CN108722445B - A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application - Google Patents
A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application Download PDFInfo
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- CN108722445B CN108722445B CN201810594148.0A CN201810594148A CN108722445B CN 108722445 B CN108722445 B CN 108722445B CN 201810594148 A CN201810594148 A CN 201810594148A CN 108722445 B CN108722445 B CN 108722445B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000006104 solid solution Substances 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 claims abstract description 35
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims abstract description 20
- -1 hydroxypropyl Chemical group 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 24
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 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 description 9
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 238000003556 assay Methods 0.000 claims description 7
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 abstract description 23
- 239000011159 matrix material Substances 0.000 abstract description 22
- 239000002699 waste material Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229910052794 bromium Inorganic materials 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 229910052740 iodine Inorganic materials 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 description 34
- 230000001699 photocatalysis Effects 0.000 description 21
- 238000001035 drying Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000012986 modification Methods 0.000 description 12
- 229910052797 bismuth Inorganic materials 0.000 description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000001476 alcoholic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- JDXXTKLHHZMVIO-UHFFFAOYSA-N 2-(3-hydroxypropyl)guanidine Chemical compound NC(=N)NCCCO JDXXTKLHHZMVIO-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003149 assay kit Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 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 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
-
- B01J35/23—
-
- B01J35/30—
-
- B01J35/39—
-
- B01J35/615—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to photochemical catalyst fields, disclose ultra-thin BiOX photocatalyst of a kind of ultra-thin solid solution of BiOX and its preparation method and application, wherein, the expression formula of the modified BiOX matrix composite photochemical catalyst is BiOXY, wherein X and Y is each independently Br or I, and X and Y is different, and the modified BiOX matrix composite photochemical catalyst be it is powdered, with a thickness of 0.20-0.23nm, specific surface area 300-320m2/g.Catalyst specific surface area with higher, it is ultra-thin, can the preferably hydroxypropyl guar in photochemical catalytic oxidation removal shale gas oil field waste under visible light, also, the preparation method reduces production cost, simplifies production technology.
Description
Technical field
The present invention relates to photochemical catalyst fields, and in particular to modified BiOX matrix composite photochemical catalyst and its preparation side
Method and application.
Background technique
Research for the oil field wastewater treatment method generated during oilfield stimulation has obtained certain achievement both at home and abroad, oil
Most of inorganic wastes in the waste water of field, such as: landwaste, proppant, inorganic salts etc. pass through the sedimentation of a series of physics, chemistry
The methods of flocculation can be removed effectively.But for polymer wherein difficult to degrade, such as: the high molecular polymers such as guanidine glue, then
It needs to consume a large amount of energy or miscellaneous chemical agent is degraded one by one, processing cost is high, equipment investment is big, process cycle
Long, easy secondary pollution.
Photocatalysis technology is a kind of new process for processing persistent organic pollutants that 20 th century laters grow up, special
Sign is by generating the extremely strong active oxygen species (ROS) of activity in the case where semiconductor catalyst acts on, and ROS almost can non-selectivity
By organic pollutant oxidative degradation difficult to degrade in waste water at non-toxic or low-toxic small-molecule substance, or even directly mineralising is dioxy
Change carbon and water and other small carboxylic acid molecules, reaches innoxious purpose.The technology has that non-selectivity, oxidability be strong, reaction speed
The advantages that degree is fast, treatment effeciency is high, without secondary pollution.Above-mentioned characteristic makes photocatalysis technology return drain field in processing shale gas
Illustrate great application space.And in photocatalysis technology field, the development of photochemical catalyst be then core the most technology it
One.And BiOX becomes the new lover of photocatalysis field in recent years.
Bismuth is a kind of green metal, BiOX as a kind of novel low-gap semiconductor, due to its is nontoxic, cheap,
Redox ability is strong, chemical property is stable and it is anti-light corrosion etc. characteristics, water pollutant degradation, in terms of obtain
It is widely applied.Since the electron-hole combined efficiency of monomer is higher, its photocatalysis performance is had adverse effect, sternly
Constrain again its in terms of practical application.Therefore, make BiOX based photocatalyst that there is bloom by modified
Catalytic performance is one of the important topic of photocatalysis research field.Current method reported in the literature has metal ion mixing, non-gold
Belong to the solid solution, compound etc. of ion doping, semiconductor.
