CN105363452A - 一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法 - Google Patents
一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法 Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title abstract description 6
- 230000002902 bimodal effect Effects 0.000 title abstract 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical group [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 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
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- 238000009938 salting Methods 0.000 claims description 4
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- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000005470 impregnation Methods 0.000 abstract description 10
- 239000013335 mesoporous material Substances 0.000 abstract description 8
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- 238000003756 stirring Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 2
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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Abstract
一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,属于天然气化工和煤化工技术领域。本发明以浸渍法制备出负载活性组分镍的双介孔结构Ni/SiO2-ZrO2催化剂,该催化剂具有较大比表面积和孔体积,且孔径分布均匀。该催化剂制备方法简单,对于甲烷部分氧化反应具有较高催化活性,并且可以有效抑制由烧结和积碳引起的催化剂失活。本发明涉及的Ni/SiO2-ZrO2双介孔材料具有两种尺寸的介孔孔径,较大的孔径可以满足反应物和产物的扩散需求,较小的孔径可以给反应物提供吸附和反应的场所,同时该材料孔径分布较窄,在一定范围内可以调节,使得其可以满足不同反应的需求,为新型工业使用催化剂的开发开辟了新的道路。本发明制备方法简单,反应条件温和,易工业化生产。
Description
技术领域
本发明一种用于甲烷部分氧化反应的双介孔Ni/SiO2-ZrO2催化剂制备方法,属于天然气化工和煤化工技术领域。具体涉及一种以浸渍法制备双介孔结构Ni/SiO2-ZrO2催化剂的方案。
背景技术
介孔SiO2是一种孔径介于2~50nm之间的一种多孔固体材料。由于其比表面积大、孔道结构规整、孔径大小可调、水热稳定性好、吸附孔容大等优点,使其在催化、医药等方面得到了广泛的应用。双介孔材料可以兼具每种孔径的优点,可以在很大程度上改善催化剂的性能。比如对于双介孔材料里的大介孔,由于其孔径较大、扩散阻力小,可以为反应物和产物提供流畅的运输通道;而小介孔,由于其比表面积大、活性位多,可以为反应物提供吸附和反应场所。目前双介孔材料制备方法主要有溶胶-凝胶法、微乳法、水热合成法、微波法,这些方法制备步骤较复杂,而且成本较高。因此,采用简单、廉价的方法制备双介孔材料是当下研究难点。
