CN108404967A - 一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法 - Google Patents
一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法 Download PDFInfo
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- CN108404967A CN108404967A CN201810139272.8A CN201810139272A CN108404967A CN 108404967 A CN108404967 A CN 108404967A CN 201810139272 A CN201810139272 A CN 201810139272A CN 108404967 A CN108404967 A CN 108404967A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 25
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 3
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002808 molecular sieve Substances 0.000 abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
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- 229910003320 CeOx Inorganic materials 0.000 abstract description 4
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- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 3
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- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 abstract 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
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- 229910052742 iron Inorganic materials 0.000 abstract 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 239000002048 multi walled nanotube Substances 0.000 abstract 1
- 150000002823 nitrates Chemical class 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
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- 235000019441 ethanol Nutrition 0.000 description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000003546 flue gas Substances 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
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- 229910052681 coesite Inorganic materials 0.000 description 2
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- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 2
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
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- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 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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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
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- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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Abstract
本发明公开了一种Ag/MSU‑1@FeCeOx/CNTs核壳结构催化剂的制备方法,属于催化剂制备技术领域。制备过程如下:采用多壁碳纳米管为载体;利用九水硝酸铁或氯化铁为铁源,六水硝酸铈或氯化铈为铈源;以超声辅助乙醇浸渍法在CNTs上原位负载Fe‑CeOx金属氧化物;利用两步法在FeCeOx/CNTs表面包覆介孔制备分子筛壳层;利用硝酸银为银源负载单质Ag粒子。本发明方法制备得到的催化剂在低温区域具有较高的脱硝协同脱汞性能和良好的抗硫抗水性能,在240℃脱硝效率可达99.6%,脱汞效率可达89.2%,对于防治氮氧化物和单质汞的排放具有良好的应用价值。
Description
技术领域
本发明涉及一种催化剂制备技术领域,具体涉及一种以FeOx-CeOx复合金属氧化物的纳米碳管为核,介孔分子筛为壳的Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法。
背景技术
氮氧化物作为大气的主要污染物之一,引发了一系列环境与健康问题,对人类生活和健康的影响日益严重。因此,对污染物气体进行脱硝处理迫在眉睫。
NH3-SCR技术是目前最成熟有效的脱硝手段,开发具有高活性、抗硫性和稳定性的低温脱硝催化剂是目前研究的热点和难点。目前现有技术中的催化剂主要有贵金属催化剂、负载型锰系催化剂等等。其中,贵金属催化剂具有优异的低温活性,但其活性温度窗口窄,选择性差,更重要的是造价昂贵,极大地限制了其实际应用。负载型锰系催化剂是目前NH3-SCR的研究热点,其组成是以TiO2、Al2O3、分子筛、炭质材料等为载体,利用浸渍法、溶胶凝胶法、共沉淀法等将锰的氧化物以高分散状态负载到载体表面。
如Jin等在文章《Effect of praseodymium additive on CeO2(ZrO2)/TiO2forselective catalytic reduction of NO by NH3》中采用采用溶胶凝胶法和浸渍法分别制备了一系列添加CeO2(ZrO2)/TiO2催化剂,并研究了其脱硝性能。研究结果显示:Pr对CeO2(ZrO2)/TiO2催化剂性能的影响在溶胶凝胶法和浸渍法中是不同的。Pr的加入往往与TiO2发生相互作用,在溶胶凝胶法中形成Ti-O-Pr结构,而在浸渍法中更容易与CeO2相互作用形成Ce-O-Pr结构。溶胶凝胶法制备的催化剂的总酸量和氧化还原性能随着Pr元素的加入而降低,导致催化剂活性下降。相比之下,用浸渍法制备的Pr催化剂具有良好的还原性,更多的酸位和更高比例的Ce3+物种,这有利于提高催化活性。
张登松等在论文《新型锰基低温脱硝催化剂的制备及其性能研究》47页中设计合成了以负载MnOx-CeOx复合金属氧化物的纳米碳管为核,介孔氧化钛为壳的meso-TiO2@MnCe/CNTs核壳结构催化剂,氧化钛壳层的介孔特性为反应气体的通过提供了通道,抑制了MnOx-CeOx纳米粒子的迁移团聚,防止了活性组分的硫酸化,从而提高了催化剂的稳定性和抗中毒性。Lin等在文章《Superior activity of MnOx-CeO2/TiO2catalyst for catalyticoxidation of elemental mercury at low flue gas temperatures》中将MnCeOx负载到TiO2表面制备脱硝催化剂,发现Mn-Ce/Ti催化剂在低温(150-250℃)下模拟烟气和SCR烟气中对Hg0氧化具有很高的活性。在Mn-Ce/Ti催化剂上的HgO氧化可能遵循Langmuir-Hinshelwood机理,催化剂表面的活性物质与邻近的Hg0反应生成Hg2+,NH3消耗了并且限制了Hg0的吸附,从而抑制了Mn-Ce/Ti催化剂上Hg0的氧化。这项研究对于发展燃煤电厂汞和氮氧化物控制技术具有重要的意义。Zhang等在文章《Simultaneous removal of elementalmercury and NO from flue gas byV2O5–CeO2/TiO2catalysts》中采用超声辅助浸渍法合成了一系列掺铈V2O5/TiO2催化剂,研究了实验室同时去除Hg0和NO的过程,结果发现1%V2O5-10%CeO2/TiO2(V1Ce10Ti)催化剂在250℃下的Hg0氧化效率最高,为81.55%,同时具有理想的NO去除效率。这说明设计纳米碳-分子筛核壳结构复合材料可以制备出高活性、高抗毒和稳定性的低温脱硝协同脱汞催化剂。
上述现有技术中所报道的催化剂,在一定程度上可以实现脱硝,但是,其脱硝脱汞性能还有待进一步提高。尤其是研究一种在低温区域具有较高的脱硝协同脱汞性能和良好的抗硫抗水性能的催化剂很有必要。
发明内容
本发明的目的在于提供一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,该方法制备得到的催化剂在低温区域具有较高的脱硝协同脱汞性能和良好的抗硫抗水性能,在240℃脱硝效率可达99.6%,脱汞效率可达89.2%,对于防治氮氧化物和单质汞的排放具有良好的应用价值。
本发明所要解决的技术问题是:
选用何种载体,如何提高催化剂的催化活性?如何制备核体和壳体,以尽最大可能避免活性组分的流失。
为解决上述技术问题,本发明采用以下技术方案:
