CN109603863A - A kind of composite solid solution photochemical catalyst and its preparation method and application - Google Patents
A kind of composite solid solution photochemical catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109603863A CN109603863A CN201811582049.7A CN201811582049A CN109603863A CN 109603863 A CN109603863 A CN 109603863A CN 201811582049 A CN201811582049 A CN 201811582049A CN 109603863 A CN109603863 A CN 109603863A
- Authority
- CN
- China
- Prior art keywords
- preparation
- solution
- photochemical catalyst
- reaction
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000006104 solid solution Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- -1 hydroxypropyl Chemical group 0.000 claims abstract description 26
- 244000007835 Cyamopsis tetragonoloba Species 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 11
- 150000002497 iodine compounds Chemical class 0.000 claims description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Inorganic materials [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 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 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011941 photocatalyst Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000003292 glue Substances 0.000 description 11
- 239000002699 waste material Substances 0.000 description 11
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 10
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003149 assay kit Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BWMDMTSNSXYYSP-UHFFFAOYSA-N 2-propylguanidine Chemical compound CCCNC(N)=N BWMDMTSNSXYYSP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 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
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to photocatalysis field, a kind of composite solid solution photochemical catalyst and its preparation method and application is disclosed.The expression formula of the photochemical catalyst is BiOBr0.5I0.5/Bi5O7Br0.5I0.5, powdered, partial size 12-15nm, specific surface area 285-300m2/g.Photochemical catalyst prepared by the present invention has the advantages such as photocatalytic activity is high, environmental-friendly, visible light-responded, the hydroxypropyl guar in the fracturing outlet liquid that can effectively degrade, and degradation process is without secondary pollution.
Description
Technical field
The present invention relates to inorganic material synthesis and photocatalysis technology fields, and in particular to a kind of composite solid solution photochemical catalyst
And its preparation method and application, chemical formula BiOBr0.5I0.5/Bi5O7Br0.5I0.5。
Background technique
The country has obtained one for the research of the fracturing outlet liquid processing method generated during shale gas exploitation both at home and abroad
Determine achievement, returns most of inorganic wastes in drain, such as: landwaste, proppant, inorganic salts etc. are heavy by a series of physics
The methods of drop, chemical flocculation can be removed effectively.But for returning polymer difficult to degrade in drain, such as: the high scores such as guanidine glue
Sub- polymer, then need to consume a large amount of energy or miscellaneous chemical agent is degraded one by one, has processing cost height, equipment
The disadvantages of investment is big, long processing period, 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 hydroxyl radical free radical (OH) of activity in the case where semiconductor catalyst acts on.Hydroxyl radical free radical almost can nothing
Selectively by organic pollutant oxidative degradation difficult to degrade in waste water at non-toxic or low-toxic small-molecule substance or even direct mine
Carbon dioxide and water and other small carboxylic acid molecules are turned to, innoxious purpose is reached.The technology has non-selectivity, oxidability
By force, the advantages that reaction speed is fast, treatment effeciency is high, without secondary pollution.Above-mentioned characteristic makes photocatalysis technology in processing shale gas
It returns drain field and illustrates great application space.And in photocatalysis technology field, the development of photochemical catalyst is then core the most
One of technology of the heart.And BiOX becomes the new lover of photocatalysis field in recent years.
BiOX becomes the focus of photocatalysis field in recent years as a kind of novel low-gap semiconductor.Due to its nothing
Poison, cheap, redox ability is strong, chemical property is stable and the characteristics such as anti-light corrosion, water pollutant degradation, antibacterial etc. just
Face is widely used.Since the electron-hole combined efficiency of monomer is higher, it is unfavorable to have to its photocatalysis performance
Influence, seriously constrain its in terms of practical application.Therefore, have BiOX based photocatalyst by modified
High photocatalysis performance is one of the important topic of photocatalysis research field.Current method reported in the literature has metal ion to mix
Miscellaneous, nonmetallic ion-doped, semiconductor solid solution, compound etc..
Zhang in 2016 et al. has found the BiOIxBr1-x mischcrystal photocatalyst of fabricated in situ under the irradiation of visible light
Be catalyzed rhodamine B when, have photocatalytic activity more stronger than monomer (Xing, Z., Wang, C.Y., Wang, L.W., Huang,
G.X., Wang, W.K. , &Yu, H.Q. (2016) .Fabrication of BiOBrxI1-x photocatalysts
withtunable vi sible light catalytic activity by modulating band structures:
Scientific Reports 6,22800.).