应用于甲烷部分氧化的催化剂主要有贵金属催化剂和非贵金属催化剂,贵金属催剂化Pt、Au等具有高活性、高选择性、抗积碳性能等优点。由于使用贵金属催化剂成本太高,难以实现工业化应用。因而国内外都很关注非贵金属催化剂的研究,在非贵金属催化剂里Ni基催化剂的活性最高,仅次于贵金属Rh,但是Ni基催化剂容易烧结和积碳导致催化剂的失活。因此,如何防止Ni基催化剂的失活是目前催化剂开发的关键问题。针对这一问题,本发明综合利用双介孔材料的优点,制备了以双介孔SiO2-ZrO2为载体Ni为活性组分的催化剂,并应用于甲烷部分氧化反应。NagaokaK.等人证实了ZrO2不仅可以提高催化剂的活性和选择性,还可以有效的减少催化剂的积碳[J.Catal.2001;197:34-42]。由于反应是在孔道内进行,可以减少由烧结和积碳引起的催化剂失活。另外因为反应是在较小的空间里完成形成,“限域效应”可以提高催化剂的活性和选择性。CN103663473A公开了一种有序双介孔二氧化硅材料及其制备方法。以正硅酸乙酯或硅酸钠为硅源,三嵌段共聚物P123为模板剂,采用先水浴处理再水热合成的方法,制备出一种孔径为1.5~4.2nm,另一种孔径为4.2~15nm的双介孔二氧化硅材料。CN102020298A公开了一种具有双介孔结构的Al2O3及其制备方法。以异丙醇铝为吕源,十六烷基三甲基溴化铵(CTAB)和非离子表面活性剂为模板剂,利用溶胶-凝胶法制备出小介孔分布在3.4~3.8nm,大介孔分布在9.8~24.5nm的双介孔Al2O3。CN101733085A公开了一种锆-铝双介孔材料及其制备方法。以仲丁醇铝或异丙醇铝为铝源,氧氯化锆或硝酸锆为锆源,脂肪酸为模板剂,制备出初级介孔孔径为3~5nm,次级介孔孔径为10~20nm的锆-铝双介孔材料。以上三种方法都使用了模板剂,提高了催化剂的制备成本。
发明内容
本发明一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,目的在于公开一种利用简单的浸渍法,在无模板剂的情况下合成规整的双介孔结构Ni/SiO2-ZrO2催化剂的方法,小介孔孔径为4.5~5.5nm,大介孔孔径约为50nm。
本发明一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于是一种采用简单的浸渍法,在无模板剂的情况下制备具有规整有序的,小介孔孔径为4.5~5.5nm,大孔孔径为50nm的,且将镍纳米颗粒限定在双介孔孔道的双介孔结构的Ni/SiO2-ZrO2催化剂的方法,具体操作步骤如下:
1)将3.0~5.0g硅胶浸渍于含有0.22~1.01gZrO2的锆源溶液中,超声分散
1~3h,得负载锆源溶液的硅胶;
2)将步骤1)得到的负载锆源溶液的硅胶在400~700℃下焙烧2~6h,得到双介孔结构的SiO2-ZrO2;
3)将步骤2)得到的双介孔结构的SiO2-ZrO2浸渍于含有0.16~0.67g镍
的镍盐溶液中,超声分散1~3h,得负载镍盐溶液的SiO2-ZrO2;
4)将步骤3)得到的负载镍盐溶液的SiO2-ZrO2转入干燥箱中,在120℃下干燥6~12h,在400~700℃下焙烧2~4h得双介孔NiO/SiO2-ZrO2;
5)将步骤4)得到的双介孔NiO/SiO2-ZrO2在400~700℃下通氢气还原1~5h,氮气保护下降至常温,得双介孔Ni/SiO2-ZrO2催化剂。
上述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于,所选用的硅胶孔分布均匀,孔径为50nm。
上述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2
催化剂制备方法,其特征在于,所选用的锆源为硝酸锆、氢氧化锆、氧化
锆溶胶或氯化锆。
上述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于,所述的镍盐溶液的溶剂是水、乙醇、乙二醇或丙三醇。
上述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于,所述的镍盐为硝酸镍、氯化镍或硫酸镍。
本发明一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法的优点在于:克服了现有技术制备双介孔结构过程复杂、成本高的问题,制备方法简单、孔容相对较大。本发明提供了一种将镍纳米颗粒限定在双介孔孔道的Ni/SiO2-ZrO2催化剂制备方法,解决了现有的甲烷部分氧化镍基催化剂容易失活的问题。制备的催化剂具有比表面积较大、孔径分布均匀、双介孔结构明显等优点,在甲烷部分氧化反应中显示出较高的催化活性。
附图说明
图1为本发明600℃焙烧后SiO2、SiO2-ZrO2、Ni/SiO2-ZrO2材料的N2-吸附脱附曲线图,相对压力大于0.6MPa时出现滞后环,说明被测材料为介孔结构。
图2为本发明600℃焙烧后SiO2、SiO2-ZrO2、Ni/SiO2-ZrO2材料的BJH孔径分布图,结果显示形成的小介孔大小4.5~5.5nm,大介孔大小50nm左右。
图3为不同焙烧温度下制备的Ni/SiO2-ZrO2催化剂性能测试结果,从图中可以看出,600℃为此催化剂的最佳制备温度。
具体实施方式
下面是本发明的实施案例,但本发明不局限于这些实施案例
实施方式1
1)将0.71g的Zr(NO3)2.5H2O溶解于7.4mL的去离子水搅拌0.5h;
2)用等体积浸渍法将步骤1)得到溶液浸渍于5.0g的较大孔径的SiO2,在600℃下焙烧2h;