一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于,依次包括以下步骤:
a、对碳纳米管进行酸化处理的步骤,通过酸化处理,在所述碳纳米管内引入含氧官能团;
b、制备核层FeCeOx/CNTs;
向步骤a经酸化处理后的碳纳米管中加入无水乙醇溶液,进行超声分散,得到稳定悬浮液;
向所述稳定悬浮液中逐滴加入含有铁盐和铈盐的乙醇混合溶液,搅拌回流一段时间;
在80℃干燥,氮气保护下煅烧5h,即得核层FeCeOx/CNTs;
c、制备介孔MSU-1分子筛膜;
将步骤b所得核层FeCeOx/CNTs加入至胶束溶液中,向所述胶束溶液中加入硅源形成稳定的水包油型硅化胶束乳浊液,在所述硅化胶束乳浊液中加入矿化剂氟盐,使得胶束表面的硅矿化形成介孔孔壁,胶束则形成孔道,然后将MSU-1@FeCeOx/CNTs核壳结构焙烧去除表面活性剂并打开孔道,形成介孔MSU-1分子筛膜;
d、向所述介孔MSU-1分子筛膜上负载银纳米粒子;
将银活性组分负载在MSU-1分子筛膜的表面或孔道中,采用微波辅助的方式进一步将银活性组分还原为银纳米粒子,即得Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂;
在步骤b中,所述乙醇混合溶液的组成为A、B、C或D;
其中:A为Fe(N03)3-9H20和Ce(N03)3-6H20,所述A中,Fe(N03)3-9H20的质量浓度为0.1-0.125g/mL,所述Ce(N03)3-6H20的质量浓度为0.006-0.008g/mL;
B为Fe(N03)3-9H20和Cecl3,其中,Fe(N03)3-9H20的质量浓度为0.1-0.125g/mL,Cecl3的质量浓度为0.0025-0.004g/mL;
C为Fecl3和Ce(N03)3-6H20,其中,Fecl3的质量浓度为0.04-0.085g/mL,所述Ce(N03)3-6H20的质量浓度为0.006-0.008g/mL;
D为Fecl3和Cecl3,其中,Fecl3的质量浓度为0.04-0.085g/mL,Cecl3的质量浓度为0.0025-0.004g/mL;
所述银纳米粒子的粒径为10-20nm。
上述技术方案所带来的直接有益技术效果为:
通过向经过酸化处理后的碳纳米管中或其表面负载铁铈复合金属氧化物粒子,其会使得金属粒子和CNTs之间产生一种特殊的金属-载体之间的作用,对催化剂的活性有一定的促进作用。
具体体现为:
碳纳米管具有独特的中空结构,有利于活性组分氧化物的分散,铈的掺杂使得铈原子进入了氧化铁的晶格结构,且有效的细化了铁氧化物颗粒,提高了催化剂的比表面积,减小了粒径,从而增加催化活性。
作为本发明的一个优选方案,步骤a中,所述酸化步骤具体包括:将原始碳纳米管浸入硝酸溶液中,超声波分散,冷凝回流处理,最后用去离子水将碳纳米管清洗至中性,并烘干备用。
经过实验研究证明,发现首先对碳纳米管进行酸化后,可在碳纳米管内引入含氧官能团,可提高催化剂的活性。
作为本发明的另一个优选方案,所述乙醇混合溶液的组成为质量浓度为0.1-0.125g/mL的Fe(N03)3-9H20和质量浓度为0.006~0.008g/mL的Ce(N03)3-6H20。
相比B,C,D而言,A组中Fe(N03)3-9H20和Ce(N03)3-6H20在乙醇中具有更好的溶解度,且形成的Fe-Ce复合氧化物更加理想高效。
优选的,步骤b中,搅拌回流10-12h,于400℃煅烧5h。
优选的,步骤c中,所述胶束溶液是利用非离子表面活性剂得到的;所述硅源为正硅酸乙酯。
优选的,步骤c中,所述的氟盐为氟化钠,所述氟化钠的加入量为0.081g。
优选的,步骤d中,所述活性组分为质量浓度为2%的银源溶液。
本发明的另一任务在于提供上述Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂在脱硝协同脱汞中的应用。
与现有技术相比,本发明所带来的有益技术效果为:
首先,单从制备方法来看,本发明选用经过酸化处理后的碳纳米管作为载体,并在其内部或表明负载铁铈氧化物,从而增加催化活性;其次,利用MSU-1分子筛为壳层,MSU-1分子筛具有丰富的介孔结构,有利于反应的发生和Ag粒子的负载;运用保护剂月桂酸和还原剂葡萄糖能够增加银纳米粒子的分散性,将纳米银的颗粒控制在10~20nm;最后,通过本发明方法制备得到的Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂在低温区域具有较高的脱硝协同脱汞性能和良好的抗硫抗水性能,在240℃脱硝效率可达99.6%,脱汞效率可达89.2%,对于防治氮氧化物和单质汞的排放具有良好的应用价值。
附图说明
下面结合附图对本发明做进一步说明:
图1为利用本发明制备得到的催化剂进行SCR脱硝协同脱汞实验,活性评价结果图;
图2为利用本发明中没有进行酸处理的碳纳米管制备得到的催化剂进行SCR脱硝协同脱汞实验,活性评价结果图;
图3为利用本发明制备得到的催化剂进行SCR脱硝协同脱汞实验,考察SO2对活性评价的影响结果图;
图4为利用本发明制备得到的催化剂进行SCR脱硝协同脱汞实验,考察H2O对活性评价的影响结果图。
具体实施方式
本发明提出了一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,为了使本发明的优点、技术方案更加清楚、明确,下面结合具体实施例对本发明做详细说明。