The BiOBr of Yang in 2015 et al. discovery fabricated in situ0.5I0.5Mischcrystal photocatalyst is under the irradiation of visible light
When being catalyzed rhodamine b, there is very strong photocatalytic activity (Yang Z, Cheng F, Dong X, et al.Controllable
in situ synthesis of BiOBrxI1-x solid solution on reduced graphene oxide with
enhanced visible light photocatalytic performance[J].Rsc Advances,2015,5(83):
68151-68158.).But the BiOBr reported in the document0.5I0.5Mischcrystal photocatalyst is only applied to degradation dye
Material is not applied in degradation hydroxypropyl guar, and synthetic method is complex, and effect is still to be improved.
Therefore, a kind of economical and effective, environmental-friendly fracturing outlet liquid polymer degradation technique or technique are explored, for slow
The environmental problem of solution development block seems increasingly important, has simultaneously for the normal production and sustainable development for ensureing shale gas
Significance.
Summary of the invention
The purpose of the invention is to overcome the above problem of the existing technology, a kind of ultra-thin solid solution of BiOX is super
Thin BiOX photocatalyst and its preparation method and application, wherein catalyst specific surface area with higher, ultra-thin, energy
It is enough that preferably photochemical catalytic oxidation removes the hydroxypropyl guar in shale gas oil field waste, also, the preparation method under visible light
Production cost is reduced, production technology is simplified.
A kind of ultra-thin BiOX photocatalyst of ultra-thin solid solution of BiOX and its preparation method and application, wherein institute
The expression formula for stating modified BiOX matrix composite photochemical catalyst is BiOXY, wherein X and Y is each independently Br or I, and X
Different with the Y and described modified BiOX matrix composite photochemical catalyst be it is powdered, with a thickness of 0.20-0.23nm, specific surface
Product is 300-320m2/g.Preferably, X Br, Y I.
Second aspect of the present invention provides a kind of preparation method of modified BiOX matrix composite photochemical catalyst, wherein
Method includes the following steps:
(1) the compound water containing bismuth element is mixed to get mixture A；
(2) the alcoholic solution B of the compound containing X element and Y element is prepared；
(3) the alcoholic solution B containing X element and the compound of Y element is added drop-wise in mixture A and is reacted, stirring is certain
A certain amount of surfactant is added after time；
(4) reactant for obtaining step (3) washs drying；
Wherein, X and Y is each independently Br or I, and X and Y is different.
Preferably, X Br, Y I.
Preferably, the compound containing X element, the compound containing Y element and the dosage of the compound containing bismuth element
Molar ratio is 1:(1-2): (1.5-2.5).
Preferably, the compound containing bismuth element is five water bismuth nitrates；Compound containing X element is potassium bromide and/or bromination
Sodium, more preferably potassium bromide；Compound containing Y element is potassium iodide.
Preferably, in step (1), the water be distilled water, and relative to described in 1mmol containing the compound of X element
And the compound containing Y element of 1mmol, the dosage of the distilled water are 20-25mL.
Preferably, in step (2), the alcohol is one of ethyl alcohol, ethylene glycol, propyl alcohol and glycerine or a variety of, excellent
It is selected as ethylene glycol, and relative to the compound containing the compound described in X element and 1mmol containing Y element described in 1mmol,
The dosage of the alcohol is 30- 40mL.
Preferably, in step (3), the condition of the reaction includes: that temperature is 20-35 DEG C, time 8-12h, is added dropwise
Rate is 1-2.5mL/ minutes.
Preferably, in step (4), the condition of the drying includes: that drying temperature is 80 DEG C of 60-, drying time 5-
24h；Preferably, drying temperature is 65-75 DEG C, drying time 7-15h.
Preferably, the surfactant be N methyl pyrrolidone, and relative to described in 1mmol containing the change of X element
Object is closed, the dosage of the surfactant is 0.3-0.5mg.
Third aspect present invention provides modification BiOX matrix composite photochemical catalyst or described above described above
The modification BiOX matrix composite photocatalyst applications that are prepared of preparation method under visible light catalysis oxidation oil field it is useless
Hydroxypropyl guar in water.
The technical solution provided according to the present invention, has the advantage that
(1) present invention optimizes the preparation process of modified BiOX matrix composite photochemical catalyst, having reduces cost, letter
The characteristics of changing production procedure；
(2) modification BiOX matrix composite photochemical catalyst of the invention has composite construction, and has ultra-thin property,
Improve photocatalytic activity；
(3) modification BiOX matrix composite photochemical catalyst of the invention is used, is greater than the visible light spoke of 420nm in wavelength
According under, the hydroxypropyl guar solution that original COD is 200mg/L removal rate in 2h is 95%, and photocatalysis performance greatly improved；
(4) present invention uses nontoxic component, reduces the harm to human health and ecological environment；
(5) the modification BiOX matrix composite photochemical catalyst that the present invention is prepared does not need to add other chemical reagent
And other preparation post-processings, a step fabricated in situ is only needed, method is simple.
Detailed description of the invention
Fig. 1 is the TEM figure of modification BiOX matrix composite photochemical catalyst prepared by embodiment according to the present invention 1；
Fig. 2 is the XRD spectra of modification BiOX matrix composite photochemical catalyst prepared by embodiment according to the present invention 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of modified BiOX matrix composite photochemical catalysts, wherein the modified halogen
The expression formula of bismuth oxide matrix composite photochemical catalyst is BiOXY, wherein it is respectively independent that X and Y is each independently Br or I, X and Y
Ground is Br or I, and the pattern of X and Y difference and the modified BiOX matrix composite photochemical catalyst is powdered, thickness
For 0.20-0.23nm, preferably 0.20-0.21nm, specific surface area is 300- 320m2/ g, preferably 305-320m2/ g, it is more excellent
It is selected as 310-315m2/g。
Under preferable case, X Br, Y I.
In the present invention, which has solid-solution structures, specific surface area with higher, and ultra-slim features are improved and urged
Change activity, can preferably under visible light (wavelength greater than 420nm visible light exposure under) photochemical catalytic oxidation remove shale
Hydroxypropyl guar in gas oil field waste reduces in addition, the modification BiOX matrix composite photochemical catalyst is nontoxic to human body
The harm of health and ecological environment.
In the present invention, what BiOXY was indicated is the mischcrystal photocatalyst being made of X and Y element, for example,
BiOBr0.5I0.5What is indicated is the mischcrystal photocatalyst being made of Br element and bromo element.
Second aspect, the present invention provides a kind of preparation methods of modified BiOX matrix composite photochemical catalyst, wherein
Method includes the following steps:
(1) the compound water containing bismuth element is mixed to get mixture A；
(2) the alcoholic solution B of the compound containing X element and Y element is prepared；
(3) the alcoholic solution B containing X element and the compound of Y element is added drop-wise in mixture A and is reacted, stirring is certain
A certain amount of surfactant is added after time；
(4) reactant for obtaining step (3) washs drying；
Wherein, X and Y is each independently Br or I, and X and Y is different.
The dosage of preparation method according to the present invention, the compound containing bismuth element can be than broad range
It is interior, it is not particularly limited, as long as guaranteeing the chemical combination containing X element in prepared modification BiOX matrix composite photochemical catalyst
The molar ratio of the content of X element in object and the Y element in the compound containing Y element is 1:1, for example, described contain X element
Compound, the compound containing Y element and the compound containing bismuth element the molar ratio of dosage can be 1:(1-2): (1.5-
2.5), preferably 1:1:(1.8-2.3), more preferably 1:1:2.In the preparation process in accordance with the present invention, the change containing X element
The molar ratio for closing the dosage of object, the compound containing Y element and the compound containing bismuth element is limited to above range, can be prepared into
To with solid-solution structures, specific surface area with higher is ultra-thin, improves the ultra-thin BiOX based solid solution light of catalytic activity
Catalyst, and can preferably under visible light (wavelength greater than 420nm visible light exposure under) photochemical catalytic oxidation remove page
Hydroxypropyl guar in rock gas oil field waste.
