CN110227540A - Afi-cha混晶分子筛及以其为载体的nh3-scr催化剂以及它们的制备方法 - Google Patents
Afi-cha混晶分子筛及以其为载体的nh3-scr催化剂以及它们的制备方法 Download PDFInfo
- Publication number
- CN110227540A CN110227540A CN201910391492.4A CN201910391492A CN110227540A CN 110227540 A CN110227540 A CN 110227540A CN 201910391492 A CN201910391492 A CN 201910391492A CN 110227540 A CN110227540 A CN 110227540A
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- CN
- China
- Prior art keywords
- cha
- afi
- molecular sieve
- sapo
- catalyst
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010457 zeolite Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 80
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002808 molecular sieve Substances 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 230000032683 aging Effects 0.000 claims description 31
- 229910001868 water Inorganic materials 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 10
- 229910052878 cordierite Inorganic materials 0.000 claims description 9
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
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- 229910052782 aluminium Inorganic materials 0.000 claims description 3
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
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- 239000001301 oxygen Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 241000269350 Anura Species 0.000 description 4
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- 239000012495 reaction gas Substances 0.000 description 4
- 238000003483 aging Methods 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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Abstract
本发明提供一种AFI‑CHA混晶分子筛及以其为载体的NH3‑SCR催化剂以及它们的制备方法。所述AFI‑CHA混晶分子筛，由AFI型的SAPO‑5分子筛和CHA型的SAPO‑34分子筛组成，其晶粒为AFI和CHA的混合晶粒。该混晶分子筛采用水热合成法合成，在制备过程中可通过改变结构导向剂，升温速率以及焙烧温度等得到。本发明在此混晶分子筛的基础上负载铜制备成铜基NH3‑SCR催化剂和相应的整体式催化剂，混晶分子筛显著提高了催化剂的催化活性和水热稳定性。
Description
技术领域
本发明属于NH3-SCR技术领域，具体涉及一种NH3-SCR催化剂。
背景技术
柴油车尾气排放的氮氧化物(NOx)是城市主要大气污染物之一，会造成酸雨和雾霾以及光化学烟雾等问题，已经成为诱发癌症等疾病的重要原因，严重威胁着人类的健康。选择性催化还原技术(SCR)是由Engelhard公司首先提出，由日本Kudamatsu发电厂首先用于固定源的脱硝。它是利用还原剂将尾气中的 NOx还原为无毒的N2和H2O。还原剂的选择非常广泛，既可以是HCs，也可以是某些醇类或者醚类等含氧有机物以及氨气或者H2等。以HCs作为还原剂来还原NOx不需要额外添加还原剂和相应的设备，HCs直接来源于燃油，因此在成本上有一定的优势。然而经过多年的研究，HC-SCR的NOx转化效率以及温度窗口等问题一直无法得到满意的效果，而且还有可能发生严重的硫中毒和积碳效应，直接影响了该方案在实车上的推广。H2-SCR的低温NOx转化效果比HC-SCR 要理想，转化顶峰在150℃左右。它在低温下不会有积碳、硫酸盐或者硝酸盐等生成。但是，该技术对H2的消耗量过大(H2/NO＝2)，而且N2O选择性也比较高，加上该技术尚处于起步阶段，目前对其认识还远远不够，因此要想商业应用，其可行性和商业化的时间都还不确定。相对于以上两种方案，NH3-SCR(NH3选择性催化还原)能够有效地净化NOx，已经成为治理柴油车尾气污染的最有效的技术之一。
NH3-SCR技术的NOx转化率和温度窗口以及N2选择性都有明显的优势。该技术最先用于固定源脱硝，后因移动源法规的出台又将其移植到了移动源上。经过多年的改进和发展，NH3-SCR技术已经成为了比较成熟可靠的技术，并且已经广泛应用于柴油车尾气处理系统。作为NH3-SCR的核心部分，NH3-SCR催化剂的研究和开发也成为了研究热点。但是目前我国以V2O5/WOx-TiO2为主的 NH3-SCR催化剂存在有较差的低温活性、高温下钒氧化物的易挥发性、较低的 N2选择性以及对SO2的强氧化性的缺点，这限制了其进一步的发展。自从1991年具有大孔的ZSM-5分子筛用于NH3-SCR领域以来，分子筛就因其具有环境友好、大比表面积和孔道复杂有序等特点，有利于金属物种在其表面和孔道内的分散，也有利于气体分子在孔道内的扩散，现已逐步成为NH3-SCR催化剂的主流材料之一。而用于NH3-SCR体系的常见分子筛类型主要包括MFI(ZSM-5)、BEA (beta)和CHA(SAPO-34和SSZ-13)等。而由于过渡金属(Fe和Cu)负载的分子筛催化剂在NH3-SCR反应中具有高活性、优异的N2选择性、较宽的温度窗口、较好的高温水热稳定性以及其废弃后对环境的无毒性，受到了广泛的关注。
此外，由于柴油车中NH3-SCR催化剂位于DPF的下游，容易受到其周期性高温再生的影响，其再生时温度可以瞬间提高到600℃，甚至可能达到800℃，再加上柴油机的燃烧特点(稀燃)又决定了尾气中始终存在着10vol.％左右的水汽，因此对于NH3-SCR催化剂又提出了高温水热稳定性的要求。
在所有的分子筛基催化剂中，又尤以具有CHA结构的小孔分子筛(SSZ-13 和SAPO-34)负载的Cu基催化剂近年来受到研究学者的广泛关注。大量实验表明该类型催化剂具有较为优异的活性，并且能够在较低温度和较宽的温度窗口实现NOx的完全转化。但对于Cu/SSZ-13催化剂而言，其高温水热老化活性差于 Cu/SAPO-34，而且还因需使用昂贵的模板剂而进一步限制了其在工业生产上的应用。而Cu/SAPO-34催化剂虽然因其有着相对较为优异的水热稳定性，已成为了最有效的NH3-SCR催化剂之一，但由于柴油车工作条件要求和国家标准对柴油车尾气排放的要求，其高温水热稳定性能仍然有待进一步提升。
