CN113429438B - 一种直接制备h型cha结构分子筛的合成方法及应用 - Google Patents
一种直接制备h型cha结构分子筛的合成方法及应用 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 91
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 40
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052772 Samarium Inorganic materials 0.000 abstract description 13
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000007873 sieving Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 31
- 238000012512 characterization method Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000003921 particle size analysis Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 150000001216 Samarium Chemical class 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- ZCTOUQUSXXVVFE-UHFFFAOYSA-M [OH-].C(=C)C1=CC=C(C=C1)[N+](C)(C)C Chemical compound [OH-].C(=C)C1=CC=C(C=C1)[N+](C)(C)C ZCTOUQUSXXVVFE-UHFFFAOYSA-M 0.000 description 1
- VBVMCFHGWOLXDH-UHFFFAOYSA-M [OH-].C1=C(C=CC=2CCCCC1=2)[N+](C)(C)C Chemical compound [OH-].C1=C(C=CC=2CCCCC1=2)[N+](C)(C)C VBVMCFHGWOLXDH-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明提供了一种直接制备H型CHA结构分子筛的合成方法及应用,以化学式为(C4H8NO)3PO和/或(C4H8NO)2PO(C4H10N)的化合物为结构导向剂,通过水热合成发直接制备H型CHA结构分子筛。本发明所述的结构导向剂具有分子拓扑结构,有助于快速高效搭建CHA分子筛骨架结构,制备的产物形貌规整,相对结晶度高,合成方法能够直接合成H型CHA结构分子筛,相对结晶度>95%。无需铵交换环节,直接干燥焙烧即可获得分子筛产品,简便易行,适宜规模化生产,钐基CHA分子筛催化剂凭借Sm元素的本征活性以及H型CHA结构分子筛理化特性,在NH3‑SCR技术中表现出优异的氨气吸附能力、低温活性,活性温度窗口、N2选择性和结构稳定性,在上述催化剂的作用下氮氧化物与还原剂发生反应转化成无害的氮气和水。
Description
技术领域
本发明属于分子筛合成技术领域,尤其是涉及一种直接制备H型CHA结构分子筛的合成方法及应用。
背景技术
据公安部统计,截至2021年3月,全国机动车保有量达3.78亿辆,其中汽车2.87亿辆。飞速发展的汽车工业促进了我国交通运输行业的长足发展,给人们的生产生活带来了极大的便利。然而,随之而来的汽车尾气污染问题日益严峻。据《移动源污染中国移动源环境管理年报(2020)》报道,2019年我国全年机动车四项污染物排放总量达1603.8万吨,其中,氮氧化物(NOX)为635.6万吨。柴油车是NOX排放的主要贡献者,占汽车排放总量的 88.9%以上。我国柴油车排放标准主要沿用欧洲排放法规,选择性催化还原(SCR)技术是催化净化柴油车NOX的主要途径。SCR系统由催化剂、尿素喷射系统、尿素储存罐和控制系统组成。其中,催化剂作为关键部件,直接决定了SCR系统的效率。