CN106745470A - A kind of zeolite-loaded doped by rare-earths TiO of modified coal ash2The method that catalytic degradation removes anthracene - Google Patents
A kind of zeolite-loaded doped by rare-earths TiO of modified coal ash2The method that catalytic degradation removes anthracene Download PDFInfo
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- CN106745470A CN106745470A CN201611075410.8A CN201611075410A CN106745470A CN 106745470 A CN106745470 A CN 106745470A CN 201611075410 A CN201611075410 A CN 201611075410A CN 106745470 A CN106745470 A CN 106745470A
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- rare
- anthracene
- zeolite
- coal ash
- earths
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 94
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010457 zeolite Substances 0.000 title claims abstract description 57
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 56
- 230000015556 catabolic process Effects 0.000 title claims abstract description 40
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003245 coal Substances 0.000 title claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010883 coal ash Substances 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 229910001122 Mischmetal Inorganic materials 0.000 claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 78
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 40
- 239000010881 fly ash Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 230000001476 alcoholic effect Effects 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 14
- 229910052724 xenon Inorganic materials 0.000 claims description 14
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 238000005286 illumination Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 235000012054 meals Nutrition 0.000 claims description 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 206010019909 Hernia Diseases 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims description 5
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 230000002285 radioactive effect Effects 0.000 claims description 5
- 239000011435 rock Substances 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 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 5
- 238000003801 milling Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000011949 solid catalyst Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- -1 rare earth compound Chemical class 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000004088 simulation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 55
- 239000000498 cooling water Substances 0.000 description 9
- 238000011160 research Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000011148 porous material Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- 239000004174 erythrosine Substances 0.000 description 1
- 229940011411 erythrosine Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- C02F1/72—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of zeolite-loaded doped by rare-earths TiO of modified coal ash2The method that catalytic degradation removes anthracene, with modified coal ash zeolite as carrier, increased the specific surface area of photochemical catalyst, hole is more firm, it is not susceptible to cave in, substantially increases the adsorption capacity of photochemical catalyst, using the doped by rare-earths TiO extracted by rare earth ore2Used as photochemical catalyst, mischmetal has adduction catalytic capability and with low cost compared with single rare earth compound, and using self-control apparatus for photoreaction, catalytic degradation efficiency is high.The present invention is high to the polyaromatic catalytic degradation efficiency such as anthracene in water, and cost is relatively low, simulation solar ray photocatalysis degraded, with good application value.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to a kind of zeolite-loaded doped by rare-earths of modified coal ash
TiO2The method that catalytic degradation removes anthracene.
Background technology
Polycyclic aromatic hydrocarbon is coal, oil, timber, tobacco, is produced during the organic matter imperfect combustion such as organic high molecular compound
Volatile hydrocarbon, be important environment and food contaminant.Hitherto it is found that have more than 200 kinds of PAHs, wherein there is phase
When part has carcinogenicity, such as benzo[α, benzo α anthracenes etc..PAHs is distributed widely in environment, and what can be lived at us is every
One corner finds, any to have organic matter to process, and discards, and the place burnt or use is likely to produce polycyclic aromatic hydrocarbon.
Today's society natural water is subject to the severe contamination of some toxic chemical substances of mankind's manufacture, and these have strong poison
The negative effect that the chemical substance of evil effect is produced to terrestrial ecosystem causes the extensive concern of people.It is reported that one
The presence of the persistence organic pollutants such as polycyclic aromatic hydrocarbon (PAHs) is able to detect that in the surface water and drinking water resource in a little areas,
The serious daily production and living for having threatened people.Polycyclic aromatic hydrocarbon is that the important persistence of class difficult degradation in the environment is organic
Pollutant, and there is " three-induced effect " mostly, it is classified as the environmental contaminants of priority acccess control including China by countries in the world.It is biological
Degraded is that current researcher pays close attention to most degrading polycyclic aromatic hydrocarbons methods, although it possesses the advantages of expense is low, degraded is thorough, but
Have that degradation efficiency is low, substrate is difficult to the shortcomings of contacting with degradation bacteria, and there are some researches show using TiO2Light degradation can be safe
The PAHs effectively gone in water removal.TiO2It is a kind of N-type semiconductor material, there is stronger oxidisability and reproducibility, is urged by it
Change that activity is high, heat resistance is strong, long action time, it is cheap the advantages of extremely people's pro-gaze, as a kind of most valued light
Catalyst.Common TiO2It is mostly powdered, although photocatalysis is strong, but it is commonly present point in wastewater treatment process
From, reclaim difficult the problems such as, thus how research is by TiO2Being fixed on carrier becomes the problem that people pay close attention to very much.Common load
Body mainly has:Glass, ceramics, activated carbon etc..Using zeolite as TiO2Carrier of photocatalyst also has many researchs, but greatly
Majority research all selection natural zeolites do carrier as carrier from the synthetic zeolite from flyash of adsorbable organic pollution
Research is rarely reported, while traditional carrying method need to obtain composite photo-catalyst by high-temperature roasting, equipment is complicated and consumes energy
It is more, therefore low temperature preparation TiO2It is also TiO in recent years2A study hotspot in preparation.Poisonous persistent organic pollutants are
Present Global is most universal, be most difficult to the pollution problem administered.Sanitary sewage can effectively be processed with traditional biological treatment, but
The compound of hundreds of high poison difficult degradations can not use biological treatment, it is necessary to search out suitable, effective processing method.Numerous studies
Show, photocatalytic method can be effectively main by hydro carbons, halogenated organic matters, surfactant, dyestuff, agricultural chemicals, phenols, aromatic hydrocarbons etc.
