CN111068679A - 用于乙烯低温催化燃烧的自支撑金属或金属氧化物核-壳结构催化剂及其制备方法 - Google Patents
用于乙烯低温催化燃烧的自支撑金属或金属氧化物核-壳结构催化剂及其制备方法 Download PDFInfo
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- CN111068679A CN111068679A CN202010039913.XA CN202010039913A CN111068679A CN 111068679 A CN111068679 A CN 111068679A CN 202010039913 A CN202010039913 A CN 202010039913A CN 111068679 A CN111068679 A CN 111068679A
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- metal
- catalyst
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- core
- cobalt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000005977 Ethylene Substances 0.000 title claims abstract description 44
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 29
- 239000011258 core-shell material Substances 0.000 title claims abstract description 27
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 30
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
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- 238000000034 method Methods 0.000 claims description 18
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
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- 239000006260 foam Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims description 12
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- 239000002131 composite material Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
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- 239000003513 alkali Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 7
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010949 copper Substances 0.000 claims description 4
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- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
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- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
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- 239000010951 brass Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
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- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
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- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
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Images
Classifications
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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
- B01J23/70—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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
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Abstract
本发明公开了一种用于乙烯低温催化燃烧的自支撑金属或金属氧化物核‑壳结构催化剂及其制备方法和应用,所述催化剂是由锚附在规整结构金属载体(ZT)上的Al2O3和/或Co3O4纳米片负载金属或金属氧化物核‑壳结构而形成的催化剂,具有如下通式:xM‑yMO/zNanosheet@ZT,其中zNanosheet@ZT表示规整结构金属载体为核、Al2O3和/或Co3O4纳米片为壳所组成的核‑壳结构,xM‑yMO为分散在Al2O3和/或Co3O4纳米片上的金属或金属氧化物,x为0~2%,y为0~10%,z为0.5~20%,余量为ZT。本发明的催化剂对于微量乙烯催化燃烧具有低温活性高、稳定性好等特点。
Description
技术领域
本发明涉及一种用于乙烯低温催化燃烧的自支撑金属或氧化物核-壳结构催化剂及其制备方法和应用,具体说,是涉及一种由锚附在规整结构载体上的Al2O3和/或Co3O4纳米片负载金属或金属氧化物核-壳结构而形成的催化剂及其制备方法,和其在微量乙烯低温催化燃烧反应中的应用,属于环境催化技术领域。
背景技术
作为一种气体植物内源激素,乙烯在植物开花、果熟、衰老和脱落过程中扮演重要角色;但是,如果周围大气受到乙烯污染,致使其含量超过一定水平,就会干扰植物正常生长发育的调节机制,逐渐引起植物生长异常,最终造成农林业的损失。同时,乙烯也是一种大气污染物,虽然会对人体产生较强的麻醉作用,但它并不像其它污染物那样直接又强烈地危害人体健康,所以没有引起人们的普遍重视。即便如此,乙烯对植物、果蔬和人类健康的影响作用依然不容忽视,加之它还会造成光化学污染,因此对乙烯污染进行有效治理势在必行(Appl. Catal. A, 2009, 370, 59-65)。
在实际生产过程中,通常有三种情况须进行乙烯脱除。第一种,气调冷库作为目前最先进的陆用和船舶用果蔬保鲜储藏技术,脱除果蔬贮藏环境中的痕量乙烯以达到延长果蔬贮藏期和货架期的目的,一直是气调贮藏技术亟待解决却又难以突破的核心问题之一(J. Nanosci. Nanotechnol., 2006, 6, 3599-3603);第二种,乙烯氧化生产环氧乙烷工业过程中会副产大量纯度较高的CO2,如果对其中ppm级的乙烯进行净化脱除,不仅能够回收得到工业级和食品级CO2,变废为宝,而且可以减轻大气污染和温室效应,实现经济效益与社会效应的双赢(Appl. Catal. A, 2012, 427-428, 73-78);第三种,伴随着石油化工及社会经济的蓬勃发展,工业废气和汽车尾气成为大气乙烯的主要来源,治理这些局部性的乙烯污染是保障人类健康和良好生态环境的必然条件。
针对这些现实问题,近年来涌现出多种乙烯脱除技术,主要包括吸附、吸收、微生物降解(Appl. Environ. Microbiol., 2000, 66, 3878-3882)、臭氧氧化和催化燃烧法(Chem. Eng. J., 2007, 132, 345-353)。通过净化处理乙烯的浓度一般需降到1 ppm以下,对于保鲜冷库中乙烯敏感型的果蔬,则须把贮藏环境中的乙烯浓度脱至0.02 ppm,而这种脱除标准是吸附法和吸收法难以企及的。虽然微生物降解法可实现低温操作(0-10 oC),却存在脱除效率低下及稳定性差的缺陷。臭氧氧化法是利用臭氧的强氧化性使乙烯完全分解,但臭氧制备困难又极易分解,其自身较大的毒性则会造成二次污染,所以至今没有被广泛应用。自Pfefferl于1974年首次提出催化燃烧的概念以来,因其良好的燃烧效率与能量利用率而被广泛用于能量利用和挥发性有机污染物(VOCs)治理过程中。因此,针对这种大流量、低浓度且无回收价值的乙烯废气,采用催化燃烧法无疑是最经济有效的处理方式。