本发明所需原料均可通过商业渠道购买获得。
实施例1:
第一步、对碳纳米管进行酸化处理的步骤:
将1.5g原始碳纳米管浸入200ml质量浓度为68%的硝酸溶液中,超声波30min分散,油浴120℃冷凝回流处理12h,最后用去离子水将碳纳米管清洗至中性,并80℃烘干备用;通过酸化处理,在碳纳米管内引入含氧官能团;
第二步、制备核层FeCeOx/CNTs;
将1.5g酸处理后纳米碳管加入40mL无水乙醇溶液中,超声分散2h,得到稳定悬浮液。随后逐滴加入40mL溶有8.82g的Fe(N03)3-9H20和0.57g的Ce(N03)3-6H20混合无水乙醇溶液,磁力搅拌下回流10h,搅拌转速为1000rpm。于80℃干燥后,在氮气保护下,于400℃煅烧5h,最终得到FeCeOx/CNTs纳米材料。
第三步、壳层MSU-1分子筛的制备
首先将5.758g聚氧乙烯醚非离子表面活性剂在室温下溶于12ml去离子水,得到均匀透明的胶束溶液,然后加入FeCeOx/CNTs纳米核层。以10g正硅酸乙酯(TEOS)为硅源,形成水包油型稳定的硅化胶束乳浊液。加入0.081gNaF作为矿化剂,所得溶液摩尔组成为SiO2:Brij35:NaF:H2O=1:0.10:0.04:100。使得胶束表面的硅矿化形成介孔孔壁,胶束则形成孔道,然后将反应物继续反应24h后,抽滤,洗涤并干燥,将所得固体于550℃下焙烧5h,去除表面活性剂并打开孔道,形成介孔MSU-1分子筛膜。
第四步、单质Ag粒子的负载
首先称取3.8549g硝酸银(AgNO3)加入120ml去离子水中,磁力搅拌30~35min,搅拌转速为1000rpm,制得质量浓度为2%的银源溶液,然后将MSU-1@FeCeOx/CNTs浸渍到盐溶液中2h,使得银活性组分充分地负载,通过洗涤,干燥去除多余的水分和杂质。采用微波辅助的溶液还原法还原银离子为银纳米粒子。
称取0.1835g月桂酸溶于18ml去离子水中并加入1ml氨水配成溶液,然后称取葡萄糖溶液的质量为1.15g,加入MSU-1@FeCeOx/CNTs核壳结构样品在微波的条件反应6h小时,经过离心(转速为10000rpm)、洗涤、干燥得到Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂。
实施例2:
与实施例1不同之处在于:第二步中,混合无水乙醇溶液中为Fe(N03)3-9H20和Cecl3,二者的质量分别为:8.82g的Fe(N03)3-9H20和0.24g的Cecl3。
实施例3:
与实施例1不同之处在于:第二步中,混合无水乙醇溶液中为Fecl3和Ce(N03)3-6H20,二者的质量分别为:4.96g的Fecl3和0.57g的Ce(N03)3-6H20。
实施例4:
与实施例1不同之处在于:第二步中,混合无水乙醇溶液中为Fecl3和Cecl3,二者的质量分别为:4.96g的Fecl3和0.24g的Cecl3。
实施例5:
第一步、将1.5g原始碳纳米管浸入200ml质量浓度为68%的硝酸溶液中,超声波30min分散,油浴120℃冷凝回流处理12h,最后用去离子水将碳纳米管清洗至中性,并80℃烘干备用。
第二步、核层FeCeOx/CNTs的制备
将1.5g酸处理后纳米碳管加入40mL无水乙醇溶液中,超声分散2h,得到稳定悬浮液。随后逐滴加入40mL溶有4.96g的Fecl3和0.24g的Cecl3混合无水乙醇溶液,磁力搅拌下回流12h,搅拌转速为1200rpm。于80℃干燥后,在氮气保护下,于400℃煅烧5h,最终得到FeCeOx/CNTs纳米材料。
第三步、壳层MSU-1分子筛的制备
首先将4.385g聚氧乙烯醚非离子表面活性剂在室温下溶于10ml去离子水,得到均匀透明的胶束溶液,然后加入步骤二得到的纳米材料。以8g正硅酸乙酯(TEOS)为硅源,形成水包油型稳定的硅化胶束乳浊液。在乳浊液中加入0.068gNaF作为矿化剂,所得溶液摩尔组成为SiO2:Brij35:NaF:H2O=1:0.10:0.04:100。使得胶束表面的硅矿化形成介孔孔壁,胶束则形成孔道,然后将反应物继续反应24h后,抽滤,洗涤并干燥,将所得固体于550℃下焙烧5h,去除表面活性剂并打开孔道,形成介孔MSU-1分子筛膜。
第四步、单质Ag粒子的负载
称取8.365g醋酸银(CH3COOAg)加入150ml去离子水中,磁力搅拌30~35min,搅拌转速1000rpm,制得质量浓度为2%的银源溶液,然后将MSU-1@FeCeOx/CNTs浸渍到盐溶液中2h,使得银活性组分充分地负载,通过洗涤,干燥去除多余的水分和杂质。采用微波辅助的溶液还原法还原银离子为银纳米粒子。首先称取0.1625g月桂酸溶于16ml去离子水中并加入0.8ml氨水配成溶液,然后称取葡萄糖溶液的质量为1.02g,加入MSU-1@FeCeOx/CNTs核壳结构样品在微波的条件反应6h小时,经过离心、洗涤、干燥得到得到Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂。
对比例1:
与实施例1不同之处在于:没有对碳纳米管进行酸化处理,而是直接将其用于制备核层FeCeOx/CNTs。
