CN107115882B - The preparation method and its purposes in catalytic degradation organic wastewater of a kind of photocatalyst crystals - Google Patents
The preparation method and its purposes in catalytic degradation organic wastewater of a kind of photocatalyst crystals Download PDFInfo
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- CN107115882B CN107115882B CN201710319713.8A CN201710319713A CN107115882B CN 107115882 B CN107115882 B CN 107115882B CN 201710319713 A CN201710319713 A CN 201710319713A CN 107115882 B CN107115882 B CN 107115882B
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- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 35
- 230000015556 catabolic process Effects 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002351 wastewater Substances 0.000 title abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 24
- 150000007513 acids Chemical class 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- 238000006365 thiocyanation reaction Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 238000003837 high-temperature calcination Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- -1 ammonium molybdate modified titanium dioxide Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 150000007974 melamines Chemical class 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 29
- 238000001994 activation Methods 0.000 description 11
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000007792 addition Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- TWWCTGIBOJFDNL-UHFFFAOYSA-N C1(=CC=CC=C1)O.ClC1=CC=CC(=C1)Cl Chemical compound C1(=CC=CC=C1)O.ClC1=CC=CC(=C1)Cl TWWCTGIBOJFDNL-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 231100001234 toxic pollutant Toxicity 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001465754 Metazoa Species 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000005789 organism growth Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to organic catalysis technical fields, and in particular to a kind of preparation method and its purposes in catalytic degradation organic wastewater, especially catalytic degradation 2 of photocatalyst crystals, 4 chlorophenesic acids.The present invention is using ammonium paramolybdate as molybdenum source, using melamine as nitrogen source, is modified to titanium dioxide using thiocyanation iron as sulphur source and source of iron, brown photocatalyst crystals are prepared by reaction in-situ, with higher specific surface area and catalytic activity, 99% or more is up to the degradation rate of 2,4 chlorophenesic acids.
Description
Technical field
The invention belongs to organic catalysis technical fields, and in particular to a kind of preparation method of photocatalyst crystals and its be catalyzed
Purposes in degradation of organic waste water, especially catalytic degradation 2,4- chlorophenesic acids.
Background technology
2,4- chlorophenesic acids (2,4-dichlorophenol) are a kind of important organic intermediates, be mainly used for chemical industry,
In insecticide, preservative and paper industry.It has the toxicity of stench peculiar smell and height, belongs to environmental hormone, can pass through food
Chain accumulates in animal body.These pollutants are all that some are difficult the organic matter being biodegradable, and are not only an impediment to aquatic organism
Growth and breeding, and are harmful to health, it be U.S.EPA priority pollutants and China's water in it is excellent
First control the toxic pollutant on pollutant blacklist.Therefore control and remove the highly toxic pollutant tool of low concentration in environment
There is important realistic meaning.Photocatalytic degradation is the effective means of toxic pollutant in Environment control.
CN101491757B discloses a kind of TiO with high selective degradation2The synthesis side of composite photo-catalyst
Method leaves special sky on the TiO2 composite photo-catalysts using the synthesis of method that engram technology and sol-gel technique are combined
Cave, this special hole pair 2,4- chlorophenesic acids have very high selectivity, the TiO2 composite photo-catalysts pair 2,4- bis-
Chlorophenol degradation speed is fast, and degradation efficiency is high；ChineseJournalofCatalysis37 (2016) 607-615 discloses one
Kind V2O5-TiO2Catalyst photocatalytic degradation 2,4 dichloro phenol:The influence of catalyst carrier and surfactant, the results showed that,
50wt%,V2O5-TiO2(it is denoted as 50V2O5-TiO2) show than simple V2O5,TiO2With the higher photocatalytic activities of P25, V2O5With
TiO2Between the modification of interaction the photocatalysis efficiency .CTAB and HTAB that can influence binary oxide catalyst dramatically increase
The catalytic efficiency of 50V2O5-TiO2 samples, wherein (50V2O5-TiO2)-CTAB catalyst shows most after reacting 30min
The addition of high 2,4 dichloro benzene Phenol degradation rate (100%) and reaction rate (2.22mg/ (Lmin)) surfactants can repair
Adorn V in binary oxide2O5And TiO2Optical and electronic property, to significantly improve its photocatalytic activity.
CN101491757B uses TiO2As active catalytic components, there is higher selectivity to 2,4- chlorophenesic acids,
But degradation rate is low（Only 85%）；Technical solution disclosed in ChineseJournalofCatalysis37 (2016) 607-615
In 2, although 4- chlorophenesic acid degradation rates have reached 100%, V2O5It is on the high side, and CTAB cetyl trimethyl brominations
The addition of ammonium also increases production cost to varying degrees.
So the catalyst degradation 2,4 dichloro phenol of a kind of low cost of exploitation, high catalytic performance has important meaning
Justice.
