CN108579797A - 一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法 - Google Patents
一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法 Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- QMGSCCRUAVAONE-UHFFFAOYSA-N zinc zirconium Chemical compound [Zn].[Zn].[Zn].[Zr] QMGSCCRUAVAONE-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- 150000001336 alkenes Chemical class 0.000 abstract description 14
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- KDHWZXMNULXDFH-UHFFFAOYSA-N [Zn].[Zr] Chemical group [Zn].[Zr] KDHWZXMNULXDFH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019647 acidic taste Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003407 synthetizing effect Effects 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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
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- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract
本发明公开了一种ZnO‑ZrO2@ZSM‑5核壳结构催化剂的制备方法,包括:ZnO‑ZrO2粉末的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)=40‑360:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO‑ZrO2:ZSM‑5为1:8‑8:1将ZnO‑ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器170‑190℃水热反应36‑48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、500‑600℃焙烧3h制得。本发明制得的催化剂在CO2加氢经甲醇制低碳烯烃两步法工艺中能同时提高二氧化碳转化率和低碳烯烃选择性的ZnO‑ZrO2@ZSM‑5核壳结构催化剂的制备方法。
Description
技术领域
本发明属化工技术领域,具体涉及一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法。
背景技术
锌锆 (ZnO-ZrO2) 二组分催化剂是CO2催化加氢合成甲醇工艺抗烧结稳定性和抗硫能力较强、且效果较好的一类金属氧化物催化剂。ZSM-5分子筛是由SiO4和AlO4四面体单元交错排列成三维交叉孔道结构的微孔硅铝分子筛,因其具有丰富可调B酸性质、较高比表面积及独特微孔产物择形功能等特点,被广泛用于甲醇催化裂化制低碳烯烃工艺(MTO)。据此,将金属氧化物和酸性分子筛进行耦合制备双功能核壳催化剂,并应用到CO2加氢经甲醇制低碳烯烃工艺中,为CO2加氢制低碳烯烃工艺新型结构催化剂设计开发开辟了一条新的路径。而现有复合催化剂活性组分为随机分布,且结构仅提供开放式反应环境,更为重要的是,以传统纳米铜粒子为活性组分的分布结构抗烧结稳定性极差,不能有效解决CO2加氢经甲醇制低碳烯烃两步法工艺中CO2加氢合成甲醇工艺和甲醇催化转化制低碳烯烃工艺要求不同反应生成和解离转化环境条件的矛盾问题,致使现有复合催化剂催化效果仍不佳。
发明内容
本发明的目的在于提供一种在CO2加氢经甲醇制低碳烯烃两步法工艺中能同时提高二氧化碳转化率和低碳烯烃选择性的ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法。
本发明的目的是通过下述技术方案实现的。
本发明的一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0 mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h,磨细制得200-400目的ZnO-ZrO2粉末。
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)= 40-360:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为1:8-8:1将ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器170-190℃水热反应36-48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、500-600℃焙烧3h, 最终制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
本发明与现有技术相比,具有明显的有益效果,从以上技术方案可知:制备一种以介孔ZnO-ZrO2为核相,微孔ZSM-5为壳相的新型核壳结构催化剂,核相ZnO-ZrO2的构造促进锌锆形成固溶结构,进而产生更多氧空位及特殊表面L酸碱性,提高CO2转化率;核相ZrO2与壳相ZSM-5形成适宜L-B酸协同催化中心,增强甲醇较低温度下的解离吸附,提高较低温度下甲醇转化率;构造以ZSM-5为壳相的特殊反应路径增强低碳烯烃选择性,抑制副产物生成;微-介孔体系的层级结构构造减弱分子的扩散限制,缓解积碳形成,延长催化剂寿命。即以本发明制得ZnO-ZrO2@ZSM-5核壳结构催化剂应用在CO2加氢制低碳烯烃工艺,在较低温度下不仅具有较高反应活性,还具有较高低碳烯烃选择性,同时还能延长催化剂反应寿命。
下面通过具体实施例对本发明作进一步说明。
具体实施方式
实施例1
一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0 mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h制得ZnO-ZrO2粉末。
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)= 40:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为1:8将200目ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器170℃水热反应36h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、500℃焙烧3h,最终制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
使用例:制得ZnO-ZrO2@ZSM-5核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中(反应压力:3.0MPa,反应温度:325℃,重时空速:3500 h-1,氮气流速:30 mL·min-1,H2/CO2摩尔比3.0:1.0),测得CO2转化率62.35%,低碳烯烃选择性81.17%。
实施例2
一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0 mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h制得ZnO-ZrO2粉末。