对上述实施例1-5以及对比例1制备得到的催化剂进行分析。分别包括脱氮脱汞、抗硫性能和抗水性能评价。具体步骤如下:脱硝脱汞活性测试实验是在自制装置中进行,该装置由模拟烟气系统、汞发生装置、固定床反应器、测汞仪和烟气分析仪组成。取1g上述实施例1-5和对比例1制备得到的Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂(40目-60目)置于石英管中,通入模拟烟道气(O2体积浓度为6%,NO体积浓度为0.1%,NH3体积浓度为0.12%,N2作平衡气),流量为1000ml/min。同时开启汞发生装置,以150mL/min的氮气为载气在40℃下将汞蒸气携带出来,与模拟烟道气混合后进入石英管反应,空速为30000h-1。升温至所需的反应温度,待其稳定后,由KANE945烟气分析仪和QM201H测汞仪监测NO浓度和汞浓度。实施例1催化剂的脱硝协同脱汞评价结果如图2,对比例1催化剂的脱硝协同脱汞评价结果如图2;测试添加SO2气氛影响时,SO2添加量为500ppm,实施例2催化剂考察SO2气氛影响,脱硝协同脱汞评价结果如图3;当测试添加H2O气氛影响时,水蒸气的添加量为5vol%,实施例5催化剂考察H2O影响,脱硝协同脱汞评价结果如图4;脱硝效率和脱汞效率的计算方法如下:
本发明制备的催化剂和过程中间产物的BET表征对比如表1所示。
表1
需要说明的是:在本说明书的教导下本领域技术人员所做出的任何等同方式,或明显变型方式均应在本发明的保护范围内。
Claims (8)
1.一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于,依次包括以下步骤:
a、对碳纳米管进行酸化处理的步骤,通过酸化处理,在所述碳纳米管内引入含氧官能团;
b、制备核层FeCeOx/CNTs;
向步骤a经酸化处理后的碳纳米管中加入无水乙醇溶液,进行超声分散,得到稳定悬浮液;
向所述稳定悬浮液中逐滴加入含有铁盐和铈盐的乙醇混合溶液,搅拌回流一段时间;
在80℃干燥,氮气保护下煅烧5h,即得核层FeCeOx/CNTs;
c、制备介孔MSU-1分子筛膜;
将步骤b所得核层FeCeOx/CNTs加入至胶束溶液中,向所述胶束溶液中加入硅源形成稳定的水包油型硅化胶束乳浊液,在所述硅化胶束乳浊液中加入矿化剂氟盐,使得胶束表面的硅矿化形成介孔孔壁,胶束则形成孔道,然后将MSU-1@FeCeOx/CNTs核壳结构焙烧去除表面活性剂并打开孔道,形成介孔MSU-1分子筛膜;
d、向所述介孔MSU-1分子筛膜上负载银纳米粒子;
将银活性组分负载在MSU-1分子筛膜的表面或孔道中,采用微波辅助的方式进一步将银活性组分还原为银纳米粒子,即得Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂;
在步骤b中,所述乙醇混合溶液的组成为A、B、C或D;
其中:A为Fe(NO3)3-9H2O和Ce(NO3)3-6H2O,所述A中,Fe(NO3)3-9H2O的质量浓度为0.1-0.125g/mL,所述Ce(NO3)3-6H2O的质量浓度为0.006-0.008g/mL,;
B为Fe(NO3)3-9H2O和Cecl3,其中,Fe(NO3)3-9H2O的质量浓度为0.1-0.125g/mL,Cecl3的质量浓度为0.0025-0.004g/mL;
C为Fecl3和Ce(NO3)3-6H2O,其中,Fecl3的质量浓度为0.04-0.085g/mL,所述Ce(NO3)3-6H2O的质量浓度为0.006-0.008g/mL;
D为Fecl3和Cecl3,其中,Fecl3的质量浓度为0.04-0.085g/mL,Cecl3的质量浓度为0.0025-0.004g/mL;
所述银纳米粒子的粒径为10-20nm。
2.根据权利要求1所述的一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于:步骤a中,所述酸化步骤具体包括:将原始碳纳米管浸入硝酸溶液中,超声波分散,冷凝回流处理,最后用去离子水将碳纳米管清洗至中性,并烘干备用。
3.根据权利要求1所述的一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于:所述乙醇混合溶液的组成为质量浓度为0.1-0.125g/mL的Fe(NO3)3-9H2O和质量浓度为0.006-0.008g/mL的Ce(NO3)3-6H2O。
4.根据权利要求1所述的一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于:步骤b中,搅拌回流10-12h,于400℃煅烧5h。
5.根据权利要求1所述的一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于:步骤c中,所述胶束溶液是利用非离子表面活性剂得到的;所述硅源为正硅酸乙酯。
6.根据权利要求1所述的一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于:步骤c中,所述的氟盐为氟化钠,所述氟化钠的加入量为0.081g。
7.根据权利要求1所述的一种Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂的制备方法,其特征在于:步骤d中,所述活性组分为质量浓度为2%的银源溶液。
8.根据权利要求1-7任一项所述的制备方法制备得到的Ag/MSU-1@FeCeOx/CNTs核壳结构催化剂在脱硝协同脱汞中的应用。
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