Organic pollutant degradation, final mineralising be CO2, H2O, and contain in organic pollution halogen atom, sulphur atom, phosphorus atoms and
Nitrogen-atoms etc. be then separately converted to X-, SO42-, PO43-, NH4+, NO3-plasma, reach the mesh that organic pollution is completely eliminated
's.
Titanium dioxide good stability, will not occur photoetch and chemical attack, low cost, and harmless.But,
There are two most obvious basic problems in optically catalytic TiO 2 technology：One is band-gap energy wider, is 3.2eV, therefore titanium dioxide
The light of the near ultraviolet part that titanium can only be equal to or less than 387.5 nanometers by wavelength is excited, and this part light only accounts for sunshine
Sub-fraction (is less than 5%), so as to sunshine can not be made full use of.Furthermore, photo-generate electron-hole is combined to easy, in dioxy
Changing the compound of photoproduction electron-hole pair on titanium surface was completed within the time less than 10-9 seconds, therefore prepared high activity light
The outstanding problem of catalyst is how to reduce the recombination probability in light induced electron and hole.Also substantial amounts of document report makes dioxy
Change the doping, carbon such as the method that titanium response wave length is moved to visible region, such as crome metal, iron, vanadium doping, nonmetallic nitrogen, carbon, boron
Sensitising agents such as the codopes such as nitrogen, iron nitrogen, iron cerium, adsorption erythrosine, thionine etc., are made with cerium oxide mostly in documents and materials
It is research object, and is immersed on porous carrier and is made heterogeneous catalysis.Using cerium oxide as research object in theory point
It is rational in analysis, but because rare earths separation is difficult in practicality, single rare earth compound price is high, and mixture
Middle various elements equally have catalytic capability, and mixture there may also be adduction.
Description
Present invention solves the technical problem that being to provide a kind of zeolite-loaded doped by rare-earths TiO2 catalysis of modified coal ash
The method of degraded removal anthracene, catalytic degradation efficiency is high, it is easy to operate, other water treatment programs can be coordinated to use.
