CN109485060B - SBA-16 molecular sieve modified by nano iron and preparation method and application thereof - Google Patents
SBA-16 molecular sieve modified by nano iron and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 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 134
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 132
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 22
- 238000005805 hydroxylation reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- -1 organic template Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 230000033444 hydroxylation Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims 3
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 description 22
- 238000002425 crystallisation Methods 0.000 description 17
- 230000008025 crystallization Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
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- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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Abstract
The invention relates to a SBA-16 molecular sieve modified by nano iron, wherein the nano iron is embedded in a framework of the molecular sieve in a simple substance form. The invention also relates to a preparation method of the SBA-16 molecular sieve modified by the nano iron, which comprises the following steps: s1, mixing a silicon source, water, an organic template agent, an iron source complex, acid and alcohol to prepare a reaction mixture; s2, carrying out hydrothermal crystallization treatment on the reaction mixture, and then carrying out post-treatment to obtain the Fe-SBA-16 molecular sieve; s3, reducing the Fe-SBA-16 molecular sieve by hydrogen to obtain the SBA-16 molecular sieve modified by the nano iron. The obtained SBA-16 molecular sieve modified by the nano-iron still has a cubic mesoporous pore structure and a higher specific surface area, and the particle size of the nano-iron in the framework is concentrated between 3 and 4 nm.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to a SBA-16 molecular sieve modified by nano-iron and a preparation method thereof.
Background
In recent years, research on supported catalysts has been greatly developed, and the supported catalysts not only solve the problem that homogeneous catalysts are difficult to recycle, but also overcome the problem of environmental pollution caused by metal loss. The mesoporous material has a high specific surface area and a regular pore channel structure, can ensure high dispersion of active sites of the supported catalyst, and maintains the original catalytic activity and selectivity of the homogeneous catalyst; in addition, the mesoporous material has abundant hydroxyl on the surface, so that the surface functionalization is easy, and simultaneously, the mesoporous material has higher chemical stability and mechanical stability, so that the material is an ideal homogeneous catalyst carrier material. Compared with the conventional hexagonal mesoporous M41S molecular sieve, the SBA-16 molecular sieve has three-dimensional pore channels which enable reactants to enter the molecular sieve more easily for reaction without causing the blockage of the pore channels of the molecular sieve. Meanwhile, the molecular sieve has larger specific surface area, regular pore size distribution, thicker pore wall and better thermal stability, and has attracted extensive attention in the aspects of catalysts, adsorbents, separating agents and nanoscience. Although the mesoporous material itself generally has substantially no catalytic activity, when it is loaded or doped with an active component having redox ability (such as a transition metal or a metal oxide), redox active centers are formed on the molecular sieve, and the redox ability is greatly improved.
The trivalent iron ions are loaded on the SBA-16 molecular sieve, so that the acid quantity and the ion exchange capacity of the molecular sieve can be obviously improved, the prepared Fe/SBA-16 has good catalytic effect in the alkylation reaction process of oxidizing alkane, phenol and benzene, but the supported molecular sieve catalyst obtained by the conventional method is easy to cause the agglomeration of metal particles in the drying and roasting processes, so that the pore channels of the molecular sieve are covered by a large amount of metal and metal oxide, and the blockage of the pore channels of the molecular sieve and the reduction of the specific surface area are caused. Thus, the selectivity of the catalyst and the lifetime of the catalyst are affected to some extent.
Therefore, the problem at present is that research and development of a nano-iron modified SBA-16 molecular sieve and a preparation method and application thereof are urgently needed.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a SBA-16 molecular sieve modified by nano-iron and a preparation method and application thereof. The invention adopts the interaction mode of iron source complex and organic template agent through electrostatic attraction to lead iron ions (Fe)3+) Enters the SBA-16 molecular sieve framework to replace silicon atoms, and then iron ions (Fe) in the framework are generated by hydrogen3+) The single iron (Fe) is directly reduced into the single iron (Fe) which is directly embedded into the molecular sieve framework, and the single iron (Fe) can not be mutually agglomerated due to the steric hindrance and the limiting effect of the molecular sieve framework and the pore channel, so that the SBA-16 molecular sieve modified by a single nano iron atom is formed.
To this end, the invention provides a nano-iron modified SBA-16 molecular sieve, wherein nano-iron is embedded in the framework of the molecular sieve in the form of a simple substance.
According to the invention, the particle size of the nano-iron is 3-4 nm; the specific surface area of the molecular sieve is more than or equal to 430m2/g。
The second aspect of the invention provides a preparation method of the nano-iron modified SBA-16 molecular sieve according to the first aspect of the invention, which comprises the following steps:
step S1, mixing a silicon source, water, an organic template agent, an iron source complex, an acid and alcohol to prepare a reaction mixture;
step S2, carrying out hydrothermal crystallization treatment on the reaction mixture, and then carrying out post-treatment to obtain the Fe-SBA-16 molecular sieve;
step S3, reducing the Fe-SBA-16 molecular sieve by hydrogen to prepare the SBA-16 molecular sieve modified by the nano iron;
wherein, in step S1, the molar ratio of the silicon source, water, organic template, iron source complex and acid is SiO2:H2O:R:Fe:H+Calculated as 1 (50-350): (0.005-0.015): (0.05-0.20): 0.08-0.25), preferably 1 (70-170): 0.008-0.013): 0.05-0.20): 0.16-022); wherein R is an organic template.
According to the method of the invention, in step S1, the temperature of the mixing is 40-60 ℃.
In some embodiments of the present invention, in step S1, the silicon source is selected from one or more of white carbon black, ethyl orthosilicate, sodium silicate and silica sol, preferably ethyl orthosilicate.
In other embodiments of the present invention, the organic templating agent is selected from the group consisting of amphiphilic nonionic triblock surfactants and/or hexamethylenetetramine; preferably, the amphiphilic nonionic triblock surfactant is selected from EO106PO70EO106(F127) And/or EO132PO50EO132(F108) More preferably EO106PO70EO106(F127)。
According to the method of the present invention, the iron source complex includes a complex formed by an iron-containing compound and ethylenediaminetetraacetic acid; preferably the iron-containing compound is selected from iron and/or ferrous salts, more preferably from one or more of potassium ferricyanide, potassium ferrocyanide, ferrous chloride and ferrous nitrate, most preferably from potassium ferricyanide. Preferably, the molar ratio of the iron-containing compound to the ethylenediaminetetraacetic acid is 1 (1-4), more preferably 1 (1.3-3.8).
In some embodiments of the invention, the acid is selected from one or more of hydrochloric acid, sulfuric acid, and nitric acid.
According to the method disclosed by the invention, the silicon source and the iron source complex can be better mutually dissolved by adding the alcohol in the step S1. In other embodiments of the present invention, the alcohol is selected from one or more of ethanol, ethylene glycol and propanol, preferably ethanol. Preferably, the molar ratio of alcohol to water is 1 (10-30), more preferably 1 (11.8-27.1).
According to the method of the present invention, in step S2, the temperature of the hydrothermal crystallization treatment is 80 to 110 ℃, preferably 90 to 100 ℃. The time of the hydrothermal crystallization treatment is 24-72h, preferably 48-60 h.
According to the method of the invention, in step S2, the post-treatment comprises filtering, washing, drying and roasting the product after the hydrothermal crystallization treatment.
In some embodiments of the invention, the drying temperature is 100-. And removing the moisture and the organic template agent on the surface of the molecular sieve through drying treatment.
In other embodiments of the present invention, the temperature of the calcination is 500-700 ℃, preferably 550-650 ℃; the roasting time is 4-7h, preferably 5-6 h. And removing the organic template agent and water in the pore channels of the molecular sieve and enhancing the strength of the molecular sieve framework and the like by roasting.
According to the method of the present invention, iron ions (Fe) in the Fe-SBA-16 molecular sieve prepared in step S23+) Is present in the framework of the molecular sieve in place of the silicon atoms in the framework of the original molecular sieve.
According to the method of the invention, in step S3, the reduction process comprises: the temperature is increased to the reduction temperature of 400-700 ℃, preferably 500-600 ℃ at the heating rate of 3-10 ℃/min, preferably 5-7 ℃/min, and the reduction is carried out for 2-8h, preferably 4-6h at the reduction temperature.
According to the method of the present invention, in the nano-iron modified SBA-16 molecular sieve prepared in step S3, iron ions (Fe) in the Fe-SBA-16 molecular sieve prepared in step S2 are reduced3+) Separated from the framework of the molecular sieve and embedded in the framework of the molecular sieve in the form of elementary substance iron.
The Fe/SBA-16 molecular sieve is prepared by a conventional loading method or a deposition method; the Fe-SBA-16 molecular sieve adopts the method of the invention, namely the iron source complex and the organic template agent lead iron ions (Fe) to be generated in an electrostatic attraction interaction mode3+) Entering into SBA-16 molecular sieve skeleton and substituting silicon atom to prepare molecular sieve; the difference between the two is that the iron source in the 'Fe/SBA-16' molecular sieve exists on the surface of the molecular sieve or in the pore canal of the molecular sieve, and the iron source in the 'Fe-SBA-16' molecular sieve exists in the framework of the molecular sieve.
In a third aspect, the invention provides a use of the nano-iron modified SBA-16 molecular sieve according to the first aspect of the invention or the nano-iron modified SBA-16 molecular sieve prepared by the method according to the second aspect of the invention in the preparation of phenol by benzene hydroxylation reaction.
The conditions for the hydroxylation reaction to produce phenol may be conventional in the art, depending on the application of the present invention.
In the supported molecular sieve obtained by the conventional supporting method, the metal is not uniformly distributed, and most of the metal exists outside the molecular sieve framework in the form of oxide or simple substance, namely exists on the surface of the molecular sieve or in a molecular sieve pore channel, so that the specific surface area of the molecular sieve is greatly reduced, and reactants are prevented from entering the molecular sieve pore channel to react; in addition, a large amount of iron simple substance or iron oxide in the prepared Fe/SBA-16 molecular sieve not only can reduce the mass transfer and diffusion effects of the molecular sieve, but also can cause the loss of metal atoms in the reaction process, so that the active components of the molecular sieve are continuously reduced, and the activity of the molecular sieve is reduced. Although the conventional deposition method can obtain a supported catalyst with uniform dispersity, the problem of easy agglomeration of metals caused in the roasting process cannot be solved.
Compared with the Fe/SBA-16 molecular sieve prepared by the conventional loading method and the deposition method, the SBA-16 molecular sieve modified by the nano-iron prepared by the method has the following characteristics: iron atoms (Fe) are embedded in a molecular sieve framework in a simple substance form, and the whole molecular sieve still has a cubic mesoporous pore structure; meanwhile, due to the steric hindrance and the size limitation of the molecular sieve, reduced iron atoms (Fe) in the framework cannot be mutually aggregated to form large particles, so that the particle size is very small and can reach several nanometers. In addition, the SBA-16 molecular sieve modified by the nano-iron prepared by the method has large specific surface area, and when the molecular sieve is used for preparing phenol by benzene hydroxylation reaction, the conversion rate of benzene and the selectivity of phenol are both high, so that a good effect is achieved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a small angle XRD pattern of a nano-iron modified SBA-16 molecular sieve prepared in example 3 of the present invention;
FIG. 2 is a HRTEM image of the SBA-16 molecular sieve modified by nano-iron prepared in example 3 of the present invention;
FIG. 3 is an XPS plot of the SBA-16 molecular sieve modified with nano-iron prepared in example 3 of the present invention.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is given, with reference to the accompanying examples and drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
The instrument and the characterization test method adopted by the invention are as follows:
(1) x-ray diffraction analysis (XRD): measuring by using an X-Pert series X-ray diffractometer manufactured by Philips;
(2) high Resolution Transmission Electron Microscopy (HRTEM): the measurement was carried out by a Rigku's model Jem-3010 high-resolution transmission electron microscope;
(3) x-ray photoelectron spectroscopy (XPS): measuring by using an ESCALB 250spectrometer type X-ray photoelectron spectrometer manufactured by Thermo company;
(4) specific surface area analysis (BET): the measurement was carried out using a full-automatic specific surface analyzer model ASAP2020, Micromeritics.
Examples
Example 1
At 60 ℃, 3.2g F127 (EO)106PO70EO106) And 70g of deionized water are sequentially added into a reactor, the mixture is stirred uniformly, 50mL of 0.1mol/L hydrochloric acid solution is added, after the mixture is stirred uniformly, a complex of 0.7g of ferrous chloride and 3.2g of ethylenediamine tetraacetic acid is added, the mixture is continuously stirred, 11g of Tetraethoxysilane (TEOS) is slowly and dropwise added, and finally 15g of ethanol is added, wherein the molar ratio of the obtained mixture is SiO2:73H2O:0.005R:0.1Fe:0.09H+And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. And after crystallization is completed, cooling to room temperature, separating and washing the reacted mixture, drying at 110 ℃, transferring the dried sample to a muffle furnace, and roasting at 500 ℃ for 4 hours to obtain Fe-SBA-16 molecular sieve raw powder. Placing Fe-SBA-16 molecular sieve raw powder at the bottom of a quartz tubeAnd introducing hydrogen, raising the temperature to 400 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 hours to obtain the SBA-16 molecular sieve modified by the nano iron. The samples obtained were analyzed by BET and the results are shown in table 1.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, and benzene, acetonitrile, a catalyst and H are mixed2O2(benzene, acetonitrile and H)2O2In a molar ratio of 1:3:2) were sequentially added to the reactor, reacted at 60 ℃ for 4 hours, and the results of measuring the conversion of benzene and the selectivity of phenol are shown in Table 2.
Example 2
The same as example 1, except that the amount of F127 was changed to 4.9g, the amount of deionized water was changed to 100g, the amount of hydrochloric acid was changed to 80mL, the amount of iron source was changed to ferrous nitrate, the amount was changed to 1.08g, the amount of ethylenediaminetetraacetic acid was changed to 6.6g, the amount of silicon source was changed to silica sol (SW-25, silica content 25 wt%), the amount was 9.6g, the amount of alcohol was changed to ethylene glycol, the amount was changed to 23g, and the molar ratio of the obtained mixture was SiO2:139H2O:0.009R:0.15Fe:0.2H+The crystallization temperature is 90 ℃, the crystallization time is 60 hours, the drying temperature is 120 ℃, the roasting temperature is 550 ℃, the roasting time is 5 hours, the hydrogen heating rate is changed to 4 ℃/min, the reduction temperature is changed to 500 ℃, the reduction time is changed to 3 hours, and the rest components and the synthesis conditions are unchanged, so that the SBA-16 molecular sieve modified by the nano iron is obtained. The samples obtained were analyzed by BET and the results are shown in table 1.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, the hydroxylation reaction conditions are the same as those of the example 1, and the measured results of the conversion rate of the benzene and the selectivity of the phenol are shown in a table 2.
Example 3
The same as example 1, except that the organic template agent was changed to F108 in an amount of 3.7g, the deionized water was changed to 80.6g, the acid was changed to nitric acid in an amount of 90mL, the iron source was changed to potassium ferrocyanide in an amount of 3.6g, the silicon source was changed to sodium silicate in an amount of 12.1g, the ethanol was changed to 7.6g, and the molar ratio of the obtained mixture was SiO2:104H2O:0.006R:0.2Fe:0.21H+The crystallization temperature is 100 ℃, the crystallization time is 54 hours, the drying temperature is changed to 130 ℃, and the roasting temperature is changed toThe degree is changed to 600 ℃, the roasting time is changed to 6h, the hydrogen reduction heating rate is changed to 5 ℃/min, the reduction temperature is changed to 550 ℃, the reduction time is changed to 4h, and the rest components and the synthesis conditions are not changed, so that the SBA-16 molecular sieve modified by the nano iron is obtained. The samples obtained were analyzed by BET and the results are shown in table 1. The obtained sample was subjected to small angle powder XRD analysis, HRTEM analysis and XPS analysis, and the results are shown in fig. 1 to 3, respectively.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, the hydroxylation reaction conditions are the same as those of the example 1, and the measured results of the conversion rate of the benzene and the selectivity of the phenol are shown in a table 2.
Example 4
The same as example 1, except that the amount of F127 was changed to 7.2g, the amount of deionized water was changed to 140.0g, the amount of hydrochloric acid was changed to 100mL, the iron source was changed to potassium ferricyanide in an amount of 1.1g, the amount of TEOS was changed to 9.6g, the alcohol was changed to propanol in an amount of 32g, and the molar ratio of the obtained mixture was SiO2:169H2O:0.012R:0.07Fe:0.22H+The crystallization temperature is 100 ℃, the crystallization time is 60 hours, the drying temperature is changed to 140 ℃, the roasting temperature is changed to 600 ℃, the roasting time is changed to 6 hours, the hydrogen reduction heating rate is changed to 6 ℃/min, the reduction temperature is changed to 600 ℃, the reduction time is changed to 6 hours, and the rest components and the synthesis conditions are unchanged, so that the nano-iron modified SBA-16 molecular sieve is obtained. The samples obtained were analyzed by BET and the results are shown in table 1.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, the hydroxylation reaction conditions are the same as those of the example 1, and the measured results of the conversion rate of the benzene and the selectivity of the phenol are shown in a table 2.
Example 5
The same as example 1, except that the organic template agent was changed to HTMA in an amount of 0.34g, the deionized water was changed to 450.8g, the acid was changed to sulfuric acid in an amount of 75mL, the iron source was changed to potassium ferricyanide in an amount of 6.4g, the ethylenediaminetetraacetic acid in an amount of 14.4g, the silicon source was changed to white carbon black (silica content: 90 wt%), in an amount of 10.8g, the alcohol was changed to ethylene glycol in an amount of 61g, and the molar ratio of the obtained mixture was SiO2:155H2O:0.015R:0.12Fe:0.09H+The crystallization temperature is changed to 100 ℃,the crystallization time is changed to 50h, the drying temperature is changed to 120 ℃, the roasting temperature is changed to 650 ℃, the roasting time is changed to 6h, the hydrogen reduction heating rate is changed to 5 ℃/min, the reduction temperature is changed to 650 ℃, the reduction time is changed to 6h, and the rest components and the synthesis conditions are unchanged, so that the SBA-16 molecular sieve modified by the nano iron is obtained. The samples obtained were analyzed by BET and the results are shown in table 1.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, the hydroxylation reaction conditions are the same as those of the example 1, and the measured results of the conversion rate of the benzene and the selectivity of the phenol are shown in a table 2.
Comparative example 1
Sequentially adding 3.1g F127 and 50.1g of deionized water into a reactor at 50 ℃, stirring uniformly, adding 14.1mL of 0.1mol/L nitric acid solution, stirring uniformly until the solution is clear, then adding 9.3g of propanol, finally adding 5.0g of sodium silicate, transferring the mixture into a crystallization kettle, heating to 90 ℃, and crystallizing at constant temperature for 48 hours. And after crystallization is completed, cooling to room temperature, separating and washing the reacted mixture, drying at 100 ℃, and then transferring the sample to a muffle furnace to roast for 4 hours at 500 ℃ to obtain the SBA-16 molecular sieve raw powder. Dispersing 5g of SBA-16 molecular sieve raw powder into 10g of ferrous chloride solution (the mass concentration of ferrous chloride is 2 wt%), adding urea to adjust the pH value of the solution to be about 8, and obtaining a reaction mixture with the molar ratio of SiO2:158H2O:0.021R:0.09Fe:0.57H+Separating and washing the reacted mixture again, drying at 100 ℃, and then transferring the sample to a muffle furnace again to roast for 4 hours at 500 ℃ to obtain the Fe/SBA-16 molecular sieve raw powder. And (3) placing the Fe/SBA-16 molecular sieve at the bottom of a quartz tube, introducing hydrogen, raising the temperature to 400 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 hours to obtain the SBA-16 molecular sieve modified by the nano iron. The samples obtained were analyzed by BET and the results are shown in table 1.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, the hydroxylation reaction conditions are the same as those of the example 1, and the measured results of the conversion rate of the benzene and the selectivity of the phenol are shown in a table 2.
Comparative example 2
Under the condition of 40 ℃, 4.4g F108 and 75.2g of deionized water are sequentially added into a reactor, uniformly stirred, then 45mL of 0.1mol/L hydrochloric acid solution is added, after uniform stirring, 6.2g of Tetraethoxysilane (TEOS) and 18.7g of ethanol are added, the mixture is transferred into a crystallization kettle, the temperature is raised to 110 ℃, and crystallization is carried out at constant temperature for 60 hours. And after crystallization is completed, cooling to room temperature, separating and washing the reacted mixture, drying at 110 ℃, and then transferring the sample to a muffle furnace to roast for 5 hours at 550 ℃ to obtain the SBA-16 molecular sieve raw powder. Adding 5g of SBA-16 molecular sieve raw powder and 1.1g of ferrous nitrate into 100g of deionized water, and fully and uniformly stirring to obtain a reaction mixture with the molar ratio of SiO2:324H2O:0.016R:0.2Fe:0.27H+Separating and washing the reacted mixture again, drying at 110 ℃, and then transferring the sample into a muffle furnace again to roast for 5 hours at 550 ℃ to obtain the Fe/SBA-16 molecular sieve raw powder. And (3) placing the Fe/SBA-16 molecular sieve at the bottom of a quartz tube, introducing hydrogen, raising the temperature to 700 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 6 hours to obtain the SBA-16 molecular sieve modified by the nano iron. The samples obtained were analyzed by BET and the results are shown in table 1.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, the hydroxylation reaction conditions are the same as those of the example 1, and the measured results of the conversion rate of the benzene and the selectivity of the phenol are shown in a table 2.
Comparative example 3
At 60 deg.C, 5.0g F127 (EO)106PO70EO106) And 124.4g of deionized water are sequentially added into the reactor, the mixture is stirred uniformly, 56mL of 0.1mol/L hydrochloric acid solution is added, after the mixture is stirred uniformly, 0.7g of ferrous chloride and 3.3g of ethylenediamine tetraacetic acid complex are added, the mixture is continuously stirred, 3.9g of Tetraethoxysilane (TEOS) is slowly and dropwise added, and finally 9.08g of ethanol is added, the molar ratio of the obtained mixture is SiO2:370H2O:0.02R:0.3Fe:0.3H+And transferring the mixture to a crystallization kettle, heating to 110 ℃, and crystallizing for 72 hours at constant temperature. After crystallization is completed, cooling to room temperature, separating and washing the reacted mixture at 110 deg.CAnd (3) drying under the condition, transferring the dried sample into a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain Fe-SBA-16 molecular sieve raw powder. Placing Fe-SBA-16 molecular sieve raw powder at the bottom of a quartz tube, introducing hydrogen, heating to 400 ℃ at a heating rate of 3 ℃/min, and keeping for 2 hours to obtain the SBA-16 molecular sieve modified by nano iron. The samples obtained were analyzed by BET and the results are shown in table 1.
The obtained molecular sieve is used for preparing phenol by hydroxylation of benzene, the hydroxylation reaction conditions are the same as those of the example 1, and the measured results of the conversion rate of the benzene and the selectivity of the phenol are shown in a table 2.
TABLE 1
TABLE 2
| Conversion of benzene/%) | Selectivity of phenol/%) | |
| Example 1 | 26.7 | 80.9 |
| Example 2 | 30.1 | 82.2 |
| Example 3 | 30.8 | 84.9 |
| Example 4 | 35.5 | 88.7 |
| Example 5 | 28.3 | 81.4 |
| Comparative example 1 | 20.1 | 51.3 |
| Comparative example 2 | 18.2 | 46.7 |
| Comparative example 3 | 0 | 0 |
As can be seen from table 1, in comparative examples 1-2 and examples 1-5, in comparative example 1, the iron source is directly deposited on the surface of the molecular sieve by precipitation, the metal active component on the dispersed catalyst obtained by this method is uniformly dispersed, and then the uniformly dispersed iron compound is directly reduced to elemental iron by hydrogen. Although the supported catalyst with high dispersity can be obtained by the method, a large amount of iron is lost in the reaction process because the iron is still on the surface of the molecular sieve, so that the catalyst loses activity; the comparative example 2 adopts a loading method, and then the iron ions can be reduced into simple substances through hydrogen reduction, but a large amount of iron compounds directly cover the surface of the molecular sieve at the early stage and simultaneously enter the pore channels of the molecular sieve, so that the effect of the reduction at the later stage is not ideal, and the iron compounds which are not reduced can cause the blockage of the pore channels of the molecular sieve; in contrast, in comparative example 3, although the synthesis method was exactly the same as that of example 1, it can be seen from the BET specific surface area value that SBA-16 molecular sieve was not synthesized due to the problem of the raw material ratio.
As can be seen from Table 2, when the nano-iron modified SBA-16 molecular sieves provided in examples 1-5 of the present invention are used in the hydroxylation reaction of benzene, the conversion rate of benzene and the selectivity of phenol are both higher than those of the molecular sieve prepared by the precipitation method in comparative example 1 and the molecular sieve prepared by the loading method in comparative example 2. In addition, in comparative example 3, since no SBA-16 molecular sieve was formed due to the problem of the compounding ratio, the conversion of benzene and the selectivity of phenol were substantially 0.
As can be seen from the analysis of the figures 1 and 2, the SBA-16 molecular sieve modified by nano-iron prepared by the method still has the cubic mesoporous structure of SBA-16, which shows that iron atoms can be orderly dispersed in the molecular sieve framework without damaging the molecular sieve structure, and meanwhile, the particle size distribution of the iron atoms is between 3 nm and 4nm, so that the active site of the molecular sieve can be effectively ensured not to be lost in the catalytic reaction process.
Analysis of FIG. 3 shows that there are two distinct characteristic peaks at 712.3eV and 725.9eV, which correspond to orbital binding energies of Fe2p3/2 and Fe2p1/2, and thus the nano-iron modified SBA-16 molecular sieve prepared by the method of the present invention is illustrated, wherein iron is embedded in the molecular sieve framework in the form of simple substance.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (16)
1. A SBA-16 molecular sieve modified by nano-iron is provided, wherein the nano-iron is embedded in the framework of the molecular sieve in a simple substance form,
the preparation method of the SBA-16 molecular sieve modified by the nano-iron comprises the following steps:
step S1, mixing a silicon source, water, an organic template agent, an iron source complex, an acid and alcohol to prepare a reaction mixture;
step S2, carrying out hydrothermal crystallization treatment on the reaction mixture, and then carrying out post-treatment to obtain the Fe-SBA-16 molecular sieve;
step S3, reducing the Fe-SBA-16 molecular sieve by hydrogen to prepare the SBA-16 molecular sieve modified by the nano iron;
wherein, in step S1, the molar ratio of the silicon source, water, organic template, iron source complex and acid is SiO2:H2O:R:Fe:H+Calculated as 1 (50-350): (0.005-0.015): 0.05-0.20): 0.08-0.25), R is organic template agent,
the molar ratio of the alcohol to the water is 1 (10-30),
the iron source complex comprises a complex formed by an iron-containing compound and ethylene diamine tetraacetic acid,
in step S3, the reduction processing includes: raising the temperature to 400-700 ℃ at the heating rate of 3-10 ℃/min, and reducing for 2-8h at the reduction temperature.
2. The molecular sieve of claim 1, wherein the nano-iron has a particle size of 3-4 nm; the specific surface area of the molecular sieve is more than or equal to 430m2/g。
3. A method of preparing the nano-iron modified SBA-16 molecular sieve of claim 1 or 2, comprising:
step S1, mixing a silicon source, water, an organic template agent, an iron source complex, an acid and alcohol to prepare a reaction mixture;
step S2, carrying out hydrothermal crystallization treatment on the reaction mixture, and then carrying out post-treatment to obtain the Fe-SBA-16 molecular sieve;
step S3, reducing the Fe-SBA-16 molecular sieve by hydrogen to prepare the SBA-16 molecular sieve modified by the nano iron;
wherein, in step S1, the molar ratio of the silicon source, water, organic template, iron source complex and acid is SiO2:H2O:R:Fe:H+The total weight of the alloy is 1 (50-350): (0.005-0.015): 0.05-0.20): 0.08-0.25); wherein R is an organic template agent, the molar ratio of the alcohol to the water is 1 (10-30),
the iron source complex comprises a complex formed by an iron-containing compound and ethylene diamine tetraacetic acid,
in step S3, the reduction processing includes: raising the temperature to 400-700 ℃ at the heating rate of 3-10 ℃/min, and reducing for 2-8h at the reduction temperature.
4. The method of claim 3, wherein the molar ratio of the silicon source, the water, the organic template, the iron source complex and the acid is SiO in step S12:H2O:R:Fe:H+The total weight of the material is 1 (70-170): (0.008-0.013): 0.05-0.20): 0.16-0.22.
5. The method of claim 3, wherein the temperature of the mixing is 40-60 ℃ in step S1.
6. The method according to any one of claims 3 to 5,
in step S1, the silicon source is selected from one or more of white carbon black, ethyl orthosilicate, sodium silicate and silica sol;
the organic template agent is selected from an amphiphilic nonionic triblock surfactant and/or hexamethylenetetramine.
7. The method of claim 6, wherein the amphiphilic nonionic triblock surfactant is selected from EO106PO70EO106And/or EO132PO50EO132。
8. The method of claim 3, wherein the iron-containing compound is selected from iron and/or ferrous salts.
9. The method of claim 8, wherein the iron-containing compound is selected from one or more of potassium ferricyanide, potassium ferrocyanide, ferrous chloride, and ferrous nitrate.
10. The method of claim 1, wherein the molar ratio of the iron-containing compound to ethylenediaminetetraacetic acid is 1 (1-4).
11. A method according to any one of claims 3 to 5, wherein the acid is selected from one or more of hydrochloric acid, sulphuric acid and nitric acid.
12. A process according to any one of claims 3 to 5, wherein the alcohol is selected from one or more of ethanol, ethylene glycol and propanol.
13. The method according to any one of claims 3 to 5, wherein in step S2, the temperature of the hydrothermal crystallization treatment is 80 to 110 ℃;
the time of the hydrothermal crystallization treatment is 24-72 h.
14. The method as claimed in claim 13, wherein the temperature of the hydrothermal crystallization is 90-100 ℃ and the time of the hydrothermal crystallization is 48-60h in step S2.
15. The method according to claim 1, wherein in step S3, the reduction process includes: raising the temperature to 500-600 ℃ at the temperature raising rate of 5-7 ℃/min, and reducing for 4-6h at the reduction temperature.
16. Use of a nano-iron modified SBA-16 molecular sieve according to claim 1 or 2 or a nano-iron modified SBA-16 molecular sieve prepared according to any one of claims 3 to 15 in the hydroxylation of benzene to produce phenol.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346792A (en) * | 2001-09-26 | 2002-05-01 | 复旦大学 | SiO2 molecular sieve with 3D pore canal and 2D mesopore structure and its synthesizing process |
| CN1939583A (en) * | 2006-09-20 | 2007-04-04 | 太原理工大学 | Production of porous molecular-sieve hydrogen-storage material |
| CN102241405A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院过程工程研究所 | Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method |
| CN102992932A (en) * | 2012-11-28 | 2013-03-27 | 浙江工业大学 | Method for removing olefin in aromatic hydrocarbon by M-SBA-15 type mesoporous molecular sieve |
| CN103936583A (en) * | 2014-05-08 | 2014-07-23 | 南京工业大学 | Method for preparing tert-butyl carboxylate by using dual-modified SBA mesoporous molecular sieve catalyst |
| CN105024054A (en) * | 2015-07-11 | 2015-11-04 | 中国计量学院 | Preparation method for polymer/hollow sulfur composite electrode material |
-
2017
- 2017-09-13 CN CN201710820537.6A patent/CN109485060B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346792A (en) * | 2001-09-26 | 2002-05-01 | 复旦大学 | SiO2 molecular sieve with 3D pore canal and 2D mesopore structure and its synthesizing process |
| CN1939583A (en) * | 2006-09-20 | 2007-04-04 | 太原理工大学 | Production of porous molecular-sieve hydrogen-storage material |
| CN102241405A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院过程工程研究所 | Reduced mesoporous aluminosilicate molecular sieve, preparation method and application thereof, and diesel oil desulfurization method |
| CN102992932A (en) * | 2012-11-28 | 2013-03-27 | 浙江工业大学 | Method for removing olefin in aromatic hydrocarbon by M-SBA-15 type mesoporous molecular sieve |
| CN103936583A (en) * | 2014-05-08 | 2014-07-23 | 南京工业大学 | Method for preparing tert-butyl carboxylate by using dual-modified SBA mesoporous molecular sieve catalyst |
| CN105024054A (en) * | 2015-07-11 | 2015-11-04 | 中国计量学院 | Preparation method for polymer/hollow sulfur composite electrode material |
Non-Patent Citations (2)
| Title |
|---|
| "Fe-SBA-16介孔分子筛的制备及其催化苯酚羟基化反应性能";赵玉梅;《化工进展》;20161231;第187-191页 * |
| "过渡金属在介孔分子筛中的高度分散及催化性能研究";吴乃瑾;《中国博士学位论文全文数据库（电子期刊）》;20170215;第27页2.2.3，第85页5.5 * |
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