CN108772097A - 一种金属-固体酸碱多功能核壳催化剂的制备方法 - Google Patents
一种金属-固体酸碱多功能核壳催化剂的制备方法 Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000002253 acid Substances 0.000 title claims abstract description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 36
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002585 base Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 34
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 239000011973 solid acid Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 238000007789 sealing Methods 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 29
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 14
- 230000000873 masking effect Effects 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [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 9
- 238000000034 method Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000935 solvent evaporation Methods 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 239000003643 water by type Substances 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000007974 melamines Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- -1 melamines Amine Chemical class 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 206010068150 Acoustic shock Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 206010037544 Purging Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J29/08—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
- B01J29/12—Noble metals
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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
- B01J29/08—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
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- 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
- B01J29/7057—Zeolite Beta
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- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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Abstract
本发明公开了一种金属‑固体酸碱多功能核壳催化剂的制备方法,将固体酸源和固体碱源按质量比为1:0.1‑1.8充分混合均匀后,于450‑580℃下密封焙烧0.1‑6小时得到固体酸碱双功能核壳催化剂,再将金属盐溶液等体积浸渍到固体酸碱双功能核壳催化剂上,经干燥、焙烧后得到金属‑固体酸碱多功能核壳催化剂。与现有技术相比,本发明制备的金属‑固体酸碱多功能核壳催化剂具有金属分散度高、可还原性高以及固体酸碱双功能核壳催化剂可控酸碱性的特点;本发明合成工艺简单,不需要多步操作,也无需额外加入价格高昂的添加剂;通过调节金属盐、固体酸源和固体碱源的种类和相对含量,可有效地调控金属的分散度和可还原性以及核壳催化剂的酸碱性和形貌。
Description
技术领域
本发明涉及催化化学技术领域,特别是一种高分散度、高可还原性的金属-固体酸碱多功能核壳催化剂的制备方法。