Invention content
The purpose of the present invention overcomes in 2,4 dichloro phenol catalytic degradation in the prior art that catalytic efficiency is low, catalyst cost
High disadvantage provides a kind of preparation method of photocatalyst crystals, and is used for catalytic degradation 2,4- chlorophenesic acids；The present invention is with secondary molybdenum
Sour ammonium is that molybdenum source is modified titanium dioxide using thiocyanation iron as sulphur source and source of iron, passes through original position using melamine as nitrogen source
Brown photocatalyst crystals are prepared in reaction, have higher specific surface area and catalytic activity.
According to an aspect of the present invention, the present invention provides a kind of preparation methods of photocatalyst crystals, including following step
Suddenly：
1）The preparation of ammonium molybdate modified titanium dioxide sol：The nothing of 200ml will be instilled at 40 DEG C of 50ml tetraisopropyl titanates
It is stirred to react in water-ethanol, back flow reaction 2h is warming up to after tetraisopropyl titanate completion of dropwise addition, it is secondary to be then cooled to 40 DEG C of additions
After ammonium molybdate is stirred to react 2h, add the hydrochloric acid of a concentration of 1mol/L of 10ml ethanol solution 2h is stirred at room temperature after stand 3 days
Obtain ammonium molybdate modified titanium dioxide sol；
2）The formalin of 20g melamines and 10ml37wt% are dissolved in 100ml water and being reacted at 50 DEG C, are then added dropwise
The aqueous solution of sodium hydroxide adjusts pH to 9.2-9.5, is stirred to react 1h；Sour regulation system pH is added dropwise into system after reaction
To 5.5-5.8, then it is added dropwise at 60 DEG C of the aqueous solution of the thiocyanation iron of 1mol/L and reacts 22h；Solvent is steamed, is dried at 100 DEG C
It is 5 microns of particulate matters below to be crushed to grain size afterwards for 24 hours；
3）By step 2）Gained whole particulate matter is added to step 1）In ammonium molybdate modified titanium dioxide sol in, 75 DEG C
Under be stirred to react under the rotating speed of 800rpm for 24 hours, then solvent evaporated, high-temperature calcination obtains brown under the atmosphere of argon gas after being evaporated
Brown powder in acetic acid at 40 DEG C is impregnated 2h, then filters to obtain filter cake by powder；Filter cake is in the high temperature under the atmosphere of argon gas
Calcine to obtain brown photocatalyst crystals；
Preferably, for calculation in the molar ratio, tetraisopropyl titanate：Ammonium paramolybdate：Thiocyanation iron=4-6:3-4:1, more preferably
Tetraisopropyl titanate：Ammonium paramolybdate：Thiocyanation iron=5:3:1；
Preferably, the high-temperature calcination temperature under the atmosphere of argon gas is 550-600 DEG C；Calcination temperature influence of the present invention is urged
The pattern and its specific surface area of agent crystal carry out calcining specific surface area up to 900m at 550-600 DEG C2/ g, is significantly greatly increased
The catalytic efficiencies of photocatalyst crystals, shortens the reaction time；
The present invention is using ammonium paramolybdate as molybdenum source, is sulphur source and source of iron to dioxy using thiocyanation iron using melamine as nitrogen source
Change titanium to be modified, brown photocatalyst crystals are prepared by reaction in-situ, there is higher specific surface area and catalytic activity.
Photocatalyst crystals prepared by the present invention can be used for photocatalytic degradation 2,4- chlorophenesic acids, specifically by catalyst crystalline substance
Body, which is placed in the aqueous solution of 2,4- chlorophenesic acids, stirs 2h, then the catalytic degradation 2 under the irradiation of ultraviolet light, 4- chlorophenesic acids,
The filtering with microporous membrane for being after reaction 0.2 micron by aperture removes photocatalyst crystals, and filtrate carries out HPLC detections and calculates
The degradation rate of 2,4 dichloro phenol.
Photocatalyst crystals catalytic degradation 2 using the present invention, 4- chlorophenesic acids, degradation rate is up to 99% or more, and is catalyzed
Agent is recyclable to apply mechanically, and recovery 10 times or more does not occur catalyst inactivation phenomenon.
When long-time uses photocatalyst crystals catalytic degradation 2, when 4- chlorophenesic acids, such as in recovery 30 times or more,
Catalyst activity will appear a degree of decline, but catalyst can be made to live by simple acid processing and high-temperature calcination
Property restore, be as follows：
The photocatalyst crystals that used catalytic activity declines are soaked in the aqueous solution of nitric acid of 0.2mol/L in 30 DEG C
12h is impregnated below, is then filtered, is washed, and is dried, is finally placed in the high-temperature calcination stove of argon atmosphere, in 780- at 100 DEG C
Photocatalyst crystals after calcining 3h must be activated at 860 DEG C, preferred calcination temperature are 800 DEG C；In catalyst activation process, find
If using the calcination temperature of catalyst preparation process, i.e., calcined at 550-600 DEG C, then catalyst activity restores unknown
Activity that is aobvious, can not being restored to before being not used, when raising calcination temperature, when reaching 780 DEG C or more, preferably 800 DEG C, catalyst
Activity can be restored to the degree before use, and 2,4- chlorophenesic acid degradation rates reach 99% or more.