The technical scheme is that：A kind of zeolite-loaded doped by rare-earths TiO2 catalytic degradations removal of modified coal ash
The method of anthracene, mainly comprises the steps of：(1) flyash pretreatment and activation：200-400 parts of powdered coal ash is set in grinding
To 40-60 mesh in standby, put into the beaker added with filter paper lid, 5-7h is dried at 130-150 DEG C, be cooled to room temperature, obtain powder
Coal ash meal, by described flyash meal and mass fraction for 18-22% HCL solution with solid-liquid ratio be 1:10-12 mixes,
1-2h is stirred under constant temperature blender with magnetic force, temperature is 80-85 DEG C, obtains mixed liquor, and described mixed liquor is distilled
Water dilution, suction filtration 3-10 time dry 8-10h to neutral, obtain the flyash after treatment is activated；
(2) preparation of modified coal ash Zeolite support：Using microwave-ultrasonic-mixed alkali melts hydro-thermal method will be flyash modified
It is zeolite, the flyash after described treatment activation is crushed to 300-400 mesh, is the mixed alkali of 8-12mol/L expecting with concentration
Liquor ratio is 1：100ml/g mixes, and is stirred simultaneously plus ultrasonic oscillation 1.5-2.5h using heating using microwave, and temperature is 80-85 DEG C, is obtained
It is old in aging reactor after drying by described modified coal ash distilled water diluting, suction filtration 3-10 times to neutral to modified coal ash
Change 12-24h, crystallization 7-9h at 100-140 DEG C, obtain modified coal ash zeolite；
(3) preparation of doped by rare-earths TiO2 photochemical catalysts：Described p-type coal ash zeolite is crushed to 300-400
Mesh, with 50-70 parts of titanate esters as predecessor, adds 40-60 parts of glacial acetic acid, 8-10 parts of concentrated nitric acid, 120-240 parts of alcoholic solution, makes
30-40min is mixed with magnetic stirring apparatus, mixing speed is 800-900r/min, obtains sol solution, by 150-200 parts
Described p-type coal ash zeolite is added in the sol solution, and 2-2.5h is stirred with 500-600r/min speed, is obtained gel and is mixed
Compound, loads reflux, continues to stir in 80-85 DEG C of water bath with thermostatic control, with acid buret by mischmetal salt/alcoholic solution
It is slowly added in described gel mixture from return duct top, continues to stir to be obstructed to magnetic stir bar stop automatically, is removed
Reflux, places 1-2h in 80-85 DEG C of water bath with thermostatic control, vapors away ethanol, and 20-24h is dried at 100-110 DEG C, crushes
To 200-300 mesh, that is, obtain doped by rare-earths TiO2 photochemical catalysts；
(4) photochemical catalyst absorption degradation anthracene：It is 1 with solid-liquid ratio in entering to make by oneself apparatus for photoreaction by the water drainage containing anthracene:
200-600 adds the doped by rare-earths TiO2Photochemical catalyst, stirs 5-15min, standing adsorption 30-40min, opens self-control
Illumination lamp source in apparatus for photoreaction carries out catalytic degradation 20-60min；
(5) anthracene photolytic efficiency analysis test：Water sample centrifugation after light reaction is degraded, taking supernatant carries out liquid liquid extraction
Take, rotate, a series of pretreatment such as nitrogen blows, the concentration of anthracene is finally determined with GC-MS.
Further, the mixed alkali described in step (2) is the pure NaOH and KOH of analysis, and proportion relation is NaOH：KOH=1:
0.5-1, adds KOH to reduce crystallization rate, improves into nuclear stability.
Further, the modified coal ash zeolite described in step (2) is P type zeolite structure, and P type zeolite specific surface area is compared
Bigger in general zeolite, pore structure stabilization is difficult to cave in, with excellent adsorption capacity.
Further, the titanate esters described in step (3) are butyl titanate or isopropyl titanate.
Further, step (3) described alcoholic solution is one or two the mixture in methyl alcohol, ethanol or isopropanol.
Further, the mischmetal salt described in step (3) is extract from radioactive Rare Earth Mine rock ballast is free of
Rare earth oxide and nitric acid product, described rare earth oxide is lanthanide oxide, and wherein Ce elements content is not small
In 40%, because rare earths separation is difficult, single rare earth compound price is high, and various elements equally have in mixture
There is catalytic capability, mixture can also play adduction.
Further, the illumination lamp source described in step (4) is hernia lamp, and intensity of illumination is 0.7-1.1mW/m2, and wavelength is
350-450nm, compares and ultraviolet lamp, and hernia lamp source is more nearly sunshine so that test data is more accurate.
Further, the self-control apparatus for photoreaction described in step (4) is stirred comprising constant temperature digital-display magnetic stirrer (1), magnetic force
Sub (2), internal layer reaction tank (3), outer layer cooling bay (4), xenon lamp (5) are mixed, outer reaction pond (4) upper end is connected to cold
But the water inlet pipe (6) and outlet pipe (7) of water, the internal layer reaction tank upper end is connected with the water inlet pipe (8) of reaction solution, bottom connection
The outlet pipe (9) for having the outlet pipe (9) of reaction solution, the reaction solution is connected with filter (10), institute through outer layer cooling bay (4)
The water inlet pipe (8) and outlet pipe (9) middle setting for stating reaction solution have valve (11), and xenon lamp (5) is arranged on internal layer reaction tank (3)
Surface, the inside front of internal layer reaction tank (3) is provided with temperature sensor (12), and the magnetic stir bar (2) is anti-in internal layer
The bottom of Ying Chi (3), lower section of the constant temperature digital-display magnetic stirrer (1) in outer layer cooling bay (4).
