CN104512900B - A kind of V-Si molecular sieve and preparation method thereof - Google Patents
A kind of V-Si molecular sieve and preparation method thereof Download PDFInfo
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- CN104512900B CN104512900B CN201310454658.5A CN201310454658A CN104512900B CN 104512900 B CN104512900 B CN 104512900B CN 201310454658 A CN201310454658 A CN 201310454658A CN 104512900 B CN104512900 B CN 104512900B
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 135
- 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
- 238000002360 preparation method Methods 0.000 title description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 80
- 238000010521 absorption reaction Methods 0.000 claims description 77
- 239000000203 mixture Substances 0.000 claims description 70
- 239000013078 crystal Substances 0.000 claims description 68
- 229910052720 vanadium Inorganic materials 0.000 claims description 67
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 67
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003795 desorption Methods 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- -1 template Chemical compound 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- RZDSZOMCGARBBI-UHFFFAOYSA-N nitric acid vanadium Chemical compound [V].[N+](=O)(O)[O-] RZDSZOMCGARBBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 3
- MANBDHUBXBMZNV-UHFFFAOYSA-N [V]=[Si] Chemical compound [V]=[Si] MANBDHUBXBMZNV-UHFFFAOYSA-N 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 238000004220 aggregation Methods 0.000 claims description 2
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 239000012002 vanadium phosphate Substances 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000033444 hydroxylation Effects 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 238000010276 construction Methods 0.000 description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 11
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 9
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000010718 Oxidation Activity Effects 0.000 description 5
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QKCRCANNYXEEPC-UHFFFAOYSA-N acetic acid;vanadium Chemical compound [V].CC(O)=O QKCRCANNYXEEPC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/08—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 the aluminium atoms being wholly replaced
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a kind of V-Si molecular sieve, it is characterised in that containing element silicon, v element and oxygen element, all or part of intra-die has hole or cavity structure, and total specific surface area >=300m2/ g, external surface area accounts for ratio >=5% of total specific surface area.V-Si molecular sieve of the invention has good catalytic oxidation effect, and the selectivity that product hydroquinones is aligned when being reacted for phenol hydroxylation is high, it is possible to improve the effective rate of utilization of oxidant.
Description
Technical field
The present invention relates to a kind of V-Si molecular sieve and preparation method thereof.
Background technology
Si molecular sieves, also referred to as total silicon zeolite, are molecular sieves that skeleton is all made up of silica element.Such as
Silicalite-1（S-1）Molecular sieve is with ZSM-5（MFI）The silica zeolite of the framework of molecular sieve of structure.Si molecular sieves
Can be directly as the material of UF membrane, it is also possible to form miscellaneous original by using the part silicon in other hetero atoms substitution skeleton
Sub- molecular screen material, has a extensive future.
Vanadium metal is incorporated into molecular sieve as introduced into V- beta-molecular sieves are formed in β type silica zeolites, is incorporated into MFI knots
VS-1 molecular sieves are formed in the molecular sieve of structure.During for catalytic oxidation, with good catalytic performance.
CN1301599A, CN1338427A and CN1338428A etc. disclose HTS and total silicon molecule with hollow-core construction
Sieve, but so far, have no that intra-die has the report of V-Si molecular sieve of void structure.
The content of the invention
The present inventor has been surprisingly found that on the basis of many experiments, the vanadium silicon molecule prepared through special process
Sifter device has special specific surface area characteristic and intra-die structure, and the selection of hydroquinones can be improved for phenol hydroxylation reaction
Property.Based on this, the present invention is formed.
It is therefore an object of the present invention to provide a kind of V-Si molecular sieve different from prior art, its preparation method and work
It is the application of catalyst.
The V-Si molecular sieve that the present invention is provided, it is characterised in that containing element silicon, v element and oxygen element, whole or portion
Dividing intra-die has hole or cavity structure, and total specific surface area >=300m2/g, and external surface area accounts for the ratio of total specific surface area
Example >=5%.
Present invention also offers a kind of method for preparing V-Si molecular sieve, the method includes：
（1）Vanadium source is contacted with template and obtains the mixture containing vanadium source Yu template；
（2）By step（1）It is described to obtain mixture with si molecular sieves mixing contact with the mixture of template containing vanadium source；
（3）By above-mentioned steps（2）The mixture for obtaining carries out hydro-thermal process under the conditions of hydrothermal crystallizing, then produces gained
Thing obtains V-Si molecular sieve.
The present invention further additionally provides application of the above-mentioned V-Si molecular sieve in phenol hydroxylation reaction.
V-Si molecular sieve of the invention has good catalytic oxidation effect, and product is aligned when being reacted for phenol hydroxylation
The selectivity of hydroquinones is high, it is possible to improve the effective rate of utilization of oxidant.
Specific embodiment
The V-Si molecular sieve that the present invention is provided, it is characterised in that containing element silicon, v element and oxygen element, whole or portion
Dividing intra-die has hole or cavity structure, and total specific surface area >=300m2/ g, external surface area accounts for the ratio of total specific surface area
Example >=5%.
The present invention provide V-Si molecular sieve in, further preferably in the case of, described external surface area is in >=20m2/g。
In general, the crystal grain for using traditional V-Si molecular sieve that conventional hydrothermal direct crystallization method obtains is non-hollow-core construction, its
The ratio that external surface area accounts for total specific surface area is general also below 5%, and traditional si molecular sieves are introduced in the form of loading
The V-Si molecular sieve crystal grain that vanadium source prepares also is non-hollow-core construction, and the ratio that external surface area accounts for total specific surface area is general
Less than 5%, and external surface area does not reach 20m typically yet2/g.In the present invention, its special specific surface of the V-Si molecular sieve
Product property, thus it is speculated that be caused by the special preparation process of V-Si molecular sieve of the invention, for example, before secondary hydro-thermal process
Vanadium source is introduced, the vanadium source of addition enables to the structure during the secondary hydrothermal crystallizing of si molecular sieves to occur in the presence of template
Certain change, so that the external surface area of V-Si molecular sieve accounts for the ratio of total specific surface area in >=5%, and external surface area
>=20m can be reached2/g。
In V-Si molecular sieve of the invention, it is further preferred that described total specific surface area is 310~600m2/ g, outer ratio
Surface area is 21~150m2/ g, and external surface area account for total specific surface area ratio be 5~25%.