Compared with prior art, the invention has the advantages that：
1）Photocatalyst crystals preparation process of the present invention is simple, is molybdenum source by ammonium paramolybdate, using melamine as nitrogen source, with
Thiocyanation iron is that sulphur source and source of iron are modified titanium dioxide, and the catalyst activity of preparation is high, the degradation of 2,4- chlorophenesic acids
Rate is up to 99% or more；
2）Photocatalyst crystals recoverable of the present invention does not decline yet in recovery 10 times or more catalytic activity,
Reduce production cost；
3）Photocatalyst crystals of the present invention can be by the way that simple acid be handled, high-temperature calcination makes revivification of catalyst, activating process letter
It is single, it is suitble to industrialized production.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Embodiment 1
One, photocatalyst crystals are prepared：
1）The preparation of ammonium molybdate modified titanium dioxide sol：The nothing of 200ml will be instilled at 40 DEG C of 50ml tetraisopropyl titanates
It is stirred to react in water-ethanol, back flow reaction 2h is warming up to after tetraisopropyl titanate completion of dropwise addition, it is secondary to be then cooled to 40 DEG C of additions
After ammonium molybdate is stirred to react 2h, add the hydrochloric acid of a concentration of 1mol/L of 10ml ethanol solution 2h is stirred at room temperature after stand 3 days
Obtain ammonium molybdate modified titanium dioxide sol；
2）The formalin of 20g melamines and 10ml 37wt% are dissolved in 100ml water and being reacted at 50 DEG C, are then added dropwise
The aqueous solution of sodium hydroxide adjusts pH to 9.2-9.5, is stirred to react 1h；Hydrochloric acid regulation system is added dropwise into system after reaction
Then pH to 5.5-5.8 is added dropwise at 60 DEG C of the aqueous solution of the thiocyanation iron of 1mol/L and reacts 22h；Solvent is steamed, is done at 100 DEG C
The dry grain size that is crushed to afterwards for 24 hours is 5 microns of particulate matters below；
3）By step 2）Gained whole particulate matter is added to step 1）In ammonium molybdate modified titanium dioxide sol in, 75 DEG C
Under be stirred to react under the rotating speed of 800rpm for 24 hours, then solvent evaporated, the 550-600 DEG C of calcining under the atmosphere of argon gas after being evaporated
3h obtains brown powder, and brown powder is impregnated 2h in acetic acid at 40 DEG C, then filters to obtain filter cake；Filter cake is in the atmosphere in argon gas
It encloses lower 550-600 DEG C of calcining 3h and obtains brown photocatalyst crystals；
It is calculated according to molar ratio in preparation process, tetraisopropyl titanate：Ammonium paramolybdate：Thiocyanation iron=5:3:1.
Two, catalytic degradation 2,4 dichloro phenol
The photocatalyst crystals 60mg of preparation is taken to be dispersed in 50ml 2, in the aqueous solution of a concentration of 30mg/L of 4- chlorophenesic acids,
2h is stirred at room temperature；Then filter filtration catalizer crystal, HPLC detect 2,4- bis- in filtrate after irradiation 5h under the ultraviolet lamp of 64W
The concentration of chlorophenol.
Wherein HPLC testing conditions are：Agilent C18 chromatographic columns, Detection wavelength 215nm, mobile phase are methanol/water（70/
30, V/V）, flow velocity 1ml/min.
Comparative example 1
It is added without ammonium paramolybdate in photocatalyst crystals preparation process, remaining raw material and the preparation method is the same as that of Example 1, and will
Method carries out 2,4 dichloro phenol Degrading experiment in the photocatalyst crystals case embodiment 1 prepared.
Comparative example 2
It is recycled after catalyst prepared by embodiment 1 is degraded, carries out the degradation of 2,4- chlorophenesic acids again,
Study recovery number（10 times, 20 times, 30 times）The performance of catalyst is assessed with the relationship of 2,4 dichloro benzene Phenol degradation rate.
Comparative example 3
By 2 recovery of embodiment, 30 photocatalyst crystals be soaked in the aqueous solution of nitric acid of 0.2mol/L in 30 DEG C with
Lower immersion 12h, is then filtered, washing, is dried, is finally placed in the high-temperature calcination stove of argon atmosphere, at 800 DEG C at 100 DEG C
Calcining 3h must activate after photocatalyst crystals.
