CN105797712B - The preparation method of molybdenum doping bismuth tungstate/montmorillonite composite material and its application in photocatalysis desulfurization - Google Patents
The preparation method of molybdenum doping bismuth tungstate/montmorillonite composite material and its application in photocatalysis desulfurization Download PDFInfo
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- CN105797712B CN105797712B CN201610214390.1A CN201610214390A CN105797712B CN 105797712 B CN105797712 B CN 105797712B CN 201610214390 A CN201610214390 A CN 201610214390A CN 105797712 B CN105797712 B CN 105797712B
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 title claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims description 9
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 8
- 238000006477 desulfuration reaction Methods 0.000 title claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 8
- 239000011733 molybdenum Substances 0.000 title claims description 8
- 230000023556 desulfurization Effects 0.000 title claims description 6
- 230000001699 photocatalysis Effects 0.000 title description 4
- 238000007146 photocatalysis Methods 0.000 title description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000000295 fuel oil Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 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 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of Mo to adulterate Bi2WO6The preparation method of/montmorillonite (MMT) composite, belongs to new chemical materialses field.Its preparation method is：Weigh a certain amount of sodium molybdate, sodium tungstate, bismuth nitrate and montmorillonite, it is added separately to be stirred by ultrasonic in a certain amount of deionized water, mixed liquor is transferred in reactor at 140~220 DEG C and is incubated a period of time, washing is multiple, the Bi that drying Mo is adulterated under certain temperature2WO6/ MMT composites.Mo doping Bi prepared by the present invention2WO6/ MMT Load Balanceds, good dispersion, experimental raw are easy to get, and without the equipment of complexity, favorable repeatability, have very high degradation effect to the thiophenic sulfur in fuel oil.
Description
Technical field
The invention belongs to new chemical materialses technical field, and in particular to adulterate Bi to Mo2WO6The preparation of/MMT composites
Method and its application in photooxidation desulfated.
Background technology
Organic sulfur compound burning in fuel oil can generate SOX, acid rain can be formed by being discharged into air, and environment is caused
Pollution.With the increasingly reinforcement of environmental consciousness, how to effectively reduce the sulfur content in oil product turns into the hot issue of research.Work
Generally use hydrodesulfurization (HDS) removes the sulfide in oil product in industry, but due to its severe reaction conditions, equipment investment
Greatly, it is and poor to thiophene and derivatives removal effect, therefore non-hydrodesulfurization turns into study hotspot.Non- hydrodesulfurization
The methods of mainly including oxidation sweetening, abstraction desulfurization, absorption desulfurization and biological desulphurization.Wherein, oxidation sweetening has operating condition
Thiophene sulfocompounds are had higher desulfuration efficiency by the features such as gently, energy consumption is low, pollution is small, before having application well
Scape.In recent years, it is proved to be a kind of method of effectively processing pollution using semiconductor catalyst photocatalysis desulfurization.
Bismuth molybdate (Bi2MoO6) it is a kind of two-dimensional semiconductor material, its energy gap is about 2.4eV, bismuth tungstate
(Bi2WO6) and Bi2MoO6Structure is similar, and a kind of two-dimensional semiconductor material, its energy gap are about 2.8eV, there is document
Report Bi2WO6、Bi2MoO6There is photocatalytic pollutant degradation under visible light.The half of both two-dimensional slice structures
There is the problem of same in conductor, i.e., light induced electron easily occurs from compound phenomenon with hole, in order to overcome this difficult, it is necessary to
The progress of other semiconductors is compound, reaches transfer electronics, reduces electron-hole from compound purpose.In the catalytic degradation mistake of reality
Cheng Zhong, catalyst powder constrain the industrial applications of catalyst and further pushed away in the presence of the problem of separation is difficult, recovery is difficult in itself
Extensively.
Come immobilized semiconductor catalyst it is the current dispersiveness for solving catalyst using the excellent nanoclay of absorption property
It is with the important method of recycling, active component is immobilized in a weight for turning into catalytic field on the clay of bigger serface
Want developing direction.