背景技术
沸石分子筛具有可调节的酸性,优异的孔道择形性和水热稳定性,它的设计合成以及性能应用在吸附、分离和催化等领域受到广泛关注,在大分子催化、精细化工领域广泛应用。类石墨相氮化碳的利用对于化学工业意义重大,在光催化和碱催化领域广泛应用。
对于催化反应中常用的金属-沸石分子筛催化剂,金属的引入通常采用金属盐溶液等体积浸渍到沸石分子筛上的方法,此传统浸渍方法存在以下不足:金属活性组分分散不均匀,过量聚集在分子筛表面,覆盖分子筛的酸中心;金属盐溶液与分子筛发生离子交换作用,影响分子筛的酸性;金属活性组分与分子筛表面的硅酸根发生强相互作用生成金属硅酸盐,金属硅酸盐难以还原,降低金属活性组分的催化作用。
发明内容
本发明的目的是要解决现有技术中存在的不足,提供一种高分散度、高可还原性金属-固体酸碱多功能核壳催化剂的制备方法。
为达到上述目的,本发明是按照以下技术方案实施的:
一种金属-固体酸碱多功能核壳催化剂的制备方法,包括以下步骤:将固体酸源和固体碱源按质量比为1:0.1-1.8充分混合均匀后,于450-580℃下密封焙烧0.1-6小时得到固体酸碱双功能核壳催化剂;将金属盐和去离子水混合后,超声震荡1-3小时充分混合均匀得到金属盐溶液,再将金属盐溶液等体积浸渍到固体酸碱双功能核壳催化剂上,固体酸碱双功能核壳催化剂作为载体,等体积浸渍就是载体的体积(即孔体积)和浸渍液的体积一致,浸渍液刚好能完全进入到孔里面,其中金属盐中的金属元素与固体酸碱双功能核壳催化剂的质量比为0.01-1:1,去离子水与固体酸碱双功能核壳催化剂的质量比为0.5-1:1;然后用玻璃棒搅拌15-20min至均匀,经90℃下干燥12小时后,于450-580℃下焙烧0.1-6小时后得到金属-固体酸碱多功能核壳催化剂。本技术方案中,固体酸源和固体碱源按质量比为1:0.1-1.8,金属盐中的金属元素和固体酸碱双功能核壳催化剂按质量比为0.01-1:1。在此物料比例下,既可以保证合成出金属-固体酸碱多功能核壳催化剂,又不会造成浪费,温度过高或过低,时间过长或过短都将会影响金属的分散度、可还原性以及核壳催化剂的酸碱性和形貌,因此焙烧温度设置为450-580℃。
优选地,所述固体酸源和固体碱源按质量比为1:0.2-1.4。在此物料比例下,固体酸源、固体碱源的相对含量适宜,使碱源均匀包覆酸源,最有利于控制核壳催化剂的酸碱性以及形貌。
优选地,所述金属盐中的金属元素与固体酸碱双功能核壳催化剂按质量比为0.01-0.2:1。在此物料比例下,金属盐中的金属元素和固体酸碱双功能核壳催化剂的相对含量适宜,使金属盐在固体酸碱双功能核壳催化剂上均匀地分散,具有高可还原性。
优选地,所述充分混合均匀后的固体酸源和固体碱源放置于锡箔纸封口的加盖坩埚内,于马弗炉中焙烧。
优选地,所述金属盐为硝酸铁、硝酸钴、硝酸镍、硝酸铜、硝酸锌、硝酸钯、硝酸银、硝酸钌、硝酸铂、硝酸锆中的一种。这些金属盐颗粒尺寸小,易溶于水,分散均匀。
优选地,所述固体酸源为ZSM-5、SAPO-34、Y或β沸石分子筛中的一种。选用沸石分子筛的原因是沸石分子筛的酸强度和酸量适宜。
优选地,所述固体碱源为单氰胺、双氰胺、尿素、硫脲、盐酸胍、三聚氰胺中的一种。由于这些固体碱源都是合成类石墨相氮化碳的前驱体,廉价易得,高温下固体碱源热解发生相互交联,形成显碱性的类石墨相氮化碳。当然固体碱源也可以选用其他含氮化合物。
优选地,所述固体酸源和固体碱源充分混合均匀的方法为机械混合法或有机溶剂蒸发诱导法。
优选地,所述机械混合法包括如下步骤:将固体酸源和固体碱源置于研钵或球磨机中,研磨10-60分钟。
优选地,所述有机溶剂蒸发诱导法包括如下步骤:将固体酸源加入到有机溶剂中,室温搅拌15-30分钟,再将固体碱源加入至上述混合溶液中,继续室温搅拌15-30分钟后,于50-100℃下加热搅拌1-3小时至有机溶剂全部蒸发为止。
优选地,所述有机溶剂为无水乙醇。由于无水乙醇廉价易得,固体酸源和固体碱源在无水乙醇中溶解性好、充分混合、分散均匀。
与现有技术相比,本发明合成工艺简单,不需要多步操作,也无需额外加入价格高昂的添加剂;金属盐溶液在显碱性的类石墨相氮化碳上生成高沸点金属氢氧化物,可有效地避免金属盐在烘干、焙烧过程中熔融长大,显著提高金属的分散度和可还原性。本发明制备的金属-固体酸碱多功能核壳催化剂既能保护分子筛酸性不受金属盐浸渍过程的影响,同时分子筛表面显碱性的类石墨相氮化碳使得浸渍的金属具有高分散度和高可还原性。而且本发明充分考虑了沸石分子筛的酸性与类石墨相氮化碳的碱性的结合,通过类石墨相氮化碳包覆沸石分子筛,达到控制分子筛酸中心数量的同时提高分子筛表面碱性的目的;通过调节金属盐、固体酸源和固体碱源的种类和相对含量,可有效地调控金属分散度、可还原性以及核壳催化剂的酸碱性和形貌。
附图说明
图1为对应实施例1、2、3、4样品的XRD谱图。
图2为对应实施例1、4样品的H2-TPR曲线。
具体实施方式
下面结合具体实施例对本发明作进一步描述,此发明的示意性实施例以及说明用来解释本发明,但并不作为对本发明的限定。
实施例1
将0.443g硝酸铜和1.05g去离子水混合后,超声震荡2小时充分混合均匀得到硝酸铜溶液,再将硝酸铜溶液加入到含有1.5gZSM-5分子筛的烧杯中,用玻璃棒搅拌20min至均匀,经90℃下干燥12小时后,500℃焙烧4小时后得到金属-固体酸碱多功能核壳催化剂。
实施例2
将2.5gZSM-5分子筛加入到37.5g无水乙醇中,室温搅拌15分钟,再将0.5g三聚氰胺加入至上述混合溶液中,继续室温搅拌15分钟后,于77℃下加热搅拌2.5小时至无水乙醇全部蒸发为止,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,540℃焙烧5小时后得到固体酸碱双功能核壳催化剂;将0.443g硝酸铜和1.05g去离子水混合后,超声震荡2小时充分混合均匀得到硝酸铜溶液,再将硝酸铜溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌20min至均匀,经90℃下干燥12小时后,500℃焙烧4小时后得到金属-固体酸碱多功能核壳催化剂。
实施例3
将2.5gZSM-5分子筛加入到25.9g无水乙醇中,室温搅拌15分钟,再将1g三聚氰胺加入至上述混合溶液中,继续室温搅拌15分钟后,于77℃下加热搅拌2.5小时至无水乙醇全部蒸发为止,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,450℃焙烧6小时后得到固体酸碱双功能核壳催化剂;将0.443g硝酸铜和1.05g去离子水混合后,超声震荡2小时充分混合均匀得到硝酸铜溶液,再将硝酸铜溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌20min至均匀,经90℃下干燥12小时后,500℃焙烧4小时后得到金属-固体酸碱多功能核壳催化剂。
实施例4
将2.5gZSM-5分子筛加入到25.9g无水乙醇中,室温搅拌15分钟,再将2g三聚氰胺加入至上述混合溶液中,继续室温搅拌15分钟后,于77℃下加热搅拌2.5小时至无水乙醇全部蒸发为止,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,550℃焙烧3小时后得到固体酸碱双功能核壳催化剂;将0.443g硝酸铜和1.05g去离子水混合后,超声震荡2小时充分混合均匀得到硝酸铜溶液,再将硝酸铜溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌20min至均匀,经90℃下干燥12小时后,500℃焙烧4小时后得到金属-固体酸碱多功能核壳催化剂。
实施例5
将2.5gSAPO-34分子筛和1.25g尿素加入至球磨罐,6500rpm下球磨1小时,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,490℃焙烧5小时后得到固体酸碱双功能核壳催化剂;将0.024g硝酸银和0.75g去离子水混合后,超声震荡2小时充分混合均匀得到硝酸银溶液,再将硝酸银溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌17min至均匀,经90℃下干燥12小时后,450℃焙烧6小时后得到金属-固体酸碱多功能核壳催化剂。
实施例6
将2.5gβ沸石分子筛加入到28.7g无水乙醇中,室温搅拌15分钟,再将1.5g盐酸胍加入至上述混合溶液中,继续室温搅拌15分钟后,于77℃下加热搅拌2.5小时至无水乙醇全部蒸发为止,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,480℃焙烧5小时后得到固体酸碱双功能核壳催化剂;将0.074g硝酸铂和0.825g去离子水混合后,超声震荡3小时充分混合均匀得到硝酸铂溶液,再将硝酸铂溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌19min至均匀,经90℃下干燥12小时后,480℃焙烧4小时后得到金属-固体酸碱多功能核壳催化剂。
实施例7
将2.5gY沸石分子筛和2g单氰胺加入至玛瑙研钵,研磨35分钟,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,500℃焙烧6小时后得到固体酸碱双功能核壳催化剂;将0.235g硝酸钌和0.9g去离子水混合后,超声震荡1小时充分混合均匀得到硝酸钌溶液,再将硝酸钌溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌15min至均匀,经90℃下干燥12小时后,500℃焙烧2小时后得到金属-固体酸碱多功能核壳催化剂。
实施例8
将2.5gβ沸石分子筛和2.25g尿素加入至球磨罐,6500rpm下球磨1小时,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,560℃焙烧5小时后得到固体酸碱双功能核壳催化剂;将0.593g硝酸钴和0.975g去离子水混合后,超声震荡3小时充分混合均匀得到硝酸钴溶液,再将硝酸钴溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌18min至均匀,经90℃下干燥12小时后,520℃焙烧5小时后得到金属-固体酸碱多功能核壳催化剂。
实施例9
将2.5gSAPO-34分子筛和2.75g尿素加入至球磨罐,6500rpm下球磨1小时,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,450℃焙烧3小时后得到固体酸碱双功能核壳催化剂;将0.467g硝酸镍和1.05g去离子水混合后,超声震荡2.5小时充分混合均匀得到硝酸镍溶液,再将硝酸镍溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌20min至均匀,经90℃下干燥12小时后,550℃焙烧4小时后得到金属-固体酸碱多功能核壳催化剂。
实施例10
将2.5gSAPO-34分子筛和3.5g硫脲加入至玛瑙研钵,研磨35分钟,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,550℃焙烧3小时后得到固体酸碱双功能核壳催化剂;将0.422g硝酸钯和1.2g去离子水混合后,超声震荡1.5小时充分混合均匀得到硝酸钯溶液,再将硝酸钯溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌18min至均匀,经90℃下干燥12小时后,580℃焙烧1小时后得到金属-固体酸碱多功能核壳催化剂。
实施例11
将2.5gY沸石分子筛和3.75g硫脲加入至球磨罐,6500rpm下球磨1小时,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,470℃焙烧4小时后得到固体酸碱双功能核壳催化剂;将1.628g硝酸铁和1.05g去离子水混合后,超声震荡1小时充分混合均匀得到硝酸铁溶液,再将硝酸铁溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌19min至均匀,经90℃下干燥12小时后,500℃焙烧6小时后得到金属-固体酸碱多功能核壳催化剂。
实施例12
将2.5gY沸石分子筛加入到40.5g无水乙醇中,室温搅拌15分钟,再将4g三聚氰胺加入至上述混合溶液中,继续室温搅拌15分钟后,于77℃下加热搅拌2.5小时至无水乙醇全部蒸发为止,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,580℃焙烧6小时后得到固体酸碱双功能核壳催化剂;将1.271g硝酸锆和1.35g去离子水混合后,超声震荡1.5小时充分混合均匀得到硝酸锆溶液,再将硝酸锆溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌16min至均匀,经90℃下干燥12小时后,450℃焙烧2小时后得到金属-固体酸碱多功能核壳催化剂。
实施例13
将2.5gβ沸石分子筛和4.5g双氰胺加入至玛瑙研钵,研磨35分钟,所得样品于90℃下干燥12小时后转移至锡箔纸封口的加盖坩埚内,510℃焙烧3小时后得到固体酸碱双功能核壳催化剂;将1.365g硝酸锌和1.5g去离子水混合后,超声震荡3小时充分混合均匀得到硝酸锌溶液,再将硝酸锌溶液加入到含有1.5g固体酸碱双功能核壳催化剂的烧杯中,用玻璃棒搅拌15min至均匀,经90℃下干燥12小时后,560℃焙烧4小时后得到金属-固体酸碱多功能核壳催化剂。
如图1所示,图1中的a-d分别对应实施例1、2、3、4样品的XRD谱图,从图中可以看出实施例1、2、4样品在2θ=36.32°、38.06°处出现较强的衍射峰,属于氧化铜的特征衍射峰,实施例3样品在2θ=36.32°、38.06°处基本没有出现衍射峰,证明实施例3的样品,氧化铜颗粒尺寸非常小,分散得非常均匀。
分别取实施例1、4制得的金属-固体酸碱多功能核壳催化剂作为样品,分别进行H2-TPR测试。
H2-TPR测样过程:先将50mg样品在500℃下高纯He气流中(50ml/min)预处理2小时,然后降温至100℃,气体切换为纯H2处理1小时,之后用He气流吹扫至基线平稳,最后以10℃/min的速率升温至900℃进行程序升温还原反应,在线使用热导池检测器检测尾气中的氢气含量变化情况。
如图2所示,图2中a-b分别对应实施例1、4样品的H2-TPR曲线,从图中可以看出浸渍到固体酸碱载体上的氧化铜还原峰向低温区移动且耗氢量增大,说明此样品中氧化铜的可还原性提高。
本发明的技术方案不限于上述具体实施例的限制,凡是根据本发明的技术方案做出的技术变形,均落入本发明的保护范围之内。
Claims (10)
1.一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于,包括以下步骤:将固体酸源和固体碱源按质量比为1:0.1-1.8充分混合均匀后,于450-580℃下密封焙烧0.1-6小时得到固体酸碱双功能核壳催化剂;将金属盐和去离子水混合后,超声震荡1-3小时充分混合均匀得到金属盐溶液,再将金属盐溶液等体积浸渍到固体酸碱双功能核壳催化剂上,其中金属盐中的金属元素与固体酸碱双功能核壳催化剂的质量比为0.01-1:1,去离子水与固体酸碱双功能核壳催化剂的质量比为0.5-1:1;然后用玻璃棒搅拌15-20min至均匀,经90℃下干燥12小时后,于450-580℃下焙烧0.1-6小时后得到金属-固体酸碱多功能核壳催化剂。
2.根据权利要求1所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述固体酸源和固体碱源按质量比为1:0.2-1.4;金属盐中的金属元素与固体酸碱双功能核壳催化剂的质量比为0.01-0.2:1。
3.根据权利要求1所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述充分混合均匀后的固体酸源和固体碱源放置于锡箔纸封口的加盖坩埚内,于马弗炉中焙烧。