Further, the application method of described self-control apparatus for photoreaction is：First open the valve of reaction solution water inlet pipe (8)
(11) accessing pending water containing anthracene is made to flow into internal layer reaction tank (3), it is 1 to add with solid-liquid ratio:200-600 adds the mischmetal to mix
Miscellaneous TiO2Photochemical catalyst, cooling water is passed through in outer layer cooling bay (4), and internal layer reaction tank is regulated and controled using temperature sensor (12)
(3) temperature keeps room temperature, opens constant temperature digital-display magnetic stirrer (1) and stirs 5-15min using magnetic stir bar (2), stands and inhales
Attached 30-40min, the xenon lamp (5) opened in self-control apparatus for photoreaction carries out catalytic degradation 20-60min, opens reaction solution outlet pipe
(9) valve (11) extracts water sample and is tested, and the valve (11) that reaction solution outlet pipe (9) is opened if anthracene concentration is up to standard passes through
Filter (10) is discharged after filtering out catalyst solid thing, repeats above step if below standard until up to standard.
Compared with prior art, beneficial effects of the present invention are embodied in：The present invention increases with modified coal ash zeolite as carrier
Add the specific surface area of photochemical catalyst, hole is more firm, be not susceptible to cave in, substantially increase the energy of adsorption of photochemical catalyst
Power, using the doped by rare-earths TiO extracted by rare earth ore2Used as photochemical catalyst, there is mischmetal adduction to be catalyzed energy
Power and with low cost compared with single rare earth compound, using self-control apparatus for photoreaction, catalytic degradation efficiency is high.The present invention is in water
The polyaromatic catalytic degradation efficiency such as anthracene it is high, cost is relatively low, simulation solar ray photocatalysis degraded, with good application value.
Brief description of the drawings
Fig. 1 is the structural representation of present invention self-control apparatus for photoreaction；
Wherein, 1- constant temperature digital-display magnetic stirrer, 2- magnetic stir bars, 3- internal layers reaction tank, 4- outer layers cooling bay, 5- xenons
Lamp, the water inlet pipe of 6- cooling waters, the outlet pipe of 7- cooling waters, the water inlet pipe of 8- reaction solutions, the outlet pipe of 9- reaction solutions, 10- mistakes
Filter, 11- valves, 12- temperature sensors.
Specific embodiment
For ease of the understanding of the present invention, below in conjunction with explanation is further explained as a example by specific embodiment, implement
Example does not constitute the restriction to the embodiment of the present invention.
Embodiment 1：
The method that a kind of zeolite-loaded doped by rare-earths TiO2 catalytic degradations of modified coal ash remove anthracene, it is main include with
Lower step：(1) flyash pretreatment and activation：By 200 parts of powdered coal ash in milling apparatus to 40 mesh, put to added with filter paper
In the beaker of lid, 5h is dried at 130 DEG C, be cooled to room temperature, obtain flyash meal, by described flyash meal and quality
Fraction be 18% HCL solution with solid-liquid ratio be 1:10 mixing, stir 1h under constant temperature blender with magnetic force, and temperature is 80 DEG C, is obtained
To mixed liquor, by described mixed liquor distilled water diluting, suction filtration 3 times to neutral, 8h is dried, after obtaining treatment activation
Flyash；
(2) preparation of modified coal ash Zeolite support：Using microwave-ultrasonic-mixed alkali melts hydro-thermal method will be flyash modified
Be zeolite, the flyash after described treatment activation be crushed to 300 mesh, with concentration for 8mol/L mixed alkali with solid-liquid ratio be 1：
100ml/g mixes, and is stirred simultaneously plus ultrasonic oscillation 1.5h using heating using microwave, and temperature is 80 DEG C, obtains modified coal ash, will
Described modified coal ash distilled water diluting, suction filtration 3 times are aged at 12h, 100-140 DEG C after drying to neutral in aging reactor
Crystallization 7h, obtains modified coal ash zeolite；Wherein, described mixed alkali is the pure NaOH and KOH of analysis, and proportion relation is NaOH：KOH
=1:0.5, add KOH to reduce crystallization rate, nuclear stability is improved into, described modified coal ash zeolite is P type zeolite
Structure, P type zeolite specific surface area is bigger compared to general zeolite, pore structure stabilization, is difficult to cave in, with excellent energy of adsorption
Power.