发明内容
本发明的目的在于针对现有技术的不足，提供一种AFI-CHA混晶分子筛及其制备方法，进一步提高Cu基分子筛NH3-SCR催化剂的催化活性和高温水热稳定性。
SAPO-34作为一种典型的CHA型小孔分子筛，骨架中含有八元环形的椭球形状的笼结构和六方体结构。SAPO系列分子筛对于合成的条件十分敏感：凝胶的组成、晶化温度和晶化时间都会对Si进入分子筛的分布产生影响，在SAPO-34 的合成过程中，因为合成条件的改变，产品中往往伴随有SAPO-5。SAPO-5分子筛是具有AFI型结构的SAPO-n系列分子筛，其中含有二个六元环和二个四元环构成的十二元环一维孔道结构，在异构化、催化裂解、羰基化和羟基化等反应中表现出了良好的催化效果。而同样是SAPO系列的SAPO-5在NH3-SCR领域鲜有相关报道。在Si取代AlPO-5骨架原子后，SAPO-5分子筛骨架带有负电荷，因此具有离子交换的能力。而且AFI分子筛结构稳定，根据SAPO-n系列分子筛的合成特性，可以变化晶化温度条件得到AFI和CHA的混合晶粒，进而提高 SAPO-34分子筛的高温水热稳定性。
本发明提供一种AFI-CHA混晶分子筛，由AFI型的SAPO-5分子筛和CHA 型的SAPO-34分子筛组成，其晶粒为AFI和CHA的混合晶粒。
新型AFI-CHA分子筛材料骨架结构拓扑学结构代码为国际沸石联合会 (IZA)提出AFI和CHA分子筛。
本发明提供一种基于上述AFI-CHA混晶分子筛的Cu/AFI-CHA负载型分子筛催化剂，其特征在于Cu负载在AFI-CHA混晶分子筛上。
本发明提供一种整体式催化剂，包括基体和Cu/AFI-CHA负载型催化剂粉末，其中Cu/AFI-CHA负载型催化剂粉负载在堇青石基体上。
本发明提供上述AFI-CHA混晶分子筛的制备方法，通过水热合成法合成合成过程中，投料摩尔比按照分子筛中，铝：磷：硅：结构导向剂(模板剂)：水的摩尔比为(0.06～0.10)：(0.06～0.10)：(0.040～0.050)：(0.12～0.35)：(0.5～6) 进行投料；
也即，合成过程中，混合溶液按照Al2O3:P2O5:SiO2:结构导向剂:H2O的摩尔比为(0.06～0.10)：(0.06～0.10)：(0.040～0.050)：(0.01～0.40)：(0.5～6)进行投料。
进一步地，所述方法包括以下步骤：
(1)将拟薄水铝石、磷酸和总用水量中的一部分水混合均匀，搅拌并常温老化制备成P/Al氧化物混合凝胶，再向混合凝胶中添加Si源、结构导向剂和剩余的水，常温静置老化得到混合溶液；
(2)将混合溶液在120～160℃保温2～20h，再加热到190～210℃保温5～30 h，自然冷却到室温后分离出固体，再在500～600℃焙烧5～8h烧除结构导向剂得到AFI～CHA混晶分子筛粉末。
进一步地，拟薄水铝石为8～15质量份，磷酸13～23质量份，Si源5～8质量份，结构导向剂1-41份。
进一步地，步骤(1)制备P/Al氧化物混合凝胶时搅拌1～24h，常温老化 1～24h。
进一步地，步骤(2)所述温度的升温速率为3～6℃·min～1。
进一步地，所述结构导向剂为三乙胺TEA。
在制备过程中可通过改变结构导向剂含量来合成一系列所需分子筛粉末：
