CN113797959B - 一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法 - Google Patents
一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法 Download PDFInfo
- Publication number
- CN113797959B CN113797959B CN202111239874.9A CN202111239874A CN113797959B CN 113797959 B CN113797959 B CN 113797959B CN 202111239874 A CN202111239874 A CN 202111239874A CN 113797959 B CN113797959 B CN 113797959B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- limited
- catalyst
- zeolite molecular
- set temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 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 36
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 31
- 239000010457 zeolite Substances 0.000 title claims abstract description 31
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 26
- 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 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 229910017090 AlO 2 Inorganic materials 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 208000012868 Overgrowth Diseases 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明属于化工领域,具体涉及一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法。本发明的技术方案如下:一种沸石分子筛包覆金属纳米颗粒催化剂,金属纳米颗粒被均匀封装在沸石分子筛的骨架结构中。催化剂的通用分子式为:α[MOq]·Hx[(AlO2)x(SiO2)y]或α[MNpOq]·Hx[(AlO2)x(SiO2)y],其中,M为金属元素,包括但不限于Cu、Ni、Fe;N为第二种金属元素,包括但不限于Zn、Zr、Ce、Mn;α、p、q、x、y为常数,且x≤y、p>0、q≥0。本发明提供的沸石分子筛包覆金属纳米颗粒催化剂及其制备方法,将金属纳米颗粒封装于沸石的α笼中,有效避免了金属的聚集和过度生长,提高了催化剂的稳定性和催化活性。
Description
技术领域
本发明属于化工领域,具体涉及一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法。
背景技术
金属纳米颗粒催化剂具有独特的晶体结构及表面特性,具有比表面积大、表面活性高等特点,因而其催化活性和选择性大大高于传统催化剂,可广泛应用于光催化、电催化、热催化等多种类型的催化体系内,在空气净化、汽车尾气处理、污水处理、降低温室效应等多个领域进行了应用。因此,探索金属纳米颗粒催化剂的易操作、性能优良的合成方法尤为重要。
传统的催化剂制备方法主要包括共沉淀法、水热法、溶胶-凝胶法、微乳液法等,但制得的催化剂多存在颗粒大小不均一、易聚集、颗粒过大、合成方法复杂等缺点。考虑到传统催化剂的活性成分易烧结、聚集后活性表面积大幅度降低等问题,目前的催化剂制备过程中多将活性成分负载于载体(如沸石等)上,采用的合成方法包括浸渍法、沉淀沉积法等,但浸渍法合成的样品活性组分分布不均匀、粒径分布较宽,而沉淀沉积法难以控制沉淀位置生成的金属颗粒较大、均匀性低。
因此,本发明采用一种“限域”的理念,将催化剂的活性组分封装于沸石的骨架结构中,并将活性组分在骨架内还原,在限制活性组分大小的同时,保障了活性组分的均匀分布,有利于增强催化剂的催化活性。
发明内容
本发明提供一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法。
本发明的技术方案如下:
一种沸石分子筛包覆金属纳米颗粒催化剂,金属纳米颗粒被均匀封装在沸石分子筛的骨架结构中。催化剂的通用分子式为:α[MOq]·Hx[(AlO2)x(SiO2)y]或α[MNpOq]·Hx[(AlO2)x(SiO2)y],其中,M为金属元素,包括但不限于Cu、Ni、Fe;N为第二种金属元素,包括但不限于Zn、Zr、Ce、Mn;α、p、q、x、y为常数,且x≤y、p>0、q≥0。
上述沸石分子筛包覆金属纳米颗粒催化剂的制备方法,当仅含有单一种类金属纳米颗粒时,催化剂的通用分子式为:α[MOq]·Hx[(AlO2)x(SiO2)y],包括以下步骤:
I1、配制一定浓度的金属M盐溶液;
I2、将活化后的沸石分子筛均匀分散在步骤I1中配制的溶液里,在设定温度下充分搅拌,再通过过滤、洗涤和干燥获得滤渣;
I3、将步骤I2中获得的滤渣在设定温度和气氛下煅烧,得到前驱体;
I4、建立微正压的恒温环境,将步骤I3中得到的前驱体在流动的还原性气体中还原一定时间,得到产品。
上述沸石分子筛包覆金属纳米颗粒催化剂的制备方法,当含有二元金属纳米颗粒时,催化剂的通用分子式为:α[MNpOq]·Hx[(AlO2)x(SiO2)y],包括以下步骤:
B1、配制一定浓度的金属M盐溶液;
B2、将活化后的沸石分子筛均匀分散在步骤B1中配制的溶液里,在设定温度下充分搅拌,再通过过滤、洗涤和干燥获得滤渣一;
B3、将步骤B2中获得的滤渣一在设定温度和气氛下煅烧,得到第一前驱体;
B4、建立微正压的恒温环境,将步骤B3中得到的第一前驱体在流动的还原性气体中还原一定时间,得到第二前驱体;
B5、将步骤B4中获得的第二前驱体均匀分散在金属N盐溶液里,在设定温度下充分搅拌,再通过过滤、洗涤和干燥获得滤渣二;
B6、将步骤B5中获得的滤渣二在设定温度和气氛下煅烧,得到第二前驱体;
B7、建立微正压的恒温环境,将步骤S6中得到的第二前驱体在流动的还原性气体中还原一定时间,得到产品。
进一步地,所述的制备方法,所述沸石分子筛包括但不限于13X、ZSM-5,活化温度为150~400℃。
进一步地,所述的制备方法,所述I3、B3、B6煅烧温度为150~400℃,煅烧气氛包括但不限于空气、N2、Ar,煅烧时间为2~6h。
进一步地,所述的制备方法,固液比为1:5~1:100,溶剂包括但不限于水、乙醇、丙酮等,设定温度为15~35℃,搅拌时间为0.5~4h。
进一步地,所述的制备方法,所述微正压为0.12~0.30MPa左右,还原温度为180~260℃,还原时间为2~4h,还原气体包括但不限于H2、H2/Ar混合气,气体流速为20~60mL/min。
本发明的有益效果为:本发明提出的一种沸石分子筛包覆金属纳米颗粒催化剂,催化剂的活性组分粒径小,分散均匀,活性位点丰富,有利于促进催化反应的进行。本发明提出的一种沸石分子筛包覆金属纳米颗粒催化剂制备方法,使催化剂的活性组分均匀地分散在沸石的骨架内,有效避免了活性金属的聚集和过度生长,提高了催化剂的稳定性和催化活性。
附图说明
图1为实施例2中样品的扫描电镜(SEM)图谱;
图2为实施例2中样品的能量色散X射线光谱(EDX)测试图;其中(a)为Cu元素在沸石13X中的分布情况,(b)为Zn元素在沸石13X中的分布情况。
具体实施方式
实施例1
将Cu(NO3)2·5H2O粉末溶解在去离子水中,配置成Cu2+浓度为0.1mol/L的硝酸铜水溶液。将Na型13X分子筛在300℃下活化4小时,将活化后的分子筛粉末加入硝酸铜溶液中,控制转速为40r/min,在室温下搅拌2h,反应结束后过滤、洗涤,在100℃烘箱内干燥过夜。以烘干后样品替代分子筛粉末,再重复上述过程两次。将最后一次烘干后的样品置于管式炉中,在N2氛围下,200℃煅烧4h,得到样品CX。
将样品CX置于微正压的环境下,以30mL/min的流速通入H2,在200℃下还原4h,得到13X分子筛包覆金属Cu纳米颗粒的催化剂CXH。实验表明,催化剂在无氧条件下长期保存,即使在干燥空气中也可保存10天以上。
将样品CXH进行X射线荧光光谱(XRF)、X射线衍射(XRD)检测分析,检测结果表明,样品在13X沸石骨架保持完整的前提下,还原了活性金属元素Cu,实现了Cu颗粒在13X沸石骨架结构内的封装。
实施例2:沸石分子筛包覆金属纳米颗粒催化剂制备第二实施例
将Cu(NO3)2·5H2O粉末溶解在去离子水中,配置成Cu2+浓度为0.1mol/L的硝酸铜水溶液。将Na型13X分子筛在300℃下活化4小时,将活化后的分子筛粉末加入硝酸铜溶液中,控制转速为40r/min,在室温下搅拌2h,反应结束后过滤、洗涤,在100℃烘箱内干燥过夜。以烘干后样品替代分子筛粉末,再重复上述过程两次。将最后一次烘干后的样品置于管式炉中,在N2氛围下,200℃煅烧4h,得到样品CX。
将样品CX置于微正压的环境下,以30mL/min的流速通入H2,在200℃下还原4h,得到催化剂CXH。
将Zn(NO3)2·6H2O粉末溶解在去离子水中,配置成0.35mol/L的硝酸锌水溶液。