随着我国机动车排放标准不断升级,NOX排放限值进一步降低,同时明确限制N2O、NH3量。国六标准阶段,因钒钨钛催化剂存在低温性能差、温度窗口窄、副产物N2O高且高热环境钒挥发等缺点,分子筛SCR催化剂被视为未来的发展趋势。该类催化剂以分子筛为载体负载活性金属构成,具备低毒、高活性、宽窗口、高选择性等优点。该类催化剂由分子筛作为载体负载活性金属构成,常见的分子筛载体有LTA、CHA、BEA、AFX结构等,常见的活性组分有Cu、Fe、Ce、Mn等。以CHA结构分子筛为代表的分子筛基SCR催化剂因其独特的微孔孔道结构和适宜的表面酸性,其催化剂在NH3-SCR反应中表现出良好的低温活性,较宽的活性温度窗口、高的氮气选择性、低毒的催化材料。其中,欧六/国六阶段应用最广泛的典型商用SCR催化剂为Cu/CHA分子筛催化剂。
目前,CHA结构分子筛存在合成周期长,难度大,成本高、废液难处理等问题,导致国六SCR后处理装置成本居高不下,限制其大规模市场应用。公开号为CN110407231A的专利公开采用新型模板剂5,6,7,8-四氢萘-2-基-三甲基氢氧化铵和/或对乙烯基苯基-N,N,N-三甲基氢氧化铵合成CHA结构分子筛,省掉了现有技术中的碱金属离子交换工序,合成步骤简单,生产成本低,无COD废水排放,对环境无污染。公开号为CN110523432A的专利公开了高酸密度、低铜的Cu-CHA分子筛催化剂,具有较宽的催化活性温度窗口,兼顾低温和高温活性,经过水热老化处理后仍然表现出良好的催化活性。同样,专利CN109867294A、CN104128200A、CN110665538B、CN108083292A、CN103818927B中均公开铜基CHA分子筛催化剂及其制备方法。然而,该体系催化剂的知识产权已被国外企业垄断,极大地限制了国内规模化应用。
发明内容
有鉴于此,本发明旨在提出一种直接制备H型CHA结构分子筛的合成方法及应用,以实现无需经过铵交换工艺可直接作为载体制备以钐元素为活性组分的CHA基分子筛SCR催化剂。
为达到上述目的,本发明的技术方案是这样实现的:
一种用于合成CHA结构分子筛的结构导向剂,所述结构导向剂包括化合物A及化合物B中的至少一种,
化合物A的化学式为(C4H8NO)3PO,
化合物B的化学式为(C4H8NO)2PO(C4H10N),
一种直接制备H型CHA结构分子筛的合成方法,应用了如上所述的结构导向剂,包括以下步骤:
步骤一、将结构导向剂与去离子水常温混合搅拌至澄清,加入铝溶胶,剧烈搅拌0.5-2h,形成溶胶-凝胶,例如可以是0.5h、0.7h、0.8h、1.0h、1.2h、1.5h、1.6h、1.8h、2h;
步骤二、在溶胶-凝胶中加入硅源及晶种,在水热合成釜内进行水热合成反应得到反应液;
步骤三、将反应液过滤,清洗滤饼,加热,得到H型CHA结构分子筛。
上述合成方法利用原料自身酸碱平衡设计中性合成体系(pH),避免引入苛性碱,经水热合成可直接制备CHA结构分子筛。
进一步地,步骤二的具体操作如下:
在溶胶-凝胶中加入硅源与晶种,搅拌均匀后转移至水热合成釜内,密闭环境下升温至155-180 ℃反应7-48h,得到反应液,例如可以是155℃下反应48h、160℃下反应40h、165℃下反应32h、170℃下反应24h、175℃下反应16h、180℃下反应7h。
进一步地,铝溶胶的有效成分包括Al2O3,硅源的有效成分包括SiO2,Al2O3、SiO2、结构导向剂、去离子水的摩尔比为1:0.1-50:0.1-20:10-200,例如可以是1:0.1:0.1:10、1:1:5:60、1:5:2:70、1:10:3:80、1:15:4:90、1:20:5:100、1:30:10:120、1:40:15:160、1:50:20:200;优选为1:1-20:0.1-5:60-100。
进一步地,所述铝溶胶的固含量为5%-50%,所述硅源包括硅溶胶、气相二氧化硅、白炭黑、正硅酸乙酯中的至少一种,所述晶种包括硅铝比小于25的CHA结构分子筛,目的是提供晶核,促进氢型CHA结构分子筛合成,其晶粒尺寸不超过5 μm,优选不超过500 nm;优选地,所述晶种包括具有CHA结构的SSZ-13分子筛、SAPO-34分子筛中的至少一种。
进一步地,步骤三的具体操作如下:
将反应液在板框压滤机中进行固液分离,用清水洗涤滤饼至少3次后,在120 ℃温度下干燥至水含量低于6 wt%,以2 ℃/min速率升温至350-450 ℃恒温1-2h,之后升温至500-550 ℃恒温3-6h,得到H型CHA结构分子筛。
一种钐基CHA分子筛催化剂,包括载体、活性组分及金属助剂,所述载体为CHA结构分子筛,所述活性组分的金属元素为Sm元素,所述金属助剂的金属元素包括Mn、Ce、W、Mo、Sn、Y、La、Pr、Nd、Zr、Nb、Pt、Pd、Ag中至少一种;优选地,所述活性组分元素分布于CHA结构分子筛D6R、CHA笼和/或表面;进一步优选地,金属助剂的金属元素包括Mn、Mo、Nd、Pt、Pd中至少一种。本发明中的钐基CHA分子筛催化剂为稀土、过渡金属元素改性Sm基CHA结构分子筛催化剂,主要目的是提升上述催化剂的低温活性、拓宽温度窗口、改善氮气选择性、抑制高温水热劣化。
进一步地,所述载体包括SSZ-13、SAPO-34、SAPO-44、ZK-4中至少一种,优选SSZ-13、SAPO-34;和/或含有CHA结构(菱沸石)的两种以上晶相结构的分子筛,具体包括八元环、十元环、十二元环分子筛中至少一种,优选八元环分子筛。
进一步地,按质量比Sm:CHA结构分子筛=0.5-15wt%,按摩尔比Sm:金属助剂=1:0.01-10;优选地,按质量比Sm:CHA结构分子筛=2.5-7.5wt%,按摩尔比Sm:金属助剂=1:0.5-5;进一步优选地,所述钐基CHA分子筛催化剂是通过离子交换法、浸渍法、溶胶凝胶法、原位合成法、熔盐合成法、一锅法、混合研磨法中至少一种合成的;进一步优选地,所述钐基CHA分子筛催化剂是通过离子交换法、浸渍法、原位合成法中至少一种合成的。
如上所述的钐基CHA分子筛催化剂在催化还原排放尾气中的氮氧化物中的应用。
相对于现有技术,本发明所述的直接制备H型CHA结构分子筛的合成方法及应用具有以下优势:
(1)本发明所述的结构导向剂具有分子拓扑结构,有助于快速高效搭建CHA分子筛骨架结构,制备的产物形貌规整,相对结晶度高;
(2)本发明所述的合成方法能够直接合成H型CHA结构分子筛,相对结晶度>95%。无需铵交换环节,直接干燥焙烧即可获得分子筛产品,简便易行,适宜规模化生产;
(3)本发明所述的钐基CHA分子筛催化剂凭借Sm元素的本征活性以及CHA结构分子筛理化特性,在NH3-SCR技术中表现出优异的氨气吸附能力、低温活性(T50=180 ℃),活性温度窗口(T90=220-575 ℃)、N2选择性和结构稳定性,在上述催化剂的作用下氮氧化物与还原剂发生反应转化成无害的氮气和水。
附图说明
构成本发明的一部分的附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:
图1为本发明实施例1制备的分子筛产物晶相结构示意图;
图2为本发明实施例2制备的分子筛产物晶相结构示意图;
图3为本发明实施例3制备的分子筛产物晶相结构示意图;
图4为钐基CHA分子筛催化剂的NOX转化率曲线示意图;
图5为本发明实施例1制备的分子筛产物微观形貌示意图;
图6为本发明实施例2制备的分子筛产物微观形貌示意图;
图7为本发明实施例3制备的分子筛产物微观形貌示意图;
图8为本发明实施例所述的结构导向剂OSDA1的1H核磁谱示意图;
图9为本发明实施例所述的结构导向剂OSDA1的13C核磁谱示意图;
图10为本发明实施例所述的结构导向剂OSDA2的1H核磁谱示意图;
图11为本发明实施例所述的结构导向剂OSDA2的13C核磁谱示意图;
图12为本发明实施例所述的结构导向剂的三维分子结构示意图。
具体实施方式
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明,均为常规生化试剂;所述实验方法,如无特殊说明,均为常规方法。
在本发明中,NH3-SCR性能测试采用的模拟烟气组成分:500 ppm NO,500 ppm NH3,10% O2,N2为平衡气,总流量为1000 ml/min,反应空速30000 h-1。
在本发明中,低温性能指标为T50,代表的是当NOX转化率达到50%时对应的温度;温度窗口指标T90,代表的是当NOX转化率超过90%时对应的温度范围。