按照分子筛中，铝：磷：硅：结构导向剂(模板剂)：水的摩尔比为(0.06～0.10)：(0.06～0.10)：(0.040～0.050)：(0.01～0.4)：(0.5～6)进行投料；可通过改变模板剂含量制备出SAPO-34，SAPO-5和AFI-CHA三种混晶分子筛粉末。制备 SAPO～34时的结构导向剂(模板剂)比例为0.35～0.40，制备SAPO～5时的结构导向剂(模板剂)比例为0.01～0.12，而制备AFI-CHA分子筛粉末时的结构导向剂(模板剂)比例为0.12～0.35。也可调节水热反应时的升温速率来合成不同类型的分子筛粉末：升温速率较快(3～6℃·min～1)时易生成混晶分子筛，而升温速率较慢(1～3℃·min～1)时易生成SAPO-34和SAPO-5分子筛粉末。
本发明提供以上述混晶分子筛作为载体制备Cu基分子筛催化剂的方法，用铜盐化合物为前驱体，将AFI-CHA混晶分子筛与铜盐溶液混合搅拌至混合物呈现粘稠状，使用铜在分子筛中均匀分散；然后将混合物静置、水浴干燥后，在马弗炉中300～600℃焙烧3～6h，得Cu/AFI～CHA负载型催化剂粉末。
进一步地，所述铜盐选自Cu(NO3)2、Cu(Ac)2、Cu(COOH)2)。
进一步地，静置时间为1～15h，水浴干燥水浴温度为50～80℃，干燥时间为 1～7h。
本发明还提供将上述Cu/AFI～CHA负载型催化剂制备成整体式催化剂的方法：将Cu/AFI～CHA负载型催化剂粉末配成浆料涂覆在堇青石基体上上，催化剂粉末在堇青石上的上载量为120～130g/L；然后将涂覆好的基体于70～150℃干燥，再在300～600℃下焙烧3～6h。
进一步地，所述堇青石基体选自美国Corning公司，400目，2.5cm3。
与现有技术相比，本发明具有以下有益效果：
通过合成新型AFI-HA结构的混晶分子筛提高了Cu-CHA催化剂的 NH3～SCR活性，并且更加稳定的结构促使其拥有比Cu分别负载于纯载体CHA 和AFI分子筛更好的水热稳定性(见实施例和对比例)。
附图说明
图1为Cu/SAPO-34，Cu/SAPO-5和Cu/AFI-CHA催化剂XRD图；
图2为Cu/SAPO-34，Cu/SAPO-5和Cu/AFI-CHA催化剂SEM图(A-对比例1，B-实施例1，C-实施例2，D-实施例3，E-对比例2)；
图3为Cu/SAPO-34和Cu/AFI-CHA高温水热老化催化剂XRD图；
图4为Cu/SAPO-34和Cu/AFI-CHA新鲜及高温水热老化催化剂SEM图(A- 对比例3，B-实施例5，C-对比例4，D-实施例6)；
图5Cu/SAPO-34，Cu/SAPO-5和Cu/AFI-CHA催化剂NH3-SCR活性图；
图6Cu/SAPO-34和Cu/AFI-CHA新鲜及高温水热老化催化剂SEM图。
具体实施方式
下面结合具体实施方式对本发明做进一步说明。下面通过具体实施方式对本发明所述方法做进一步说明。以下实施方式仅作为本发明的一个实施案例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将15g拟薄水铝石、23g磷酸和72g的水混合均匀，搅拌12h，常温老化 12h，制备成P/Al氧化物混合凝胶。加入6g上海纳尔科公司提供的44nm大小Si溶胶作为Si源，加入20g结构导向剂TEA，并加入剩余的36g蒸馏水混合均匀并搅拌24h，常温静置老化12h得到混合溶液。将混合溶液转移到水热釜中，置于烘箱中以5°·min～1的升温速率升温至160℃保持10h，再加热到200 ℃反应20h。自然冷却到室温后离心洗涤4次。最后在550℃焙烧6h烧除结构导向剂得到SAPO-34、SAPO-5混合的AFI-CHA分子筛粉末，根据XRD中 SAPO-5和SAPO-34的衍射主峰强度计算SAPO-5/SAPO-34为3.16。
实施例2
将15g拟薄水铝石、23g磷酸和72g的水混合均匀，搅拌12h，常温老化 12h，制备成P/Al氧化物混合凝胶。加入6g上海纳尔科公司提供的44nm大小Si溶胶作为Si源，加入35g结构导向剂TEA，并加入剩余的36g蒸馏水混合均匀并搅拌24h，常温静置老化12h得到混合溶液。将混合溶液转移到水热釜中，置于烘箱中以4°·min～1的升温速率升温至160℃保持10h，再加热到200 ℃反应20h。自然冷却到室温后离心洗涤4次。最后在550℃焙烧6h烧除结构导向剂得到AFI～CHA分子筛粉末。