The content of the invention
The technical problems to be solved by the invention are：Report in recent years on montmorillonite-loaded semi-conducting material is more,
But on the compound Mo doping Bi of montmorillonite2WO6Document be also not seen reported at present.
This patent is prepared for Mo by hydro-thermal method and adulterates Bi2WO6/ MMT, preparation method are to weigh a certain amount of sodium molybdate, tungsten
Sour sodium, bismuth nitrate and montmorillonite, Bi is adulterated with Mo by optimizing montmorillonite2WO6Raw material sodium molybdate, sodium tungstate and bismuth nitrate
The technological parameters such as mass ratio, hydrothermal temperature and hydro-thermal time come control Mo adulterate Bi2WO6The pattern of/MMT composites and point
Cloth state, so as to obtain the product of Load Balanced, good dispersion.
The present invention specific embodiment be：A certain amount of sodium molybdate, sodium tungstate, bismuth nitrate and montmorillonite are weighed, respectively
It is added to ultrasound in a certain amount of deionized water and stirs a period of time, mixed liquor is transferred in reactor at 140~200 DEG C
Lower insulation a period of time, washing is multiple, the Bi that drying Mo is adulterated under certain temperature2WO6/ MMT composites.
In described preparation method, X=Mo/ (W+Mo) mol ratio is between 1/10~1/1, the Bi of Mo doping2WO6Phase
Mass ratio for montmorillonite is 1/2~1/8.
In described preparation method, the product after hydro-thermal is needed by repeatedly washing to eliminate impurity, and at 60~100 DEG C
12~24h of lower insulation.
In described preparation method, hydrothermal temperature is 140~200 DEG C, and the hydro-thermal time is 16~24h.
Present invention employs the Mo doping that a kind of more easy chemical technology has prepared Load Balanced, good dispersion
Bi2WO6/ MMT composites, without the equipment of complexity, chemical raw material used is cheap, and assay reproducibility is good, has very high
Commercial introduction is worth.
Present invention also offers a kind of above-mentioned Mo doping Bi2WO6The application process of/MMT composites, i.e., it is compound using this
Material carries out the thiophenic sulfur in photochemical catalytic oxidation removing fuel oil as catalyst.Desulfurization is in photochemical reaction instrument
Carry out, be analog light source with 300W xenon lamps, it is only visible to ensure to remove the non-visible light that all wavelengths are less than 420 nanometers
Light irradiation.The mould oil (200ppm) containing dibenzothiophenes and catalyst that prepare in advance are added in reactor, then
By mixed solution constant agitation 30 minutes in the dark, to establish adsorption-desorption balance.Then, 30wt%H is used2O2Aqueous solution conduct
(mol ratio for ensureing O/S is 4 to oxidant：1) and it is added in reaction system, is then irradiated with 300W xenon lamps.By solution example
Collect once, and centrifuged with supercentrifuge within every 30 minutes.The sulfur content of simulation oil is detected by Ultraluminescence sulphur measuring instrument.It is de-
Sulphur rate (%) calculates according to following equation：
D=(1-C/C0) × 100%
Wherein, C0It is the sulfur content in initial soln, C is sulfur content of the solution in time t after catalytic reaction.
The beneficial effects of the present invention are：This patent is prepared for Mo by hydro-thermal method and adulterates Bi2WO6/ MMT composites, instead
Answer process simple, raw material is cheap and easily-available.Montmorillonite is the chief component of bentonite clay mineral, has layer frame structure, can
To provide huge specific surface area, due to the special laminate structure of montmorillonite, easy ultrasonic stripping means is on the one hand utilized
Cause to slide between layers, peel off up to spreading out, obtain the montmorillonite thin slice of large surface, the mineral tool after stripping
There is bigger specific surface area, there is stronger suction-operated to organic matter, effectively prevent conventional montmorillonite intercalation interlayer region
Loaded optic catalyst, light is caused to be blocked by montmorillonite interlayer region, so as to cause the limited technical problem of light absorbs.And profit
With the excellent adsorption capacity of montmorillonite, make the scattered and repetition that catalyst is rapid with organic matter, fully contacts, and solves catalyst
The problem of utilization；On the other hand it is dissolved by two kinds of semiconductor dopings, introduces doped energy-band and change energy gap, realize simultaneously
Photo-generate electron-hole efficiently separates so that desulfuration efficiency is significantly improved the photochemical catalyst under visible light.