Although the preparation for the BiOIxBr1-x mischcrystal photocatalyst reported in above-mentioned document has used the simplest heavy
Shallow lake method, but the performance of photochemical catalyst itself is still lower, it is still undesirable to the utilization rate of luminous energy, it needs further modified to mention
Its high intrinsic photocatalysis performance.
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
This is pressed the purpose of the invention is in order to overcome the above problem of the existing technology, providing a kind of removal and returns hydroxyl in liquid
The photochemical catalyst and its preparation method and application of propyl guanidine glue, the catalyst compare more existing BiOIxBr1-x solid solution photocatalysis
Agent and Bi5O7IxBr1-xMischcrystal photocatalyst has better performance, and the preparation method of the catalyst reduces production cost,
Production technology is simplified, preparation method is simple, mild condition, the BiOBr of preparation0.5I0.5/Bi5O7Br0.5I0.5Composite solid solution light
Catalyst photochemical catalytic oxidation can remove the hydroxypropyl guar in fracturing outlet liquid under visible light.
To achieve the goals above, first aspect present invention provides a kind of composite solid solution photochemical catalyst, wherein described
Photochemical catalyst expression formula is BiOBr0.5I0.5/Bi5O7Br0.5I0.5。
Second aspect of the present invention provides a kind of composite solid solution photochemical catalyst BiOBr0.5I0.5/Bi5O7Br0.5I0.5System
Preparation Method, method includes the following steps:
(1) the ethylene glycol solution A for configuring bismuth-containing element compound, prepares bromine-containing compound and the aqueous solution containing iodine compound
Solution B is added drop-wise in solution A carries out the first reaction under agitation by B, and the first obtained the first product of reaction is carried out the
The second product that second reaction obtains is washed drying by two reactions；
(2) bismuth-containing compound, concentrated nitric acid and water are mixed, prepares solution C, prepare bromine-containing compound and containing iodine compound
The product of certain mass step (1) and solution D are added drop-wise in solution C carry out the first reaction simultaneously under agitation by aqueous solution D
The pH for adjusting solution is alkalinity, the first product that the first reaction obtains is carried out the second reaction, second that the second reaction is obtained
Product washs drying.
Preferably, bismuth-containing compound is five water bismuth nitrates, is potassium iodide or sodium iodide, preferably iodate containing iodine compound
Potassium；Bromine-containing compound is potassium bromide or sodium bromide, preferably potassium bromide.
Preferably, in step (1), relative to the bismuth-containing compound of 1mmol, the dosage of ethylene glycol is 10-50ml,
And relative to iodine compound and bromide is contained described in 1mmol, the dosage of water is 10-50ml.
Preferably, in step (2), relative to the bismuth-containing compound of 1mmol, the dosage of water is 10-50ml, described
The dosage of concentrated nitric acid is 2-5ml, and relative to iodine compound and bromide is contained described in 1mmol, the dosage of water is 10-
50ml。
Preferably, in step (1) and (2), it is described first reaction condition include: stirring rate be 50-100 turn/
It is stirred 10-40 minutes under conditions of minute, drop rate is 1-2.5ml/ minutes.
Preferably, in step (1) and (2), it is 10-15MPa that the condition of second reaction, which includes: pressure, and temperature is
140-180 DEG C, time 14-18h；Preferably, pressure 12-14MPa, temperature are 150-170 DEG C, time 15-17h.
Preferably, the washing methods be respectively with deionized water and washes of absolute alcohol for several times, it is preferable that first spend from
Sub- water cleans 3 times, then with washes of absolute alcohol 3 times.
Preferably, it is 60-80 DEG C that the condition of the drying, which includes: drying temperature, drying time 5-24h, it is preferable that dry
Dry temperature is 65-75 DEG C, drying time 7-15h.
Third aspect present invention provides above-mentioned composite solid solution photochemical catalyst BiOBr0.5I0.5/Bi5O7Br0.5I0.5's
The photochemical catalyst that preparation method or the preparation method are prepared is used to remove the hydroxypropyl guar in fracturing fluid recovery (backflow) liquid.