将CXH粉末按照固液比为1:10加入硝酸锌溶液中,控制转速为40r/min,在室温下搅拌2h,反应结束后过滤、洗涤,在100℃烘箱内干燥过夜。将烘干后的样品置于管式炉中,在N2氛围下,200℃煅烧4h,得到样品CZX。
将样品CZX置于微正压的环境下,以30mL/min的流速通入H2,在200℃下还原4h,得到13X分子筛包覆金属Cu-ZnO纳米颗粒的催化剂CZXH。实验表明,催化剂在无氧条件下长期保存,即使在干燥空气中也可保存10天以上。
如图1所示,结构规则、大小较为均匀的多面立方体平铺在界面,未出现明显的破损情况,其为13X分子筛在高分辨电子扫描镜头下直观展示的微观形貌。
如图2所示,能量色散X射线光谱(EDX)测试显示(a)为Cu元素在沸石13X中的分布情况,(b)为Zn元素在沸石13X中的分布情况;可以看出,两种元素均匀分散在沸石13X的孔道中,无大面积聚集,实现了沸石骨架约束下的金属纳米颗粒催化剂的制备。
将样品CZXH进行X射线衍射(XRD)、扫描电子显微镜(SEM)、能量色散X射线光谱(EDX)等检测分析,检测结果表明:CZXH催化剂中出现了明显的13X特征衍射峰和Cu的特征衍射峰,铜元素和锌元素均匀分散在沸石骨架中,成功制备了沸石骨架约束下金属纳米颗粒催化剂。
CZXH催化剂的催化性能测试在固定床反应器中进行;当反应温度为250℃、反应压力为3.0MPa时,使用1g催化剂实现的单床CO2转化率约为10%,甲醇(MeOH)选择性可达97%左右,优于现有催化剂。在290℃、3.0MPa下,反应4h左右时的CO2转化率约为10.4%,连续反应120h后,CO2转化率依然稳定在9.8%左右,其他各项性能指标均未出现明显下降,表明制备的分子筛包覆金属纳米颗粒CZXH催化剂具有良好的稳定性。
Claims (2)
1.一种沸石分子筛包覆金属纳米颗粒催化剂的制备方法,其特征在于,金属纳米颗粒被均匀封装在沸石分子筛的α笼中;催化剂的通用分子式为:α[MNpOq]·Hx[(AlO2)x(SiO2)y];其中,M为金属元素,包括但不限于Cu、Ni、Fe;N为第二种金属元素,包括但不限于Zn、Zr、Ce、Mn;α、p、q、x、y为常数,且x≤y、p>0、q≥0;包括以下步骤:
B1、配制一定浓度的金属M盐溶液;
B2、将活化后的沸石分子筛均匀分散在步骤B1中配制的溶液里,在设定温度下充分搅拌,再通过过滤、洗涤和干燥获得滤渣一;
B3、将步骤B2中获得的滤渣一在设定温度和气氛下煅烧,得到第一前驱体;设定温度为150~400℃,煅烧气氛包括但不限于空气、N2、Ar,煅烧时间为2~6 h;
B4、建立微正压的恒温环境,将步骤S3中得到的第一前驱体在流动的还原性气体中还原一定时间,得到第二前驱体;所述微正压为0.12~0.30 MPa,还原温度为180~260℃,还原时间为2~4 h,还原气体包括但不限于H2、H2/Ar混合气,气体流速为20~60 mL/min;
B5、将步骤B4中获得的第二前驱体均匀分散在金属N盐溶液里,在设定温度下充分搅拌,再通过过滤、洗涤和干燥获得滤渣二;固液比为1:5~1:100,溶剂包括但不限于水、乙醇、丙酮,设定温度为15~35℃,搅拌时间为0.5~4 h;
B6、将步骤B5中获得的滤渣二在设定温度和气氛下煅烧,得到第二前驱体;设定温度为150~400℃,煅烧气氛包括但不限于空气、N2、Ar,煅烧时间为2~6 h;
B7、建立微正压的恒温环境,将步骤S6中得到的第二前驱体在流动的还原性气体中还原一定时间,得到产品。
2.根据权利要求1所述的制备方法,其特征在于,所述沸石分子筛包括但不限于13X、ZSM-5,活化温度为150~400℃。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111239874.9A CN113797959B (zh) | 2021-10-25 | 2021-10-25 | 一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111239874.9A CN113797959B (zh) | 2021-10-25 | 2021-10-25 | 一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113797959A CN113797959A (zh) | 2021-12-17 |
CN113797959B true CN113797959B (zh) | 2022-09-06 |
Family
ID=78898169