Brief description of the drawings
Fig. 1 is montmorillonite (MMT), Mo doping Bi2WO6The XRD spectra of/MMT samples；
Fig. 2 is Bi2W0.6Mo0.4O6The TEM photos of/MMT samples；
Fig. 3 is Bi2W0.6Mo0.4O6The high-resolution TEM photos of/MMT samples；
Fig. 4 is MMT, Bi2WO6/MMT、Bi2W0.6Mo0.4O6/MMT、Bi2W0.8Mo0.2O6/ MMT samples are to dibenzothiophenes
Degradation rate curve.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1：
Weigh 0.97g bismuth nitrate, 0.096g sodium molybdates, 0.198g sodium tungstates, 0.5g montmorillonites are separately added into 15ml and go
In ionized water ultrasound and stir 30min, mixed liquor is transferred in reactor at 180 DEG C and is incubated 24h, repeatedly washing after, in 80
12h is dried at DEG C, obtains the Bi of Mo doping2WO6/ MMT (X=0.4) composite.
X-ray powder diffraction experiment is carried out to gained sample, and its pattern and structure are observed under transmission electron microscope, according to reality
Apply the Bi that Mo made from the technological parameter of example 1 is adulterated2WO6/ MMT and Bi2WO6/ MMT, the XRD spectrum of montmorillonite are as shown in Figure 1.
There is montmorillonite and Bi in the XRD of composite2WO6Respective characteristic diffraction peak, Mo doping Bi2WO6After form solid solution
Phase, there is not Bi in XRD spectrum2MoO6Characteristic peak, successfully prepared Bi2W0.6Mo0.4O6/ MMT (X=0.4) composite wood
Material.
Bi2W0.6Mo0.4O6The TEM photos of/MMT samples and its high-resolution TEM photos of fringe region are as shown in Figure 3.From figure
In as can be seen that the montmorillonite of big sheet successfully loads the Bi of strip2W0.6Mo0.4O6, three-dimensional net structure is formed, with XRD
Result it is consistent.
Using MMT, Bi2WO6/MMT、Bi2W0.6Mo0.4O6/ MMT and Bi2W0.8Mo0.2O6/ MMT samples are carried out as catalyst
Thiophenic sulfur in photochemical catalytic oxidation removing fuel oil, obtains degradation rate curve such as Fig. 4 institute of the above-mentioned sample to dibenzothiophenes
Show, it can be seen that Bi2WO6/ MMT is about 53.4%, Bi to the degradation rate of dibenzothiophenes2W0.6Mo0.4O6/MMT(X
=0.4) sample to the degradation rate of dibenzothiophenes up to more than 95%.
Embodiment 2：
Weigh 0.97g bismuth nitrate, 0.048g sodium molybdates, 0.264g sodium tungstates, 0.5g montmorillonites are separately added into 15ml and go
In ionized water ultrasound and stir 30min, mixed liquor is transferred in reactor at 140 DEG C and is incubated 20h, repeatedly washing after 100
16h is dried at DEG C, obtains the Bi of Mo doping2WO6/ MMT (X=0.2) composite, reaches to the degradation rate of dibenzothiophenes
71.4%.
Embodiment 3：
Weigh 0.97g bismuth nitrate, 0.024g sodium molybdates, 0.296g sodium tungstates, 0.5g montmorillonites are separately added into 15ml and go
In ionized water ultrasound and stir 30min, mixed liquor is transferred in reactor at 200 DEG C and is incubated 16h, repeatedly washing after 80 DEG C
Lower drying 12h, obtain the Bi of Mo doping2WO6/ MMT (X=0.1) composite, subsequent detection such as embodiment 1.
Embodiment 4：
Weigh 0.97g bismuth nitrate, 0.0726g sodium molybdates, 0.232g sodium tungstates, 0.5g montmorillonites are separately added into 15ml and go
In ionized water ultrasound and stir 30min, mixed liquor is transferred in reactor at 160 DEG C and is incubated 18h, repeatedly washing after 60 DEG C
Lower drying 20h, obtain the Bi of Mo doping2WO6/ MMT (X=0.3) composite.Subsequent detection such as embodiment 1.
Embodiment 5：
Weigh 0.97g bismuth nitrate, 0.121g sodium molybdates, 0.165g sodium tungstates, 0.5g montmorillonites are separately added into 15ml and go
In ionized water ultrasound and stir 30min, mixed liquor is transferred in reactor at 180 DEG C and is incubated 22h, repeatedly washing after 70 DEG C
Lower drying 18h, obtain the Bi of Mo doping2WO6/ MMT (X=0.5) composite.Subsequent detection such as embodiment 1.
Comparative example 1：
Agitating mode in embodiment 1 is changed into routine to be sufficiently stirred, is not added with ultrasonic stripping, montmorillonite does not form big table
The thin slice in face, other conditions are same as Example 1, and Bi is made2W0.6Mo0.4O6/ MMT (X=0.4) composite, and as
Catalyst carries out photooxidation desulfated experiment, using the method for testing of embodiment 1, as a result shows, no ultrasound is peeled off montmorillonite-loaded
Sample is only 63% or so to the degradation rate of dibenzothiophenes.
Claims (5)
- A kind of 1. preparation method of molybdenum doping bismuth tungstate/montmorillonite composite material, it is characterised in that：The preparation method technique is such as Under：Sodium molybdate, sodium tungstate, bismuth nitrate and montmorillonite are weighed in proportion, are sequentially added into deionized water and are carried out ultrasound simultaneously It is stirred, mixed liquor is transferred in reactor and carries out hydro-thermal reaction, insulation, hydrothermal product is mixed through washing, drying Mo Miscellaneous Bi2WO6/ MMT composites；Wherein, X=Mo/ (W+Mo) mol ratio is between 1/10~1/1, the Bi of Mo doping2WO6 Relative to montmorillonite mass ratio be 1/2~1/8, hydrothermal temperature be 140~200 DEG C, the hydro-thermal reaction time be 16~ 24h。
- 2. the preparation method of molybdenum doping bismuth tungstate/montmorillonite composite material as claimed in claim 1, it is characterised in that：It is described Preparation method in, the dosage of deionized water is：100-600mL, the time of ultrasonic agitation is：15-60min.
- 3. the preparation method of molybdenum doping bismuth tungstate/montmorillonite composite material as claimed in claim 1, it is characterised in that：It is described Preparation method in, holding temperature after hydro-thermal reaction is 60~100 DEG C, and soaking time is 12~24h.
- 4. the preparation method of molybdenum doping bismuth tungstate/montmorillonite composite material as claimed in claim 1, it is characterised in that：It is described Preparation method in, product after hydro-thermal is washed 3 times, drying temperature：50-90℃.
- 5. the application of molybdenum doping bismuth tungstate/montmorillonite composite material made from a kind of preparation method as claimed in claim 1, its It is characterised by：Molybdenum doping bismuth tungstate/the montmorillonite composite material is used for photochemical catalytic oxidation desulfurization as catalyst.
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| CN110898828A (en) * | 2019-12-03 | 2020-03-24 | 重庆科技学院 | Preparation method of photocatalyst for degrading organic matters in fracturing flow-back fluid of oil and gas field |
| CN113215413B (en) * | 2021-04-13 | 2022-04-22 | 华南理工大学 | Desulfurizing agent and method for preparing zero-carbon smelting precursor by removing sulfur in waste lead paste |
| CN114588927A (en) * | 2022-03-28 | 2022-06-07 | 福州大学 | Bismuth tungstate composite photocatalyst and preparation method and application thereof |
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| RU2313389C1 (en) * | 2006-10-13 | 2007-12-27 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Catalyst, method for preparation thereof, method for preparing carrier for this catalyst, and diesel fraction desulfurization process |
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