The technical solution provided according to the present invention, usefulness of the present invention are mainly reflected in:
(1) present invention optimizes the preparation process of such photochemical catalyst, there is the spy for reducing cost, simplifying production procedure
Point；
(2) photochemical catalyst of the invention has solid solution, complex double structure, improves photocatalytic activity；
(3) BiOBr of the present invention is used0.5I0.5/Bi5O7Br0.5I0.5Composite solid solution photochemical catalyst is greater than in wavelength
Under the visible light exposure of 420nm, the hydroxypropyl guar solution that original COD is 200mg/L removal rate in 2h is 98%, is substantially mentioned
High photocatalysis performance；
(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, only needs a step fabricated in situ, and method is simple.
Detailed description of the invention
Fig. 1 is BiOBr0.5I0.5/Bi5O7Br0.5I0.5The XRD diagram of compound solid solution photochemical catalyst.
Fig. 2 is BiOBr0.5I0.5/Bi5O7Br0.5I0.5The TEM of photochemical catalyst schemes.
Specific embodiment
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 factory, Xi'an He Pu Biotechnology Co., Ltd
Family.
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
The present embodiment indicates that the photochemical catalyst being prepared using preparation method of the invention and application.
(1) by 2mmolBi (NO3)3·5H2O, which is dissolved in 40ml ethylene glycol, obtains solution A, by 1mmolKBr and 1mmol KI
It is dissolved in 40ml deionized water and obtains solution B, be added drop-wise to solution B dropwise with 1.5ml/ minutes drop rates with rubber head dropper
In solution A, solution is transferred to 100ml polytetrafluoroethylene (PTFE) height after stirring 30min on magnetic stirring apparatus with the rate of 80r/min
Pyroreaction is carried out in pressure reaction kettle, reaction temperature is 160 DEG C, and reaction time 16h naturally cools to room temperature, so after reaction
Use deionized water and washes of absolute alcohol 3 times respectively afterwards, finally dry 10h, the BiOBr prepared at 70 DEG C0.5I0.5Light
Catalyst；
(2) by 1mmolBi (NO3)3·5H2O, which is dissolved in 5ml concentrated nitric acid and 20ml deionized water, obtains solution C, will
0.5mmolKBr and 0.5mmolKI, which is dissolved in 10ml deionized water, obtains solution D, with rubber head dropper by solution D with 1.5ml/ points
The drop rate of clock is added drop-wise in solution C dropwise, and the BiOBr that 0.25g is above-mentioned0.5I0.5Photochemical catalyst is added thereto, and is used in combination
PH is adjusted to 12.3 by 2mol/LNaOH solution.Solution is shifted after stirring 30min on magnetic stirring apparatus with the rate of 80r/min
Pyroreaction is carried out into 100ml polytetrafluoroethylene (PTFE) autoclave, reaction temperature is 160 DEG C, reaction time 16h, reaction
After naturally cool to room temperature, then use deionized water and washes of absolute alcohol 3 times respectively, finally the dry 10h at 70 DEG C, obtains
The BiOBr of preparation0.5I0.5/Bi5O7Br0.5I0.5Photochemical catalyst.
And XRD characterization is carried out to the photochemical catalyst, and as shown in Figure 1, it can be seen from figure 1 that the catalyst crystal is good, peak position out
It sets and shows that the catalyst is BiOBr0.5I0.5/Bi5O7Br0.5I0.5Rich bismuth mischcrystal photocatalyst.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Embodiment 2
The present embodiment indicates that the photochemical catalyst being prepared using preparation method of the invention and application.According to reality
Apply the identical method of example 1 and prepare photochemical catalyst, institute the difference is that, in step (1) and step (2), in constant temperature oven instead
Answering temperature is 170 DEG C, reaction time 15h.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Embodiment 3
The present embodiment indicates that the photochemical catalyst being prepared using preparation method of the invention and application.According to reality
Apply the identical method of example 1 and prepare photochemical catalyst, institute the difference is that, pH is adjusted to 11.6 in step (2), in step (1)
In step (2), reaction temperature is 150 DEG C in constant temperature oven, reaction time 18h.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Embodiment 4
The present embodiment indicates that the photochemical catalyst being prepared using preparation method of the invention and application.According to reality
Apply the identical method of example 1 and prepare photochemical catalyst, institute the difference is that, pH is adjusted to 11 in step (2).
