CN108855151A - A kind of preparation method and applications of ultra-thin bismuth oxyiodide photochemical catalyst - Google Patents
A kind of preparation method and applications of ultra-thin bismuth oxyiodide photochemical catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 22
- 229910052797 bismuth Inorganic materials 0.000 claims description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000011941 photocatalyst Substances 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000000203 mixture Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 3
- -1 Polypropylene Polymers 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical compound CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 claims 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical group CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 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 description 5
- 238000013019 agitation Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 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
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002351 wastewater Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- WTCBONOLBHEDIL-UHFFFAOYSA-M Sodium iodate Chemical compound [Na+].[O-]I(=O)=O WTCBONOLBHEDIL-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 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
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 239000012530 fluid Substances 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
- 239000010805 inorganic waste Substances 0.000 description 1
- 150000002500 ions Chemical class 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
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 230000008569 process Effects 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229940043267 rhodamine b Drugs 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000638 stimulation Effects 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
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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
- 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
-
- B01J35/30—
-
- B01J35/39—
-
- B01J35/615—
-
- 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
- C02F2101/38—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- 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 a kind of preparation method and applications of ultra-thin bismuth oxyiodide photochemical catalyst, wherein, the expression formula of the ultra-thin bismuth oxyiodide photochemical catalyst is BiOI, the ultra-thin bismuth oxyiodide photochemical catalyst is powdered, with a thickness of 0.21-0.24nm, specific surface area 280-310m2/g.Catalyst specific surface area with higher, it is ultra-thin, can the preferably polyacrylamide 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 the preparation method of ultra-thin bismuth oxyiodide photochemical catalyst and its answers
With.
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 polymerizations such as polyacrylamide
Object, then need to consume a large amount of energy or miscellaneous chemical agent is degraded one by one, and processing cost is high, equipment investment is big, place
Manage period length, 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.
When the BiOI photochemical catalyst of Fan in 2016 et al. discovery fabricated in situ is catalyzed rhodamine b under the irradiation of visible light,
With very strong photocatalytic activity (Fan W, Li H, Zhao F, et al.Boosting the photocatalytic
performance of(001)BiOI:enhancing donor density and separation efficiency of
photogenerated electrons and holes[J].Chemical Communications,2016,52(30):
5316-5319.).But the BiOI photochemical catalyst reported in the document is only applied to degradation of dye, is not applied to drop
It solves in polyacrylamide, and synthetic method is complex, 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 bismuth oxyiodide photochemical catalyst
Preparation method and applications, wherein catalyst specific surface area with higher, it is ultra-thin, can preferably under visible light
Photochemical catalytic oxidation removes the polyacrylamide in shale gas oil field waste, also, the preparation method reduces production cost, simplifies
Production technology.
A kind of preparation method and applications of ultra-thin bismuth oxyiodide photochemical catalyst, wherein the ultra-thin bismuth oxyiodide light is urged
The expression formula of agent be BiOI, the ultra-thin bismuth oxyiodide photochemical catalyst be it is powdered, with a thickness of 0.21-0.24nm, specific surface
Product is 280-310m2/g。
Second aspect of the present invention provides a kind of preparation method of ultra-thin bismuth oxyiodide photochemical catalyst, wherein this method packet
Include following steps：
(1) compound containing bismuth element is mixed to get mixture A with water；
(2) the alcoholic solution B of the element containing I is prepared；
(3) the alcoholic solution B of the compound of the element containing I is added drop-wise in mixture A and is reacted, stirring adds after a certain period of time
Enter a certain amount of surfactant；
(4) reactant for obtaining step (3) washs drying；
Preferably, the molar ratio of the dosage of the compound and compound containing bismuth element of the element containing I is 1：(1-2)：
(1.5-2.5)。
Preferably, the compound containing bismuth element is five water bismuth nitrates；The compound of the element containing I is potassium iodide and/or iodate
Sodium, more preferably potassium iodide.
Preferably, in step (1), the water is distilled water, and the bismuth-containing element compound relative to 1mmol,
The dosage of the distilled water is 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 the compound relative to the element containing I described in 1mmol, the dosage of the alcohol is 15-20mL.
Preferably, in step (3), the condition of the reaction includes：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：Drying temperature is 60-80 DEG C, drying time 5-
24h；Preferably, drying temperature is 65-75 DEG C, drying time 7-15h.
Preferably, the surfactant is N methyl pyrrolidone, and the chemical combination relative to the element containing I described in 1mmol
Object, the dosage of the surfactant are 0.3-0.5mg.
Third aspect present invention provides ultra-thin bismuth oxyiodide photochemical catalyst described above or preparation side described above
Poly- propionamide of the ultra-thin bismuth oxyiodide photocatalyst applications that method is prepared under visible light in catalysis oxidation oil field waste.