In the present invention, total specific surface area refers to BET specific surface area；And external surface area refers to the outer of V-Si molecular sieve
The surface area on surface, can be also simply referred to as external surface area.Total specific surface area and external surface area etc. can be according to ASTM D4222-
98 standard methods are measured.
V-Si molecular sieve of the invention, 2 θ in its XRD spectrum have diffraction maximum, preferably 2 θ at 5 ° -9 ° at 0.5 ° -9 °
There is diffraction maximum；460cm in FT-IR collection of illustrative plates-1、975cm-1、800cm-1、1080cm-1Nearby there is absorption；In UV-Vis collection of illustrative plates
In 200-300nm at have absorption, preferably have absorption at 200-260nm.Thus prove, crystal grain of the invention is hollow-core construction
V-Si molecular sieve there is the essential characteristic of V-Si molecular sieve.
V-Si molecular sieve of the invention, v element is 0.05~10 with the mass ratio of element silicon:100, more preferably 0.1~
5:100, particularly preferably 0.2~2:100 further optimizing the catalysis activity of V-Si molecular sieve of the invention.
V-Si molecular sieve of the invention, it is in 25 DEG C, P/P0=0.10, the benzene that adsorption time is measured under conditions of 1 hour
Adsorbance is at least 25mg/g, preferably at least 35mg/g；Between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature
There is hysteresis loop, in relative pressure P/P0When near=0.60, N2 adsorption amount difference is big when N2 adsorption amount is with absorption during its desorption
The 2% of N2 adsorption amount when it is adsorbed；The radical length of the chamber portion of hollow crystal grain be 0.1~500nm, preferably 0.5~
300nm；The internal crystal grain with hole or cavity structure accounts for the 50%~100% of whole crystal grain in the material；The material cavity portion
The shape divided is not changeless, can be that rectangle, circle, irregular polygon etc. are variously-shaped, or these shapes
In the combination of one or more；Its crystal grain can be single crystal grain or the aggregation crystal grain being gathered into by multiple crystal grain.
Present invention also offers a kind of method for preparing V-Si molecular sieve, the method includes：
（1）Vanadium source is contacted with template and obtains the mixture containing vanadium source Yu template；
（2）By step（1）It is described to obtain mixture with si molecular sieves mixing contact with the mixture of template containing vanadium source；
（3）By above-mentioned steps（2）The mixture for obtaining carries out hydro-thermal process under the conditions of hydrothermal crystallizing, then produces gained
Thing is reclaimed and obtains V-Si molecular sieve.
According to preparation method of the invention, optional wider range of the species in described vanadium source, every material containing vanadium
（For example can be the compound containing v element and/or vanadium simple substance）The purpose of the present invention is capable of achieving, in the present invention, preferred institute
Say that vanadium source is the compound containing v element, can be one or more in inorganic vfanadium compound, organic vfanadium compound.It is inorganic
The various inorganic salts and its hydrate of vfanadium compound such as vanadium（Such as vanadium trichloride, vanadium tetrachloride, phosphoric vanadium, nitric acid vanadium, dichloro
Vanadyl, vanadic sulfate, vanadium phosphate etc.）, metavanadic acid and its esters（Such as ammonium metavanadate, sodium metavanadate）, vanadic acid and its esters（Such as vanadium
Sour ammonium, sodium vanadate etc.）, vanadium oxide（Such as three vanadium oxides, vanadium pentoxide）；The various organic acids of organic vfanadium compound such as vanadium
Salt or organic ligand compound, such as acetic acid salt, acetylacetonate complex.
According to preparation method of the invention, described si molecular sieves can be MFI structure（Such as S-1）, MEL structures（Such as S-
2）, BEA structures（Such as Beta）, MWW structures（Such as MCM-22）, two-dimentional hexagonal structure（Such as MCM-41, SBA-15）, MOR structures（Such as
MOR）, TUN structures（Such as TUN）With the si molecular sieves of other structures（Such as ZSM-48, MCM-48）In at least one.Preferable case
Under, described si molecular sieves are in the si molecular sieves of the si molecular sieves, the si molecular sieves of MEL structures and BEA structures of MFI structure
Plant or various, more preferably the si molecular sieves of MFI structure.Described si molecular sieves are commercially available, it is also possible to be prepared into
Arrive, the method for preparing described si molecular sieves is known to those skilled in the art, will not be repeated here.
In the present invention, described V-Si molecular sieve be by the similar secondary hydrothermal treatment process of si molecular sieves in template
V element is introduced in the presence of agent to prepare.
According to the method for the present invention, in order to improve the vanadium prepared according to the method for preparing V-Si molecular sieve of the invention
The catalytic oxidation activity of si molecular sieves, the preferably described temperature that vanadium source is contacted with template is 20~80 DEG C, more preferably 25
~60 DEG C.
According to the method for the present invention, described vanadium source is contacted with template according to foregoing contact conditions can enter one
Step improves the catalytic oxidation activity of V-Si molecular sieve of the invention, optional wider range of the time of described contact, for this hair
Bright, the time that further preferably described vanadium source contacts with template is 1~240min, more preferably 5~120min.