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Comparative example 1
The preparation and application of BiOI photochemical catalyst.
By 2mmolBi (NO3)3·5H2O, which is dissolved in 40ml deionized water, obtains solution A, by 2mmolKI be dissolved in 40ml go from
Sub- water obtains solution B, and solution B is added drop-wise in solution A dropwise, is stirred on magnetic stirring apparatus with the rate of 100r/min
Solution is transferred in 100ml polytetrafluoroethylene (PTFE) autoclave after 30min and carries out pyroreaction, reaction temperature is 160 DEG C, instead
It is 16h between seasonable, room temperature is naturally cooled to after reaction, deionized water and washes of absolute alcohol 3 times is then used respectively, finally 70
Dry 10h, the BiOI photochemical catalyst prepared at DEG C.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Comparative example 2
This comparative example indicates that prepared BiOBr photochemical catalyst and application.
By 2mmolBi (NO3)3·5H2O is dissolved in 40ml deionized water, under conditions of stirring rate is 80 revs/min
30min is stirred, 40ml is then instilled dropwise dissolved with the deionized water solution of 2mmolKBr, is 80 revs/min in stirring rate
Under the conditions of stir 2h, after product deionized water and dehydrated alcohol are washed 3 times, dry 10h, is prepared at 70 DEG C
BiOBr photochemical catalyst.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Comparative example 3
BiOBr0.5I0.5The preparation and application of photochemical catalyst.
By 2mmolBi (NO3)3·5H2O, which is dissolved in 40ml deionized water, obtains solution A, by 1mmolKBr and 1mmol KI
It is dissolved in 40ml deionized water and obtains solution B, be added drop-wise to solution B dropwise with 1.5ml/ minutes drop rates with rubber head dropper
In solution A, solution is transferred to 100ml polytetrafluoroethylene (PTFE) height after stirring 30min on magnetic stirring apparatus with the rate of 80r/min
Pyroreaction is carried out in pressure reaction kettle, reaction temperature is 160 DEG C, and reaction time 16h naturally cools to room temperature, so after reaction
Use deionized water and washes of absolute alcohol 3 times respectively afterwards, finally dry 10h, the BiOBr prepared at 70 DEG C0.5I0.5Light
Catalyst.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Comparative example 4
Prepare photochemical catalyst in the same manner as shown in Example 1, institute the difference is that, in step (2), by solution
PH is adjusted to 7.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Comparative example 5
Prepare photochemical catalyst in the same manner as shown in Example 1, institute the difference is that, in step (2), constant temperature dries
Without pyroreaction in case, the solution after stirring is directly washed into drying.
Hydroxypropyl of the photocatalyst applications that above-mentioned preparation method is obtained under visible light in catalysis oxidation oil field waste
Guanidine glue, the results are shown in Table 1.
Table 1
| Catalyst type | COD removal rate (%) in 2h |
| Embodiment 1 | 98.0 |
| Embodiment 2 | 97.2 |
| Embodiment 3 | 96.6 |
| Embodiment 4 | 95.3 |
| Comparative example 1 | 35.2 |
| Comparative example 2 | 36.5 |
| Comparative example 3 | 42.0 |
| Comparative example 4 | 39.6 |
| Comparative example 5 | 37.9 |
From table 1, it is apparent that comparative example 1-4, it is found that catalytic effect is best in photochemical catalyst of the invention
For embodiment 1,2hCOD removal rate has reached 98.0%.Comparative example 1-3 and embodiment 1-4 discovery is compared, embodiment is formed different
Matter junction structure substantially increases Photocatalytic Degradation Property.Comparative example 4 and the discovery of comparative example 5 are compared in neutrallty condition and without high temperature item
Under part, photochemical catalyst of the present invention can not be formed, and bad to hydroxypropyl guar degradation effect.Therefore, light of the invention is urged
Agent can preferably photochemical catalytic oxidation removes the hydroxypropyl guar in shale gas oil field waste, also, the system under visible light
Preparation Method reduces production cost, simplifies production technology.
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. a kind of composite solid solution photochemical catalyst and its preparation method and application, which is characterized in that the expression of the photochemical catalyst
Formula is BiOBr0.5I0.5/Bi5O7Br0.5I0.5, can be used to remove pressure and return hydroxypropyl guar in liquid.
