CN111744547A - 一种共晶催化剂及其固态离子交换法制备与应用 - Google Patents
一种共晶催化剂及其固态离子交换法制备与应用 Download PDFInfo
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- CN111744547A CN111744547A CN202010611200.6A CN202010611200A CN111744547A CN 111744547 A CN111744547 A CN 111744547A CN 202010611200 A CN202010611200 A CN 202010611200A CN 111744547 A CN111744547 A CN 111744547A
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- sapo
- ion exchange
- molecular sieve
- eutectic
- catalyst
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- 230000005496 eutectics Effects 0.000 title claims abstract description 42
- 238000005342 ion exchange Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 39
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- 238000003756 stirring Methods 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- 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 39
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- 239000012691 Cu precursor Substances 0.000 claims abstract description 17
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- 230000008569 process Effects 0.000 claims abstract description 14
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 claims abstract description 5
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims description 2
- IJCCOEGCVILSMZ-UHFFFAOYSA-L copper;dichlorate Chemical compound [Cu+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IJCCOEGCVILSMZ-UHFFFAOYSA-L 0.000 claims description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
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- QYJPSWYYEKYVEJ-FDGPNNRMSA-L copper;(z)-4-oxopent-2-en-2-olate Chemical compound [Cu+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QYJPSWYYEKYVEJ-FDGPNNRMSA-L 0.000 claims 1
- 229940076286 cupric acetate Drugs 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 229960004643 cupric oxide Drugs 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 10
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- 230000036571 hydration Effects 0.000 abstract description 8
- 238000006703 hydration reaction Methods 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 5
- -1 molecular sieve hydrates Chemical class 0.000 abstract description 4
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- 239000000843 powder Substances 0.000 description 10
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