The purpose of the present invention, the use of described si molecular sieves, template, vanadium source and water are capable of achieving according to preceding solution
Optional wider range of amount, generally, the consumption mol ratio of described si molecular sieves, template, vanadium source and water is 100：
0.005~20：0.0005~15：20~5000, preferably 100：0.005~20：0.001~10：20~2000, particularly preferably
It is 100：1~15：0.1~8：20~1000, wherein, si molecular sieves are with SiO2Meter, vanadium source is in terms of v element.
According to the method for the present invention, optional wider range of the condition of described hydrothermal crystallizing treatment, for the present invention, preferably
The condition of described crystallization includes：In confined conditions the temperature of crystallization be 80~200 DEG C, preferably 100~180 DEG C, more preferably
It is 110~175 DEG C；Time is 6~96h, preferably 24~96h.
In the preferred method of the present invention, in order to improve the catalytic oxidation activity of V-Si molecular sieve, described hydrothermal crystallizing bar
Part is less than 1.2 in being more preferably crystallization kettle containing formation saturated steam at reaction conditions and with the weight ratio of molecular sieve
Water（With reference to the mol ratio of above-mentioned material amounts, i.e., more preferably si molecular sieves and the consumption weight ratio of water are 100：17~
120, mol ratio is 100：20~400）, the treating capacity of si molecular sieves is at least 10 g/l（Reactor volume）.In reactor
In, the amount proportioning of water is preferably the saturation vapour amount for not exceeding its absorption of molecular sieve.Being essentially all in system of the present invention can
For space provides enough saturated vapor amounts, but remaining water is less than molecular sieve saturated extent of adsorption.In other words, as will
More than molecular sieve saturated extent of adsorption, but reaction system is typically also met in saturated humidity（Steam vapour amount）.Here it is this hair
Needed in bright technical scheme control reactor in containing at reaction conditions formed saturated steam and with the weight ratio of molecular sieve
Water less than 1.2, the treating capacity of molecular sieve is at least 10 g/l（Reactor volume）The reason for.Such as, volume is 100
The reactor container of milliliter, reaching saturated humidity needs 0.5 gram of water, then the molecular sieve for adding can be 20 grams, or 1 gram
Deng.It is 0.2 gram such as to add 1 gram molecule to sieve adsorpting water quantity, then 20 gram molecules sieve at most cannot be more than 4 grams of water, but at least
Want more than 0.5 gram.
According to the method for the present invention, optional wider range of the species of described template specifically can be according to being prepared
The species of the V-Si molecular sieve for obtaining is selected, in this regard, those skilled in the art can know.For the present invention, preferably institute
Say that template is one or more in tetra-alkyl ammonium hydroxide, hydramine and alkylamine.
According to the method for the present invention, optional wider range of the species of described tetra-alkyl ammonium hydroxide is commonly used in the art
Tetra-alkyl ammonium hydroxide is capable of achieving the purpose of the present invention, and for the present invention, preferably described tetra-alkyl ammonium hydroxide is tetrapropyl
One or more in ammonium hydroxide, tetraethyl ammonium hydroxide and TBAH.
It is as previously mentioned, optional wider range of the species of described alkylamine in the present invention, for the present invention, preferably described alkane
Base amine is the alkylamine of C2~C10, and it is R that more preferably described alkylamine is selected from formula1(NH2)nAlkylamine, wherein, R1For C1~
The alkyl or alkylidene of C6, n are 1 or 2, and particularly preferably described alkylamine is in ethamine, n-butylamine, butanediamine and hexamethylene diamine
One or more.
It is as previously mentioned, optional wider range of the species of described hydramine in the present invention, for the present invention, preferably described hydramine
It is the hydramine of C2~C5, it is (HOR that more preferably described hydramine is selected from formula2)mNH(3~m)Hydramine, described R2It is the alkane of C1~C4
Base；M is 1,2 or 3；More preferably described hydramine is one or more in MEA, diethanol amine and triethanolamine.
It is described to reclaim typically by the filtering of crystallization products therefrom, by filtering products therefrom according to the method for the present invention
The process that solid is dried, is calcined is obtained, its method is well known to the skilled person, for example, will dry one by solid obtained by filtering
As in room temperature to carrying out at a temperature of between 200 DEG C, remaining condition is also well known to those skilled in the art, herein no longer emphasis
Repeat.
V-Si molecular sieve of the invention compared to the si molecular sieves without vanadium or load vanadium si molecular sieves, with more preferable
Catalytic oxidation activity, and for showing especially prominent in phenol hydroxylation reaction, the selectivity of hydroquinones is improved in product, is pushed away
Survey is because its special structure causes.Therefore, invention further provides V-Si molecular sieve of the invention in phenolic hydroxy
Change the application in reaction.
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In comparative example and embodiment, agents useful for same is commercially available AR.
In the present invention, the X-ray diffraction of sample is carried out on Siemens D5005 type x-ray diffractometers（XRD）Crystalline phase
Figure is determined, and radiographic source is K α（Cu）, the θ of test scope 2 is at 0.5 °~30 °.The fourier infrared of sample（FT-IR）Spectrogram exists
It is measured on Nicolet8210 type Fourier infrared spectrographs, 400~1400cm of test scope-1.Sample solid is ultraviolet-and can
See diffusing reflection spectrum（UV-vis）Measured on SHIMADZUUV-3100 type ultraviolet-visual spectrometers, test scope 200~
1000nm.Total specific surface area and external surface area of sample, benzene adsorbance, the adsorption isotherm of nitrogen absorption under low temperature and desorption isothermal
Whether there is hysteresis loop between line, and when near relative pressure P/P0=0.60, when N2 adsorption amount is with absorption during its desorption
Data such as 2% of N2 adsorption amount are static in Micromeritics companies ASAP2405 when whether N2 adsorption amount difference is adsorbed more than it
It is measured according to ASTM D4222-98 standard methods on n2 absorption apparatus.The transmission electron microscope analysis TEM of sample is in FEI Co.
Tecnai G2Obtained on F20S-TWIN type transmission electron microscopes, 100 crystal grain are counted, so as to obtain the cavity of hollow crystal grain
Partial radical length and the internal crystal grain with hole or cavity structure accounts for the data such as the percentage of whole crystal grain.
In the present invention, the analysis of each composition in activity rating system is carried out using gas-chromatography, entered by correcting normalization method
Row is quantitative, and can refer to prior art is carried out, and the evaluation such as conversion ratio, selectivity of product of reactant is calculated on this basis and is referred to
Mark（Concrete outcome is shown in Table 1）.
In test case：
Embodiment 1
（1）At 25 DEG C, by the TPAOH aqueous solution（Concentration is 15 weight %）Contacted with vanadium trichloride stirring
30min, obtains the mixture containing TPAOH and vanadium chloride；
（2）At 60 DEG C, stirring contact 0.5h obtains mixture during si molecular sieves S-1 is added into said mixture（
In this contact process, according to needing to add water or do not add water, if step（1）Feed intake and disclosure satisfy that the requirement that feeds intake of water, then need not
Add water, if it is not satisfied, additionally can then be connect with si molecular sieves stirring in the mixture containing TPAOH and vanadium chloride
Water is added when tactile, remaining embodiment is similar to, and explanation is not repeated）；Wherein, it is ensured that the molar ratio of each material is：Silicon
Source（Si molecular sieves）:Alkali source template（TPAOH）:Vanadium source（Vanadium chloride）:Water=100:10:0.5:500, wherein,
In terms of SiO2, vanadium source is in terms of v element for silicon source；
（3）Said mixture is transferred in stainless steel sealed reactor, the crystallization at 170 DEG C of temperature and self-generated pressure
144h, by the filtering of gained crystallization product, washes with water, and is dried 120 minutes in 110 DEG C, then in 550 DEG C of roasting temperatures 3
Hour, obtain V-Si molecular sieve（Through XRF composition analysis, vanadium weight/mass percentage composition is 1.5；It is hollow knot to characterize crystal grain through TEM
Structure；It is have diffraction maximum at 5 ° -9 ° in 2 θ in XRD crystalline phase figures；In FT-IR, 460cm-1、800cm-1、975cm-1、
1080cm-1Nearby there is absorption；In UV-Vis, there is absorption at 220nm,；It is in 25 DEG C, P/P0=0.10, adsorption time 1 is small
When under conditions of the benzene adsorbance that measures be 76mg/g；Exist between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature
Hysteresis loop, in relative pressure P/P0When near=0.60, N2 adsorption amount difference is more than it when N2 adsorption amount is with absorption during its desorption
The 2% of N2 adsorption amount during absorption；The radical length of the chamber portion of hollow crystal grain is 5~120nm；Inside has hole or cavity
The crystal grain of structure accounts for the 80% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area are accounted for always than table
The ratio of area is shown in Table 1）.
Comparative example 1
This comparative example is by " Zeolites, 1992, Vol.12:943~950 " method described in prepares TS-1 molecules
Sieve the process of sample.
22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOHs, and adds 59.8 grams of distilled water, mixing
Uniformly after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C, the hydrating solution of tetraethyl orthosilicate is obtained, with vigorous stirring lentamente
The solution that addition is made up of 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols, 3 are stirred by gained mixture at 75 DEG C
Hour, obtain clear colloid.This colloid is put into stainless steel sealed reactor, constant temperature places 3 at a temperature of 170 DEG C
My god, obtain the mixture of crystallization product；By the filtering of this mixture, wash with water, and in 110 DEG C of dryings 60 minutes, obtain TS-1
Former powder, by this TS-1 original powder in 550 DEG C of roasting temperatures 3 hours, obtains TS-1 molecular sieves（Through XRF composition analysis, its Ti mass
Percentage composition is 2.6；It is have diffraction maximum at 5 ° -9 ° in 2 θ in XRD crystalline phase figures；It is non-hollow-core construction to characterize crystal grain through TEM；
In FT-IR, 460cm-1、800cm-1、960cm-1、1080cm-1Nearby there is absorption；In UV-Vis, there is absorption at 210nm；
It is in 25 DEG C, P/P0=0.10, the benzene adsorbance that adsorption time is measured under conditions of 1 hour is 27mg/g；Its nitrogen absorption under low temperature
Adsorption isotherm and desorption isotherm between be substantially not present hysteresis loop, in relative pressure P/P0When near=0.60, it takes off
The 2% of N2 adsorption amount when N2 adsorption amount difference is not more than its absorption when N2 adsorption amount is with absorption when attached；Crystal grain do not have substantially hole or
Cavity structure.The ratio that its yield, total specific surface area, external surface area and external surface area account for total specific surface area is shown in Table 1）.
Comparative example 2
Method according to comparative example 1 prepares V-Si molecular sieve, unlike, titanium is replaced by the equimolar phosphoric vanadium in vanadium source
Source, obtains V-Si molecular sieve（Through XRF composition analysis, V weight/mass percentage compositions are 2.1；It it is 5 ° -9 ° in 2 θ in XRD crystalline phase figures
There is diffraction maximum at place；It is non-hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、960cm-1、1080cm-1
Nearby there is absorption；In UV-Vis, there is absorption at 210nm；It is in 25 DEG C, P/P0=0.10, the adsorption time condition of 1 hour
Under the benzene adsorbance that measures be 22mg/g；It is substantially not present between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature stagnant
Ring afterwards, in relative pressure P/P0When near=0.60, N2 adsorption amount difference is not more than it when N2 adsorption amount is with absorption during its desorption
The 2% of N2 adsorption amount during absorption；Crystal grain does not have hole or cavity structure substantially.Its yield, total specific surface area, external surface area with
And external surface area accounts for the ratio of total specific surface area and is shown in Table 1）.