2. a kind of preparation method of composite solid solution photochemical catalyst, which is characterized in that method includes the following steps:
(1) the ethylene glycol solution A for configuring bismuth-containing element compound, prepares bromine-containing compound and the aqueous solution B containing iodine compound,
Solution B is added drop-wise in solution A under stirring condition and carries out the first reaction, it is anti-that the first product that the first reaction obtains is carried out second
It answers, the second product that the second reaction obtains is washed into drying；
(2) bismuth-containing compound, concentrated nitric acid and water are mixed, prepares solution C, prepare bromine-containing compound and containing the water-soluble of iodine compound
The product of certain mass step (1) and solution D are added drop-wise in solution C under agitation and carry out the first reaction and adjust by liquid D
The pH of solution is alkalinity, the first product that the first reaction obtains is carried out the second reaction, the second product that the second reaction is obtained
Wash drying.
3. preparation method according to claim 2, wherein bismuth-containing compound is five water bismuth nitrates, is iodine containing iodine compound
Change potassium or sodium iodide, preferably potassium iodide；Bromine-containing compound is potassium bromide or sodium bromide, preferably potassium bromide.
4. preparation method according to claim 2, wherein the bismuth-containing chemical combination in step (1), relative to 1mmol
Object, the dosage of ethylene glycol are 10-50mL, and relative to, containing iodine compound and bromide, the dosage of water is described in 1mmol
10-50mL。
5. preparation method according to claim 2, wherein the bismuth-containing chemical combination in step (2), relative to 1mmol
Object, the dosage of water are 10-50mL, and the dosage of the concentrated nitric acid is 2-5mL, and relative to containing iodine compound described in 1mmol
And bromide, the dosage of water are 10-50mL.
6. preparation method according to claim 2, wherein in step (1) and (2), the condition packet of first reaction
It includes: being stirred 10-40 minutes under conditions of stirring rate is 50-100 revs/min, drop rate is 1-2.5mL/ minutes.
7. preparation method according to claim 2, wherein in step (1) and (2), the condition packet of second reaction
Include: temperature is 140-180 DEG C, time 14-18h；Preferably, temperature is 150-170 DEG C, time 15-17h.
8. preparation method according to claim 2, wherein the washing methods is to use deionized water and dehydrated alcohol respectively
Cleaning is for several times, it is preferable that is first cleaned 3 times with deionized water, then with washes of absolute alcohol 3 times.
9. preparation method according to claim 2, wherein the condition of the drying includes: that drying temperature is 60-80 DEG C,
Drying time is 5-24h, it is preferable that drying temperature is 65-75 DEG C, drying time 7-15h.
10. light made from preparation method described in any one of photochemical catalyst claimed in claims 1-2 or claim 1-9
Catalyst is applied to remove the hydroxypropyl guar in fracturing fluid recovery (backflow) liquid under visible light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811582049.7A CN109603863A (en) | 2018-12-24 | 2018-12-24 | A kind of composite solid solution photochemical catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811582049.7A CN109603863A (en) | 2018-12-24 | 2018-12-24 | A kind of composite solid solution photochemical catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109603863A true CN109603863A (en) | 2019-04-12 |
Family
ID=66010578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811582049.7A Pending CN109603863A (en) | 2018-12-24 | 2018-12-24 | A kind of composite solid solution photochemical catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109603863A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111482187A (en) * | 2020-04-15 | 2020-08-04 | 重庆科技学院 | Preparation method of bismuth-rich composite photocatalyst for treating oilfield flowback fluid |
| CN113908863A (en) * | 2021-11-16 | 2022-01-11 | 西南石油大学 | Fracturing flowback fluid purification experimental method based on photocatalytic reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107469840A (en) * | 2017-09-25 | 2017-12-15 | 西南石油大学 | A kind of preparation method and its usage of the solid complex photochemical catalysts of BiOBrxI1 x/BiOBr |