(3) preparation of doped by rare-earths TiO2 photochemical catalysts：Described p-type coal ash zeolite is crushed to 300 mesh, with
50 parts of titanate esters are predecessor, add 40 parts of glacial acetic acid, 8 parts of concentrated nitric acids, 120 parts of alcoholic solutions, are mixed using magnetic stirring apparatus and stirred
30min is mixed, mixing speed is 800r/min, obtains sol solution, the p-type coal ash zeolite described in 150 parts is added described molten
In sol solution, 2h is stirred with 500r/min speed, obtain gel mixture, load reflux, in 80 DEG C of water bath with thermostatic control relayings
, from return duct top be slowly added in described gel mixture mischmetal salt/alcoholic solution with acid buret by continuous stirring,
Continue to stir to be obstructed to magnetic stir bar stop automatically, remove reflux, 1h is placed in 80 DEG C of waters bath with thermostatic control, vapor away second
Alcohol, 20h is dried at 100 DEG C, is crushed to 200 mesh, that is, obtain doped by rare-earths TiO2Photochemical catalyst；Wherein, described titanium
Acid esters is butyl titanate or isopropyl titanate, and the alcoholic solution is one or two the mixing in methyl alcohol, ethanol or isopropanol
Thing, described mischmetal salt is from the product without the rare earth oxide being extract in radioactive Rare Earth Mine rock ballast with nitric acid
Thing, described rare earth oxide is lanthanide oxide, and wherein Ce elements content is not less than 40%, due to rare earths separation
Difficulty, single rare earth compound price is high, and various elements equally have catalytic capability in mixture, and mixture can also rise
To adduction.
(4) photochemical catalyst absorption degradation anthracene：It is 1 with solid-liquid ratio in entering to make by oneself apparatus for photoreaction by the water drainage containing anthracene:
200 add the doped by rare-earths TiO2Photochemical catalyst, stirs 5min, standing adsorption 30min, opens self-control apparatus for photoreaction
In illumination lamp source carry out catalytic degradation 20min；Wherein, described illumination lamp source is hernia lamp, and intensity of illumination is 0.7mW/m2, ripple
A length of 350nm, compares and ultraviolet lamp, and hernia lamp source is more nearly sunshine so that test data is more accurate.Wherein, institute
The self-control apparatus for photoreaction stated includes constant temperature digital-display magnetic stirrer, magnetic stir bar, internal layer reaction tank, outer layer cooling bay, xenon
Lamp, outer reaction pond upper end is connected to the water inlet pipe and outlet pipe of cooling water, the internal layer reaction tank upper end connection
There is the water inlet pipe of reaction solution, bottom is connected with the outlet pipe of reaction solution, and the outlet pipe of the reaction solution connects through outer layer cooling bay
Filter is connected to, the water inlet pipe and outlet pipe middle setting of the reaction solution have valve, and xenon lamp is being arranged on internal layer reaction tank just
Top, the inside front of internal layer reaction tank is provided with temperature sensor, and the magnetic stir bar is in the bottom of internal layer reaction tank, institute
Constant temperature digital-display magnetic stirrer is stated in the lower section of outer layer cooling bay.Wherein, the application method of described self-control apparatus for photoreaction is：
First opening the valve of reaction solution water inlet pipe makes accessing pending water containing anthracene flow into internal layer reaction tank, and it is 1 to add with solid-liquid ratio:200 add
The doped by rare-earths TiO2Photochemical catalyst, cooling water is passed through in outer layer cooling bay, and internal layer is regulated and controled using temperature sensor
Reaction tank temperature keeps room temperature, opens constant temperature digital-display magnetic stirrer and stirs 5min, standing adsorption using magnetic stir bar
30min, the xenon lamp opened in self-control apparatus for photoreaction carries out catalytic degradation 20min, and the valve for opening reaction solution outlet pipe is extracted
Water sample is tested, after the valve that reaction solution outlet pipe is opened if anthracene concentration is up to standard is filtered catalyst solid thing
Discharge, repeats the above steps until up to standard if below standard.
(5) anthracene photolytic efficiency analysis test：Water sample centrifugation after light reaction is degraded, taking supernatant carries out liquid liquid extraction
Take, rotate, a series of pretreatment such as nitrogen blows, the concentration of anthracene is finally determined with GC-MS.