Comparative example 3
To be calcined after vanadium trichloride and the direct mechanical mixtures of S-1（Roasting condition is with embodiment 1）Obtain loading the silicon point of vanadium
Son sieve, V weight/mass percentage compositions are 1.5 during the consumption in wherein vanadium source causes the V-Si molecular sieve for preparing.（In XRD crystalline phase figures
In, it is have diffraction maximum at 5 ° -9 ° in 2 θ；It is non-hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、
1080cm-1Nearby there is absorption, and in 960cm-1Nearby without substantially absorption；In UV-Vis, there is absorption at 210nm；It is 25
DEG C, P/P0=0.10, the benzene adsorbance that adsorption time is measured under conditions of 1 hour is 31mg/g；The absorption of its nitrogen absorption under low temperature
Hysteresis loop is substantially not present between thermoisopleth and desorption isotherm, in relative pressure P/P0When near=0.60, nitrogen during its desorption
The 2% of N2 adsorption amount when N2 adsorption amount difference is not more than its absorption when adsorbance is with absorption；Crystal grain does not have hole or cavity knot substantially
Structure.The ratio that its yield, total specific surface area, external surface area and external surface area account for total specific surface area is shown in Table 1）.
Comparative example 4
By vanadium trichloride and the direct mechanical mixtures of S-1 and then roasting prepared according to CN1338428A methods（Roasting condition
With embodiment 1）Obtain loading the si molecular sieves of vanadium, the consumption of wherein vanadium chloride causes V matter in the V-Si molecular sieve for preparing
Amount percentage composition is 1.5.（It is have diffraction maximum at 5 ° -9 ° in 2 θ in XRD crystalline phase figures；It is hollow-core construction to characterize crystal grain through TEM；
In FT-IR, 460cm-1、800cm-1、1080cm-1Nearby there is absorption, and in 960cm-1Nearby without substantially absorption；In UV-Vis
In, there is absorption at 210nm,；It is in 25 DEG C, P/P0=0.10, the benzene adsorbance that adsorption time is measured under conditions of 1 hour is
34mg/g；There is hysteresis loop between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature, in relative pressure P/P0=
When near 0.60, the 2% of N2 adsorption amount when N2 adsorption amount difference is adsorbed more than it when N2 adsorption amount is with absorption during its desorption；It is internal
Crystal grain with hole or cavity structure accounts for the 95% of whole crystal grain.Its yield, total specific surface area, external surface area and outer ratio
The ratio that surface area accounts for total specific surface area is shown in Table 1）.
Embodiment 2
（1）At 25 DEG C, by the TPAOH aqueous solution（Concentration is 20 weight %）Contacted with the stirring of phosphoric vanadium
30min, obtains the mixture containing TPAOH and vanadium chloride；
（2）At 25 DEG C, stirring contact 0.5h obtains mixture during si molecular sieves S-1 is added into said mixture；Its
In, it is ensured that the molar ratio of each material is：Silicon source（Si molecular sieves）:Alkali source template（TPAOH）:Vanadium source（Chlorine
Change vanadium）:Water=100:15:0.1:800, wherein, in terms of SiO2, vanadium source is in terms of v element for silicon source；
（3）Said mixture is transferred in stainless steel sealed reactor, the crystallization at 160 DEG C of temperature and self-generated pressure
120h, by the filtering of gained crystallization product, washes with water, and is dried 120 minutes in 110 DEG C, then in 550 DEG C of roasting temperatures 3
Hour, obtain V-Si molecular sieve（Through XRF composition analysis, V weight/mass percentage compositions are 1.0；In XRD crystalline phase figures, 2 θ be 5 °-
There is diffraction maximum at 9 °；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、1080cm-1
Nearby there is absorption；In UV-Vis, there is absorption at 220nm；It is in 25 DEG C, P/P0=0.10, the adsorption time condition of 1 hour
Under the benzene adsorbance that measures be 57mg/g；There is hysteresis loop between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature,
In relative pressure P/P0When near=0.60, nitrogen when N2 adsorption amount difference is adsorbed more than it when N2 adsorption amount is with absorption during its desorption
The 2% of adsorbance；The radical length of the chamber portion of hollow crystal grain is 5~150nm；Crystalline substance of the inside with hole or cavity structure
Grain accounts for the 90% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area account for the ratio of total specific surface area
Example is shown in Table 1）.
Embodiment 3
（（1）At 35 DEG C, by the tetraethyl ammonium hydroxide aqueous solution（Concentration is 28 weight %）Contacted with the stirring of nitric acid vanadium
30min, obtains the mixture containing tetraethyl ammonium hydroxide and nitric acid vanadium；
（2）At 50 DEG C, stirring contact 0.5h obtains mixture during si molecular sieves S-1 is added into said mixture；Its
In, it is ensured that the molar ratio of each material is：Silicon source（Si molecular sieves）:Alkali source template（Tetraethyl ammonium hydroxide）:Vanadium source（Nitre
Sour vanadium）:Water=100:10:0.2:600, wherein, in terms of SiO2, vanadium source is in terms of v element for silicon source；
（3）Said mixture is transferred in stainless steel sealed reactor, the crystallization at 170 DEG C of temperature and self-generated pressure
96h, by the filtering of gained crystallization product, washes with water, and is dried 120 minutes in 110 DEG C, then small in 550 DEG C of roasting temperatures 3
When, obtain V-Si molecular sieve（Through XRF composition analysis, V weight/mass percentage compositions are 0.84；It it is 5 ° -9 ° in 2 θ in XRD crystalline phase figures
There is diffraction maximum at place；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、1080cm-1It is attached
Closely there is absorption；In UV-Vis, there is absorption at 230nm；It is in 25 DEG C, P/P0=0.10, adsorption time is under conditions of 1 hour
The benzene adsorbance for measuring is 72mg/g；There is hysteresis loop between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature,
Relative pressure P/P0When near=0.60, nitrogen is inhaled when N2 adsorption amount difference is adsorbed more than it when N2 adsorption amount is with absorption during its desorption
The 2% of attached amount；The radical length of the chamber portion of hollow crystal grain is 5~150nm；Crystal grain of the inside with hole or cavity structure
Account for the 88% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area account for the ratio of total specific surface area
It is shown in Table 1）.
Embodiment 4
（1）At 30 DEG C, by the TPAOH aqueous solution（Concentration is 15 weight %）Contacted with vanadium tetrachloride stirring
30min, obtains the mixture containing TPAOH and vanadium chloride；
（2）At 60 DEG C, stirring contact 0.5h obtains mixture during si molecular sieves S-1 is added into said mixture；Its
In, it is ensured that the molar ratio of each material is：Silicon source（Si molecular sieves）:Alkali source template（TPAOH）:Vanadium source（Four
Vanadium chloride）:Water=100:5:1:1200, wherein, silicon source is with SiO2Meter, vanadium source is in terms of v element；
（3）Said mixture is transferred in stainless steel sealed reactor, the crystallization at 120 DEG C of temperature and self-generated pressure
72h, by the filtering of gained crystallization product, washes with water, and is dried 120 minutes in 110 DEG C, then small in 550 DEG C of roasting temperatures 3
When, obtain V-Si molecular sieve（Through XRF composition analysis, V weight/mass percentage compositions are 6.6；It it is 5 ° -9 ° in 2 θ in XRD crystalline phase figures
There is diffraction maximum at place；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、1080cm-1It is attached
Closely there is absorption；In UV-Vis, there is absorption near 240nm；It is in 25 DEG C, P/P0=0.10, the adsorption time condition of 1 hour
Under the benzene adsorbance that measures be 63mg/g；There is hysteresis loop between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature,
In relative pressure P/P0When near=0.60, nitrogen when N2 adsorption amount difference is adsorbed more than it when N2 adsorption amount is with absorption during its desorption
The 2% of adsorbance；The radical length of the chamber portion of hollow crystal grain is 5~100nm；Crystalline substance of the inside with hole or cavity structure
Grain accounts for the 60% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area account for the ratio of total specific surface area
Example is shown in Table 1）.
Embodiment 5
（1）At 40 DEG C, by the TPAOH aqueous solution（Concentration is 25 weight %）Contacted with the stirring of acetic acid vanadium
30min, obtains the mixture containing TPAOH and acetic acid vanadium；
（2）At 25 DEG C, stirring contact 0.5h obtains mixture during si molecular sieves S-1 is added into said mixture；Its
In, it is ensured that the molar ratio of each material is：Silicon source（Si molecular sieves）:Alkali source template（TPAOH）:Vanadium source（Second
Sour vanadium）:Water=100:18:2:600, wherein, in terms of SiO2, vanadium source is in terms of v element for silicon source；
（3）Said mixture is transferred in stainless steel sealed reactor, the crystallization 24 at 170 DEG C of temperature and self-generated pressure
Hour, by the filtering of gained crystallization product, wash with water, and dried 120 minutes in 110 DEG C, then in 550 DEG C of roasting temperatures 3
Hour, obtain V-Si molecular sieve（Through XRF composition analysis, its V weight/mass percentage composition is 3.6；In XRD crystalline phase figures, it is in 2 θ
There is diffraction maximum at 5 ° -9 °；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、
1080cm-1Nearby there is absorption；In UV-Vis, there is absorption at 230nm；It is at 25 DEG C, and P/P0=0.10, adsorption time 1 is small
When under conditions of the benzene adsorbance that measures be 59mg/g；Exist between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature
Hysteresis loop, in relative pressure P/P0When near=0.60, N2 adsorption amount difference is more than it when N2 adsorption amount is with absorption during its desorption
The 2% of N2 adsorption amount during absorption；The radical length of the chamber portion of hollow crystal grain is 5~90nm；Inside has hole or cavity knot
The crystal grain of structure accounts for the 95% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area account for total specific surface
Long-pending ratio is shown in Table 1）.
Embodiment 6
（1）At 25 DEG C, by the TPAOH aqueous solution（Concentration is 15 weight %）Contacted with ammonium metavanadate stirring
30min, obtains the mixture containing TPAOH and vanadium chloride；
（2）At 40 DEG C, stirring contact 0.5h obtains mixture during si molecular sieves S-1 is added into said mixture；Its
In, it is ensured that the molar ratio of each material is：Silicon source（Si molecular sieves）:Alkali source template（TPAOH）:Vanadium source（Partially
Ammonium vanadate）:Water=100:12:1.5:1000, wherein, silicon source is with SiO2Meter, vanadium source is in terms of v element；
（3）Said mixture is transferred in stainless steel sealed reactor, the crystallization 36 at 170 DEG C of temperature and self-generated pressure
Hour, by the filtering of gained crystallization product, wash with water, and dried 120 minutes in 110 DEG C, then in 550 DEG C of roasting temperatures 3
Hour, obtain V-Si molecular sieve（Through XRF composition analysis, its V weight/mass percentage composition is 2.8；In XRD crystalline phase figures, it is in 2 θ
There is diffraction maximum at 5 ° -9 °；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、
1080cm-1Nearby there is absorption；In UV-Vis, there is absorption at 220-250nm；It is in 25 DEG C, P/P0=0.10, adsorption time
The benzene adsorbance measured under conditions of 1 hour is 81mg/g；Between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature
There is hysteresis loop, in relative pressure P/P0When near=0.60, N2 adsorption amount difference is big when N2 adsorption amount is with absorption during its desorption
The 2% of N2 adsorption amount when it is adsorbed；The radical length of the chamber portion of hollow crystal grain is 5~180nm；Inside have hole or
The crystal grain of cavity structure accounts for the 98% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area are accounted for always
The ratio of specific surface area is shown in Table 1）.
Embodiment 7
Method according to embodiment 6 prepares V-Si molecular sieve, unlike, silicon source:Alkali source template:Vanadium source:Water=100:
1:12:150, obtain V-Si molecular sieve（Through XRF composition analysis, its V weight/mass percentage composition is 5.9；In XRD crystalline phase figures, in 2 θ
To have diffraction maximum at 5 ° -9 °；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、
1080cm-1Nearby there is absorption；In UV-Vis, there is absorption at 230-260nm；It is in 25 DEG C, P/P0=0.10, adsorption time
The benzene adsorbance measured under conditions of 1 hour is 85mg/g；Between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature
There is hysteresis loop, in relative pressure P/P0When near=0.60, N2 adsorption amount difference is big when N2 adsorption amount is with absorption during its desorption
The 2% of N2 adsorption amount when it is adsorbed；The radical length of the chamber portion of hollow crystal grain is 5~210nm；Inside have hole or
The crystal grain of cavity structure accounts for the 95% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area are accounted for always
The ratio of specific surface area is shown in Table 1）.
Embodiment 8
Method according to embodiment 7 prepares V-Si molecular sieve, unlike, vanadium source is replaced by vanadium acetylacetonate, obtains vanadium
Si molecular sieves（Through XRF composition analysis, its V weight/mass percentage composition is 3.2；It is have diffraction at 5 ° -9 ° in 2 θ in XRD crystalline phase figures
Peak；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、1080cm-1Nearby there is absorption；
In UV-Vis, there is absorption at 230-260nm；It is in 25 DEG C, P/P0=0.10, adsorption time is measured under conditions of 1 hour
Benzene adsorbance be 70mg/g；There is hysteresis loop between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature, relative
Pressure P/P0When near=0.60, N2 adsorption amount when N2 adsorption amount difference is adsorbed more than it when N2 adsorption amount is with absorption during its desorption
2%；The radical length of the chamber portion of hollow crystal grain is 5~50nm；Crystal grain of the inside with hole or cavity structure accounts for whole
The 88% of crystal grain.The ratio that its yield, total specific surface area, external surface area and external surface area account for total specific surface area is shown in Table 1）.
Embodiment 9
Method according to embodiment 7 prepares V-Si molecular sieve, unlike, step（1）The temperature that template is contacted with vanadium source
Spend is 10 DEG C；
Prepare V-Si molecular sieve（Through XRF composition analysis, its V weight/mass percentage composition is 2.9；In XRD crystalline phase figures,
It is have diffraction maximum at 5 ° -9 ° in 2 θ；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、1080cm-1Nearby there is absorption；In UV-Vis, there is absorption at 240nm；It is in 25 DEG C, P/P0=0.10, adsorption time 1
The benzene adsorbance measured under conditions of hour is 48mg/g；Deposited between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature
In hysteresis loop, in relative pressure P/P0When near=0.60, N2 adsorption amount difference is more than when N2 adsorption amount is with absorption during its desorption
The 2% of N2 adsorption amount during its absorption；The radical length of the chamber portion of hollow crystal grain is 5~40nm；Inside has hole or cavity
The crystal grain of structure accounts for the 76% of whole crystal grain.Its yield, total specific surface area, external surface area and external surface area are accounted for always than table
The ratio of area is shown in Table 1）.
Embodiment 10
Method according to embodiment 1 prepares V-Si molecular sieve, unlike, each material is mixed simultaneously, specific by such as
Lower step is carried out：
At 60 DEG C, by the TPAOH aqueous solution（Concentration is 16 weight %）, vanadium source, si molecular sieves mix
Contact 5h obtains mixture；Wherein, it is ensured that the molar ratio of each material is：Silicon source（Si molecular sieves）:Alkali source template（4 third
Base ammonium hydroxide）:Vanadium source（Vanadium chloride）:Water=100:10:0.5:500, wherein, in terms of SiO2, vanadium source is in terms of v element for silicon source；
Said mixture is transferred in stainless steel sealed reactor, the crystallization 196h at 170 DEG C of temperature and self-generated pressure,
By the filtering of gained crystallization product, wash with water, and dry 120 minutes in 110 DEG C, then in 550 DEG C of roasting temperatures 3 hours,
Obtain V-Si molecular sieve（Through XRF composition analysis, V weight/mass percentage compositions are 1.6；It is have at 5 ° -9 ° in 2 θ in XRD crystalline phase figures
Diffraction maximum；It is hollow-core construction to characterize crystal grain through TEM；In FT-IR, 460cm-1、800cm-1、975cm-1、1080cm-1Nearby have
Absorb；In UV-Vis, there is absorption at 230-250nm；It is in 25 DEG C, P/P0=0.10, adsorption time is under conditions of 1 hour
The benzene adsorbance for measuring is 46mg/g；There is hysteresis loop between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature,
Relative pressure P/P0When near=0.60, nitrogen is inhaled when N2 adsorption amount difference is adsorbed more than it when N2 adsorption amount is with absorption during its desorption
The 2% of attached amount；The radical length of the chamber portion of hollow crystal grain is 5~30nm；Crystal grain of the inside with hole or cavity structure is accounted for
The 60% of whole crystal grain.The ratio that its yield, total specific surface area, external surface area and external surface area account for total specific surface area is shown in
Table 1）.
