剂的制备方法,其特征在于:含氢气氛中除氢之外的其它气体为氮气、氩气和氦气中的一种或两种以上。
7.一种权利要求1或2所述抗烧结高分散贵金属催化剂在催化重整、烷烃转化或汽车尾气的吸收消除处理中的应用。
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