Preparation method according to the present invention, the compound containing bismuth element can be five water bismuth nitrates；Compound containing X element
It can be potassium bromide and/or sodium bromide, preferably potassium bromide；The compound of the element containing Y can be potassium iodide.
Preparation method according to the present invention, in step (1), the water is distilled water, and is contained relative to described in 1mmol
The dosage of the compound of bismuth element, the distilled water can be 20-25mL, for example, the dosage of the distilled water can be
20mL, 21mL, 22mL, 23mL, 24mL, 25mL, under preferable case, the dosage of the distilled water is 20mL.
Preparation method according to the present invention, in step (2), the alcohol is in ethyl alcohol, ethylene glycol, propyl alcohol and glycerine
It is one or more, preferably ethylene glycol, and relative to described in 1mmol containing described in X element and 1mmol containing the change of Y element
Object is closed, the dosage of the alcohol can be 30-40mL, for example, the dosage of the alcohol can be 30mL, 32mL, 34mL, 36mL,
38mL, 40mL, under preferable case, the dosage of the alcohol is 40mL.
Preparation method according to the present invention, in step (3), the condition of the reaction includes: that temperature can be 20-35
DEG C, the time can be 8-12h；Under preferable case, temperature can be 30 DEG C of 25-, and the time can be 8-9h；In system of the invention
In Preparation Method, the alcoholic solution B for preparing the compound of the element containing X and Y is slowly dropped to compound and water containing bismuth element dropwise
Mixture A in, wherein drop rate can be 1-2.5mL/ minute, it is preferable that drop rate be 1.5-2mL/ minutes, In
In preparation method of the invention, the drop rate is limited within above range, can be prepared with solid-solution structures,
Specific surface area with higher, ultra-thin, the ultra-thin BiOX based solid solution photochemical catalyst for improving catalytic activity can be more preferable
Under visible light exposure of the wavelength greater than 420nm, photochemical catalytic oxidation removes the hydroxypropyl guar in shale gas oil field waste on ground.
Preparation method according to the present invention, wherein in step (4), by reactant washing and drying treatment, wherein described
Dry temperature can be 60-80 DEG C, for example, the temperature of the drying can be 62 DEG C, 64 DEG C, 66 DEG C, 68 DEG C, 70 DEG C, 72
DEG C, 74 DEG C, 76 DEG C, 78 DEG C, 80 DEG C；Preferably, the drying temperature is 65-75 DEG C, it is highly preferred that the drying temperature is
70℃.In addition, the drying time can be 5-24h, for example, the drying time can be 5h, 6h, 7h, 8h, 9h, 12h,
15h, 18h, 21h, for 24 hours；Preferably, the drying time is 7-15h, it is highly preferred that the drying time is 9-12h, it is optimal
Selection of land, the drying time are 10h.In addition, the equipment of shown drying is not particularly limited, for example, can carry out in an oven.
Preparation method according to the present invention, the surfactant can be polyvinylpyrrolidone, and relative to 1mmol
The compound containing X element, the dosage of the surfactant can be 0.3-0.5mg, preferably 0.35-0.45mg.
Preparation method according to the present invention, the reaction (a step fabricated in situ) carries out under stirring conditions, for stirring
The equipment mixed is not particularly limited, for example, can be agitating paddle, mixing pump etc.；Stirring rate is also not particularly limited, example
Such as, stirring rate can be 50-100 revs/min.
The third aspect, the present invention also provides modification BiOX matrix composite photochemical catalyst described above or above-mentioned institutes
Modification BiOX matrix composite photocatalyst applications catalysis oxidation oil field under visible light that the preparation method stated is prepared
Hydroxypropyl guar in waste water.