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- 230000000694 effects Effects 0.000 description 8
- 239000002149 hierarchical pore Substances 0.000 description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 7
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- 150000002500 ions Chemical class 0.000 description 4
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- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种共晶催化剂及其固态离子交换法制备与应用,属于氮氧化物控制技术领域。制备方法为将SAPO‑18与SAPO‑34两相共生的分子筛在铵盐水溶液中进行交换,得到铵型的SAPO‑18与SAPO‑34两相共生的分子筛;将铜前驱物与铵型的SAPO‑18与SAPO‑34两相共生的分子筛在水中搅拌30s‑120s,得到悬浮液;将该悬浮液进行真空旋蒸后进行研磨,然后在空气气氛下焙烧,焙烧过程中发生固态离子交换,得到Cu‑SAPO‑18与Cu‑SAPO‑34两相共生的共晶催化剂。本发明制备得到的催化剂提高了原有Cu‑SAPO‑18催化活性与Cu‑SAPO‑34低温水化性能和抗SO2中毒性能;且Cu的负载量能精确控制;解决小孔分子筛在液相离子交换时因水合Cu2+直径过大需多次交换的技术问题。
Description
技术领域
本发明涉及氮氧化物控制技术领域,更具体的来说,涉及一种共晶催化剂及其固态离子交换法制备与应用。
背景技术
NOx(主要包括NO和NO2)作为一种典型的大气污染物,可形成酸雨、光化学烟雾、雾霾。其中柴油车尾气NOx控制是目前大气污染控制领域的重要研究内容。NH3-SCR是目前最有应用前景的柴油车尾气净化技术之一。传统铜基中、大孔分子筛高温水热稳定较差,而小孔分子筛负载催化材料具有优良的催化活性和水热稳定性,因此近年来备受国内外研究者的关注,成为最具应用前景的NH3-SCR催化材料。纯相的SAPO-18分子筛具有较弱的表面酸性,并且需要使用价格较高的专用模板剂N,N-二异丙基乙胺(DIPEA),且极易伴生SAPO-5杂晶(J.Catal.2014,319:36-43),而SAPO-34因在低温下暴露于水蒸气会破坏SAPO-34骨架,其中不可逆的硅醇缩合和Si-O-Al键的断裂水解是SAPO-34骨架塌陷的关键步骤(J.Catal.2015,322:84-90)。而SAPO-18/34共晶分子筛兼具2种晶相结构的优点,用于催化反应时往往表现出比单一分子筛更优的性能,并且在NH3-SCR领域没有过报道。此外,目前常见的Cu基分子筛催化剂制备方法为液相离子交换法,这种方法因工艺中含有洗涤、过滤、干燥等多个步骤,产生大量工业废水,不符合绿色化学的发展方向,而小孔CHA、AEI分子筛(0.38nm)在液相离子交换时因水合Cu2+直径(0.79nm)过大需多次交换才能得到理想的Cu负载量。这都极大限制了工业化应用的步伐。最后分级孔因减少传质阻力能提高分子筛抗硫中毒性能(Chem.Eng.J.2020,379:122376、J.Hazardous Mater.2020,385:121593、ChemCatChem.2019,11:4744-4754)。
SAPO-34/SAPO-18共晶分子筛在有氧化合物制备低碳烯烃的应用由来已久(Ind.Eng.Chem.Res.2018,57:10398-10402、ChemSusChem.2018,11:812-3820),专利CN106564912B、CN103418431A、CN102992339A、CN103878018B、CN105174286A等公开了一种SAPO-34/SAPO-18共生复合分子筛的制备方法并应有在有氧化合物制低碳烯烃,侧重点都是利用SAPO-18酸性位点与酸强度较SAPO-34少,形成共晶分子筛有利于抑制结焦的形成,增加催化剂寿命,这与NH3-SCR的调控思想有所不同。
另外,CN108654680A公开了Cu-SSZ-13催化剂浸渍-低温固态离子交换法及其NH3-SCR应用。但此方法侧重于SSZ-13为载体,没有体现在在其他分子筛上应用的普遍性与差异性。而专利CN106163659A虽然公布了在低温通过固态离子交换生产金属交换沸石的普适性方法,但是交换氛围需要有毒气体NH3,其离子交换机理与固态离子交换也不同,且NOx转化率较低,不利于工业化。
发明内容
本发明解决了现有技术中纯相分子筛制备催化剂活性低、水化性能和抗SO2中毒性能差,液相离子交换工艺中涉及洗涤、过滤、干燥等多个步骤,产生大量工业废水,Cu的负载量不能精确控制的技术问题,以及小孔CHA、AEI分子筛(0.38nm)在液相离子交换时因水合Cu2+直径(0.79nm)过大需多次交换的技术问题,提供了一种共晶催化剂及其固态离子交换法制备与应用。本发明制备得到的共晶催化剂活性高,抗水化性能和抗SO2中毒性能好,铜的负载量能精确控制,且与铜的离子交换更加彻底。
根据本发明的第一方面,提供了一种共晶催化剂的固态离子交换制备方法,包括以下步骤:
(1)将SAPO-18与SAPO-34两相共生的分子筛在铵盐水溶液中进行交换,得到铵型的SAPO-18与SAPO-34两相共生的分子筛;
(2)将铜前驱物与步骤(1)得到的铵型的SAPO-18与SAPO-34两相共生的分子筛在水中搅拌30s-120s,得到悬浮液;将该悬浮液进行真空旋蒸,然后进行研磨,再在空气气氛下焙烧,焙烧过程中发生固态离子交换,得到Cu-SAPO-18与Cu-SAPO-34两相共生的共晶催化剂。
优选地,所述铜前驱物为硝酸铜、乙酸铜、氯化铜、氟化铜、氯酸铜、高氯酸铜、乙酰丙酮铜,氧化铜、草酸铜或氧化亚铜。
优选地,所述铜前驱物中铜元素与铵型的SAPO-18与SAPO-34两相共生的分子筛的质量之比为(1-10):100。
优选地,步骤(2)中所述焙烧的温度为400℃-750℃,焙烧的时间为5h-12h;所述真空旋转蒸的时间为10min-20min。
优选地,所述的SAPO-18与SAPO-34两相共生的分子筛的制备方法包括以下步骤:
S1:将磷酸溶解于水中,加入拟薄水铝石和硅溶胶,然后再加入模板剂、造孔剂和晶种,搅拌均匀,得到混合物;
S2:将步骤S1中得到的混合物在180℃-200℃条件下进行水热反应,反应时间为96h-192h,产物经过离心、干燥、焙烧和研磨后,即得到SAPO-18与SAPO-34两相共生的分子筛。
优选地,所述混合物中SiO2、Al2O3、P2O5、模板剂和水的物质的量之比为(0.2~0.8):1.0:0.9:2:45。
优选地,步骤S2中所述焙烧的温度为400℃~750℃。
优选地,所述造孔剂为P123、F127和CTAB中的至少一种。
按照本发明的另一方面,提供了任一所述方法制备得到的Cu-SAPO-18与Cu-SAPO-34两相共生的共晶催化剂。
按照本发明的另一方面,提供了所述的共晶催化剂用于氨法选择性催化还原氮氧化物催化剂的应用。
总体而言,通过本发明所构思的以上技术方案与现有技术相比,主要具备以下的技术优点:
(1)本发明中的SAPO-18/34共晶分子筛结合了SAPO-18的高稳定性与SAPO-34的高酸密度,克服了SAPO-34低温水化环境结构易坍塌的缺点,同时提高了纯相Cu-SAPO-18的催化活性与纯相Cu-SAPO-34的抗低温水化性能。
(2)本发明中Cu基分子筛催化剂制备方法为固相离子交换法,相比于液相离子交换时因水合Cu2+直径(0.79nm)过大需多次交换的技术问题,固相离子交换法能一次精确控制铜的负载量,同时减少了工业废水的排放。
(3)本发明所制备的SAPO-18/34共晶分子筛催化剂在催化活性、抗低温水化性能、抗SO2中毒性能上均优于纯相Cu-SAPO-18与纯相Cu-SAPO-34。
(4)本发明所用固态离子交换法制备的SAPO-18/34共晶分子筛催化剂在催化活性上优于同等条件下传统水溶液浸渍离子交换法所制备的SAPO-18/34共晶分子筛催化剂。将铜前驱物与铵型的SAPO-18与SAPO-34两相共生的分子筛在水中快速搅拌30s-120s,得到悬浮液,将该悬浮液进行真空旋蒸10-20min即可,真空旋蒸目的一是避免Cu离子在液相环境交换,二是将水去除后创造了固态离子交换的环境,这样Cu离子交换与焙烧同时进行,Cu离子在高温驱动下能占据能量最有利、最稳定的锚定位点,而液相离子交换需要较长交换时间(至少24h)后再焙烧,并且在溶液中水合Cu2+半径过大,无法保证Cu离子最优的占据能量最有利、最稳定的锚定位点,因此其活性不如同等条件下的固态离子交换法。
(5)本发明优选地,制备得到的SAPO-18/34共晶分子筛具有微孔(<2nm)和介孔(2~50nm)的分级孔结构,利用介孔结构的高流通扩散性及微孔结构的高催化活性,结合两种孔结构优势互补得到的分级孔分子筛加快传质速率,避免硫酸盐物种的沉积,在抗SO2性能上优于单一的微孔分子筛。
附图说明
图1是本发明的实施例1催化剂与对比例1、2的XRD图。
图2是本发明的实施例1催化剂与对比例1、2、3的NOx转化率图。
图3是本发明的实施例1-4催化剂NOx转化率图。
图4是本发明的实施例1催化剂与对比例2均为80℃老化16h后的NOx转化率图。
图5是在350℃时SO2对本发明的实施例1和对比例4催化剂的NH3-SCR反应活性影响图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明中一种共晶催化剂的固态离子交换制备方法,包括以下步骤:
(1)将磷酸溶解于去离子水中,加入拟薄水铝石、硅溶胶于室温下搅拌均匀;
(2)随后加入模板剂、造孔剂和晶种,搅拌得到均一的混合物A;
(3)将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、干燥、焙烧、研磨得到分级孔H-SAPO-18/34,再经过NH4Cl在水溶液中交换得到分级孔NH4-SAPO-18/34;
(4)将含Cu前驱物与分级孔NH4-SAPO-18/34在一定量去离子水中搅拌1min得到悬浮液B,立马将悬浮液B转移到旋转蒸发仪中真空旋蒸15min得到C,C研磨均匀后在空气气氛下焙烧,焙烧过程中发生固态离子交换得到分级孔Cu-SAPO-18/34共晶催化剂。
所述混合物A中SiO2、Al2O3、P2O5、模板剂以及水的物质的量之比为(0.2~0.8):1.0:0.9:2:45。
实施例1
本实施例采用的Cu前驱体为三水合硝酸铜(Cu(NO3)2 3H2O),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:2TEA:45H2O,F127为造孔剂所制得的NH4-SAPO-18/34为载体,焙烧条件为空气氛围下600℃焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入6.07g三乙胺(TEA)、0.5g F127和0.1gSAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃水干燥12h、空气氛围下600℃焙烧5h得到H-SAPO-18/34,称取10g H-SAPO-18/34与10.6gNH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18/34;
称取0.076g Cu(NO3)2 3H2O与1g NH4-SAPO-18/34加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸15min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下600℃焙烧5h得到Cu-SAPO-18/34催化剂,命名为分级孔Cu-SAPO-18/34共晶催化剂-1。
实施例2
本实施例采用的Cu前驱体为氧化铜(CuO),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:2TEA:45H2O,F127为造孔剂所制得的NH4-SAPO-18/34为载体,焙烧条件为空气氛围下750℃焙烧8h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入6.07g三乙胺(TEA)、0.5g F127和0.1gSAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃干燥12h、空气氛围下750℃焙烧8h得到H-SAPO-18/34,称取10g H-SAPO-18/34与10.6g NH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18/34;
称取0.025g CuO与1g NH4-SAPO-18/34加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸20min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下750℃焙烧8h得到Cu-SAPO-18/34催化剂,命名为分级孔Cu-SAPO-18/34共晶催化剂-2。
实施例3
本实施例采用的Cu前驱体为三水合硝酸铜(Cu(NO3)2 3H2O),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:0.2DIPEA:1.8TEA:45H2O,P123为造孔剂所制得的NH4-SAPO-18/34为载体,焙烧条件为空气氛围下600℃焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入0.78gN,N二异丙基乙胺(DIPEA)与5.46g三乙胺(TEA)、0.5g P123和0.1gSAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃干燥12h、空气氛围下600℃焙烧5h得到H-SAPO-18/34,称取10g H-SAPO-18/34与10.6g NH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18/34;
称取0.076g Cu(NO3)2 3H2O与1g NH4-SAPO-18/34加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸10min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下600℃焙烧5h得到Cu-SAPO-18/34催化剂,命名为分级孔Cu-SAPO-18/34共晶催化剂-3。
实施例4
本实施例采用的Cu前驱体为氧化亚铜(Cu2O),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:2TEA:45H2O,CTAB为造孔剂所制得的NH4-SAPO-18/34为载体,焙烧条件为空气氛围下750℃焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入6.07g三乙胺(TEA)、0.5g CTAB和0.1gSAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃干燥12h、空气氛围下750℃焙烧5h得到H-SAPO-18/34,称取10g H-SAPO-18/34与10.6g NH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18/34;
称取0.023g Cu2O与1g NH4-SAPO-18/34加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸15min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下750℃焙烧5h得到Cu-SAPO-18/34催化剂,命名为分级孔Cu-SAPO-18/34共晶催化剂-4。
实施例5
本实施例采用的Cu前驱体为三水合硝酸铜(Cu(NO3)2 3H2O),使用混合物A比例为0.2SiO2:1.0Al2O3:0.9P2O5:2TEA:45H2O,F127为造孔剂所制得的NH4-SAPO-18/34为载体,焙烧条件为空气氛围下600焙焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入1.2g硅溶胶搅拌1h;再加入6.07g三乙胺(TEA)、0.5g F127和0.1gSAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于190℃水热8天得到水热产物,产物经过离心分离、110水干燥12h、空气氛围下600℃焙烧5h得到H-SAPO-18/34,称取10g H-SAPO-18/34与10.6gNH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18/34;
称取0.38g Cu(NO3)2 3H2O与1g NH4-SAPO-18/34加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸20min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下600℃焙烧5h得到Cu-SAPO-18/34催化剂,命名为分级孔Cu-SAPO-18/34共晶催化剂-5。
对比例1
本对比例采用纯相NH4-SAPO-18为载体。本实施例采用的Cu前驱体为三水合硝酸铜(Cu(NO3)2 3H2O),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:2DIPEA:45H2O,F127为造孔剂所制得的NH4-SAPO-18为载体,焙烧条件为空气氛围下600℃焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入7.83g N,N二异丙基乙胺(DIPEA)、0.5gF127和0.1g SAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃干燥12h、空气氛围下600℃焙烧5h得到H-SAPO-18,称取10g H-SAPO-18与10.6gNH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18;
称取0.076g Cu(NO3)2 3H2O与1g NH4-SAPO-18加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸15min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下600℃焙烧5h得到Cu-SAPO-18催化剂。
对比例2
本对比例采用纯相NH4-SAPO-34为载体。本实施例采用的Cu前驱体为三水合硝酸铜(Cu(NO3)2 3H2O),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:3TEA:45H2O,F127为造孔剂所制得的NH4-SAPO-34为载体,焙烧条件为空气氛围下600℃焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入9.11g三乙胺(TEA)、0.5g F127和0.1gSAPO34晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃干燥12h、空气氛围下600℃焙烧5h得到H-SAPO-34,称取10g H-SAPO-34与10.6g NH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-34;
称取0.076g Cu(NO3)2 3H2O与1g NH4-SAPO-34加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸15min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下600℃焙烧5h得到Cu-SAPO-34催化剂。
对比例3
本实施例采用传统水溶液浸渍离子交换法。采用的Cu前驱体为三水合硝酸铜(Cu(NO3)2 3H2O),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:2TEA:45H2O,F127为造孔剂所制得的NH4-SAPO-18/34为载体,焙烧条件为空气氛围下600℃焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入6.07g三乙胺(TEA)、0.5g F127和0.1gSAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃干燥12h、空气氛围下600℃焙烧5h得到H-SAPO-18/34,称取10g H-SAPO-18/34与10.6g NH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18/34;
称取0.076g Cu(NO3)2 3H2O与1g NH4-SAPO-18/34加入到含有10ml去离子水的50ml烧杯中室温浸渍24h发生液相离子交换,然后于110℃烘干,研磨均匀后于马弗炉中空气氛围下600℃焙烧5h得到Cu-SAPO-18/34催化剂。
对比例4
本实施例采用不加造孔剂。采用Cu前驱体为三水合硝酸铜(Cu(NO3)23H2O),使用混合物A比例为0.6SiO2:1.0Al2O3:0.9P2O5:2TEA:45H2O所制得的NH4-SAPO-18/34为载体,焙烧条件为空气氛围下600℃焙烧5h。
具体过程如下:将6.23g磷酸加入到23.3g去离子水中搅拌5min,随后加入4.25g拟薄水铝石搅拌2h、加入3.6g硅溶胶搅拌1h;再加入6.07g三乙胺(TEA)和0.1g SAPO-18晶种搅拌3h得到均一的混合物A;将上述混合物A彻底转移到聚四氟乙烯内衬的反应釜中于180℃水热4天得到水热产物,产物经过离心分离、110℃干燥12h、空气氛围下600℃焙烧5h得到H-SAPO-18/34,称取10g H-SAPO-18/34与10.6g NH4Cl在150ml水溶液中于80℃交换6h得NH4-SAPO-18/34;
称取0.076g Cu(NO3)2 3H2O与1g NH4-SAPO-18/34加入到含有10ml去离子水的50ml烧杯中搅拌1min,随后彻底转移到旋转蒸发仪上于60℃真空旋蒸15min,所得粉末于110℃烘干,研磨均匀后于马弗炉中空气氛围下600℃焙烧5h得到Cu-SAPO-18/34催化剂。
催化剂的水热老化采用如下方法:
将整体式催化剂放入老化装置,按5℃/min升温速率升至80℃,并通入空气和10%水蒸气,在该温度维持16h。
催化剂的评价采用如下方法:
将2g催化剂加入到6ml去离子水中,充分搅拌配制成浆液,将堇青石载体浸没在上述浆液中使浆液充满每个孔道,然后将其放置在100℃烘箱干燥2h,烘干其中的水分,即为制备的整体式催化剂,将其放入固定床活性评价装置中,模拟烟气组成为1000ppm NO,1100ppm NH3,5%O2和10%H2O,反应空速为30000h-1。
由图1可知,通过调节模板剂DIPEA与TEA的用量可得到纯相Cu-SAPO-18、共晶Cu-SAPO-18/34以及纯相Cu-SAPO-34。
由图2可知,共晶Cu-SAPO-18/34的活性比纯相Cu-SAPO-18以及纯相Cu-SAPO-34都好,另外在制备工艺上固态离子交换法制备的共晶Cu-SAPO-18/34活性优于传统水溶液浸渍离子交换法制备的共晶Cu-SAPO-18/34活性。
由图3可知,无论采用Cu(NO3)2 3H2O、CuO还是Cu2O为含Cu前驱物,也无论采用P123、F127还是CTAB为造孔剂所制备的分级孔Cu-SAPO-18/34共晶催化剂都具有优异的SCR活性。突出了该法的普适性。
由图4可知,分级孔Cu-SAPO-18/34共晶催化剂因含有一定比例的Cu-SAPO-18骨架,因此可以避免Cu-SAPO-34在低温水化中的骨架坍塌问题。
由图5可知,利用介孔结构的高流通扩散性及微孔结构的高催化活性与水热稳定性,结合两种孔结构优势互补得到的分级孔分子筛加快传质速率,避免硫酸盐物种的沉积,在抗SO2性能上优于单一的微孔分子筛。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种共晶催化剂的固态离子交换制备方法,其特征在于,包括以下步骤:
(1)将SAPO-18与SAPO-34两相共生的分子筛在铵盐水溶液中进行交换,得到铵型的SAPO-18与SAPO-34两相共生的分子筛;
(2)将铜前驱物与步骤(1)得到的铵型的SAPO-18与SAPO-34两相共生的分子筛在水中搅拌30s-120s,得到悬浮液;将该悬浮液进行真空旋蒸,然后进行研磨,再在空气气氛下焙烧,焙烧过程中发生固态离子交换,得到Cu-SAPO-18与Cu-SAPO-34两相共生的共晶催化剂。
2.如权利要求1所述的共晶催化剂的固态离子交换制备方法,其特征在于,所述铜前驱物为硝酸铜、乙酸铜、氯化铜、氟化铜、氯酸铜、高氯酸铜、乙酰丙酮铜,氧化铜、草酸铜或氧化亚铜。
3.如权利要求1所述的共晶催化剂的固态离子交换制备方法,其特征在于,所述铜前驱物中铜元素与铵型的SAPO-18与SAPO-34两相共生的分子筛的质量之比为(1-10):100。
4.如权利要求1所述的共晶催化剂的固态离子交换制备方法,其特征在于,步骤(2)中所述焙烧的温度为400℃-750℃,焙烧的时间为5h-12h;所述真空旋转蒸的时间为10min-20min。
5.如权利要求1所述的共晶催化剂的固态离子交换制备方法,其特征在于,所述的SAPO-18与SAPO-34两相共生的分子筛的制备方法包括以下步骤:
S1:将磷酸溶解于水中,加入拟薄水铝石和硅溶胶,然后再加入模板剂、造孔剂和晶种,搅拌均匀,得到混合物;
S2:将步骤S1中得到的混合物在180℃-200℃条件下进行水热反应,反应时间为96h-192h,产物经过离心、干燥、焙烧和研磨后,即得到SAPO-18与SAPO-34两相共生的分子筛。
6.如权利要求5所述的共晶催化剂的固态离子交换制备方法,其特征在于,所述混合物中SiO2、Al2O3、P2O5、模板剂和水的物质的量之比为(0.2~0.8):1.0:0.9:2:45。
7.如权利要求5所述的共晶催化剂的固态离子交换制备方法,其特征在于,步骤S2中所述焙烧的温度为400℃~750℃。
8.如权利要求5所述的共晶催化剂的固态离子交换制备方法,其特征在于,所述造孔剂为P123、F127和CTAB中的至少一种。
9.如权利要求1-8任一所述方法制备得到的Cu-SAPO-18与Cu-SAPO-34两相共生的共晶催化剂。
10.如权利要求9所述的共晶催化剂用于氨法选择性催化还原氮氧化物催化剂的应用。
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