实施例3
将15g拟薄水铝石、23g磷酸和54g的水混合均匀，搅拌12h，常温老化 12h，制备成P/Al氧化物混合凝胶。加入6g上海纳尔科公司提供的44nm大小Si溶胶作为Si源，加入20g结构导向剂TEA，并加入剩余的54g蒸馏水混合均匀并搅拌24h，常温静置老化12h得到混合溶液。将混合溶液转移到水热釜中，置于烘箱中以6℃·min～1的升温速率升温至160℃保持10h,再加热到200 ℃反应20h。自然冷却到室温后离心洗涤4次。最后在550℃焙烧6h烧除结构导向剂得到AFI～CHA分子筛粉末。
实施例4
将15g拟薄水铝石、23g磷酸和72g的水混合均匀，搅拌12h，常温老化 12h，制备成P/Al氧化物混合凝胶。加入6g上海纳尔科公司提供的44nm大小Si溶胶作为Si源，加入12g结构导向剂TEA，并加入剩余的36g蒸馏水混合均匀并搅拌24h，常温静置老化12h得到混合溶液。将混合溶液转移到水热釜中，置于烘箱中以3℃·min～1的升温速率升温至160℃保持10h，再加热到 200℃反应20h。自然冷却到室温后离心洗涤4次。最后在550℃焙烧6h烧除结构导向剂得到AFI-CHA分子筛粉末。
对比例1
将15g拟薄水铝石、17g磷酸和48g的水混合均匀，搅拌12h，常温老化 24h，制备成P/Al氧化物混合凝胶。加入8g上海纳尔科公司提供的44nm大小Si溶胶作为Si源，加入35g结构导向剂TEAOH，并加入剩余的24g蒸馏水混合均匀并搅拌12h，常温静置老化12h得到混合溶液。将混合溶液转移到水热釜中，置于烘箱中以3℃·min～1的升温速率升温至160℃保持20h,再加热到200℃反应30h。自然冷却到室温后离心洗涤5次。最后在600℃焙烧5h烧除结构导向剂得到SAPO-34分子筛粉末。
对比例2
将8g拟薄水铝石、13g磷酸和12g的水混合均匀，搅拌12h，常温老化 12h，制备成P/Al氧化物混合凝胶。加入6g上海纳尔科公司提供的44nm大小 Si溶胶作为Si源，加入10g结构导向剂TEA，并加入剩余的8g蒸馏水混合均匀并搅拌1h，常温静置老化24h得到混合溶液。将混合溶液转移到水热釜中，置于烘箱中以1℃·min～1的升温速率升温至140℃保持10h,再加热到200℃反应20h。自然冷却到室温后离心洗涤2次。最后在500℃焙烧8h烧除结构导向剂得到SAPO-5分子筛粉末。
按照以下方法将实施例1-4和对比例1-2制备的分子筛制备成负载型催化剂，进一步制作成整体式催化剂：
用铜盐化合物(如：Cu(NO3)2、Cu(Ac)2和Cu(COOH)2)为前驱体制备Cu负载型AFI/CHA混晶分子筛催化剂，将铜盐化合物溶于去离子水中配成一定浓度的金属盐溶液，分别称取10g制备好的SAPO-34，SAPO-5和AFI-CHA混晶分子筛倒入铜盐溶液中搅拌30min，连续搅拌至混合物呈现粘稠状以保证铜物种在分子筛中均匀分散。将此混合物静置10h后转移至80℃水浴上干燥6h，然后在马弗炉中500℃焙烧4h，得到Cu/CHA、Cu/AFI和Cu/AFI-CHA负载型催化剂粉末。
将Cu/SAPO-34，Cu/SAPO-5和Cu/AFI-CHA分子筛基催化剂分别通过以下涂覆技术涂覆在堇青石载体上(美国Corning公司，400目，2.5cm3)制作成整体式催化剂，具体方法如下：
a)将所得Cu/SAPO-34，Cu/SAPO-5和Cu/AFI-CHA分子筛基催化剂粉末分别与醋酸锆、醋酸混合均匀制成涂覆浆液，并控制浆料固含量为45％，浆料中醋酸锆含量为3％，醋酸含量为3％；
b)将涂覆在堇青石蜂窝陶瓷基体上，控制催化剂的上载量180g/L；
c)将涂覆好的基体由室温逐步升温至100℃进行干燥，然后在500℃焙烧4，得到整体式Cu/SAPO-34、Cu/SAPO-5和Cu/AFI-CHA分子筛基催化剂。