The present invention prepares ultra-thin BiOBr using the precipitation method0.5I0.5Mischcrystal photocatalyst, what is obtained is ultra-thin
BiOBr0.5I0.5Mischcrystal photocatalyst catalytic activity is better than single BiOBr and BiOI monomer.The specific surface area of catalyst is
300-320m2/ g, the increase of specific surface area improve the catalytic activity of catalyst.Prepared photochemical catalyst can be under visible light
More light induced electrons are inspired, electron-hole recombination rate substantially reduces, and photocatalytic activity significantly improves, especially in fracturing fluid
Returning has very high activity in the removal of hydroxypropyl guar in drain, and preparation method is simple, mild condition, reach reduction at
Originally, the purpose for simplifying production procedure, can be applied to the removal of hydroxypropyl guar in fracturing fluid recovery (backflow) liquid.
The present invention will be described in detail by way of examples below.
Photocatalytic activity test:
Photocatalytic activity test is characterized by the hydroxypropyl guar in oxidation removal oil field waste under visible light,
It is middle to use 500W xenon lamp as light source, the visible light of 420~780nm range is obtained after optical filter, catalyst per dosage is
The original COD control of 0.05g, hydroxypropyl guar solution are 200mg/L, and COD is carried out with a Water Test Kits after catalysis oxidation
Measurement, sampling amount 1mL.
Wherein, COD is COD (Chemical Oxygen Demand), is chemically to measure to need in water sample
The amount for the reducing substances to be oxidized.
Water Test Kits model DR6100A is purchased from producer, Xi'an He Pu Biotechnology Co., Ltd.
SEM Electronic Speculum model ZEISS EV0 MA15 is purchased from karr Zeiss micro-image Co., Ltd.
Embodiment 1
The present embodiment indicates that the ultra-thin BiOBr being prepared using preparation method of the invention0.5I0.5Solid solution
Photochemical catalyst and application.
Five water bismuth nitrate of 2mmol is weighed with assay balance to be dissolved in 20mL distilled water, takes 1mmol potassium bromide and 1mmol iodine
Change potassium and be dissolved in 40mL ethylene glycol and be added the surfactant N methyl pyrrolidone of 0.4mg, then will be contained with rubber head dropper upper
It states the ethylene glycol solution of compound and the above-mentioned aqueous solution containing five water bismuth nitrates was added dropwise with 1.5mL/ minutes drop rates
In, under room temperature under 60 revs/min of stirring rate after magnetic agitation 10h, cleans and collect precipitating；This is deposited in baking
10h, obtained solid powder, i.e., ultra-thin BiOBr are dried in case at 70 DEG C0.5I0.5Mischcrystal photocatalyst.
And the BiOBr ultra-thin to this0.5I0.5Mischcrystal photocatalyst carries out SEM characterization, as shown in Figure 1, can from Fig. 1
See, the catalyst be it is powdered, thickness is between 0.20-0.23nm；
And the BiOBr ultra-thin to this0.5I0.5Mischcrystal photocatalyst carries out XRD characterization, as shown in Fig. 2, can from Fig. 2
See, which has ultra-thin property, and it can be seen that ultra-thin BiOBr from the XRD spectra0.5I0.5Solid solution photocatalysis
Agent has all diffraction maximums of BiOBr monomer and BiOI monomer, and ultra-thin BiOBr0.5I0.5In mischcrystal photocatalyst
Widthization is presented in the diffraction maximum of BiOBr, illustrates ultra-thin BiOBr0.5I0.5The ultra-thin property of mischcrystal photocatalyst.
The BiOBr ultra-thin to this0.5I0.5Mischcrystal photocatalyst carries out specific surface area test and photocatalytic activity test, with
And the BiOBr that will be obtained0.5I0.5Mischcrystal photocatalyst is applied to the hydroxypropyl guanidine under visible light in catalysis oxidation oil field waste
Glue, the results are shown in Table 1.
Embodiment 2
The present embodiment indicates that the ultra-thin BiOBr being prepared using preparation method of the invention0.5I0.5Solid solution
Photochemical catalyst and application.
Five water bismuth nitrate of 1.8mmol is weighed with assay balance to be dissolved in 25mL distilled water, takes 1mmol potassium bromide and 1mmol
Potassium iodide is dissolved in 30mL ethylene glycol and the surfactant N methyl pyrrolidone of 0.4mg is added, then will be contained with rubber head dropper
The above-mentioned aqueous solution containing five water bismuth nitrates was added dropwise with 2mL/ minutes drop rates in the ethylene glycol solution of above compound
In, under room temperature under 90 revs/min of stirring rate after magnetic agitation 9h, cleans and collect precipitating；This is deposited in baking
9h, obtained solid powder, i.e., ultra-thin BiOBr are dried in case at 80 DEG C0.5I0.5Mischcrystal photocatalyst.
The BiOBr ultra-thin to this0.5I0.5Mischcrystal photocatalyst carries out specific surface area test and photocatalytic activity test, with
And the BiOBr that will be obtained0.5I0.5Mischcrystal photocatalyst is applied to the hydroxypropyl guanidine under visible light in catalysis oxidation oil field waste
Glue, the results are shown in Table 1.
Embodiment 3
The present embodiment indicates that the ultra-thin BiOBr being prepared using preparation method of the invention0.5I0.5Solid solution
Photochemical catalyst and application.
Five water bismuth nitrate of 2.3mmol is weighed with assay balance to be dissolved in 23mL distilled water, takes 1mmol potassium bromide and 2mmol
Potassium iodide is dissolved in 30mL ethylene glycol and the surfactant N methyl pyrrolidone of 0.5mg is added, then will be contained with rubber head dropper
The ethylene glycol solution of above compound was added dropwise above-mentioned containing the water-soluble of five water bismuth nitrates with 1.5mL/ minutes drop rates
In liquid, under room temperature under 70 revs/min of stirring rate after magnetic agitation 8h, cleans and collect precipitating；This is deposited in
12h, obtained solid powder, i.e., ultra-thin BiOBr are dried in baking oven at 60 DEG C0.5I0.5Mischcrystal photocatalyst.
The BiOBr ultra-thin to this0.5I0.5Mischcrystal photocatalyst carries out specific surface area test and photocatalytic activity test, with
And the BiOBr that will be obtained0.5I0.5Mischcrystal photocatalyst is applied to the hydroxypropyl guanidine under visible light in catalysis oxidation oil field waste
Glue, the results are shown in Table 1.
Embodiment 4
The present embodiment indicates that the ultra-thin BiOBr being prepared using preparation method of the invention0.5I0.5Solid solution
Photochemical catalyst and application.
Ultra-thin BiOBr is prepared in the same manner as shown in Example 10.5I0.5Mischcrystal photocatalyst, institute's difference
It is, the dosage of potassium iodide is 1.5mmol.
To the ultra-thin BiOBr of the modification0.5I0.5Mischcrystal photocatalyst carries out specific surface area test and photocatalytic activity
Test, and the ultra-thin BiOBr that will be obtained0.5I0.5Mischcrystal photocatalyst is applied to catalysis oxidation oil field waste under visible light
In hydroxypropyl guar, the results are shown in Table 1.
Comparative example 1
This comparative example indicates that prepared BiOI and application.
It is dissolved in 20mL distilled water the preparation method comprises the following steps: weighing five water bismuth nitrate of 1mmol with assay balance, takes 1mmol iodate
Potassium is added in above-mentioned five water aqueous bismuth nitrate solution, under room temperature under 60 revs/min of stirring rate after magnetic agitation 8h, clearly
It washes and collects precipitating；This is precipitated into dry 12h, obtained solid powder, i.e. BiOI photochemical catalyst at 60 DEG C in an oven.
Specific surface area test and photocatalytic activity test are carried out to the BiOI photochemical catalyst, and obtained BiOI light is urged
Agent is applied to the hydroxypropyl guar under visible light in catalysis oxidation oil field waste, and the results are shown in Table 1.
Comparative example 2
This comparative example indicates that prepared BiOBr and application.
It is dissolved in 20mL distilled water the preparation method comprises the following steps: weighing five water bismuth nitrate of 1mmol with assay balance, takes 1mmol bromination
Potassium is added in above-mentioned five water aqueous bismuth nitrate solution, under room temperature under 60 revs/min of stirring rate after magnetic agitation 8h, clearly
It washes and collects precipitating；This is precipitated into dry 12h, obtained solid powder, i.e. BiOBr photochemical catalyst at 60 DEG C in an oven.