4.根据权利要求1所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述金属盐为硝酸铁、硝酸钴、硝酸镍、硝酸铜、硝酸锌、硝酸钯、硝酸银、硝酸钌、硝酸铂、硝酸锆中的一种。
5.根据权利要求1所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述固体酸源为ZSM-5、SAPO-34、Y或β沸石分子筛中的一种。
6.根据权利要求1所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述固体碱源为单氰胺、双氰胺、尿素、硫脲、盐酸胍、三聚氰胺中的一种。
7.根据权利要求1所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述固体酸源和固体碱源充分混合均匀的方法为机械混合法或有机溶剂蒸发诱导法。
8.根据权利要求7所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述机械混合法包括如下步骤:将固体酸源和固体碱源置于研钵或球磨机中,研磨10-60分钟。
9.根据权利要求7所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述有机溶剂蒸发诱导法包括如下步骤:将固体酸源加入到有机溶剂中,室温搅拌15-30分钟,再将固体碱源加入至上述混合溶液中,继续室温搅拌15-30分钟后,于50-100℃下加热搅拌1-3小时至有机溶剂全部蒸发为止。
10.根据权利要求9所述的一种金属-固体酸碱多功能核壳催化剂的制备方法,其特征在于:所述有机溶剂为无水乙醇。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111871448A (zh) * | 2020-08-03 | 2020-11-03 | 西北大学 | 一种用于提高甲烷无氧芳构化反应性能的催化剂及其制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102872904A (zh) * | 2012-10-12 | 2013-01-16 | 常州大学 | 一种择形催化剂的制备方法 |
CN103381371A (zh) * | 2013-07-16 | 2013-11-06 | 常州大学 | 一种氮化碳/微孔分子筛复合材料的制备方法 |
KR101466648B1 (ko) * | 2013-05-22 | 2014-12-01 | 한국에너지기술연구원 | 제올라이트-질화탄소화합물 복합체의 제조방법 및 이를 이용한 이산화탄소의 선택적 흡착 |
CN106732328A (zh) * | 2016-11-29 | 2017-05-31 | 福州大学 | 三维结构金属氧化物/石墨相碳化氮复合材料及其制备 |
CN106861746A (zh) * | 2017-03-22 | 2017-06-20 | 北京师范大学 | 一种氮化碳负载单分散氧化态金属原子催化材料的制备方法 |
CN107297217A (zh) * | 2017-06-01 | 2017-10-27 | 西安交通大学 | 一种多孔薄层石墨相氮化碳载铂光催化剂及其制备方法和应用 |
-
2018
- 2018-07-02 CN CN201810717666.7A patent/CN108772097A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102872904A (zh) * | 2012-10-12 | 2013-01-16 | 常州大学 | 一种择形催化剂的制备方法 |
KR101466648B1 (ko) * | 2013-05-22 | 2014-12-01 | 한국에너지기술연구원 | 제올라이트-질화탄소화합물 복합체의 제조방법 및 이를 이용한 이산화탄소의 선택적 흡착 |
CN103381371A (zh) * | 2013-07-16 | 2013-11-06 | 常州大学 | 一种氮化碳/微孔分子筛复合材料的制备方法 |
CN106732328A (zh) * | 2016-11-29 | 2017-05-31 | 福州大学 | 三维结构金属氧化物/石墨相碳化氮复合材料及其制备 |
CN106861746A (zh) * | 2017-03-22 | 2017-06-20 | 北京师范大学 | 一种氮化碳负载单分散氧化态金属原子催化材料的制备方法 |
CN107297217A (zh) * | 2017-06-01 | 2017-10-27 | 西安交通大学 | 一种多孔薄层石墨相氮化碳载铂光催化剂及其制备方法和应用 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111871448A (zh) * | 2020-08-03 | 2020-11-03 | 西北大学 | 一种用于提高甲烷无氧芳构化反应性能的催化剂及其制备方法 |
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