除非另外指出,在本发明说明书和权利要求说明书里出现的所有数字,如温度、时间以及浆料投料质量百分比等数值均不应该被理解为绝对精确值,该数值是在本领域内的普通技术人员所理解的、公知技术所允许的误差范围内。
下面结合实施例及附图来详细说明本发明。
实施例1
取25gOSDA1溶解于190ml去离子水,常温充分搅拌,缓慢滴加固含量30%铝溶胶10.9g,加毕后剧烈搅拌1h,形成乳白色溶胶-凝胶;随后加入30%硅溶胶60g、SSZ-13分子筛晶种0.05g,搅拌均匀后转移至水热合成釜内,升温至165 ℃晶化反应24h。
反应结束后,使用板框压滤机进行固液分离,用清水反复洗涤滤饼3次,120 ℃干燥至产物水含量低于6 wt%后进行焙烧,以2 ℃/min速率升温至350 ℃恒温1h,随后升温至550 ℃恒温6h,获得白色粉末固体产物。
产物晶相结构表征结果如图1所示,XRD表征结果显示上述固体产物是具备CHA结构的SAPO-34分子筛,相对结晶度>95%;XRF表征显示产物中Na、K碱金属含量低于50ppm;产物微观形貌如图5所示,激光粒度分析结果显示粒度区间集中分布在1-5 μm;SEM表征显示产物呈现立方体块状形貌。
实施例2
本实例催化剂的制备条件、各原料加入量和制备流程同实施例1,区别在于,本实施例使用OSDA2结构导向剂替代OSDA1。
产物晶相结构表征结果如图2所示,所得固体产物经XRD表征,显示具备CHA结构的SAPO-34分子筛,相对结晶度>95%;经XRF表征,显示产物中Na、K碱金属含量低于50ppm;产物微观形貌如图6所示,经激光粒度分析,结果显示粒度区间集中分布在1-5 μm;经SEM表征,显示产物呈现立方体块状形貌。
实施例3
本实例催化剂的制备条件和制备流程同实施例1,区别在于,本实施例使用OSDA1/OSDA2=1:1的复合结构引导剂替代OSDA1。
产物晶相结构表征结果如图3所示,所得固体产物经XRD表征,显示具备CHA结构的SAPO-34、SSZ-13分子筛混晶产物,相对结晶度>95%;经XRF表征,显示产物中Na、K碱金属含量低于50ppm,硅铝比(SiO2/Al2O3)为13.4;产物微观形貌如图7所示,经激光粒度分析,结果显示粒度区间集中分布在1-5 μm;经SEM表征,显示产物呈现立方体块状形貌。
实施例4
本实例催化剂的制备条件和制备流程同实施例3,区别在于,本例使用等摩尔的正硅酸乙酯替代硅溶胶。
所得固体产物经XRD表征,显示具备CHA结构的SAPO-34、SSZ-13分子筛混晶产物,相对结晶度>95%;经XRF表征,显示产物中Na、K碱金属含量低于50ppm,硅铝比(SiO2/Al2O3)为13.4;经激光粒度分析,结果显示粒度区间集中分布在1-5 μm;经SEM表征,显示产物呈现立方体块状形貌。
对比例1
N,N,N-三甲基-1-金刚烷氢氧化铵是当前工业合成Na型CHA结构SSZ-13分子筛的主流模板剂。
本对比例采用与实施例1相同的制备条件、各原料加入量和制备流程,区别在于使用N,N,N-三甲基-1-金刚烷氢氧化铵替代OSDA1。
经XRD表征显示,所得固体产物为无定型,没有CHA结构分子筛特征衍射峰。
对比例2
Cu-TEPA(四乙烯五胺铜)是当前一步法制备铜基CHA结构SSZ-13分子筛催化剂的主流模板剂。
本对比例采用与实施例1相同的制备条件、各原料加入量和制备流程,区别在于使用等摩尔的Cu-TEPA替代OSDA1。
经XRD表征显示,所得固体产物不具备CHA结构分子筛特征衍射峰。
实施例5
本实施例采用离子交换法,分子筛载体选取实施例3制备的分子筛产物,具体如下:
配制1 mol/L 硝酸钐溶液,量取200g置于500ml烧杯中,加入10g分子筛,搅拌均匀分散;密闭情况下升温至80 ℃恒温搅拌反应6 h;恒温结束后,过滤、反复洗涤滤饼3次,获得固体粉体;120 ℃干燥6h,550 ℃恒温焙烧5h,即得到钐基CHA分子筛催化剂。
实施例6
本实施例采用混合研磨法,分子筛载体选取实施例3制备的分子筛产物,具体如下:
称取0.8g硝酸钐,溶于20g去离子水中,加入10g分子筛,搅拌均匀分散;转移至行星式球磨机中,持续研磨4 h,控制粒度分布在0.5-1 μm,蒸发干燥,获得固体粉体;120 ℃干燥6h,550 ℃恒温焙烧5h,即得到钐基CHA分子筛催化剂。
