CN109985659A - 一种co2定向转化制备芳烃的催化剂及其制备方法 - Google Patents
一种co2定向转化制备芳烃的催化剂及其制备方法 Download PDFInfo
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- CN109985659A CN109985659A CN201910321493.1A CN201910321493A CN109985659A CN 109985659 A CN109985659 A CN 109985659A CN 201910321493 A CN201910321493 A CN 201910321493A CN 109985659 A CN109985659 A CN 109985659A
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- 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 22
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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- 239000002184 metal Substances 0.000 claims description 7
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
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- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
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- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
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- 239000013065 commercial product Substances 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WNEYXFDRCSFJCU-UHFFFAOYSA-N propan-1-amine;hydrate Chemical compound [OH-].CCC[NH3+] WNEYXFDRCSFJCU-UHFFFAOYSA-N 0.000 description 1
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- 229920000428 triblock copolymer Polymers 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/78—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
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
本发明公开了一种CO2定向转化制备芳烃的催化剂,涉及催化加氢技术领域,以金属氧化物为核,以分子筛为壳的核壳结构催化剂,所述金属有机化合物的金属离子中心为Zn2+、Zr2+、Fe3+、Co2+、Ni2+、Cu2+、Cr3+、Mn2+中的一种或多种;所述分子筛为ZSM‑5、MCM‑41、SAPO、MCM‑22、USY、SBA‑15中的一种或多种。本发明提供的CO2定向转化制备芳烃催化剂具有结构、性质均一且可精确调控的特点,制备过程工艺简单,重复性高。所制备的催化剂具有CO2转化率高、芳烃选择性高、寿命长、适用范围广等优点。所制备的催化剂可直接应用于CO2定向转化制备芳烃类化合物中,具有工业化的价值。