Specific surface area test and photocatalytic activity test, and the BiOBr light that will be obtained are carried out to the BiOBr photochemical catalyst
Catalyst is applied to the hydroxypropyl guar under visible light in catalysis oxidation oil field waste, and the results are shown in Table 1.
Comparative example 3
This comparative example indicates that prepared unmodified BiOBr0.5I0.5Mischcrystal photocatalyst and application.
The preparation method comprises the following steps:
Five water bismuth nitrate of 2mmol is weighed with assay balance to be dissolved in 23mL distilled water, takes 1mmol potassium iodide and 1mmol bromine
Change potassium be dissolved in 40mL ethylene glycol, then with rubber head dropper by the ethylene glycol solution containing potassium iodide and potassium bromide with 1.5mL/ minutes
Drop rate be added dropwise in the aqueous solution of five above-mentioned water bismuth nitrates, under room temperature in 70 revs/min of stirring rate
After lower magnetic agitation 8h, cleans and collect precipitating；This is precipitated and dries 12h at 60 DEG C in an oven, obtained solid powder,
I.e. unmodified BiOBr0.5I0.5Mischcrystal photocatalyst.
To the unmodified BiOBr0.5I0.5Mischcrystal photocatalyst carries out specific surface area test and photocatalytic activity test,
And the unmodified BiOBr that will be obtained0.5I0.5Mischcrystal photocatalyst is applied under visible light in catalysis oxidation oil field waste
Hydroxypropyl guar, the results are shown in Table 1.
Table 1
It was found from above embodiments and comparative example and the result of table 1: being prepared using method of the invention ultra-thin
BiOBr0.5I0.5Mischcrystal photocatalyst specific surface area 289m with higher2g-1, with a thickness of 0.22-0.25nm, ultra-thin property
Matter, in 2h, COD removal rate is up to 95% to the efficiency of removal hydroxypropyl guar as shown in table 1 under visible light, and monomer is in 2h
When COD removal rate be only 26% and 29%；In addition, the value of band-gap energy (eV) illustrates that carrier separation is high-efficient.Therefore,
Ultra-thin BiOBr of the invention0.5I0.5Mischcrystal photocatalyst can preferably photochemical catalytic oxidation removes shale under visible light
Hydroxypropyl guar in gas oil field waste, also, the preparation method reduces production cost, simplifies production technology.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (2)
1. a kind of ultra-thin BiOX based solid solution photochemical catalyst, which is characterized in that the ultra-thin BiOX based solid solution light
The expression formula of catalyst is BiOBr0.5I0.5, wherein the ultra-thin BiOX based solid solution photochemical catalyst be it is powdered, it is average
With a thickness of 0.22nm, specific surface area 289m2/g；
The preparation method of the ultra-thin BiOX based solid solution photochemical catalyst the following steps are included:
Five water bismuth nitrate of 2mmol is weighed with assay balance to be dissolved in 20mL distilled water, takes 1mmol potassium bromide and 1mmol potassium iodide
It is dissolved in 40mL ethylene glycol and is added the surfactant N methyl pyrrolidone of 0.4mg, then above-mentionedization will be contained with rubber head dropper
The ethylene glycol solution for closing object was added dropwise in the above-mentioned aqueous solution containing five water bismuth nitrates with 1.5mL/ minutes drop rates, room
Under the conditions of temperature under 60 revs/min of stirring rate after magnetic agitation 10h, cleans and collect precipitating；In an oven by the precipitating
Dry 10h, obtained ultra-thin BiOX based solid solution photochemical catalyst solid powder at 70 DEG C.
2. ultra-thin BiOX based solid solution photocatalyst applications described in claim 1 catalysis oxidation oil field under visible light is useless
Hydroxypropyl guar in water.
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| CN107824203A (en) * | 2017-11-02 | 2018-03-23 | 西南石油大学 | Rich bismuth mischcrystal photocatalyst and its preparation method and application |
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