Catalyst after activation is according to the method catalytic degradation 2,4 dichloro phenol in embodiment 1.
The catalytic degradation result of above-described embodiment 1 and its comparative example 1-3 are detected using HPLC, and calculate degradation rate
（ ）, the results are shown in Table 1：
1 2,4 dichloro benzene Phenol degradation rate of table
The above result shows that the addition of ammonium paramolybdate improves the activity of catalyst in catalyst preparation process of the present invention,
Increase 2,4 dichloro benzene Phenol degradation rate；In addition activity is substantially without decline after recovery 10 times for catalyst of the present invention, when returning
Receipts apply mechanically after 30 times can by the method for nitric acid dousing, high-temperature calcination come activated catalyst, after activation of catalyst its activity with make
With preceding almost the same（2,4 dichloro benzene Phenol degradation rate is 99.2%）
In addition in catalyst activation process（Catalyst to apply mechanically 30 times is activation object）Have studied calcination temperature pair
The influence of catalytic activity, table 2 list influence of the activation temperature to catalyst activity（Activation process with comparative example 3, difference lies in
Calcination temperature is different；Catalytic degradation tests reference implementation example 1）；
Influence of 2 calcination temperature of table to catalytic performance
The above result shows that activation temperature is key influence factor in catalyst activation process, when activation temperature is at 800 DEG C
When left and right, the catalyst after activation can make 2,4- chlorophenesic acid degradation rates reach 99% or more.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.
Claims (5)
1. a kind of preparation method of photocatalyst crystals, it is characterised in that：Include the following steps：
1）The preparation of ammonium molybdate modified titanium dioxide sol：The anhydrous of 200mL will be instilled at 40 DEG C of 50mL tetraisopropyl titanates
It is stirred to react in ethyl alcohol, back flow reaction 2h is warming up to after tetraisopropyl titanate completion of dropwise addition, be then cooled to 40 DEG C and secondary molybdenum is added
After sour ammonium is stirred to react 2h, the ethanol solution for adding the hydrochloric acid of a concentration of 1mol/L of 10mL is stirred at room temperature after 2h and to stand 3 days
Ammonium molybdate modified titanium dioxide sol；
2）The formalin of 20g melamines and 10mL 37wt% are dissolved in 100mL water and being reacted at 50 DEG C, and hydrogen is then added dropwise
The aqueous solution of sodium oxide molybdena adjusts pH to 9.2-9.5, is stirred to react 1h；Sour regulation system pH is added dropwise into system after reaction extremely
Then 5.5-5.8 is added dropwise at 60 DEG C of the aqueous solution of the thiocyanation iron of 1mol/L and reacts 22h；Solvent is steamed, is dried for 24 hours at 100 DEG C
After be crushed to grain size be 5 microns of particulate matters below；
3）By step 2）Gained whole particulate matter is added to step 1）In ammonium molybdate modified titanium dioxide sol in, at 75 DEG C in
It is stirred to react under the rotating speed of 800rpm for 24 hours, then solvent evaporated, high-temperature calcination obtains brown powder under the atmosphere of argon gas after being evaporated
Brown powder in acetic acid at 40 DEG C is impregnated 2h, then filters to obtain filter cake by end；Filter cake high-temperature calcination under the atmosphere of argon gas
Obtain brown photocatalyst crystals；
The photocatalyst crystals be used for catalytic degradation 2,4- chlorophenesic acids, the specific steps are：Photocatalyst crystals 60mg is taken to be dispersed in
In the aqueous solution of a concentration of 30mg/L of 50mL 2,4- chlorophenesic acid, 2h is stirred at room temperature；Then 5h is irradiated under the ultraviolet lamp of 64W
Filter filtration catalizer crystal afterwards, HPLC detect the concentration of 2,4- chlorophenesic acids in filtrate.
2. preparation method according to claim 1, it is characterised in that：For calculation in the molar ratio, tetraisopropyl titanate：Para-molybdic acid
Ammonium：Thiocyanation iron=4-6:3-4:1.
3. preparation method according to claim 2, it is characterised in that：For calculation in the molar ratio, more preferably four isopropyl of metatitanic acid
Ester：Ammonium paramolybdate：Thiocyanation iron=5:3:1.
4. preparation method according to claim 1, it is characterised in that：The high-temperature calcination temperature under the atmosphere of argon gas is
550-600℃。
5. a kind of method of photocatalyst crystals activation, the photocatalyst crystals are prepared by preparation method described in claim 1,
It is characterized in that：The photocatalyst crystals that used catalytic activity declines are soaked in the aqueous solution of nitric acid of 0.2mol/L in 30 DEG C
12h is impregnated below, is then filtered, is washed, and is dried, is finally placed in the high-temperature calcination stove of argon atmosphere, at 800 DEG C at 100 DEG C
Lower calcining 3h must activate after photocatalyst crystals.
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