Description
技术领域
本发明属于催化加氢技术领域,具体涉及一种CO2定向转化制备芳烃的催化剂及其制备方法。
背景技术
随着经济的快速发展,全球能源需求的日益增长,碳排放压力也日益增加。将CO2转化为化学品或燃料,一方面可以解决大气中CO2浓度增加引发的环境问题,另一方面还可以降低对化石燃料的依赖度,对我国乃至全球命运共同体的能源结构、生态环境、人民生活都具有重要意义。由于CO2化学性质稳定,同时受制于C-C键间的动力学壁垒,CO2选择性转化制备甲醇、甲烷、甲酸等C1化合物相对比较容易实现,目前已经得到了广泛、深入的研究。然而,受制于ASF产物分布的限制,CO2加氢转化产物中C5~C11含量较低。
CN201610832357公开了一种二氧化碳加氢制取芳烃的方法,该发明采用铁基二氧化碳加氢制低碳烯烃催化剂作为第一组分,以改性或不改性分子筛作为第二组分,混合后得到相应催化剂;该催化剂催化下CO2转化率为33%, C5+烃选择性可以达到65%,其中芳烃占C5+烃的63%。CN201711407175公开了一种用于二氧化碳一步加氢制备芳烃的催化剂及其制备方法和应用,该发明使用纳米金属氧化物与ZSM-5分子筛机械混合、研磨混合或球磨混合,所得催化剂催化二氧化碳加氢产物中C5+含量可以达到80%,芳烃选择性可以达到70%以上。研究表明,CO2总是首先在金属氧化物作用下被活化,然后活化生成的中间组分在分子筛作用下经历碳链增长、转移、成环等过程生成芳烃,其反应过程为连串过程。然而,上述发明涉及的催化剂均为金属氧化物与分子筛通过物理混合方式结合,混合程度在微观上无法控制的,难以实现金属氧化物、分子筛组分的连串催化、耦合作用,从而限制了其催化CO2定向转化芳烃的效率。同时,关于机械混合催化剂催化CO2芳构化的研究(Wei J, Ge Q J,Yao R W, et al. Nat Commun, 2017, 8: 1-8;Gao P, Li S G, Bu X N, et al. NatChem, 2017, 9: 1019-1024;Wang Y, Tan L, Tan M H, et al. ACS Catal, 2019, 9:895-901)表明:如果金属氧化物和分子筛混合的非常均匀,反应产物主要为CH4;而如果让二者在空间上产生一定的距离,就可以得到高收率的汽油馏分烃。然而,过大的组分空间距离又会导致中间组分过多,芳构化效率降低。然而现有的机械混合制备方式并没有定量控制组分间距离的手段和方法,这无疑对该催化剂体系工业化应用带来稳定性、可重复性的困扰。
发明内容
为了精确调控金属氧化物中心与分子筛酸中心及孔道之间的距离,调控CO2加氢芳构产物的分布,实现CO2一步高效定向转化为芳烃,本发明提出了一种CO2定向转化制备芳烃催化剂及其制备方法。本发明以金属有机骨架化合物材料封装于分子筛中得到相应的金属氧化物@分子筛催化剂,利用金属有机骨架化合物金属、配体、结构的可调性以及分子筛的催化作用,就可以从微观角度建立集成CO2加氢、芳构于一体的 “纳米反应器”,实现CO2高效活化及原位扩散芳构化:即CO2扩散进入中空分子筛,随后在内部金属氧化物活性位活化生成中间产物,中间产物在分子筛表面酸性位及孔道的作用下定向生成芳烃。通过对金属有机骨架化合物材料结构及封装过程的调控,从而精确控制金属氧化物和分子筛的相对位置,就可以达到控制产物分布、定向生成芳烃化合物的目的。
为达到上述目的,本发明是通过以下的技术方案来实现的。
一种CO2定向转化制备芳烃的催化剂,以金属氧化物为核,以分子筛为壳的核壳结构催化剂,所述金属有机化合物的金属离子中心为Zn2+、Zr2+、Fe3+、Co2+、Ni2+、Cu2+、Cr3+、Mn2+中的一种或多种;所述分子筛为ZSM-5、MCM-41、SAPO、MCM-22、USY、SBA-15中的一种或多种。
进一步地所述金属氧化物的前驱体为金属有机骨架化合物。
进一步地还提供了一种CO2定向转化制备芳烃的催化剂的制备方法,包括以下步骤:
1)将金属盐中的一种或多种与有机配体混合,溶解、分散于溶剂中,并于80~200℃水热处理1~48h,得到的混合物抽滤或蒸干溶剂得到相应金属有机骨架化合物A;
2)将步骤1)得到的金属有机骨架化合物分散于硅源、铝源溶液中的一种或多种,加入模板剂,混合均匀后置于100~240℃水热处理,然后过滤、干燥得到固体粉末B;将固体粉末于300~600℃煅烧1~5h,即得。
进一步地所述步骤2)中将得到的固体粉末B分散于铝源或硅源溶液中的一种,加入模板剂,混合均匀后置于100~240℃水热处理,然后过滤、干燥得到固体粉末C,将该固体粉末于300~600℃煅烧1~5h,即得。
进一步地所述步骤1)中金属盐为Zn2+、Zr2+、Fe3+、Co2+、Ni2+、Cu2+、Cr3+、Mn2+的硝酸盐、氯化物、硫酸盐、醋酸盐中的一种或多种。
进一步地所述步骤1)中溶剂为水、甲醇、乙醇、甲酸、乙酸、丙酮、N,N-二甲基甲酰胺中的一种或多种。
进一步地所述步骤1)中有机配体为含氮杂环类、羧酸类化合物中的一种或两种。
进一步地所述步骤2)中硅源溶液为硅溶胶、硅酸钠、正硅酸乙酯中的一种或多种的乙醇或水溶液;所述铝源溶液为铝溶胶、偏铝酸钠、硝酸铝中的一种或多种的乙醇或水溶液。
进一步地所述步骤2)中模板剂为四丙基氢氧化铵、二乙胺、聚乙二醇、四丙基溴化铵、十六烷基三甲基溴化铵、P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物)、F127(聚丙二醇与环氧乙烷的加聚物)、哌啶、六亚甲基亚胺中的一种或多种。
有益效果:与现有技术相比,本发明的优点在于:
1)催化剂具有组成、结构、性质均一且可精确调控的特点;
2)制备过程工艺简单、可控,重复性高;
3)具有CO2转化率高、芳烃选择性高等优点。
附图说明
图1为实施例1-6中所制备核壳结构催化剂的电镜表征图,其中1、2、3、4、5、6分别对应实施例1-6中的催化剂。
具体实施方式
下面结合实例对本发明作进一步的详细说明。本发明所用的原料均为市售产品。
实施例1
一种CO2定向转化制备芳烃的催化剂,以ZnO为核,以ZSM-5分子筛为壳的核壳结构Zn@ZSM-5催化剂。
一种CO2定向转化制备芳烃的Zn@ZSM-5催化剂的制备方法:包括以下步骤:
1)将六水合硝酸锌和对苯二甲酸按照摩尔比3:1的比例混合,称取50g混合物分散于500mL的N,N-二甲基甲酰胺中,搅拌混合均匀,置于水热釜中于150℃水热处理12h,抽滤、干燥得到金属骨架化合物A1;
2)将A1分散于500mL硅溶胶(二氧化硅含量15%(w%))中,然后加入10g硝酸铝与0.5g四丙基氢氧化铵,调节pH至9,置于水热釜中于180℃处理36h,抽滤、干燥得固体粉末B1;将固体粉末B1放入马弗炉中于500℃煅烧3h得到催化剂,记为Zn@ZSM-5。
实施例2
一种CO2定向转化制备芳烃的催化剂,以ZrO2为核,以MCM-41和ZSM-5分子筛为壳的核壳结构Zr@MCM-41@ZSM-5催化剂。
一种CO2定向转化制备芳烃的Zr@MCM-41@ZSM-5催化剂的制备方法:包括以下步骤:
1)将氯化锆和均苯三甲酸按照摩尔比5:1的比例混合,称取40g溶于300mL N,N-二甲基甲酰胺/甲酸(体积比1:1)混合溶液中,搅拌均匀后置于水热釜120℃水热反应18h,抽滤、干燥得到金属骨架化合物A2;
2)将固体粉末A2分散于300mL硅溶胶(二氧化硅含量15%(w%))中,加入0.2g十六烷基三甲基溴化铵,调节pH至10,然后180℃水热处理36h,将抽滤、干燥得到固体粉末B2;将固体粉末B2分散于质量浓度20%的硝酸铝水溶液,加入0.3g四丙基氢氧化铵、0.1g聚乙二醇,调节pH至9后置于水热釜于160℃水热处理72h,抽滤、干燥得固体粉末C2,将固体粉末C2放入马弗炉中于500℃煅烧3h得到催化剂,记为Zr@MCM-41@ZSM-5。
实施例3
一种CO2定向转化制备芳烃的催化剂,以ZnO、CoO为核,以ZSM-5分子筛为壳的核壳结构ZnCo@ZSM-5催化剂。
一种CO2定向转化制备芳烃的ZnCo@ZSM-5催化剂的制备方法:包括以下步骤:
1)将六水合硝酸锌和对苯二甲酸按照摩尔比3:1的比例混合,称取50g混合物分散于500mL的N,N-二甲基甲酰胺中,搅拌混合均匀,置于水热釜中于150℃水热处理12h,抽滤、干燥得到金属有机骨架化合物A3;将六水合硝酸钴和2-甲基咪唑按照摩尔比4:1的比例混合,称取50g混合物分散于300mL甲醇中,混合均匀后置于水热釜中100℃处理12h,抽滤、干燥得到金属有机骨架化合物A4;
2)将固体粉末A3、A4按质量比1:1混合,分散于300mL二氧化硅质量浓度15%的硅溶胶中,加入300mL氧化铝质量浓度15%的铝溶胶与0.5g四丙基氢氧化铵,调节pH至9,置于水热釜中于180℃处理72h,抽滤、干燥得固体粉末B3;将固体粉末B3放入马弗炉中于400℃煅烧5h得到催化剂,记为CoZn@ZSM-5。
实施例4
一种CO2定向转化制备芳烃的催化剂,以CuO、NiO为核,以SBA-15 、SAPO分子筛为壳的核壳结构CuNi@ SBA-15 @ SAPO催化剂。
一种CO2定向转化制备芳烃的CuNi@ SBA-15 @ SAPO催化剂的制备方法:包括以下步骤:
1)将二水合硝酸铜、六水合硝酸镍、2-甲基咪唑、苯三甲酸按照摩尔比1:1:5:3的比例混合,称取60g混合物分散于500mL的N,N-二甲基甲酰胺/甲醇(体积比1:1)混合溶液中搅拌均匀后置于水热釜120℃处理18h,抽滤、干燥得到固体粉末A5;
2)将固体粉末A5分散于300mL质量分数20%正硅酸乙酯的乙醇溶液中,加入0.3g P123和0.2gF127,调节pH至11,然后140℃水热处理72h,抽滤、干燥得到固体粉末B4;将固体粉末B4分散于质量浓度20%的硝酸铝水溶液,加入0.5g二乙胺,调节pH至8后置于水热釜于180℃水热处理24h,抽滤、干燥得固体粉末C4,将固体粉末C4放入马弗炉中于500℃煅烧3h得到催化剂,记为CuNi@ SBA-15 @ SAPO。
实施例5
一种CO2定向转化制备芳烃的催化剂,以Fe2O3为核,以USY、MCM-41分子筛为壳的核壳结构Fe@USY@MCM-41催化剂。
一种CO2定向转化制备芳烃的Fe@USY@MCM-41催化剂的制备方法:包括以下步骤:
1)将硫酸亚铁和均三甲苯按照摩尔比1.5:1的比例混合,称取50g混合物分散于500mL的水/乙醇混合液(体积比1:1),搅拌混合均匀,置于水热釜中于130℃水热处理24h,抽滤、干燥得到金属有机骨架化合物A6;
2)将固体粉末A6分散于500mL质量浓度15%的硅酸钠水溶液,然后加入10g偏铝酸钠与0.5g三乙胺,调节pH至8,置于水热釜中于160℃处理72h,抽滤、干燥得固体粉末B5;将固体粉末B5分散于质量浓度20%的正硅酸乙酯乙醇溶液,然后加入0.3g十六烷基三甲基溴化铵,调节pH至10,置于水热釜中于160℃处理72h,抽滤、干燥得固体粉末C5,将固体粉末C5放入马弗炉中于500℃煅烧3h得到催化剂,记为Fe@USY@MCM-41。
实施例6
一种CO2定向转化制备芳烃的催化剂,以MnO、Cr2O3为核,以MCM-22分子筛为壳的核壳结构MnCr@MCM-22催化剂。
一种CO2定向转化制备芳烃的MnCr@MCM-22催化剂的制备方法:包括以下步骤:
1)将醋酸锰、硝酸铬和对苯二甲酸按照摩尔比2:2:1的比例混合,称取50g混合物分散于500mL的乙酸/丙酮混合液(体积比1:1),搅拌混合均匀,置于水热釜中于150℃水热处理24h,抽滤、干燥得到金属有机骨架化合物A7;
2)将固体粉末A7分散于300mL二氧化硅质量分数15%的硅溶胶中,然后加入0.2g哌啶和0.2g六亚甲基亚胺,得到的混合物置于水热釜中于200℃处理24h,抽滤、干燥得固体粉末B6;将固体粉末B6放入马弗炉中于500℃煅烧3h得到催化剂,记为MnCr@MCM-22。
如附图1中实施例1-6中所制备催化剂的电镜图所示,催化剂的基本形貌为空腔核壳结构:壳层结构为分子筛多孔结构,内部封装金属氧化物,不同的金属氧化物、不同的分子筛、不同的制备方法表现出不同的结构单元大小和形状。