Embodiment 2：
A kind of zeolite-loaded doped by rare-earths TiO of modified coal ash2The method that catalytic degradation removes anthracene, it is main include with
Lower step：(1) flyash pretreatment and activation：By 300 parts of powdered coal ash in milling apparatus to 50 mesh, put to added with filter paper
In the beaker of lid, 6h is dried at 140 DEG C, be cooled to room temperature, obtain flyash meal, by described flyash meal and quality
Fraction be 20% HCL solution with solid-liquid ratio be 1:11 mixing, stir 1.5h under constant temperature blender with magnetic force, and temperature is 83 DEG C,
Mixed liquor is obtained, by described mixed liquor distilled water diluting, suction filtration 7 times to neutral, 9h is dried, after obtaining treatment activation
Flyash；
(2) preparation of modified coal ash Zeolite support：Using microwave-ultrasonic-mixed alkali melts hydro-thermal method will be flyash modified
It is zeolite, the flyash after described treatment activation is crushed to 350 mesh, with concentration for the mixed alkali of 10mol/L is with solid-liquid ratio
1：100ml/g mixes, and is stirred simultaneously plus ultrasonic oscillation 2h using heating using microwave, and temperature is 83 DEG C, obtains modified coal ash, will
Described modified coal ash distilled water diluting, suction filtration 3-10 times are aged 20h to neutral in aging reactor after drying, brilliant at 120 DEG C
Change 8h, obtain modified coal ash zeolite；Wherein, described mixed alkali is the pure NaOH and KOH of analysis, and proportion relation is NaOH：KOH=
1:0.5-1, adds KOH to reduce crystallization rate, improves into nuclear stability.Described modified coal ash zeolite is P type zeolite
Structure, P type zeolite specific surface area is bigger compared to general zeolite, pore structure stabilization, is difficult to cave in, with excellent energy of adsorption
Power.
(3) preparation of doped by rare-earths TiO2 photochemical catalysts：Described p-type coal ash zeolite is crushed to 350 mesh, with
60 parts of titanate esters are predecessor, add 50 parts of glacial acetic acid, 9 parts of concentrated nitric acids, 170 parts of alcoholic solutions, are mixed using magnetic stirring apparatus and stirred
35min is mixed, mixing speed is 850r/min, obtains sol solution, the p-type coal ash zeolite described in 170 parts is added described molten
In sol solution, 2h is stirred with 550r/min speed, obtain gel mixture, load reflux, in 83 DEG C of water bath with thermostatic control relayings
, from return duct top be slowly added in described gel mixture mischmetal salt/alcoholic solution with acid buret by continuous stirring,
Continue to stir to be obstructed to magnetic stir bar stop automatically, remove reflux, 1.5h is placed in 83 DEG C of waters bath with thermostatic control, vapor away
Ethanol, 22h is dried at 105 DEG C, is crushed to 250 mesh, that is, obtain doped by rare-earths TiO2Photochemical catalyst；Wherein, it is described
Titanate esters are butyl titanate or isopropyl titanate, and the alcoholic solution is the mixed of one or two in methyl alcohol, ethanol or isopropanol
Compound, described mischmetal salt is from without the rare earth oxide being extract in radioactive Rare Earth Mine rock ballast and nitric acid
Product, described rare earth oxide is lanthanide oxide, and wherein Ce elements content is not less than 40%, due to rare earth element point
From difficulty, single rare earth compound price is high, and various elements equally have catalytic capability in mixture, and mixture can also
Play adduction.
(4) photochemical catalyst absorption degradation anthracene：It is 1 with solid-liquid ratio in entering to make by oneself apparatus for photoreaction by the water drainage containing anthracene:
400 add the doped by rare-earths TiO2Photochemical catalyst, stirs 10min, standing adsorption 35min, opens self-control light reaction dress
Illumination lamp source in putting carries out catalytic degradation 40min；Wherein, described self-control apparatus for photoreaction includes constant temperature digital display magnetic agitation
Device, magnetic stir bar, internal layer reaction tank, outer layer cooling bay, xenon lamp, outer reaction pond upper end are connected to cooling water
Water inlet pipe and outlet pipe, the internal layer reaction tank upper end are connected with the water inlet pipe of reaction solution, and bottom is connected with the water outlet of reaction solution
Pipe, the outlet pipe of the reaction solution is connected with filter through outer layer cooling bay, in the water inlet pipe and outlet pipe of the reaction solution
Between be provided with valve, xenon lamp is arranged on the surface of internal layer reaction tank, and the inside front of internal layer reaction tank is provided with TEMP
Device, in the bottom of internal layer reaction tank, the constant temperature digital-display magnetic stirrer is in the lower section of outer layer cooling bay for the magnetic stir bar.