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)= 80:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为8:1将300目ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器180 ℃水热反应48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、550℃焙烧3h, 最终制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
使用例:制得ZnO-ZrO2@ZSM-5核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中(反应压力:3.0MPa,反应温度:325℃,重时空速:3500 h-1,氮气流速:30 mL·min-1,H2/CO2摩尔比3.0:1.0),测得CO2转化率61.70%,低碳烯烃选择性81.32%。
实施例3
一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h制得ZnO-ZrO2粉末。
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O) = 200:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为1:3将400目ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器190℃水热反应48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120 ℃干燥12h、600℃焙烧3h,最终制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
使用例:制得ZnO-ZrO2@ZSM-5核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中(反应压力:3.0 MPa,反应温度:325℃,重时空速:3500 h-1,氮气流速:30 mL·min-1,H2/CO2摩尔比3.0:1.0),测得CO2转化率64.50%,低碳烯烃选择性81.70%。
实施例4
一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h制得ZnO-ZrO2粉末。
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)= 360:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为3:1将200目ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器180℃水热反应48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、500℃焙烧3h, 最终制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
使用例:制得ZnO-ZrO2@ZSM-5核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中(反应压力:3.0MPa,反应温度:325 ℃,重时空速:3500 h-1,氮气流速:30 mL·min-1,H2/CO2摩尔比3.0:1.0),测得CO2转化率62.38%,低碳烯烃选择性81.22%。
实施例5
一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h制得ZnO-ZrO2粉末。
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)= 360:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为1:5将300目ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器180℃水热反应48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、500℃焙烧3h, 最终制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
使用例:制得ZnO-ZrO2@ZSM-5核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中(反应压力:3.0MPa,反应温度:325℃,重时空速:3500 h-1,氮气流速:30 mL·min-1,H2/CO2摩尔比3.0:1.0),测得CO2转化率55.17%,低碳烯烃选择性73.41%。
实施例6
一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h制得ZnO-ZrO2粉末。
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)= 360:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为5:1将200目ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器180℃水热反应48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、500 ℃焙烧3h, 最终制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
使用例:制得ZnO-ZrO2@ZSM-5核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中(反应压力:3.0MPa,反应温度:325℃,重时空速:3500 h-1,氮气流速:30 mL·min-1,H2/CO2摩尔比3.0:1.0),测得CO2转化率57.22%,低碳烯烃选择性63.59%。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,任何未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (2)
1.一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,包括以下步骤:
(1)ZnO-ZrO2的制备:按原料摩尔配比NH4CO3:Zr(NO3)4·5H2O: Zn(NO3)2·6H2O=2.2:1.0:0.2,搅拌下,以3ml/min的流速将1.0 mol·L-1碳酸铵溶液加至锌锆混合溶液中形成沉淀,70℃下持续搅拌老化2h,冷却至室温,过滤,洗涤,110℃烘干4h,500℃焙烧3h,磨细制得ZnO-ZrO2粉末;
(2)ZnO-ZrO2@ZSM-5核壳结构催化剂的制备:按原料摩尔配比n(TEOS):n(NaAlO2):n(TPAOH):n(H2O)= 40-360:1:19:4015搅拌下,依次将NaAlO2、TPAOH和TEOS加入到去离子水中,持续搅拌均匀,室温下搅拌老化3h形成溶胶体系,按核壳质量比ZnO-ZrO2:ZSM-5为1:8-8:1将ZnO-ZrO2粉末投入至该体系中继续搅拌均匀,于均相反应器170-190℃水热反应36-48h,冷却至室温、离心、去离子水洗涤、无水乙醇洗涤、120℃干燥12h、500-600℃焙烧3h,制得ZnO-ZrO2@ZSM-5核壳结构催化剂。
2.如权利要求1所述的一种ZnO-ZrO2@ZSM-5核壳结构催化剂的制备方法,其中:第(1)步中ZnO-ZrO2粉末的目数为200-400目。
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