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111239874.9A Active CN113797959B (zh) | 2021-10-25 | 2021-10-25 | 一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113797959B (zh) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5026673A (en) * | 1989-06-23 | 1991-06-25 | University Of Delaware | Stable zeolite-supported transition metal catalysts, methods for making them, and uses thereof |
CN103272634B (zh) * | 2013-05-28 | 2015-07-22 | 常州大学 | 纳米金属负载型分子筛催化剂的制备方法 |
JP6379273B2 (ja) * | 2014-04-10 | 2018-08-22 | ダンマークス・テクニスケ・ユニヴェルシテット | ゼオライト及びゼオタイプに金属ナノ粒子を組み入れる一般的方法 |
CN109731608B (zh) * | 2019-01-30 | 2021-05-25 | 中国科学院过程工程研究所 | 一种封装金属纳米颗粒的无钠硅铝分子筛的双功能催化剂及其制备方法 |
CN109647493B (zh) * | 2019-01-30 | 2021-05-11 | 中国科学院过程工程研究所 | 一种封装金属纳米颗粒的纯硅s-1分子筛催化剂、制备方法及其应用 |
CN110560153B (zh) * | 2019-09-24 | 2021-08-17 | 东北大学 | 一种铝共享金属-沸石双功能催化剂及制备方法和应用 |
-
2021
- 2021-10-25 CN CN202111239874.9A patent/CN113797959B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN113797959A (zh) | 2021-12-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101703935B (zh) | 一种负载型金属催化剂及其制备方法 | |
CN110327933B (zh) | 二氧化碳加氢制备甲醇的催化剂及其制备方法和应用 | |
CN113058633B (zh) | 氮化硼空心复合材料及其制备方法与应用 | |
CN102275962B (zh) | 一种纳米氧化铝的制备方法及应用 | |
JP5715726B2 (ja) | 実質的に面心立方構造を有するルテニウム微粒子およびその製造方法 | |
CN110404535B (zh) | 一种负载型钯催化剂及制备方法与应用 | |
CN112844446B (zh) | 一种溶剂配位金属催化剂的制备方法及应用 | |
CN107207274A (zh) | 一种具有多核共壳结构的微米氧化铈颗粒及其制备方法 | |
CN110773192A (zh) | 一种碳负载高熵单原子催化剂的制备方法 | |
CN114405505B (zh) | 一种铂修饰铟基氧化物催化剂及其制备方法和应用 | |
CN112452328A (zh) | NiO@SiO2@CoAl-LDH多级核壳催化剂的制备方法 | |
CN113713796B (zh) | 一种Ni-NiO/C-TiO2核壳结构纳米棒状材料光催化剂的制备方法 | |
CN110560153A (zh) | 一种铝共享金属-沸石双功能催化剂及制备方法和应用 | |
CN108273488B (zh) | 一种纳米片状二氧化铈/多孔炭复合材料的制备方法 | |
CN113797959B (zh) | 一种沸石分子筛包覆金属纳米颗粒催化剂及其制备方法 | |
CN113600194B (zh) | 一种含不同价态钴的纳米光催化剂、制备方法及其应用 | |
CN113398929A (zh) | 一种用于CO2催化加氢制甲醇的Cu/TiO2催化剂及其制备方法 | |
CN113731407A (zh) | 一种TiO2基贵金属催化剂及其制备方法和应用 | |
CN113083325A (zh) | 一种氨硼烷水解制氢用催化剂Ru1-xCox/P25及其制备方法 | |
CN115318282A (zh) | 一种钌-钛双组分催化剂及其制备方法与应用 | |
CN112892570A (zh) | 多级孔Co-N-C复合材料及其制备方法与应用 | |
CN111482174A (zh) | CuO/TiO2纳米片的制备方法 | |
CN116196952B (zh) | 原位生长于固定床上的氨裂解制氢催化剂及其制备方法 | |
CN114471580B (zh) | 一种负载型镍镓催化剂的合成及其应用方法 | |
CN115672299B (zh) | 二氧化钛纳米线及其制备方法、脱硝催化剂及其制备方法、烟气脱硝的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |