CN109502598A - The method of one-step synthesis method mesoporous tungsten trioxide and zirconia-supported SBA-15 - Google Patents
The method of one-step synthesis method mesoporous tungsten trioxide and zirconia-supported SBA-15 Download PDFInfo
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- CN109502598A CN109502598A CN201711272308.1A CN201711272308A CN109502598A CN 109502598 A CN109502598 A CN 109502598A CN 201711272308 A CN201711272308 A CN 201711272308A CN 109502598 A CN109502598 A CN 109502598A
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 18
- 238000001354 calcination Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 229920001451 polypropylene glycol Polymers 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000002835 absorbance Methods 0.000 description 24
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000011088 calibration curve Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 4
- 229940074439 potassium sodium tartrate Drugs 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 4
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HNHMZSPNOIWDEN-UHFFFAOYSA-N O.[O-2].[Zr+4].[Cl+] Chemical compound O.[O-2].[Zr+4].[Cl+] HNHMZSPNOIWDEN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- ACXCKRZOISAYHH-UHFFFAOYSA-N molecular chlorine hydrate Chemical compound O.ClCl ACXCKRZOISAYHH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- 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
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic 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
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of methods that one-step method prepares mesoporous tungsten trioxide Yu zirconia-supported SBA-15, are named as ZrO2‑WO3/ SBA-15, belongs to technical field of inorganic nanometer material.Preparation step is as follows: using one polypropylene glycol of polyethylene glycol, one polyethylene glycol three block high molecular surfactant as template, tungsten source is added and forms total template, adds silicon source, is eventually adding zirconium source, then calcining forms meso-hole structure after crystallization.Mesoporous ZrO of the invention2‑WO3/ SBA-15 molecular sieve has the advantages that (1) solvent of the invention only has water, without other solvents, therefore will not generate by-product, be environmentally friendly；(2) the mesoporous ZrO of one-step synthesis method is used2‑WO3/ SBA-15, easy to operate, preparation time is short, saves preparation cost, and meso-hole structure is preferable, and repeatability is high；(3) mesoporous ZrO of the invention2‑WO3/ SBA-15 molecular sieve has good photocatalysis performance；(4) mesoporous ZrO of the invention2‑WO3/ SBA-15 molecular sieve has good ammonia nitrogen removal effect.
Description
Technical field:
The present invention relates to the preparation method of a kind of one-step synthesis method mesoporous tungsten trioxide and zirconia-supported SBA-15, lives
Entitled ZrO2-WO3/ SBA-15, belongs to technical field of inorganic nanometer material.
Technical background:
Currently, waste water from dyestuff, since its discharge amount is big, concentration is high, difficult the features such as decolourizing, very big environmental pollution is caused.
And ammonia nitrogen waste water will lead to water body fish, algae mortality, be environmental problem now urgently to be resolved.
Light degradation processing is carried out to waste water from dyestuff studies have shown that catalysis material can be used.However much have to dyestuff
The material of preferable photocatalysis performance can only all carry out light degradation under ultraviolet light, and ultraviolet light only accounts for a small portion of sunlight
Point, which has limited the application ranges of catalysis material.
CN104229924A reports the synthetic method introducing rare earth element in graphene, thus the conduct under mercury lamp
The catalyst of photocatalysis dyestuff.
CN104229924A is reported under ultraviolet irradiation, and the titanium dioxide of synthesized high-energy surface exposure is to rhodamine B
There is good light degradation effect.
CN104229924A reports the WO of synthesis3Composite coating has the application in outdoor optical degradation of formaldehyde.
It can be seen that WO3Light degradation can be carried out under visible light, and there is good practical application effect.
And ZrO2It in addition to this and a kind of good adsorbent is a kind of excellent photochemical catalyst,.
CN201710300477.5, which is reported, a kind of prepares ZrO2The method of oxide can be used to CO absorption2, meanwhile, it uses
ZrO2Modified organic amine, it may have CO absorption2Effect.
CN201611245548.8 is reported with preparation ZrO2Oxide process heavy metal wastewater thereby, the ZrO of preparation2Oxide
Large specific surface area has more active sites, has better suction-operated.
The processing of ammonia nitrogen waste water generally uses bioanalysis to remove ammonia nitrogen.CN201710211783.1 is reported using bioanalysis
The method for eliminating ionic ammonia nitrogen waste water.
CN201611263509.0 reports a kind of self refresh stripping device removal ammonia nitrogen, and it is certainly rotten that a kind of microorganism is utilized
Organic composite deamidization, to carry out NH_3-N treating.
Mesoporous material has a kind of new material of the uniform cellular structure of nanoscale and high surface area, and being that one kind is good urges
Active component is introduced mesoporous supports by load or direct synthesis, can provide and live required for catalysis reaction by agent carrier
Property position.Compared with conventional carrier, the active component dispersion degree on mesoporous material is more preferable, and contact of the reactant with activated centre is more
Sufficiently, it is especially suitable for big flow, the reaction system of high-speed.
US5672556 reports a series of synthesis side introducing transition metal species in MCM-41 mesoporous material skeleton
Method, these transition metal species include Ti, V, Sn, Zr, Zn, Cu, Co, Cr etc..
US6391278, which is reported, to be synthesized at room temperature using electroneutral primary amine or diamines as template containing transition metal species
HMS series mesoporous material, these transition metal species include Ti, V, Sn, Zr, Zn, Cu, Cr etc..
Up to the present, the mesoporous ZrO of one-step synthesis method2-WO3/ SBA-15 has not been reported for catalysis material.
Summary of the invention:
The technical problem to be solved by the present invention is to be not directed to one-step method in conventional art to prepare load tungsten and zirconium in skeleton
Mesoporous silica molecular sieve ZrO2-WO3The problem of/SBA-15, provides a kind of new mesoporous ZrO2-WO3/ SBA-15 molecule
The preparation method of sieve.The molecular sieve of this method preparation has biggish specific surface area, and dispersion performance is good and dispersion capacity is big, is used for
Light-catalyzed reaction, reactivity are higher.In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of mesoporous
ZrO2-WO3The preparation method of/SBA-15 molecular sieve is with polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer M
Template, to be selected from tetraethyl orthosilicate, silica solution, waterglass or white carbon black as silicon source, to be selected from ammonium metatungstate, para-tungstic acid
Ammonium, sodium tungstate or tungsten hexachloride are tungsten source, to be zirconium source in acid selected from basic zirconium chloride, zirconium hydroxide, zirconium acetate or zirconyl nitrate
Property under the conditions of, feed molar proportion it is as follows:
1SiO2: 0.01~0.03M:3~10H+: 50~200H2O:0.03~0.25WO3: 0.01~0.2ZrO2
It is 20~170 DEG C in crystallization temperature, pressure is hydrothermal crystallizing 6~120 hours under the self-generated pressure of gel mixture
ZrO needed for obtaining2-WO3/ SBA-15 molecular sieve；
It is cruel to be selected from positive silicic acid second for silicon source preferred embodiment in above-mentioned technical proposal；Tungsten source preferred embodiment is selected from sodium tungstate.Template
Agent polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer M molecular formula is H (- OCH2-CH2-)x[-OCH(CH3)
CH2-]y(OCH2CH2-)zOH average molecular weight is 5800, abbreviation P123.Preparation method preferred embodiment is before crystallization, 20
First template M is dissolved in acidic aqueous solution at~60 DEG C, tungsten source is then added and forms common mode plate, adds the solution of silicon source,
It is eventually adding zirconium source.Crystallization temperature preferred scope is 100 DEG C；Hydrothermal crystallizing time preferred scope is 24 hours.
The SBA-15 of the tungstenic and zirconium that synthesize in above-mentioned technical proposal need to be fired removed template method processing, and calcination process can
It is chosen at Muffle furnace or is carried out in tube furnace；The optional temperature programming under an inert atmosphere of heating mode is roasted, heating rate is 1
~10 DEG C, maturing temperature can choose 350 DEG C~800 DEG C, preferably 500 DEG C~750 DEG C.Calcining time is that oxidizing atmosphere 1~20 is small
When, preferably 3~9 hours；Inert atmosphere 1~10 hour, preferably 3~6 hours.The present invention is mesoporous by introducing tungsten and zirconium
The skeleton of SBA-15 molecular sieve, greatly improves specific surface area of catalyst, the dispersion degree of the tungsten increased, to improve catalysis
Agent reactivity worth achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment:
Example one
2.0gP123, which is dissolved in 65ml deionized water, is stirred at room temperature 3h, and 10ml 2molL is added-1Hydrochloric acid solution in 40
It DEG C is vigorously stirred 1h, the 10ml aqueous solution of 0.72g (40%) Disodium tungstate (Na2WO4) dihydrate is added, forms clear solution after stirring 1h, is delayed
It is slow that 4.5g tetraethyl orthosilicate is added dropwise, it is separately added into 0.1283g (m (ZrO2): m (SiO2)=3%, similarly hereinafter) chlorine hydrate oxidation
Zirconium, for 24 hours in 40 DEG C of stirrings.Solution is transferred in water heating kettle, 100 DEG C it is still aging for 24 hours, take out, successively use deionized water, second
Alcohol washs three times, 60 DEG C of dry 8h, 550 DEG C of calcining 6h.
It is accurate to measure 100mL10mgL-1Rhodamine B solution in beaker, the catalyst of 0.10g is added, in the dark
1h is stirred, then sampling is irradiated by light source of the xenon lamp of 200W, sample 1 time every 30min, takes 6 samples, sample is through centrifugation point
From taking supernatant liquor, absorbance measured at optimal absorption wavelength (552nm) with ultraviolet-uisible spectrophotometer, according to formulaWherein D is degradation rate, A0For initial soln absorbance, A is surplus solution absorbance).Finally calculate
Degradation rate to rhodamine B is 80.0%.
Prepare 50mgL-1NH4Cl solution takes 100ml, and 0.10g sample is added, and stirring is shaken at 30 DEG C, is existed respectively
It is respectively sampled after 10,20,30,40,60,90,120min, constant volume, 1.0ml potassium sodium tartrate solution is added, shakes up, adds Na Shi
Reagent 1.5ml, shakes up.After placing 10min, at wavelength 420nm, with 20mm cuvette, reference is made with water, measures absorbance.
The mass concentration of ammonia nitrogen is according to formula in waterWherein ρNFor the mass concentration (mgL of ammonia nitrogen in water sample-1), AsFor
The absorbance of water sample, AbFor the absorbance of blank test, a is the intercept of calibration curve, and b is the slope of calibration curve.Finally count
Calculate ammonia nitrogen removal frank be 82.7%.
Example two
2.0gP123, which is dissolved in 65ml deionized water, is stirred at room temperature 3h, and 10ml 2molL is added-1Hydrochloric acid solution in 40
It DEG C is vigorously stirred 1h, the 10ml aqueous solution of 0.72g (40%) Disodium tungstate (Na2WO4) dihydrate is added, forms clear solution after stirring 1h, is delayed
It is slow that 4.5g tetraethyl orthosilicate is added dropwise, it is separately added into 0.2139g (5%) chlorine hydrate zirconium oxide, for 24 hours in 40 DEG C of stirrings.It will be molten
Liquid is transferred in water heating kettle, 100 DEG C it is still aging for 24 hours, take out, successively use deionized water, ethanol washing three times, 60 DEG C of dryings
8h, 550 DEG C of calcining 6h.
It is accurate to measure 100mL10mgL-1Rhodamine B solution in beaker, the catalyst of 0.10g is added, in the dark
1h is stirred, then sampling is irradiated by light source of the xenon lamp of 200W, sample 1 time every 30min, takes 6 samples, sample is through centrifugation point
From taking supernatant liquor, absorbance measured at optimal absorption wavelength (552nm) with ultraviolet-uisible spectrophotometer, according to formulaWherein D is degradation rate, A0For initial soln absorbance, A is surplus solution absorbance).Finally calculate
Degradation rate to rhodamine B is 86.6%.
Prepare 50mgL-1NH4Cl solution takes 100ml, and 0.10g sample is added, and stirring is shaken at 30 DEG C, is existed respectively
It is respectively sampled after 10,20,30,40,60,90,120min, constant volume, 1.0ml potassium sodium tartrate solution is added, shakes up, adds Na Shi
Reagent 1.5ml, shakes up.After placing 10min, at wavelength 420nm, with 20mm cuvette, reference is made with water, measures absorbance.
The mass concentration of ammonia nitrogen is according to formula in waterWherein ρNFor the mass concentration (mgL of ammonia nitrogen in water sample-1), AsFor
The absorbance of water sample, AbFor the absorbance of blank test, a is the intercept of calibration curve, and b is the slope of calibration curve.Finally count
Calculate ammonia nitrogen removal frank be 80.4%.
Example three
2.0g P123, which is dissolved in 65ml deionized water, is stirred at room temperature 3h, and 10ml 2molL is added-1Hydrochloric acid solution in 40
It DEG C is vigorously stirred 1h, the 10ml aqueous solution of 0.72g (40%) Disodium tungstate (Na2WO4) dihydrate is added, forms clear solution after stirring 1h, is delayed
It is slow that 4.5g tetraethyl orthosilicate is added dropwise, it is separately added into 0.2995g (7%) chlorine hydrate zirconium oxide, for 24 hours in 40 DEG C of stirrings.It will be molten
Liquid is transferred in water heating kettle, 100 DEG C it is still aging for 24 hours, take out, successively use deionized water, ethanol washing three times, 60 DEG C of dryings
8h, 550 DEG C of calcining 6h.
It is accurate to measure 100mL10mgL-1Rhodamine B solution in beaker, the catalyst of 0.10g is added, in the dark
1h is stirred, then sampling is irradiated by light source of the xenon lamp of 200W, sample 1 time every 30min, takes 6 samples, sample is through centrifugation point
From taking clear 2 liquid in upper layer, absorbance measured at optimal absorption wavelength (552nm) with ultraviolet-uisible spectrophotometer, according to formulaWherein D is degradation rate, A0For initial soln absorbance, A is surplus solution absorbance).Finally calculate
Degradation rate to rhodamine B is 82.8%.
Prepare 50mgL-1NH4Cl solution takes 100ml, and 0.10g sample is added, and stirring is shaken at 30 DEG C, is existed respectively
It is respectively sampled after 10,20,30,40,60,90,120min, constant volume, 1.0ml potassium sodium tartrate solution is added, shakes up, adds Na Shi
Reagent 1.5ml, shakes up.After placing 10min, at wavelength 420nm, with 20mm cuvette, reference is made with water, measures absorbance.
The mass concentration of ammonia nitrogen is according to formula in waterWherein ρNFor the mass concentration (mgL of ammonia nitrogen in water sample-1), AsFor
The absorbance of water sample, AbFor the absorbance of blank test, a is the intercept of calibration curve, and b is the slope of calibration curve.Finally count
Calculate ammonia nitrogen removal frank be 77.4%.
Example four
2.0g P123, which is dissolved in 65ml deionized water, is stirred at room temperature 3h, and 10ml 2molL is added-1Hydrochloric acid solution in 40
It DEG C is vigorously stirred 1h, the 10ml aqueous solution of 0.72g (40%) Disodium tungstate (Na2WO4) dihydrate is added, forms clear solution after stirring 1h, is delayed
It is slow that 4.5g tetraethyl orthosilicate is added dropwise, it is separately added into 0.385g (9%) chlorine hydrate zirconium oxide, for 24 hours in 40 DEG C of stirrings.By solution
Be transferred in water heating kettle, 100 DEG C it is still aging for 24 hours, take out, successively use deionized water, ethanol washing three times, 60 DEG C of dry 8h,
550 DEG C of calcining 6h.
It is accurate to measure 100mL10mgL-1Rhodamine B solution in beaker, the catalyst of 0.10g is added, in the dark
1h is stirred, then sampling is irradiated by light source of the xenon lamp of 200W, sample 1 time every 30min, takes 6 samples, sample is through centrifugation point
From taking supernatant liquor, absorbance measured at optimal absorption wavelength (552nm) with ultraviolet-uisible spectrophotometer, according to formulaWherein D is degradation rate, A0For initial soln absorbance, A is surplus solution absorbance).Finally calculate
Degradation rate to rhodamine B is 84.4%.
Prepare 50mgL-1NH4Cl solution takes 100ml, and 0.10g sample is added, and stirring is shaken at 30 DEG C, is existed respectively
It is respectively sampled after 10,20,30,40,60,90,120min, constant volume, 1.0ml potassium sodium tartrate solution is added, shakes up, adds Na Shi
Reagent 1.5ml, shakes up.After placing 10min, at wavelength 420nm, with 20mm cuvette, reference is made with water, measures absorbance.
The mass concentration of ammonia nitrogen is according to formula in waterWherein ρNFor the mass concentration (mgL of ammonia nitrogen in water sample-1), AsFor
The absorbance of water sample, AbFor the absorbance of blank test, a is the intercept of calibration curve, and b is the slope of calibration curve.Finally count
Calculate ammonia nitrogen removal frank be 75.3%.
Claims (7)
1. a kind of method that one-step method prepares mesoporous tungsten trioxide Yu zirconia-supported SBA-15, is named as ZrO2-WO3/SBA-
15 molecular sieves, using polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer M as template, to be selected from positive silicic acid tetrem
Ester, silica solution, waterglass or white carbon black are silicon source, to be selected from ammonium metatungstate, ammonium paratungstate, sodium tungstate or tungsten hexachloride as tungsten
Source, using, as zirconium source, in acid condition, feed molar is with such as selected from basic zirconium chloride, zirconium hydroxide, zirconium acetate or zirconyl nitrate
Under:
1SiO2: 0.01~0.03M:3~10H+: 50~200H2O:0.03~0.25WO3: 0.01~0.2ZrO2
It is 20~170 DEG C in crystallization temperature, pressure is to obtain within hydrothermal crystallizing 6~120 hours under the self-generated pressure of gel mixture
Required ZrO2-WO3/ SBA-15 molecular sieve.
2. mesoporous ZrO according to claim 12-WO3The preparation method of/SBA-15 molecular sieve, it is characterised in that tungsten source choosing
From sodium tungstate.
3. mesoporous ZrO according to claim 12-WO3The preparation method of/SBA-15 molecular sieve, it is characterised in that silicon source choosing
From tetraethyl orthosilicate.
4. mesoporous ZrO according to claim 12-WO3The preparation method of/SBA-15 molecular sieve, it is characterised in that zirconium source choosing
From basic zirconium chloride.
5. mesoporous ZrO according to claim 12-WO3The preparation method of/SBA-15 molecular sieve, it is characterised in that crystallization temperature
Degree is 100 DEG C, crystallization time 24 hours.
6. mesoporous ZrO according to claim 12-WO3The preparation method of/SBA-15 molecular sieve, it is characterised in that in crystallization
Before, first template M is dissolved in acidic aqueous solution at 20~60 DEG C, tungsten source is then added and forms common mode plate, adds silicon
The solution in source is eventually adding zirconium source.
7. mesoporous ZrO according to claim 12-WO3The preparation method of/SBA-15 molecular sieve, it is characterised in that acid water
The acid of solution is selected from hydrochloric acid.
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