一种CO2定向转化制备芳烃的催化剂的运用:摩尔比1:3的CO2与氢气经混合器进入固定床反应器,反应器中填装实施例1~6中制备的催化剂,控制反应温度为350℃,反应空速2000mL/gcat/h,产物经GC-MS分析,计算得到相应的转化率与产物分布如下表所示。
催化剂 | CO<sub>2</sub>转化率 | CH<sub>4</sub>含量 | C<sub>2</sub>~ C<sub>4</sub>含量 | C<sub>5+</sub>含量 | C<sub>5+</sub>中芳烃含量 |
实施例1 | 44.7% | 2.7% | 13.6% | 83.7% | 83.6% |
实施例2 | 47.3% | 3.8% | 15.8% | 80.4% | 87.1% |
实施例3 | 53.2% | 3.3% | 11.9% | 84.8% | 85.8% |
实施例4 | 37.9% | 5.2% | 17.6% | 77.2% | 75.7% |
实施例5 | 43.6% | 7.4% | 18.5% | 74.1% | 80.5% |
实施例6 | 39.3% | 7.1% | 20.6% | 72.3% | 78.4% |
本发明按照上述实施例进行了说明,应当理解,上述实施例不以任何形式限定本发明,凡采用等同替换或等效变换方式所获得的技术方案,均落在本发明的保护范围之内。
Claims (9)
1.一种CO2定向转化制备芳烃的催化剂,其特征在于,以金属氧化物为核,以分子筛为壳的核壳结构催化剂,所述金属有机化合物的金属离子中心为Zn2+、Zr2+、Fe3+、Co2+、Ni2+、Cu2+、Cr3+、Mn2+中的一种或多种;所述分子筛为ZSM-5、MCM-41、SAPO、MCM-22、USY、SBA-15中的一种或多种。
2.根据权利要求1所述的一种CO2定向转化制备芳烃的催化剂,其特征在于,所述金属氧化物的前驱体为金属有机骨架化合物A。
3.根据权利要求1或2所述的一种CO2定向转化制备芳烃的催化剂的制备方法,其特征在于,包括以下步骤:
1)将金属盐中的一种或多种与有机配体混合,溶解、分散于溶剂中,并于80~200℃水热处理1~48h,得到的混合物抽滤或蒸干溶剂得到金属有机骨架化合物A;
2)将上述金属有机骨架化合物分散于硅源、铝源溶液中的一种或多种,加入模板剂,混合均匀后置于100~240℃水热处理,然后过滤、干燥得到固体粉末B;将固体粉末于300~600℃煅烧1~5h,即得。
4.根据权利要求3所述的一种CO2定向转化制备芳烃的催化剂的制备方法,其特征在于,所述步骤2)中将所得固体粉末B分散于铝源或硅源溶液中的一种,加入模板剂,混合均匀后置于100~240℃水热处理,然后过滤、干燥得到固体粉末C,将该固体粉末于300~600℃煅烧1~5h,即得。
5.根据权利要求3或4所述的一种CO2定向转化制备芳烃的催化剂的制备方法,其特征在于,所述步骤1)中金属盐为Zn2+、Zr2+、Fe3+、Co2+、Ni2+、Cu2+、Cr3+、Mn2+的硝酸盐、氯化物、硫酸盐、醋酸盐中的一种或多种。
6.根据权利要求3或4所述的一种CO2定向转化制备芳烃的催化剂的制备方法,其特征在于,所述步骤1)中溶剂为水、甲醇、乙醇、甲酸、乙酸、丙酮、N,N-二甲基甲酰胺中的一种或多种。
7.根据权利要求3或4所述的一种CO2定向转化制备芳烃的催化剂的制备方法,其特征在于,所述步骤1)中有机配体为含氮杂环类、羧酸类化合物中的一种或两种。
8.根据权利要求3或4所述的一种CO2定向转化制备芳烃的催化剂的制备方法,其特征在于,所述步骤2)中硅源溶液为硅溶胶、硅酸钠、正硅酸乙酯中的一种或多种的乙醇或水溶液;所述铝源溶液为铝溶胶、偏铝酸钠、硝酸铝中的一种或多种的乙醇或水溶液。
9.根据权利要求3或4所述的一种CO2定向转化制备芳烃的催化剂的制备方法,其特征在于,所述步骤2)中模板剂为四丙基氢氧化铵、二乙胺、聚乙二醇、四丙基溴化铵、三乙胺、十六烷基三甲基溴化铵、P123、F127、哌啶、六亚甲基亚胺中的一种或多种。
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