| CN108435215A (en) * | 2018-03-22 | 2018-08-24 | 西南石油大学 | Remove the photochemical catalyst and its preparation method and application of hydroxypropyl guar in fracturing fluid recovery (backflow) liquid |
| CN108722445A (en) * | 2018-06-11 | 2018-11-02 | 西南石油大学 | A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application |
-
2018
- 2018-12-24 CN CN201811582049.7A patent/CN109603863A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107469840A (en) * | 2017-09-25 | 2017-12-15 | 西南石油大学 | A kind of preparation method and its usage of the solid complex photochemical catalysts of BiOBrxI1 x/BiOBr |
| CN108435215A (en) * | 2018-03-22 | 2018-08-24 | 西南石油大学 | Remove the photochemical catalyst and its preparation method and application of hydroxypropyl guar in fracturing fluid recovery (backflow) liquid |
| CN108722445A (en) * | 2018-06-11 | 2018-11-02 | 西南石油大学 | A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 方稳等: "BiOBrxI1-x半导体微球的制备、热稳定性及其光催化性能", 《人工晶体学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111482187A (en) * | 2020-04-15 | 2020-08-04 | 重庆科技学院 | Preparation method of bismuth-rich composite photocatalyst for treating oilfield flowback fluid |
| CN111482187B (en) * | 2020-04-15 | 2022-08-12 | 重庆科技学院 | Preparation method of bismuth-rich composite photocatalyst for treating oilfield flowback fluid |
| CN113908863A (en) * | 2021-11-16 | 2022-01-11 | 西南石油大学 | Fracturing flowback fluid purification experimental method based on photocatalytic reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103979664B (en) | A kind of OMS-2 activates the method for persulphate degradation of organic waste water | |
| CN103386306B (en) | Cu/CuxO/TiO2 heterojunction visible light catalyst, as well as preparation method and application thereof | |
| CN102078807B (en) | Er<3+>:YAlO3/TiO2-loaded photocatalyst and preparation method thereof | |
| CN105084511A (en) | Method for degrading organic waste water by activating persulfate through manganese-cobalt composite oxide | |
| CN106563477B (en) | A kind of tri compound visible light catalyst and its preparation method and application | |
| CN100453167C (en) | Method for preparing mesoporous titanium dioxide optical catalyst using plant peels and films | |
| CN107469840A (en) | A kind of preparation method and its usage of the solid complex photochemical catalysts of BiOBrxI1 x/BiOBr | |
| CN104014326A (en) | Efficient photocatalyst for bismuth vanadate nanorod and preparation method of catalyst | |
| CN109603863A (en) | A kind of composite solid solution photochemical catalyst and its preparation method and application | |
| CN105195190A (en) | Heterojunction photocatalyst SnS2/g-C3N4 as well as preparation method and application thereof | |
| CN109289851A (en) | One-step synthesis prepares Fe3O4The method of/mesoporous carbon composite material and its catalyzing oxidizing degrading sulfamethazine | |
| CN108722445B (en) | A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application | |
| CN107583655B (en) | Modified BiOX matrix composite photochemical catalyst and its preparation method and application | |
| CN109382120A (en) | A kind of preparation method of the modified two-dimentional composite photo-catalyst of zirconyl oxyhalides bismuthino | |
| CN101298045A (en) | Metal/titanium dioxide catalyst for catalytic oxidation and preparation method thereof | |
| CN104258873A (en) | Preparation method for composite ozone catalysis and oxidation catalyst | |
| CN108855151A (en) | A kind of preparation method and applications of ultra-thin bismuth oxyiodide photochemical catalyst | |
| CN103143397B (en) | Production method and application of nanometer TiO2/expanded graphite composite sponge | |
| CN108435215B (en) | Remove the photochemical catalyst and its preparation method and application of hydroxypropyl guar in fracturing fluid recovery (backflow) liquid | |
| CN103977800B (en) | The synthetic method of nuclear shell structure nano magnetic FeOOH ozone catalyst | |
| CN110252334A (en) | A kind of doped nano manganese dioxide composite material, preparation method and applications | |
| CN108031464A (en) | Bi preparation by sol-gel2MoO6Method for preparing halloysite composite photocatalytic material | |
| CN102351272A (en) | Method for degrading perfluorooctanoic acid in water through visible light catalysis | |
| CN102489291B (en) | Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst | |
| CN101798092A (en) | Polyferro-silicate, preparation method thereof and applications thereof in water treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190412 |
|
| WD01 | Invention patent application deemed withdrawn after publication |