The technical solution provided according to the present invention, has the following advantages that：
(1) present invention optimizes the preparation process of ultra-thin bismuth oxyiodide photochemical catalyst, having reduces cost, simplifies production stream
The characteristics of journey；
(2) ultra-thin bismuth oxyiodide photochemical catalyst of the invention has double-layer structure, and has ultra-thin property, improves light
Catalytic activity；
(3) ultra-thin bismuth oxyiodide photochemical catalyst of the invention is used, it is former under visible light exposure of the wavelength greater than 420nm
The polyacrylamide solution that beginning COD is 100mg/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 ultra-thin bismuth oxyiodide photochemical catalyst that is prepared of the present invention do not need to add other chemical reagent and other
Preparation post-processing, only need a step fabricated in situ, method is simple.
Detailed description of the invention
Fig. 1 is the TEM figure for changing ultra-thin bismuth oxyiodide photochemical catalyst prepared by embodiment according to the present invention 1；
Fig. 2 is the XRD spectra of ultra-thin bismuth oxyiodide 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 ultra-thin bismuth oxyiodide photochemical catalysts, wherein the ultra-thin bismuth oxyiodide light
The expression formula of catalyst is BiOI, the pattern of the ultra-thin bismuth oxyiodide photochemical catalyst be it is powdered, with a thickness of 0.20-
0.25nm, preferably 0.21-0.24nm, specific surface area 270-330m2/ g, preferably 275-320m2/ g, more preferably 280-
310m2/g。
In the present invention, which has double-layer structure, 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
Polyacrylamide in gas oil field waste reduces in addition, the ultra-thin bismuth oxyiodide photochemical catalyst is nontoxic to human health and life
The harm of state environment.
Second aspect, the present invention provides a kind of preparation methods of ultra-thin bismuth oxyiodide photochemical catalyst, wherein this method packet
Include following steps：
(1) compound containing bismuth element is mixed to get mixture A with water；
(2) the alcoholic solution B of the element containing I is prepared；
(3) the alcoholic solution B of the compound of the element containing I is added drop-wise in mixture A and is reacted, stirring adds after a certain period of time
Enter a certain amount of surfactant；
(4) reactant for obtaining step (3) washs drying；
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 compound and bismuth-containing of the element containing I in prepared ultra-thin bismuth oxyiodide photochemical catalyst
The molar ratio of the content of the compound of element is 1：1, for example, the use with the compound containing bismuth element of the element containing I
The molar ratio of amount can be 1：(1-2), preferably more preferably 1：1.In the preparation process in accordance with the present invention, the element containing I
The molar ratio of the dosage of compound, compound containing bismuth element is limited to above range, can be prepared with double-layer structure,
Specific surface area with higher, it is ultra-thin, improve the ultra-thin bismuth oxyiodide photochemical catalyst of catalytic activity, and can be preferably can
Polyacrylamide under light-exposed (under visible light exposure of the wavelength greater than 420nm) in photochemical catalytic oxidation removal shale gas oil field waste
Amine.
Preparation method according to the present invention, the compound containing bismuth element can be five water bismuth nitrates；The compound of the element containing I
It can be potassium iodide and/or sodium iodide, preferably 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 compound of bismuth element, the dosage of 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
One or more, preferably ethylene glycol, and the compound relative to the element containing I described in 1mmol, the dosage of the alcohol can be
15-20mL, for example, the dosage of the alcohol can be 15mL, 16mL, 17mL, 18mL, 19mL, 20mL, it is described under preferable case
The dosage of alcohol is 20mL.
Preparation method according to the present invention, in step (3), the condition of the reaction includes：Temperature can be 20-35
DEG C, the time can be 8-12h；Under preferable case, temperature can be 25-30 DEG C, and the time can be 8-9h；In preparation of the invention
In method, the alcoholic solution B for preparing the compound of the element containing I is slowly dropped to the mixing of compound and water containing bismuth element dropwise
In object A, wherein drop rate can be 1-2.5mL/ minutes, it is preferable that drop rate is 1.5-2mL/ minutes, in the present invention
Preparation method in, the drop rate is limited within above range, can be prepared with double-layer structure, have compared with
High specific surface area, ultra-thin, the ultra-thin bismuth oxyiodide photochemical catalyst for improving catalytic activity can preferably be greater than in wavelength
Under the visible light exposure of 420nm, photochemical catalytic oxidation removes the polyacrylamide in shale gas oil field waste.
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 N methyl pyrrolidone, and relative to 1mmol
The element containing I compound, 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 ultra-thin bismuth oxyiodide photochemical catalyst described above or preparations described above
Polyacrylamide of the ultra-thin bismuth oxyiodide photocatalyst applications that method is prepared under visible light in catalysis oxidation oil field waste
Amine.
The present invention prepares ultra-thin BiOI photochemical catalyst using the precipitation method, and obtained ultra-thin BiOI photochemical catalyst catalysis is lived
Property be better than the BiOI monomer without superthin structure.The specific surface area of catalyst is 280-310m2The increase of/g, specific surface area improve
The catalytic activity of catalyst.Prepared photochemical catalyst can inspire more light induced electrons under visible light, and electron-hole is compound
Rate substantially reduces, and photocatalytic activity significantly improves, and has in the removal of polyacrylamide especially in fracturing fluid recovery (backflow) liquid very high
Activity, and preparation method is simple, mild condition, achievees the purpose that reduce cost, simplifies production procedure, can be applied to pressure break
Liquid returns the removal of polyacrylamide in drain.
The present invention will be described in detail by way of examples below.
Photocatalytic activity test：
Photocatalytic activity test is characterized by the polyacrylamide 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, polyacrylamide solution are 100mg/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 of Xi'an He Pu Biotechnology Co., Ltd.
SEM Electronic Speculum model ZEISS EV0MA15 is purchased from karr Zeiss micro-image Co., Ltd.
Embodiment 1
The present embodiment is indicated that the ultra-thin BiOI photochemical catalyst being prepared using preparation method of the invention and answered
With.
Five water bismuth nitrate of 2mmol is weighed with assay balance to be dissolved in 20mL distilled water, and 1mmol potassium iodide is taken to be dissolved in 20mL second
In glycol and it is added the surfactant N methyl pyrrolidone of 0.4mg, then with rubber head dropper by the second two containing above compound
Alcoholic solution was added dropwise in the above-mentioned aqueous solution containing five water bismuth nitrates with 1.5mL/ minutes drop rates, was existed under room temperature
Under 60 revs/min of stirring rate after magnetic agitation 10h, cleans and collect precipitating；This precipitating is done at 70 DEG C in an oven
Dry 10h, obtained solid powder, i.e., ultra-thin BiOI photochemical catalyst.
And TEM characterization is carried out to the ultra-thin BiOI photochemical catalyst, as shown in Figure 1, it can be seen from figure 1 that the catalyst is
Powdered, thickness is between 0.21-0.24nm；
And XRD characterization is carried out to the ultra-thin BiOI photochemical catalyst, as shown in Fig. 2, it can be seen in fig. 2 that the catalyst has
There is ultra-thin property, and it can be seen that ultra-thin BiOI photochemical catalyst has all diffraction of BiOI monomer from the XRD spectra
Peak, and widthization is presented in its diffraction maximum in ultra-thin BiOI photochemical catalyst, illustrates the ultra-thin property of ultra-thin BiOI photochemical catalyst.
Specific surface area test and photocatalytic activity test are carried out to the ultra-thin BiOI photochemical catalyst, and super by what is obtained
Polyacrylamide of the thin BiOI photocatalyst applications under visible light in catalysis oxidation oil field waste, the results are shown in Table 1.
Embodiment 2
The present embodiment is indicated that the ultra-thin BiOI photochemical catalyst being prepared using preparation method of the invention and answered
With.
Five water bismuth nitrate of 1.8mmol is weighed with assay balance to be dissolved in 25mL distilled water, and 1mmol potassium iodide is taken to be dissolved in 15mL
In ethylene glycol and it is added the surfactant N methyl pyrrolidone of 0.4mg, then with rubber head dropper by the second containing above compound
Glycol solution was added dropwise in the above-mentioned aqueous solution containing five water bismuth nitrates with 2mL/ minutes drop rates, was existed under room temperature
Under 90 revs/min of stirring rate after magnetic agitation 9h, cleans and collect precipitating；This precipitating is dry at 80 DEG C in an oven
9h, obtained solid powder, i.e., ultra-thin BiOI photochemical catalyst.
Specific surface area test and photocatalytic activity test carried out to the ultra-thin BiOI photochemical catalyst, and will be obtained
Polyacrylamide of the BiOI photocatalyst applications under visible light in catalysis oxidation oil field waste, the results are shown in Table 1.
Embodiment 3
The present embodiment is indicated that the ultra-thin BiOI photochemical catalyst being prepared using preparation method of the invention and answered
With.
Five water bismuth nitrate of 2.3mmol is weighed with assay balance to be dissolved in 23mL distilled water, and 1mmol potassium iodide is taken to be dissolved in 30mL
In ethylene glycol and it is added the surfactant N methyl pyrrolidone of 0.5mg, then with rubber head dropper by the second containing above compound
Glycol solution was added dropwise in the above-mentioned aqueous solution containing five water bismuth nitrates with 1.5mL/ minutes drop rates, under room temperature
Under 70 revs/min of stirring rate after magnetic agitation 8h, cleans and collect precipitating；This precipitating is done at 60 DEG C in an oven
Dry 12h, obtained solid powder, i.e., ultra-thin BiOI photochemical catalyst.
Specific surface area test and photocatalytic activity test carried out to the ultra-thin BiOI photochemical catalyst, and will be obtained
Hydroxypropyl guar of the BiOI photocatalyst applications under visible light in catalysis oxidation oil field waste, the results are shown in Table 1.
Embodiment 4
The present embodiment is indicated that the ultra-thin BiOI photochemical catalyst being prepared using preparation method of the invention and answered
With.
Prepare ultra-thin BiOI photochemical catalyst in the same manner as shown in Example 1, institute the difference is that, potassium iodide
Dosage 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 polyacrylamide by obtained ultra-thin BiOI photocatalyst applications under visible light in catalysis oxidation oil field waste
Amine, the results are shown in Table 1.
Comparative example 1
This comparative example indicates that the prepared BiOI without superthin structure and application.
Preparation method is：Five water bismuth nitrate of 1mmol is weighed with assay balance to be dissolved in 20mL distilled water, 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 polyacrylamide under visible light in catalysis oxidation oil field waste, and the results are shown in Table 1.
Table 1
It was found from above embodiments and comparative example and the result of table 1：It is prepared using method of the invention ultra-thin
BiOI photochemical catalyst specific surface area 300m with higher2g-1, with a thickness of 0.21-0.23nm, ultra-thin property is gone under visible light
Except in 2h, COD removal rate is up to 95% as shown in table 1 for the efficiency of polyacrylamide, and the BiOI without superthin structure is in 2h
COD removal rate is only 20%；In addition, the value of band-gap energy (eV) illustrates that carrier separation is high-efficient.Therefore, of the invention super
Thin BiOI photochemical catalyst can preferably photochemical catalytic oxidation removes the polyacrylamide in shale gas oil field waste under visible light
Amine, 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 (12)
1. a kind of ultra-thin bismuth oxyiodide photochemical catalyst, which is characterized in that the expression formula of the ultra-thin bismuth oxyiodide photochemical catalyst is
BiOI, the ultra-thin bismuth oxyiodide photochemical catalyst be it is powdered, with a thickness of 0.21-0.24nm, specific surface area 280-310m2/
g。
2. ultra-thin bismuth oxyiodide photochemical catalyst according to claim 1, wherein the ultra-thin bismuth oxyiodide photochemical catalyst
Expression formula is BiOI.
3. a kind of preparation method of ultra-thin bismuth oxyiodide photochemical catalyst, which is characterized in that this approach includes the following steps：
(1) compound containing bismuth element is mixed to get mixture A with water；
(2) the alcoholic solution B of the element containing I is prepared；
(3) the alcoholic solution B of the compound of the element containing I is added drop-wise in mixture A and is reacted, stirring is added one after a certain period of time
Quantitative surfactant；
(4) reactant for obtaining step (3) washs drying.
4. preparation method according to claim 3, wherein the expression formula of prepared ultra-thin bismuth oxyiodide photochemical catalyst is
BiOI。
5. preparation method according to claim 3 or 4, wherein the compound and the chemical combination containing bismuth element of the element containing I
The molar ratio of the dosage of object is 1：(1-2)：(1.5-2.5).
6. the preparation method according to claim 3 or 5, wherein the compound containing bismuth element is five water bismuth nitrates；Containing I member
The compound of element is potassium iodide and/or sodium iodide, preferably potassium iodide.
7. preparation method according to claim 3, wherein in step (1), the water is distilled water, and relative to
The compound containing bismuth element of 1mmol, the dosage of the distilled water are 20-25mL.
8. preparation method according to claim 3, wherein in step (2), the alcohol be ethyl alcohol, ethylene glycol, propyl alcohol and
One of glycerine is a variety of, preferably ethylene glycol, and relative to described in 1mmol containing containing described in X element and 1mmol
The compound of Y element, the dosage of the alcohol are 10-15mL.
9. preparation method according to claim 3, wherein in step (3), the condition of the reaction includes：Temperature is
20-35 DEG C, time 8-12h, drop rate is 1-2mL/ minutes.
10. preparation method according to claim 3, wherein in step (4), the condition of the drying includes：Dry temperature
Degree is 60-80 DEG C, drying time 5-24h；Preferably, drying temperature is 65-75 DEG C, drying time 7-15h.
11. the preparation method according to any one of claim 3-10, wherein the surfactant is N methyl pyrrole
Pyrrolidone, and the compound relative to the element containing I described in 1mmol, the dosage of the surfactant are 0.3-0.5mg.
12. system described in any one of ultra-thin bismuth oxyiodide photochemical catalyst of any of claims 1 or 2 or claim 3-11
Polypropylene of the ultra-thin bismuth oxyiodide photocatalyst applications that Preparation Method is prepared under visible light in catalysis oxidation oil field waste
Amide.
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