实施例7
本实施例采用浸渍法,分子筛载体选取实施例3制备的分子筛产物,具体如下:
称取0.8g硝酸钐,溶于20g去离子水中,加入10g分子筛,搅拌均匀分散;密闭情况下升温至80 ℃恒温搅拌反应6 h;恒温结束后,恒温结束后,减压搅拌蒸干,获得固体粉体;120 ℃干燥6h,550 ℃恒温焙烧5h,即得到钐基CHA分子筛催化剂。
实施例8
本实施例采用原位合成法,分子筛载体选取实施例3制备的分子筛产物,具体如下:
取15g OSDA1和10g OSDA2溶解于190ml去离子水,常温充分搅拌,缓慢滴加固含量30%铝溶胶10.9g,加毕后剧烈搅拌1h,形成乳白色溶胶-凝胶;随后加入30%硅溶胶60g、SSZ-13分子筛晶种0.05g,搅拌均匀后,加入1.6g硝酸钐、5g氨水,搅拌均匀转移至水热合成釜内,升温至165 ℃晶化反应24h。
反应结束后,使用板框压滤机进行固液分离,用清水反复洗涤滤饼3次,120 ℃干燥至产物水含量低于6 wt%后进行焙烧,以2 ℃/min速率升温至350 ℃恒温1h,随后升温至550 ℃恒温6h,获得钐基CHA分子筛催化剂。
实施例9
本实施例是在实施例5制备的催化剂基础上,引入Mn、Fe元素改性,具体如下:
取实施例5中催化剂产物20g,搅拌均匀分散于150g去离子水溶液中,加入5g硝酸锰溶液(50wt%)和2g硝酸铁溶液,密闭情况下升温至80 ℃恒温搅拌反应6 h;恒温结束后,减压搅拌蒸干,得到土黄色固体粉末。
将上述土黄色固体粉末120 ℃干燥6h,550 ℃恒温焙烧5h,即得到改性钐基CHA分子筛催化剂。
实施例10
将实施例9制备的改性钐基CHA分子筛催化剂制成40-60目粉末样,在微型固定床反应器上进行NH3-SCR催化性能评价。使用的石英反应管尺寸为15mm,评价测试升温速率5℃/min。模拟气氛组成:500 ppm NO,500 ppm NH3,10% O2,N2为平衡气,总流量为1000 ml/min,反应空速30000 h-1。测试结果如图4所示。
测试结果表明,上述催化剂的NOX起燃温度T50=180 ℃,活性温度窗口T90=220-575℃。
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、改进等,均应包含在本发明的保护范围之内。
Claims (4)
2.一种直接制备H型CHA结构分子筛的合成方法,应用了如权利要求1所述的结构导向剂,其特征在于,包括以下步骤:
步骤一、将结构导向剂与去离子水混合搅拌至澄清,加入铝溶胶,剧烈搅拌形成溶胶-凝胶,铝溶胶的有效成分包括Al2O3;
步骤二、在溶胶-凝胶中加入硅源与晶种,搅拌均匀后转移至水热合成釜内,密闭环境下升温至155-180 ℃反应7-48h,得到反应液,硅源的有效成分包括SiO2,Al2O3、SiO2、结构导向剂、去离子水的摩尔比为1:0.1-50:0.1-20:10-200;
步骤三、将反应液过滤,清洗滤饼,加热,得到H型CHA结构分子筛。
3.根据权利要求2所述的合成方法,其特征在于:所述铝溶胶的固含量为5%-50%,所述硅源包括硅溶胶、气相二氧化硅、白炭黑、正硅酸乙酯中的至少一种,所述晶种包括硅铝比小于25的CHA结构分子筛。
4.根据权利要求2所述的合成方法,其特征在于,步骤三的具体操作如下:
将反应液在板框压滤机中进行固液分离,用清水洗涤滤饼至少3次后,在120 ℃温度下干燥至水含量低于6 wt%,以2 ℃/min速率升温至350-450 ℃恒温1-2h,之后升温至500-550 ℃恒温3-6h,得到H型CHA结构分子筛。
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US7226569B2 (en) * | 2005-06-23 | 2007-06-05 | Chevron U.S.A. Inc. | Reduction of oxides of nitrogen in a gas stream using molecular sieve SSZ-56 |
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