上述在负载铜和制备成整体式催化剂是，铜负载量和整体式催化剂上催化剂的上载相同。
采用XRD分析实施例1-4和对比例1-2制备的分子筛的结构，结果如图1 所示。可以发现合成了CHA结构的SAPO-34和AFI结构的SAPO-5，以及不同 AFI-CHA比例的混晶分子筛。
采用SEM表征单晶和混晶SAPO-n的形貌特征，结果如图2所示。从图中可以看到SAPO-34样品的晶粒呈现出立方块状，与文献报道的SAPO-34典型的形貌特征相一致。而图中显示AFI-CHA混晶除了有立方块状的晶粒，还出现了六棱柱状的晶粒，这是SAPO-5的典型形貌特征。
催化剂性能测试一：
在实验室自组装的多路固定连续流动的微型反应器中进行NH3-SCR转化效率测试，模拟的柴油车尾气组成和实验条件见表1。测试之前，先将整体式催化剂在反应气(模拟柴油车尾气)中550℃进行预处理。然后采用降温测试的方法，在每个温度点平衡后进行活性测试。未转化的NO、NO2和N2O采用傅立叶红外气体分析仪(Thermol Fisher Scientific)进行测试。
表1：模拟尾气条件
Cu/CHA、Cu/AFI和Cu/AFI-CHA分子筛催化剂NH3-SCR活性结果如图5 所示。从图5中可以发现，具有AFI结构的对比例2的催化剂表现出较差的 NH3-SCR活性，最高转化率仅在450℃达到65％；实施例2和实施例3的活性与具有CHA结构的对比例1相差不大，而实施例1Cu/AFI-CHA新鲜活性明显高于对比例1，在300-150℃的温度区间内，其最大NOx转化率均相差约13％。
实施例5
为考察AFI-CHA混晶结构对整体式Cu/AFI-CHA催化剂水热稳定性的影响。取10g本发明制备的具有AFI-CHA结构的混晶分子筛按照上述相同方法(等体积浸渍法)制备Cu/AFI-CHA分子筛催化剂。
实施例6
为考察AFI-CHA混晶结构对整体式Cu/AFI-CHA催化剂水热稳定性的影响。将实施例5制备的Cu/AFI-CHA整体式催化剂，在含10vol.％H2O的流动空气中， 800℃水热老化12h后进行活性测试，反应气组成与测试方法与催化剂性能测试一中相同。
对比例3
为考察CHA结构的SAPO-34结构对整体式Cu/CHA催化剂水热稳定性的影响。取10g本发明制备的具有CHA结构的SAPO-34分子筛按照上述相同的等体积浸渍法制备Cu/CHA分子筛催化剂作为参比催化剂3。然后根据相应的涂覆方法，将得到的Cu/CHA催化剂粉末涂覆到堇青石蜂窝陶瓷基体上，最终得到得 Cu/CHA整体式柴油车用NH3-SCR催化剂。
对比例4
将根据对比例3制备的Cu/CHA整体式催化剂，在含10vol.％H2O的流动空气中，800℃水热老化不同时间(24～72h)后进行活性测试，反应气组成与测试方法与表1与催化剂性能测试一中相同。
从图3XRD中可以看到实施例3样品与文献中报道的典型SAPO-34结构衍射峰相符。而实施例5的AFI-CHA混晶分子筛中除了出现SAPO-34结构的XRD 衍射峰，也出现了SAPO-5的特征衍射峰。经过高温水热老化后，两个样品的 SAPO-34结构衍射峰强都减弱了，但是对比例4单晶样品的SAPO-34衍射峰强减弱的比实施例6混晶样品更加明显。此外，混晶样品中的SAPO-5特征衍射峰在高温水热老化后强度增加了。从XRD的分析结果可知，AFI-CHA混晶样品在高温水热后保持更好的结晶度。
从图4中可以发现两个新鲜样品中的SAPO-34晶粒粒径大小相似，皆为 2-5μm。高温水热老化后，Cu/SAPO-34样品中晶粒的形貌遭到了很明显的破坏，大部分立方块状结构遭受破坏，出现无定型结构。反观老化后的Cu/AFI-CHA样品，结构保持的比SAPO-34完整。结果说明混晶Cu/AFI-CHA在高温水热后保持更好的结构完整性，稳定的结构有利于其拥有更优的高温水热稳定性。