Test case
This test case is used for phenol for illustrating the molecular sieve that the method for the method of the present invention and prior art is prepared
The effect of hydroxylated catalytic oxidation.
By the molecular sieve of above-described embodiment and comparative example according to molecular sieve:Phenol:Acetone=1:20:16 weight ratio feeds intake,
It is well mixed in a there-necked flask with condenser pipe, 80 DEG C is warming up to, then under stirring, according to phenol:Peroxide
Change hydrogen=3:1 mol ratio adds the aqueous hydrogen peroxide solution that concentration is 27.5 weight %, reacts 3 hours at this temperature, gained
Product uses HP-5 capillary columns on 6890N type gas chromatographs（30m×0.25mm）Phenol conversion is determined, be the results are shown in Table
1。
Table 1
As can be seen from Table 1：The crystal grain that the present invention is prepared is the V-Si molecular sieve of hollow-core construction compared to common vanadium
Si molecular sieves, the vanadium silicon molecule that the hydroquinones in being reacted for phenol hydroxylation is selectively prepared higher than prior art
Sieve；Not only selected with preferable hydroquinones especially with the V-Si molecular sieve that currently preferred method is prepared
Property, and the effective rate of utilization with more preferable catalytic oxidation activity and oxidant.Meanwhile, using currently preferred method system
The yield of the standby V-Si molecular sieve for obtaining is higher.
Claims (13)
1. a kind of V-Si molecular sieve, it is characterised in that contain element silicon, v element and oxygen element, all or part of intra-die
With cavity structure, and total specific surface area >=300m2/ g, external surface area >=20m2/ g, external surface area accounts for total specific surface area
Ratio >=5%, 2 θ in the XRD spectrum of the molecular sieve have diffraction maximum at 0.5 ° -9 °；460cm in FT-IR collection of illustrative plates-1、
975cm-1、800cm-1、1080cm-1Nearby there is absorption；Have absorption at 200~300nm in UV-Vis collection of illustrative plates, v element with
The mass ratio of element silicon is 0.05~10:100；It is in 25 DEG C, P/P0=0.10, adsorption time is measured under conditions of 1 hour
Benzene adsorbance is at least 35mg/g；There is hysteresis loop between the adsorption isotherm and desorption isotherm of its nitrogen absorption under low temperature, in phase
To pressure P/P0When near=0.60, N2 adsorption when N2 adsorption amount difference is adsorbed more than it when N2 adsorption amount is with absorption during its desorption
The 2% of amount.
2. according to the V-Si molecular sieve of claim 1, wherein, described total specific surface area is 310~600m2/ g, external surface area
It is 21~150m2/ g, and external surface area account for total specific surface area ratio be 5~25%.
3., according to the V-Si molecular sieve of claim 1, there is its intra-die the crystal grain of cavity structure to account for the 50% of whole crystal grain
~100%.
4., according to the V-Si molecular sieve of claim 1, the radical length of its intra-die chamber portion is 0.5~300nm.
5. according to the V-Si molecular sieve of claim 1, it is characterised in that the shape of the chamber portion of its intra-die be selected from rectangle,
One or several combination in circular and irregular polygon.
6. according to the V-Si molecular sieve of claim 1, it is characterized by its crystal grain is single crystal grain or is gathered into by multiple crystal grain
Aggregation crystal grain.
7. a kind of method for preparing V-Si molecular sieve, it is characterised in that the method includes：
(1) vanadium source is contacted the mixture obtained containing vanadium source Yu template with template, described template is tetraalkyl hydrogen-oxygen
Change one or more in ammonium, hydramine and alkylamine；
(2) mixture will be obtained with si molecular sieves mixing contact with the mixture of template containing vanadium source described in step (1), it is described
Si molecular sieves be selected from least one in MFI, MEL, BEA, MWW, two-dimentional hexagonal structure, MOR, TUN structure si molecular sieves, silicon
The consumption mol ratio of molecular sieve, template, vanadium source and water is 100：0.005~20：0.05~15：20~5000, si molecular sieves
With SiO2Meter, vanadium source is in terms of v element；
(3) mixture that above-mentioned steps (2) are obtained is carried out into hydro-thermal process under the conditions of hydrothermal crystallizing, then obtains recovery product
To V-Si molecular sieve, the condition of described hydrothermal crystallizing treatment includes：The temperature for processing in confined conditions is 80~200 DEG C, when
Between in 6~96h, and crystallization kettle containing forming saturated steam at reaction conditions and be less than with the weight ratio of molecular sieve
1.2 water, the treating capacity of si molecular sieves is at least 10 g/l reactor volumes.
8. according to the method for claim 7, wherein, described includes the condition that vanadium source contacts with template：The temperature of contact
It it is 20~80 DEG C, the time of contact is 1~240min.
9. according to the method described in claim 7, wherein, the consumption in described si molecular sieves and vanadium source causes the vanadium silicon for preparing
V element and the mass ratio of element silicon are 0.05~10 in molecular sieve:100.
10. according to the method for any one in claim 7~9, wherein, described vanadium source is inorganic vfanadium compound or organic vanadium
One or more of compound.
11. according to claim 10 method, wherein, described inorganic vfanadium compound is selected from vanadium trichloride, vanadium tetrachloride, pentachloro-
Change vanadium, nitric acid vanadium, dichloro vanadyl, vanadic sulfate, vanadium phosphate, metavanadic acid, ammonium metavanadate, sodium metavanadate, vanadic acid, ammonium vanadate, vanadic acid
One or more in sodium, three vanadium oxides, vanadium pentoxide.
12. according to claim 10 method, wherein, described organic vfanadium compound is selected from the organic acid salt of vanadium or organic matches somebody with somebody
Body compound.
Application of the V-Si molecular sieve of one of 13. the claims 1~6 in phenol hydroxylation reaction.
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