Wherein, the application method of described self-control apparatus for photoreaction is：The valve for first opening reaction solution water inlet pipe makes accessing pending water containing anthracene
Internal layer reaction tank is flowed into, it is 1 to add with solid-liquid ratio:400 add the doped by rare-earths TiO2Photochemical catalyst, in outer layer cooling
Cooling water is passed through in pond, room temperature is kept using temperature sensor regulation and control internal layer reaction tank temperature, open constant temperature digital display magnetic agitation
Device stirs 10min, standing adsorption 35min using magnetic stir bar, and the xenon lamp opened in self-control apparatus for photoreaction carries out catalysis drop
Solution 40min, the valve extraction water sample for opening reaction solution outlet pipe is tested, and reaction solution outlet pipe is opened if anthracene concentration is up to standard
Valve be filtered after catalyst solid thing and discharge, repeated the above steps if below standard until up to standard.
(5) anthracene photolytic efficiency analysis test：Water sample centrifugation after light reaction is degraded, taking supernatant carries out liquid liquid extraction
Take, rotate, a series of pretreatment such as nitrogen blows, the concentration of anthracene is finally determined with GC-MS.
Embodiment 3：
A kind of zeolite-loaded doped by rare-earths TiO of modified coal ash2The method that catalytic degradation removes anthracene, it is main include with
Lower step：(1) flyash pretreatment and activation：By 400 parts of powdered coal ash in milling apparatus to 60 mesh, put to added with filter paper
In the beaker of lid, 7h is dried at 150 DEG C, be cooled to room temperature, obtain flyash meal, by described flyash meal and quality
Fraction be 22% HCL solution with solid-liquid ratio be 1:12 mixing, stir 2h under constant temperature blender with magnetic force, and temperature is 85 DEG C, is obtained
To mixed liquor, by described mixed liquor distilled water diluting, suction filtration 10 times to neutral, 10h is dried, after obtaining treatment activation
Flyash；
(2) preparation of modified coal ash Zeolite support：Using microwave-ultrasonic-mixed alkali melts hydro-thermal method will be flyash modified
It is zeolite, the flyash after described treatment activation is crushed to 400 mesh, with concentration for the mixed alkali of 12mol/L is with solid-liquid ratio
1：100ml/g mixes, and is stirred simultaneously plus ultrasonic oscillation 2.5h using heating using microwave, and temperature is 85 DEG C, obtains modified coal ash,
By described modified coal ash distilled water diluting, suction filtration 10 times to neutral, 24h is aged after drying in aging reactor, it is brilliant at 140 DEG C
Change 9h, obtain modified coal ash zeolite；Wherein, described mixed alkali is the pure NaOH and KOH of analysis, and proportion relation is NaOH：KOH=
1:1, add KOH to reduce crystallization rate, improve into nuclear stability.Described modified coal ash zeolite is P type zeolite structure,
P type zeolite specific surface area is bigger compared to general zeolite, pore structure stabilization, is difficult to cave in, with excellent adsorption capacity.
(3) preparation of doped by rare-earths TiO2 photochemical catalysts：Described p-type coal ash zeolite is crushed to 400 mesh, with
70 parts of titanate esters are predecessor, add 60 parts of glacial acetic acid, 10 parts of concentrated nitric acids, 240 parts of alcoholic solutions, are mixed using magnetic stirring apparatus and stirred
40min is mixed, mixing speed is 900r/min, obtains sol solution, the p-type coal ash zeolite described in 200 parts is added described molten
In sol solution, 2.5h is stirred with 600r/min speed, obtain gel mixture, reflux is loaded, in 85 DEG C of waters bath with thermostatic control
Continue to stir, mischmetal salt/alcoholic solution is slowly added to described gel mixture from return duct top with acid buret
In, continue to stir to be obstructed to magnetic stir bar stop automatically, reflux is removed, 2h is placed in 85 DEG C of waters bath with thermostatic control, volatilize
Fall ethanol, 24h is dried at 110 DEG C, be crushed to 300 mesh, that is, obtain doped by rare-earths TiO2Photochemical catalyst；Wherein, it is described
Titanate esters be butyl titanate or isopropyl titanate, the alcoholic solution be methyl alcohol, ethanol or isopropanol in one or two
Mixture, described mischmetal salt is from without the rare earth oxide and nitric acid being extract in radioactive Rare Earth Mine rock ballast
Product, described rare earth oxide is lanthanide oxide, and wherein Ce elements content is not less than 40%, due to rare earth element
Difficulty is separated, single rare earth compound price is high, and various elements equally have catalytic capability in mixture, and mixture is also
Adduction can be played.
