CN109499587A - The preparation of the ultra-thin U-BiOBr/BiOI photochemical catalyst of organic boron in a kind of processing fracturing outlet liquid - Google Patents
The preparation of the ultra-thin U-BiOBr/BiOI photochemical catalyst of organic boron in a kind of processing fracturing outlet liquid Download PDFInfo
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- CN109499587A CN109499587A CN201910025056.5A CN201910025056A CN109499587A CN 109499587 A CN109499587 A CN 109499587A CN 201910025056 A CN201910025056 A CN 201910025056A CN 109499587 A CN109499587 A CN 109499587A
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- biobr
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- organic boron
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000012545 processing Methods 0.000 title claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 29
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract 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 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 150000002484 inorganic compounds Chemical class 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- XWNOTOKFKBDMAP-UHFFFAOYSA-N [Bi].[N+](=O)(O)[O-] Chemical compound [Bi].[N+](=O)(O)[O-] XWNOTOKFKBDMAP-UHFFFAOYSA-N 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 229960004756 ethanol Drugs 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 bismuthino Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LWBFNUKTNRHYKJ-UHFFFAOYSA-N Br.CCCCCCCCCCCCCCCC Chemical compound Br.CCCCCCCCCCCCCCCC LWBFNUKTNRHYKJ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000003149 assay kit Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 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 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002994 raw material Substances 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
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000000280 vitalizing effect Effects 0.000 description 1
- 238000005406 washing 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
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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 a kind of preparations of the ultra-thin U-BiOBr/BiOI photochemical catalyst of organic boron in processing fracturing outlet liquid.Five water bismuth nitrate of 2mmol will be contained under agitation and potassium iodide containing 0.5mmol is dissolved in a certain amount of dehydrated alcohol, 5mlN- methyl pyrrolidone is taken to be added in above-mentioned dehydrated alcohol, it stirs evenly, the ethylene glycol solution of 35mL cetyl trimethylammonium bromide containing 0.5mmol is added dropwise, after being added dropwise to complete, 60min is stirred, mixed solution is transferred in reaction kettle and in an oven to react 16h under the conditions of 160 DEG C, precipitating is cleaned and collected, this is deposited in in 70 DEG C of baking oven dry 12h.The i.e. ultra-thin U-BiOBr/BiOI photocatalytic compound of obtained solid powder.Prepared catalyst enhances the response of visible light, has higher catalytic activity, especially organic boron has very high activity in removal fracturing outlet liquid, and preparation method is simple, mild condition, can be applied to the removal of organic boron in fracturing outlet liquid.
Description
Technical field
The present invention relates to a kind of catalyst, and in particular to a kind of ultra-thin composite junction of bismuthino for photocatalytic-oxidation fluidized polymer
Structure catalyst, in particular to it is a kind of for the visible light of organic boron to be rung in photochemical catalytic oxidation removal fracturing fluid recovery (backflow) liquid under visible light
The ultra-thin U-BiOBr/BiOI photocatalytic compound preparation method and its usage answered.
Background technique
Currently, both at home and abroad for generate during oilfield stimulation with high viscosity, high COD, high salinity characteristic pressure
Splitting the main method for returning drain processing use has natural evaporation, freeze thawing, filtering, ozone oxidation, chemical flocculation, electric flocculation, reverse osmosis
Thoroughly, distillation etc..By the development of many decades, many new technologies are also applied, such as: Ecosphere ozone treatment, ozone/
Ultrasonic wave/electric flocculation/reverse osmosis compound, MI SWACO technology, Clean Wave technology, mechanical vapor recompression technology are also able to
Using, but these technologies are mainly handled the inorganic matter in fracturing outlet liquid, for guanidine a large amount of in fracturing outlet liquid
Glue, organic boron, petroleum-type, high molecular polymer and other various organics additives, processing means are extremely limited, and due to
Fracturing outlet liquid is inhibited to microorganism and toxic effect, such as guanidine glue, crosslinking agent low polymer are difficult to hydrolyze
It is utilized by microorganism, this biochemical system processing for allowing for carrying out fracturing outlet liquid most original does not only have organic matter therein
Play the role of generating degradation, will cause bigger injury instead, therefore, it is necessary to for the polymer degradation in fracturing outlet liquid
It is studied, is of great significance simultaneously for the normal production and sustainable development for ensureing shale gas.
Photocatalysis technology is a kind of new process for processing persistent organic pollutants that 20 th century laters grow up, special
Point is that catalytic action occurs with persistent organic pollutants under the action of light using photochemical catalyst.Reaction mechanism is to work as photon
Energy when being greater than the energy of forbidden bandwidth, light can electronics in vitalizing semiconductor, electronics is raw from valence to conduction band
At light induced electron (there is reproducibility), and corresponding photohole (there is oxidisability) is generated in valence band, electrons and holes difference
It is diffused into semiconductor surface, is reacted on surface with organic pollutant.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, photochemical catalyst itself is not involved in chemical reaction, only provides reaction interface, and certain catalyst may participate in the electronics of photoinduction
Process.And BiOX becomes the new lover of photocatalysis field in recent years.
BiOX is as a kind of novel low-gap semiconductor, since its is nontoxic, cheap, redox ability is strong, changes
Learn the characteristics such as the stable and anti-light corrosion of property, water pollutant degradation, in terms of be widely used.But photon
Absorption efficiency and carrier separation efficiency are the two big key problems that semiconductor light-catalyst faces.Numerous Photocatalyst sides
The research in face is carried out around this 2 points.Such as: doping, dye sensitization, surface plasmon resonance effect be for
Improve the photon absorption efficiency of photochemical catalyst；The use of co-catalyst is to improve carrier separation efficiency；Carbon material is repaired
Decorations, composite photo-catalyst construct the photon absorption efficiency and carrier separation efficiency that can improve photochemical catalyst simultaneously.However these
Method needs to carry out secondary modification to photochemical catalyst by other chemical reagent mostly.It can be same by two dimensional crystal thickness ultrathinization
Its own defect density of Shi Tigao and electric field intensity inside high, to improve the photon absorption efficiency and carrier point of photochemical catalyst itself
From efficiency, it is the important means for improving the photocatalysis performance of catalyst, can fundamentally solves catalysis material activity function
Not high situation widens light-catalysed application field.
Xia in 2016 et al. has found the ultra-thin U-C synthesized by ionic liquid3N4/Bi4O5I2Photocatalytic compound is can
When being catalyzed rhodamine and bis-phenol under light-exposed irradiation, photocatalytic activity is substantially increased compared to monomer, (Xia, J., et al.,
Construction of ultrathin C3N4/Bi4O5I2layered nanojunctions via ionic liquid
with enhanced photocatalytic performance and mechanisminsight.Applied
Catalysis B:Environmental,2016.191:p.235-245.).The side that Qiu in 2017 et al. passes through fabricated in situ
Method synthesizing new SnS2/ BiOBr photochemical catalyst degrades rhodamine photocatalysis efficiency greater than monomer BiOBr under visible light, (Qiu,
F.,et al.,In-situ synthesis of novel Z-scheme SnS2/BiOBr photocatalysts with
superior photocatalytic efficiency under visible light.Journal of Colloid and
Interface Science,2017.493:p.1-9.)。
The synthesis for the photochemical catalyst reported in above-mentioned document is only applied to degradation of dye and phenols, is not applied to drop
The organic boron in oil field waste is solved, and synthetic method is complex, effect is still to be improved.
Summary of the invention
It is urged in view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of ultra-thin composite construction zirconyl oxyhalides bismuthino light
The preparation method of agent and its fabricated in situ, the catalyst have the performance of better oxidative degradation organic boron, the catalyst
Preparation method reduces production cost, simplifies production technology, the U-BiOBr/BiOI catalyst for having ultra-thin property of preparation
Photochemical catalytic oxidation it can remove the organic boron in shale gas oil field waste under visible light.
In order to achieve the above object, present invention employs following preparation methods:
The preparation of the ultra-thin U-BiOBr/BiOI photochemical catalyst of organic boron, feature exist in a kind of processing fracturing outlet liquid
Be a kind of in, the catalyst with in-situ synthetic method it is Bi according to Bi element, Br element and I elemental mole ratios in catalyst:
The U-BiOBr/BiOI photochemical catalyst that the ultra-thin BiOBr nano material and BiOI of Br:I=4:1:1 is combined, has good
Photocatalytic activity.
A kind of ultra-thin U-BiOBr/ as described above for organic boron in photochemical catalytic oxidation fracturing outlet liquid under visible light
The preparation method of BiOI photocatalytic compound, described method includes following steps:
(1) under agitation, the compound of the bismuth element containing 2mmol and 0.5mmol compound containing iodine are dissolved in one
In quantitative dehydrated alcohol, and 5mlN- methyl pyrrolidone (NMP) is added；
(2) that above-mentioned dehydrated alcohol is added dropwise in a certain amount of ethylene glycol solution of the brominated element compound of 0.5mmol is molten
In liquid, after being added dropwise to complete, it is sufficiently stirred to obtain mixed solution；
(3) gained mixed solution is put into high-temperature high-pressure reaction kettle, is reacted under certain temperature a period of time, washing is dry
It is dry to get arrive ultra-thin U-BiOBr/BiOI photocatalytic compound.
The present invention uses the ultra-thin U-BiOBr/BiOI photocatalytic compound of hydro-thermal method preparation, obtained catalyst
Activity is better than BiOBr and BiOI monomer and BiOBr/BiOI photochemical catalyst.Catalyst degrades organic boron COD's in the present invention
Rate highest, rate raising increase the catalytic activity of catalyst.Prepared photochemical catalyst can inspire under visible light more
More light induced electrons, electron-hole recombination rate reduce, and photocatalytic activity significantly improves, and especially oxidation organic boron has very high work
Property, and preparation method is simple, mild condition, achievees the purpose that reduce cost, simplifies production procedure, can be applied to oxidation pressure break
Return the organic boron in drain.
The present invention is by the way that a certain amount of NMP is added dropwise into the dehydrated alcohol containing bismuth element and iodine and containing the second of bromo element
Glycol solution, stirring after a certain period of time, are reacted in high-temperature high-pressure reaction kettle, are washed drying, are obtained ultra-thin U-BiOBr/
BiOI photocatalytic compound.
The inorganic compound containing bismuth element is selected from five water bismuth nitrates.
Preferably, any one or two kind of the inorganic compound containing iodine in potassium iodide and sodium iodide
Mixture, preferably potassium iodide.
Preferably, it is described dissolution five water bismuth nitrate of 2mmol and 0.5mmol potassium iodide dehydrated alcohol dosage be 20~
50mL, such as 20mL, 25mL, 30mL, 35mL, 40mL, 45mL, 50mL, preferably 40mL.
Preferably, the preferred cetyl trimethylammonium bromide of the inorganic compound containing bromo element.
Preferably, the ethylene glycol dosage of the dissolution cetyl trimethylammonium bromide is 20~40mL, such as 20mL,
25mL, 30mL, 35mL, 40mL, preferably 35mL.
Preferably, the mixing time is 20~60min, such as 20min, 30min, 40min, 50min, 60min, preferably
60min。
Preferably, the reaction temperature in a kettle is 140~180 DEG C, such as 140 DEG C, 150 DEG C, and 160 DEG C, 170
DEG C, 180 DEG C, preferably 160 DEG C.
Preferably, the reaction time in a kettle is 14~18h, such as 14h, 15h, 16h, 17h, 18h, preferably
16h, the pyroreaction carry out in an oven.
Preferably, the temperature of the drying is 60~80 DEG C, such as 62 DEG C, 64 DEG C, and 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 70 DEG C.
Preferably, the drying time be 5~for 24 hours, such as 5h, 6h, 7h, 8h, 9h, 12h, 15h, 18h, 21h are for 24 hours, excellent
Select 7~15h, further preferred 9~12h, most preferably 10h.The drying carries out in an oven.
It is a kind of under visible light in catalysis oxidation fracturing outlet liquid organic boron ultra-thin U-BiOBr/BiOI complex light
The purposes of catalyst, the ultra-thin U-BiOBr/BiOI photocatalytic compound are used for photochemical catalytic oxidation organic boron under visible light.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention optimizes the preparation process of such photochemical catalyst, the mesh for reducing cost, simplifying production procedure has been reached
's；
(2) photochemical catalyst of the present invention has composite construction, and has ultra-thin property, improves photocatalytic activity；
(3) ultra-thin U-BiOBr/BiOI photocatalytic compound of the present invention is used, it is visible greater than 420nm in wavelength
Under light irradiation, organic B solution that original COD is 200mg/L removal rate in 75min is 90%, and photocatalytic greatly improved
Energy；
(4) present invention uses nontoxic component, reduces the harm to human health and ecological environment；
(5) photochemical catalyst that the present invention is prepared does not need after adding other chemical reagent and other preparations
Reason, fabricated in situ, method are simple.
Attached drawing and Detailed description of the invention
Fig. 1 is the XRD spectra of ultra-thin U-BiOBr/BiOI photocatalytic compound of the present invention；
Fig. 2 is the TEM figure of ultra-thin U-BiOBr/BiOI photocatalytic compound of the present invention；
Fig. 3 is that ultra-thin U-BiOBr/BiOI composite photo-catalyst of the present invention and BiOI, BiOBr and BiOBr/BiOI drop
Solve the effect contrast figure of organic boron；
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment 1
It weighs five water bismuth nitrate of 0.9702g respectively with assay balance and 0.083g potassium iodide is dissolved in 40mL dehydrated alcohol,
5mlN- methyl pyrrolidone (NMP) is measured with graduated cylinder to be added in above-mentioned solution, is stirred evenly, is weighed 0.1823g hexadecane bromide
Change ammonium to be dissolved in 35mL ethylene glycol, then is added the ethylene glycol solution containing cetyl trimethylammonium bromide dropwise with rubber head dropper
Enter in above-mentioned five water bismuth nitrate and the dehydrated alcohol of potassium iodide, under room temperature after magnetic agitation 60min, mixed solution is shifted
Into reaction kettle and in an oven to react 16h under the conditions of 160 DEG C, precipitating is cleaned and collected, this is deposited in 70 DEG C of baking oven
Middle dry 12h.The i.e. ultra-thin U-BiOBr/BiOI photocatalytic compound of obtained solid powder.
The various performances of the 1 ultra-thin and BiOI/BiOBr photocatalytic compound of gained of example, single BiOI and BiOBr
Value is listed in table one.As can be seen from the table, embodiment 1 prepares ultra-thin U-BiOBr/BiOI photochemical catalyst 75min under visible light
The efficiency of organic boron of degrading is 95%, is about 1.6 times of BiOI/BiOBr, about 4 times of BiOI, about 2 times of BiOBr.
Photocatalytic activity test carries out table by the organic boron in oxidation removal fracturing outlet liquid under visible light in table one
Sign obtains the visible light of 420~780nm range, catalyst per dosage wherein using 500W xenon lamp as light source after optical filter
For 0.05g, the original COD control of organic B solution is 200mg/L, one Water Test Kits model of COD after catalysis oxidation
DR6100A it) is measured, sampling amount 1mL.
Table 1
It should be noted that and understand, in the case where not departing from the scope of the present invention required by appended claims,
Various modifications and improvements can be made to the present invention of foregoing detailed description.It is therefore desirable to which the range of the technical solution of protection is not
It is limited by given any specific exemplary teachings.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff is it will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary element of the various raw materials of product of the present invention
Addition, the selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. the preparation of the ultra-thin U-BiOBr/BiOI photochemical catalyst of organic boron in a kind of processing fracturing outlet liquid, which is characterized in that
It with in-situ synthetic method is Bi:Br:I according to Bi element, Br element and I elemental mole ratios in catalyst that the catalyst, which is a kind of,
The U-BiOBr/BiOI photochemical catalyst that the ultra-thin BiOBr nano material and BiOI of=4:1:1 is combined, there is good light to urge
Change activity.
2. the ultra-thin U-BiOBr/BiOI complex light of organic boron is urged in a kind of processing fracturing outlet liquid as described in claim 1
The preparation method of agent, which is characterized in that described method includes following steps:
(1) under agitation, the compound of the bismuth element containing 2mmol is dissolved in 0.5mmol compound containing iodine a certain amount of
Dehydrated alcohol in, and 5mlN- methyl pyrrolidone (NMP) is added；
(2) a certain amount of ethylene glycol solution of the brominated element compound of 0.5mmol is added dropwise in above-mentioned ethanol solution,
After being added dropwise to complete, it is sufficiently stirred to obtain mixed solution；
(3) gained mixed solution is put into high-temperature high-pressure reaction kettle, a period of time is reacted under certain temperature, wash drying, i.e.,
Obtain ultra-thin U-BiOBr/BiOI photocatalytic compound.
3. method according to claim 2, which is characterized in that the inorganic compound containing bismuth element is selected from five water nitric acid
Bismuth；The mixture of any one or two kind of the inorganic compound containing iodine in potassium iodide and sodium iodide, preferably
Potassium iodide；
Preferably, the dosage of the dissolution five water bismuth nitrate of 2mmol and the dehydrated alcohol of 0.5mmol potassium iodide is 20~50mL,
Such as 20mL, 25mL, 30mL, 35mL, 40mL, 45mL, 50mL, preferably 40mL.
4. the method as described in claim 2-3, which is characterized in that the preferred cetyl front three of the compound containing bromo element
Base ammonium bromide；
Preferably, the ethylene glycol dosage of the dissolution cetyl trimethylammonium bromide is 20~40mL, such as 20mL, 25mL,
30mL, 35mL, 40mL, preferably 35mL.
5. the method as described in claim 2-4, which is characterized in that the mixing time is 20~60min, such as 20min,
30min, 40min, 50min, 60min, preferably 60min.
6. the method as described in claim 2-5, which is characterized in that the reaction temperature in a kettle is 140~180
DEG C, such as 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, preferably 160 DEG C.
7. the method as described in claim 2-6, which is characterized in that the reaction time in a kettle is 14~18h, example
Such as 14h, 15h, 16h, 17h, 18h, preferably 16h, the pyroreaction carries out in an oven.
8. method as claimed in claim 2-7, which is characterized in that the temperature of the drying is 60~80 DEG C, such as 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 70 DEG C.
9. the method as described in claim 2-8, which is characterized in that the drying time is 5~for 24 hours, such as 5h, 6h, 7h,
8h, 9h, 12h, 15h, 18h, 21h, for 24 hours, preferably 7~15h, further preferred 9~12h, most preferably 10h, the drying are drying
It is carried out in case.
10. a kind of ultra-thin U- for organic boron in photochemical catalytic oxidation fracturing outlet liquid under visible light as described in claim 1
The purposes of BiOBr/BiOI photocatalytic compound, which is characterized in that the ultra-thin U-BiOBr/BiOI photocatalytic compound
For photochemical catalytic oxidation organic boron under visible light.
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