3)将0.78g的Ni(NO3)2.6H2O溶解于4.2mL的去离子水搅拌0.5h;
4)同样使用等体积浸渍法将3)得到的溶液浸渍于3.0g步骤2)得到的双介孔SiO2-ZrO2,在110℃下干燥12h,在400℃,500℃,600℃,700℃下焙烧4h;
5)制备出催化剂粉碎至40~60目,在常压,反应温度600℃,空速5×104mL·g-1·h-1条件下,甲烷转化率为80-90%。
实施方式2
1)将0.71g的Zr(NO3)2.5H2O和0.78g的Ni(NO3)2.6H2O同时溶解于7.4mL的去离子水搅拌0.5h;
2)用等体积浸渍法将步骤1)得到溶液浸渍于5.0g的较大孔径的SiO2,在110℃下干燥12h,在600℃下焙烧4h;
3)制备出催化剂粉碎至40~60目,在常压,反应温度600℃,空速5×104
mL·g-1·h-1条件下,甲烷转化率为83%。
实施方式3
1)用去离子水将含有0.44gZrO2的溶胶稀释至7.5mL搅拌0.5h;
2)用等体积浸渍法将步骤1)得到溶液浸渍于5.0g的较大孔径的SiO2,在700℃下焙烧4h;
3)将0.78g的Ni(NO3)2.6H2O溶解于4.2mL的乙醇搅拌0.5h;
4)同样使用等体积浸渍法将3)得到的溶液浸渍于3g步骤2)得到的双介孔SiO2-ZrO2,在80℃下真空干燥12h,在600℃下焙烧4h;
5)制备出催化剂粉碎至40~60目,在常压,反应温度600℃,空速5×104mL·g-1·h-1条件下,甲烷转化率为85%。
实施方式4
1)用乙醇将含有0.88gZrO2的溶胶稀释至7.5mL搅拌1h;
2)用等体积浸渍法将步骤1)得到溶液浸渍于5.0g的较大孔径的SiO2,在600℃下焙烧4h;
3)将1.65g的Ni(NO3)2.6H2O溶解于3.9mL的乙二醇搅拌1h;
4)同样使用等体积浸渍法将3)得到的溶液浸渍于3.0g步骤(2)得到的双介孔SiO2-ZrO2,在80℃下真空干燥12h,在600℃下焙烧4h;
5)制备出催化剂粉碎至40~60目,在常压,反应温度700℃,空速5×104mL·g-1·h-1条件下,甲烷转化率为97%。
实施方式5
1)将1.42g的Zr(NO3)2.5H2O溶解于7.4mL的去离子水搅拌0.5h;
2)用等体积浸渍法将步骤1)得到溶液浸渍于5.0g的较大孔径的SiO2,在700℃下焙烧4h;
3)将0.64g的NiCl2.6H2O溶解于4.2mL的去离子水搅拌0.5h;
4)同样使用等体积浸渍法将3)得到的溶液浸渍于3.0g步骤2)得到的双介孔SiO2-ZrO2,在110℃下干燥12h,在500℃下焙烧4h;
5)制备出催化剂粉碎至40~60目,在常压,反应温度700℃,空速5×104mL·g-1·h-1条件下,甲烷转化率为93%。
Claims (5)
1.一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于是一种采用简单的浸渍法,在无模板剂的情况下制备具有规整有序的,小介孔孔径为4.5~5.5nm,大孔孔径约为50nm的,且将镍纳米颗粒限定在双介孔孔道的双介孔结构的Ni/SiO2-ZrO2催化剂的方法,具体操作步骤如下:
1)将3.0~5.0g硅胶浸渍于含有0.22~1.01gZrO2的锆源溶液中,超声分散
1~3h,得负载锆源溶液的硅胶;
2)将步骤1)得到的负载锆源溶液的硅胶在400~700℃下焙烧2~6h,得到双介孔结构的SiO2-ZrO2;
3)将步骤2)得到的双介孔结构的SiO2-ZrO2浸渍于含有0.16~0.67g镍
的镍盐溶液中,超声分散1~3h,得负载镍盐溶液的SiO2-ZrO2;
4)将步骤3)得到的负载镍盐溶液的SiO2-ZrO2转入干燥箱中,在120℃下干燥6~12h,在400~700℃下焙烧2~4h得双介孔NiO/SiO2-ZrO2;
5)将步骤4)得到的双介孔NiO/SiO2-ZrO2在400~700℃下通氢气还原1~5h,氮气保护下降至常温,得双介孔Ni/SiO2-ZrO2催化剂。
2.按照权利要求1所述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于所选用的硅胶孔分布均匀,孔径为50nm。
3.按照权利要求1所述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于所选用的锆源为硝酸锆、氢氧化锆、氧化锆溶胶或氯化锆。
4.按照权利要求1所述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于,所述的镍盐溶液的溶剂是水、乙醇、乙二醇或丙三醇。
5.按照权利要求1所述一种用于甲烷部分氧化反应的双介孔结构Ni/SiO2-ZrO2催化剂制备方法,其特征在于所述的镍盐为硝酸镍、氯化镍或硫酸镍。
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