微量乙烯的催化脱除过程须在较低的反应温度下进行,例如冷库的环境温度一般低于10 oC,而且低浓度乙烯燃烧所释放的热量不足以维持过高的反应温度。因此,开发具有室温催化活性的燃烧催化剂是实现微量乙烯催化脱除的必由之路。长期以来,科学家们在研制高效稳定的燃烧催化剂方面倾注了极大的工作热情,但针对微量乙烯催化燃烧脱除的专用催化剂却鲜有问津,迄今为止仅有有限的几种催化剂被报道,包括Cu-Mn霍加拉特催化剂、CuCrO非贵金属氧化物、以及Pt/Rh/CeO2/γ-Al2O3负载型贵金属催化剂,然而乙烯完全转化的温度基本保持在200-300 oC,始终无法克服低温活性不足和催化效率低等难题。郝郑平等先是发现nano-Au/Co3O4(Au负载量为4 wt.%)催化剂在室温条件下具有很高的痕量乙烯(ppb级)脱除活性,但在微量乙烯(50 ppm)脱除过程中则快速积碳失活,反应仅1 h,乙烯转化率就迅速从100%降到50%(Environ. Sci. Technol., 2008, 42, 8947-8951);后来,该课题组又首次报道了一种0 oC下能够达到76%乙烯转化率的Au/meso-Co3O4催化剂,通过介孔Co3O4活性反应面上纳米金活性相的构建和乙烯分子C-C键的低温活化,成功实现了微量乙烯的室温催化脱除,展现出诱人的应用前景(J. Am. Chem. Soc., 2010, 132,2608-2613)。尽管如此,报道中并未提及Au/meso-Co3O4的稳定性能,因此该催化剂离实际工业化尚有一定距离。另外,含乙烯废气通常具有流通量大、组成复杂和反应条件变动剧烈等特点,因而对燃烧催化剂的要求也是多方面的:不仅要有高的室温催化活性和稳定性,还要具备渗透性好、压降低的特点。面对诸多诉求,结构化催化剂和反应器(StructuredCatalyst and Reactors, SCRs)成为必然选择,即在寻求和研制优良催化活性组分和助剂的同时,还必须加强能与催化剂达到良好“传质/传热”协同效果的SCRs过程强化研究。
当前,SCRs技术已经成为多相催化和催化反应工程领域的重要成就之一,被广泛证实能显著优化固体催化剂床层的流体力学行为和提高床层内部的传质/传热性能,成为催化与化工交叉领域的热点和国际前沿(A. Cybulski, J. A. Moulijn, Structuredcatalysts and reactors, New York, CRC Press, 2006)。催化反应虽是一个表/界面过程,但在反应器宏尺度下往往会受到催化床层内的流动与传递过程的制约,致使催化剂性能受到负面影响。SCRs技术的优势在于能对催化剂的大小和形状等细节进行精准设计,将传统反应器中彼此耦合的因素(如反应动力学、流体力学和传质/传热)解耦合,因而能在一定程度上对各因素进行单独优化或调控,进而提升反应过程的效率、选择性和稳定性。SCRs技术将催化剂和反应器看做一个整体,从宏观尺度上来设计催化剂,这种特性使之成为石油化工和精细化工等行业革新和过程强化的强有力工具。因此,如何将金属或金属氧化物纳米颗粒简单高效地、结构和尺寸可控地负载到规整载体表面,实现宏-微-纳跨尺度一步设计合成是至关重要的。
发明内容
针对现有技术存在的上述问题,本发明提供一种宏-微-纳跨尺度一步设计合成的自支撑金属或金属氧化物核-壳结构催化剂及其制备方法和应用,实现金属或金属氧化物纳米颗粒在规整结构载体上的成功锚附,使之在微量乙烯催化燃烧反应中具备低温催化活性高、稳定性好、传质/传热速率快和渗透性能好(大空隙率和低压力降)等诸多优势,以实现反应器内流动和传递与表界面乙烯催化燃烧反应的协同耦合。
为解决上述技术问题,本发明采用如下技术方案:
一种自支撑金属或金属氧化物核-壳结构催化剂,是一种由锚附在规整结构金属载体(ZT)上的Al2O3和/或Co3O4纳米片(Nanosheet)负载金属(M)或金属氧化物(MO)核-壳结构而形成的催化剂,具有如下通式:xM-yMO/zNanosheet@ZT,其中zNanosheet@ZT表示规整结构金属载体为核、Al2O3或Co3O4纳米片为壳所组成的核-壳结构,xM-yMO为分散在Al2O3或Co3O4纳米片上的金属或金属氧化物,ZT表示金属相骨架,x表示M在整装式催化剂中所占的质量百分数,y表示MO在整装式催化剂中所占的质量百分数,z表示纳米片在整装式催化剂中所占的质量百分数;且x为0~2%,y为0~10%,z为0.5~20%,余量为规整结构金属ZT所占的质量百分数。
作为优选方案,所述的M选自金、银、铂、钌、钯、铑、镍、铜等过渡金属中的至少一种;所述的MO选自碱土金属、镧系稀土金属、硼、铝、镓、钛、锆、锌、钴、锰氧化物中的至少一种;所述的Nanosheet通过水热生长得到的氢氧化物或类水滑石纳米片同晶型转变而来,为铝或钴的氧化物中的至少一种。
作为优选方案,所述ZT的材质为镍、铜、铝、不锈钢、白铜、黄铜等金属中的任意一种。
作为一种优选方案,所述ZT是直径为4~150微米的纤维或由该纤维烧结而成的具有三维多孔结构的规整式金属纤维。
作为另一种优选方案,所述ZT为20~150 PPI的泡沫金属。
作为进一步优选方案,所述的自支撑金属或金属氧化物核-壳结构催化剂的孔隙率为60~98%。
一种制备本发明所述的自支撑金属或金属氧化物核-壳结构催化剂的方法,包括如下步骤:
a) 首先用酸或碱对金属相骨架ZT进行处理,再将ZT投入铝源和/或钴源以及碱源水溶液的不锈钢水热釜中在一定温度下进行水热处理,降至室温后对样品进行清洗和干燥,实现拟薄水铝石AlOOH纳米片或氢氧化钴Co(OH)2纳米片或钴铝类水滑石CoAl-HT纳米片在ZT表面的锚附生长,制得自支撑Nanosheet@ZT核壳结构复合载体;
b) 用含至少一种金属M离子的有机溶液浸渍所制得的Nanosheet@ZT载体,并经过烘干、焙烧和还原,AlOOH纳米片或Co(OH)2纳米片或CoAl-HT纳米片同晶型转变成Al2O3和/或Co3O4纳米片,最终制得所述的自支撑金属或金属氧化物核-壳结构催化剂,记为:xM-yMO/zNanosheet@ZT催化剂。
作为进一步优选方案,步骤a)中的酸或碱处理是将金属相骨架ZT放入酸或碱溶液中,在室温~60 oC下进行处理。所述的酸优选为无机酸,例如:盐酸;所述的碱优选为无机碱,例如:氢氧化钠。
步骤a)中所述铝源为偏铝酸钠、硝酸铝、硫酸铝或氯化铝;所述钴源为硝酸钴、醋酸钴、硫酸钴或氯化钴;所述碱源为尿素、氢氧化钠、碳酸钠或碳酸氢钠。
步骤a)中的水热处理温度为80~300℃,水热处理时间为0.5~100小时。
作为进一步优选方案,步骤b)中所述的有机溶液为醇溶液、酮溶液、醚溶液或甲苯溶液等。
步骤b)中的焙烧温度为200~600℃,焙烧气氛为空气或高纯保护气氛(例如:纯度等于或高于99.999%的氮、氢、氩或氦气气氛),焙烧时间为1~6小时。
本发明所述的自支撑金属或氧化物核-壳结构催化剂可应用于微量乙烯低温催化燃烧反应。
与现有技术相比,本发明提供的自支撑金属或氧化物核-壳结构催化剂在性能上具有纳米颗粒尺寸和结构可控、结构稳定抗烧结、金属-载体相互作用强、传质传热性能好、渗透率高等优点,在使用中具有易于成型、易于装填、易于存放等优点,且其制备方法简单、原料易得、利于大规模生产;能同时满足环境催化领域中的大空速、低压降的要求,是微量乙烯低温催化燃烧反应的优良催化剂,具有显著性工业应用价值。
附图说明
图1是实施例1制备的自支撑1Pd-1Au/5Co3O4@Al-foam催化剂的扫描电镜图;
图2是实施例1制备的自支撑1Pd-1Au/5Co3O4@Al-foam催化剂的X-射线衍射图;
图3是实施例1制备的1Pd-1Au/5Co3O4@Al-foam催化剂在C2H4催化氧化反应中的催化性能;
图4是实施例2制备的0.4Au-1.5CeO2/5Al2O3@SS-fiber催化剂在C2H4催化氧化反应中的催化性能;
图5是实施例3制备的0.8Au/2Co3O4-5Al2O3@Ni-fiber催化剂在C2H4催化氧化反应中的催化性能。
具体实施方式
下面结合实施例和附图对本发明的技术方案作进一步阐明:
实施例1
1、称取泡沫铝5克,用1wt%的氢氧化钠溶液处理5分钟,经蒸馏水洗净后放入不锈钢水热釜中,加入含1.14克硝酸钴 [Co(NO3)2.6H2O]和2.016克尿素(NH2CONH2)的混合溶液80毫升,在100 oC下水热处理12小时。降至室温后,用蒸馏水洗涤多次并干燥,得到含有丰富表面羟基的锚附片状氢氧化钴的自支撑Co(OH)2@Al-foam复合载体;
2、称取步骤1制得的自支撑Co(OH)2@Al-foam复合载体5克,用含0.05克Pd的Pd(OAc)2和0.05克HAuCl4的丙酮溶液,在室温下进行等体积浸渍4小时,烘干后,在氮气中于300℃焙烧2小时,即得锚附Co3O4的泡沫铝载体上负载Au-Pd合金的结构化催化剂。
经电感耦合等离子原子发射光谱测定得知:本实施例所制备的催化剂中,Pd的质量含量为0.95%,Au的质量含量为0.90%,Co3O4的质量含量为4.91%;因此,本实施例所制备的催化剂简记为:1Pd-1Au/5Co3O4@Al-foam。
经宏观测量得知:本实施制备的自支撑1Pd-1Au/5Co3O4@Al-foam催化剂的孔隙率为80%。
图1是本实施例制备的自支撑1Pd-1Au/5Co3O4@Al-foam催化剂的扫描电镜图。
图2是本实施例制备的自支撑1Pd-1Au/5Co3O4@Al-foam催化剂的X-射线衍射图结果,由图2可见,除金属相载体Al-foam的衍射峰以外,检测到Co3O4的特征衍射峰,由于Pd和Au的负载量较低,未检测到两者的衍射峰。
在本实施例步骤1中的水热温度可以是140℃或180℃,水热处理时间可以是2~24小时,其余均与本实施例相同。
在本实施例步骤2中,所使用的钯前躯体还可以是乙酰丙酮钯、醋酸钯、氯化钯或氯钯酸铵。
实施例2
1、称取不锈钢纤维片(纤维直径20微米,简写为SS-fiber)5克,用浓度为1wt%的稀硝酸水溶液处理10分钟,经蒸馏水洗净后放入不锈钢水热釜中,加入含0.714克偏铝酸钠(NaAlO2)和2.016克尿素(NH2CONH2)的混合溶液70毫升,在120 oC下水热处理12小时。降至室温后,用蒸馏水洗涤多次并干燥,得到含有丰富表面羟基的锚附片状拟薄水铝石的自支撑AlOOH@SS-fiber复合载体;
2、称取步骤1制得的自支撑AlOOH@SS-fiber复合载体5克,用含0.025克Au的HAuCl4和0.208克硝酸铈 [Ce(NO3)3·6H2O]的丙酮溶液,在室温下进行等体积浸渍4小时,烘干后,在氮气中于550 oC焙烧2小时,即得锚附γ-Al2O3的不锈钢纤维载体上负载Au-CeO2催化剂。
经电感耦合等离子原子发射光谱测定得知:本实施例所制备的催化剂中,Au的质量含量为0.43%,CeO2的质量含量为1.5%;Al2O3的质量含量为5.1%;因此,本实施例所制备的催化剂简记为:0.4Au-1.5CeO2/5Al2O3@SS-fiber。
经宏观测量得知:本实施制备的自支撑0.4Au-1.5CeO2/5Al2O3@SS-fiber催化剂的孔隙率为75%。
在本实施例步骤1中的水热温度可以是140℃或180℃,水热处理时间可以是2~24小时,其余均与本实施例相同。
实施例3
1、称取镍纤维片(纤维直径8微米,简写为Ni-fiber)5克,用浓度为1wt%的稀硝酸水溶液处理10分钟,经蒸馏水洗净后放入不锈钢水热釜中,加入含0.714克偏铝酸钠(NaAlO2)、0.57克硝酸钴 [Co(NO3)2.6H2O]和2.016克尿素(NH2CONH2)的混合溶液70毫升,在140 oC下水热处理6小时。降至室温后,用蒸馏水洗涤多次并干燥,得到含有丰富表面羟基的锚附片状钴铝类水滑石的自支撑CoAl-HT@Ni-fiber复合载体;
2、称取步骤1制得的自支撑CoAl-HT@Ni-fiber复合载体5克,用含0.05克Au的HAuCl4丙酮溶液,在室温下进行等体积浸渍2小时,烘干后,在氮气中于550 oC焙烧2小时,即得锚附钴铝复合氧化物的镍纤维载体上负载Au催化剂。
经电感耦合等离子原子发射光谱测定得知:本实施例所制备的催化剂中,Au的质量含量为0.83%,Co3O4的质量含量为2.1%;Al2O3的质量含量为5.1%;因此,本实施例所制备的催化剂简记为:0.8Au/2Co3O4-5Al2O3@Ni-fiber。
经宏观测量得知:本实施制备的自支撑0.8Au/2Co3O4-5Al2O3@Ni-fiber催化剂的孔隙率为70%。
在本实施例步骤1中的水热温度可以是120℃或180℃,水热处理时间可以是2~24小时,其余均与本实施例相同。
应用例1
在固定床反应器上考察实施例1制备的1Pd-1Au/5Co3O4@Al-foam催化剂在微量C2H4催化燃烧反应中的催化性能:反应物为C2H4和空气的混合气;固定床反应器是一个内径为8毫米的石英管,原料气进入催化剂床层进行反应,反应产物进入色谱在线分析,利用氢火焰检测器(FID)进行分析。FID检测器之前安装镍转化炉,将反应生成物二氧化碳转化成甲烷,再通过FID检测器分析定量。
反应条件:催化剂用量0.3克,气时空速为20000 mL∙h-1∙g-1,气体组成是空气中含有100 ppm的C2H4。在上述条件下考察温度对催化性能的影响,实验结果见图3所示。
应用例2
在固定床反应器上考察实施例2制备的0.4Au-1.5CeO2/5Al2O3@SS-fiber催化剂在微量C2H4催化燃烧反应中的催化性能:反应物为C2H4和空气的混合气;固定床反应器是一个内径为8毫米的石英管,原料气进入催化剂床层进行反应,反应产物进入色谱在线分析,利用氢火焰检测器(FID)进行分析。FID检测器之前安装镍转化炉,将反应生成物二氧化碳转化成甲烷,再通过FID检测器分析定量。
反应条件:催化剂用量0.3克,气时空速为20000 mL∙h-1∙g-1,气体组成是空气中含有100 ppm的C2H4。在上述条件下考察温度对催化性能的影响,实验结果见图4所示。
应用例3
在固定床反应器上考察实施例3制备的0.8Au/2Co3O4-5Al2O3@Ni-fiber催化剂在微量C2H4催化燃烧反应中的催化性能:反应物为C2H4和空气的混合气;固定床反应器是一个内径为8毫米的石英管,原料气进入催化剂床层进行反应,反应产物进入色谱在线分析,利用氢火焰检测器(FID)进行分析。FID检测器之前安装镍转化炉,将反应生成物二氧化碳转化成甲烷,再通过FID检测器分析定量。
反应条件:催化剂用量0.3克,气时空速为20000 mL∙h-1∙g-1,气体组成是空气中含有100 ppm的C2H4。在上述条件下考察温度对催化性能的影响,实验结果见图5所示。
最后有必要在此说明的是:以上实施例只用于对本发明的技术方案作进一步详细地说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。
Claims (10)
1.一种自支撑金属或金属氧化物核-壳结构催化剂,其特征在于:所述催化剂是一种由锚附在规整结构金属载体(ZT)上的Al2O3和/或Co3O4纳米片(Nanosheet)负载金属(M)或金属氧化物(MO)核-壳结构而形成的催化剂,具有如下通式:xM-yMO/zNanosheet@ZT,其中:zNanosheet@ZT表示规整结构金属载体为核、Al2O3和/或Co3O4纳米片为壳所组成的核-壳结构,ZT表示金属相规整结构骨架基体,x表示M在整装式催化剂中所占的质量百分数,y表示MO在整装式催化剂中所占的质量百分数,z表示Nanosheet在整装式催化剂中所占的质量百分数;且x为0~2%,y为0~10%,z为0.5~20%,余量为规整结构金属ZT所占的质量百分数。
2.如权利要求1所述的自支撑金属或金属氧化物核-壳结构催化剂,其特征在于:所述的金属选自金、银、铂、钌、钯、铑、镍、铜中的至少一种;所述的金属氧化物选自碱土金属、镧系稀土金属、硼、铝、镓、钛、锆、锌、钴、锰氧化物中的至少一种;所述的Nanosheet通过水热生长得到的氢氧化物或类水滑石纳米片同晶型转变而来;所述ZT的材质为镍、铜、铝、不锈钢、白铜、黄铜中的任意一种。
3.如权利要求1所述的自支撑金属或金属氧化物核-壳结构催化剂,其特征在于:所述ZT是直径为4~150微米的纤维或由该纤维烧结而成的具有三维多孔结构的规整式金属纤维;或者,所述ZT为20~150 PPI的泡沫金属。
4.如权利要求1-3中任意一项所述的自支撑金属或金属氧化物核-壳结构催化剂,其特征在于:所述催化剂的孔隙率为60~98%。
5.一种制备权利要求1所述的自支撑金属或金属氧化物核-壳结构催化剂的方法,其特征在于,包括如下步骤:
a) 首先用酸或碱对金属相骨架ZT进行处理,再将ZT投入铝源和/或钴源以及碱源水溶液的不锈钢水热釜中在一定温度下进行水热处理,降至室温后对样品进行清洗和干燥,实现拟薄水铝石AlOOH纳米片或氢氧化钴Co(OH)2纳米片或钴铝类水滑石CoAl-HT纳米片在ZT表面的锚附生长,制得自支撑Nanosheet@ZT核壳结构复合载体;
b) 用含至少一种金属M离子的有机溶液浸渍所制得的Nanosheet@ZT载体,并经过烘干、焙烧和还原,AlOOH纳米片或Co(OH)2纳米片或CoAl-HT纳米片同晶型转变成Al2O3和/或Co3O4纳米片,最终制得所述的自支撑金属或金属氧化物核-壳结构催化剂,记为:xM-yMO/zNanosheet@ZT催化剂。
6.如权利要求5所述的方法,其特征在于,所述铝源为偏铝酸钠、硝酸铝、硫酸铝或氯化铝;所述钴源为硝酸钴、醋酸钴、硫酸钴或氯化钴;所述碱源为尿素、氢氧化钠、碳酸钠或碳酸氢钠。
7.如权利要求5所述的方法,其特征在于,所述浸渍金属M离子的有机溶液为丙酮、乙醇、甲苯中的至少一种。
8.如权利要求5所述的方法,其特征在于,所述步骤a)中水热处理温度为80~300℃,水热处理时间为0.5~100小时。
9.如权利要求5所述的方法,其特征在于,所述步骤b)中焙烧温度为200~600℃,焙烧时间为1~6小时。
10.权利要求1-3中任意一项所述的自支撑金属或氧化物核-壳结构催化剂在微量乙烯低温催化燃烧反应中的应用。
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