图6为对比例3和实施例5分子筛新鲜和高温水热老化催化剂NH3-SCR活性结果。从图中可以看到在200～450℃的温度区间内，两个新鲜催化剂的NOx转化率很接近，最高转化率约为90％。在低温段(150～200℃)，实施例5的活性比对比例3更好，这是可能是由于混晶AFI-CHA中介孔的比例更大，有利于低温段反应气体的扩散。在高温段(450～550℃)，对比例3催化剂的活性更好。经过高温水热老化后，实施例6的活性保持的比对比例4样品好，实施例6老化催化剂的最高NOx转化率几乎没有下降，而对比例4老化催化剂的最高NOx转化率下降了8％，说明本发明方法制备份催化剂低温活性和水热稳定性更好。
此外，从催化剂N2O的生成结果可以看到四种催化剂水热老化前后催化剂的N2O副产物生成量都低于3ppm，说明催化剂在老化前后的N2选择性都很高。
Claims (10)
1.一种AFI-CHA混晶分子筛，其特征在于，由AFI型的SAPO-5分子筛和CHA型的SAPO-34分子筛组成，其晶粒为AFI和CHA的混合晶粒。
2.一种基于AFI-CHA混晶分子筛的Cu/AFI-CHA负载型分子筛催化剂，其特征在于，Cu负载在AFI-CHA混晶分子筛上，所述AFI-CHA混晶分子筛由AFI型的SAPO-5分子筛和CHA型的SAPO-34分子筛组成，其晶粒为AFI和CHA的混合晶粒。
3.一种整体式催化剂，包括基体和Cu/AFI-CHA负载型催化剂粉末，其中Cu/AFI-CHA负载型催化剂粉负载在堇青石基体上，所述Cu/AFI-CHA负载型催化剂的载体为AFI-CHA混晶分子筛，所述AFI-CHA混晶分子筛由AFI型的SAPO-5分子筛和CHA型的SAPO-34分子筛组成，其晶粒为AFI和CHA的混合晶粒。
4.权利要求1所述AFI-CHA混晶分子筛的制备方法，其特征在于，通过水热合成法合成，合成过程中，投料摩尔比按照分子筛中铝：磷：硅：结构导向剂(模板剂)：水的摩尔比为(0.06～0.10)：(0.06～0.10)：(0.040～0.050)：(0.12～0.35)：(0.5～6)进行投料。
5.根据权利要求4所述方法，其特征在于，包括以下步骤：
(1)将拟薄水铝石、磷酸和总用水量中的一部分水混合均匀，搅拌并常温老化制备成P/Al氧化物混合凝胶，再向混合凝胶中添加Si源、结构导向剂和剩余的水，常温静置老化得到混合溶液；
(2)将混合溶液在120～160℃保温2～20h，再加热到190～210℃保温5～30h，自然冷却到室温后分离出固体，再在500～600℃焙烧5～8h烧除结构导向剂得到AFI～CHA混晶分子筛粉末；
步骤(1)和步骤(2)中通过改变结构导向剂的投料比例、混合溶液的保温和焙烧温度以及所述温度的升温速率，得到不同AFI/CHA混晶比例的分子筛。
6.根据权利要求5所述方法，其特征在于，拟薄水铝石为8～15质量份，磷酸13～23质量份，Si源5～8质量份，结构导向剂1-41质量份。
7.根据权利要求5或6所述方法，其特征在于，步骤(2)所述温度的升温速率为3～6℃·min～1。
8.根据权利要求5或6所述方法，其特征在于，所述结构导向剂为三乙胺或四乙基氢氧化铵。
9.权利要求1所述混晶分子筛作为载体制备Cu基分子筛催化剂的方法，其特征在于，用铜盐化合物为前驱体，将AFI-CHA混晶分子筛与铜盐溶液混合搅拌至混合物呈现粘稠状，使用铜在分子筛中均匀分散；然后将混合物静置、水浴干燥后，在马弗炉中300～600℃焙烧3～6h，得Cu/AFI-CHA负载型催化剂粉末。
10.Cu/AFI-CHA负载型催化剂制备成整体式催化剂的制备方法，其特征在于，将权利要求2所述Cu/AFI～CHA负载型催化剂粉末配成浆料涂覆在堇青石基体上上，催化剂粉末在堇青石上的上载量为120～130g/L；然后将涂覆好的基体于70～150℃干燥，再在300～600℃下焙烧3～6h。
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