(4) photochemical catalyst absorption degradation anthracene：It is 1 with solid-liquid ratio in entering to make by oneself apparatus for photoreaction by the water drainage containing anthracene:
600 add the doped by rare-earths TiO2Photochemical catalyst, stirs 15min, standing adsorption 40min, opens self-control light reaction dress
Illumination lamp source in putting carries out catalytic degradation 60min；Wherein, described illumination lamp source is hernia lamp, and intensity of illumination is 1.1mW/m2,
Wavelength is 450nm, is compared and ultraviolet lamp, and hernia lamp source is more nearly sunshine so that test data is more accurate.Wherein,
Described self-control apparatus for photoreaction comprising constant temperature digital-display magnetic stirrer, magnetic stir bar, internal layer reaction tank, outer layer cooling bay,
Xenon lamp, outer reaction pond upper end is connected to the water inlet pipe and outlet pipe of cooling water, and the internal layer reaction tank upper end connects
The water inlet pipe of reaction solution is connected to, bottom is connected with the outlet pipe of reaction solution, and the outlet pipe of the reaction solution passes through outer layer cooling bay
Filter is connected with, the water inlet pipe and outlet pipe middle setting of the reaction solution have valve, and xenon lamp is arranged on internal layer reaction tank
Surface, the inside front of internal layer reaction tank is provided with temperature sensor, the magnetic stir bar in the bottom of internal layer reaction tank,
The constant temperature digital-display magnetic stirrer is in the lower section of outer layer cooling bay.Wherein, the application method of described self-control apparatus for photoreaction
For：First opening the valve of reaction solution water inlet pipe makes accessing pending water containing anthracene flow into internal layer reaction tank, and it is 1 to add with solid-liquid ratio:600 add
Enter the doped by rare-earths TiO2Photochemical catalyst, cooling water is passed through in outer layer cooling bay, using in temperature sensor regulation and control
Layer reaction tank temperature keeps room temperature, opens constant temperature digital-display magnetic stirrer and stirs 15min, standing adsorption using magnetic stir bar
40min, the xenon lamp opened in self-control apparatus for photoreaction carries out catalytic degradation 60min, and the valve for opening reaction solution outlet pipe is extracted
Water sample is tested, after the valve that reaction solution outlet pipe is opened if anthracene concentration is up to standard is filtered catalyst solid thing
Discharge, repeats the above steps until up to standard if below standard.
(5) anthracene photolytic efficiency analysis test：Water sample centrifugation after light reaction is degraded, taking supernatant carries out liquid liquid extraction
Take, rotate, a series of pretreatment such as nitrogen blows, the concentration of anthracene is finally determined with GC-MS.
It is that, for the ease of understanding embodiments of the invention, the present invention can also have other to implement using above-mentioned technical proposal
Example, protection scope of the present invention is not limited to this.Without departing from the spirit and substance of the case in the present invention, art
Technical staff works as can make various corresponding changes and deformation according to the present invention, but these corresponding changes and deformations belong to this
The scope of the claims of invention.
Claims (7)
1. the zeolite-loaded doped by rare-earths TiO of a kind of modified coal ash2The method that catalytic degradation removes anthracene, it is characterised in that bag
Containing following steps：
(1) flyash pretreatment and activation：By 200-400 parts of powdered coal ash in milling apparatus to 40-60 mesh, put to added with
In the capacity bucket of filter paper lid, 5-7h is dried at 130-150 DEG C, be cooled to room temperature, obtain flyash meal, by described fine coal
Grey meal and mass fraction for 18-22% HCL solution with solid-liquid ratio be 1:10-12 mixes, and is stirred under constant temperature blender with magnetic force
Mix 1-2h, temperature is 80-85 DEG C, obtains mixed liquor, by described mixed liquor distilled water diluting, suction filtration 3-10 time extremely in
Property, 8-10h is dried, obtain the flyash after treatment activation；
(2) preparation of modified coal ash Zeolite support：It will flyash modified be to boil to use microwave-ultrasonic-mixed alkali to melt hydro-thermal method
Stone, 300-400 mesh is crushed to by the flyash after described treatment activation, with the mixed alkali that concentration is 8-12mol/L with solid-liquid ratio
It is 1：100ml/g mixes, and is stirred simultaneously plus ultrasonic oscillation 1.5-2.5h using heating using microwave, and temperature is 80-85 DEG C, is changed
Property flyash, by described modified coal ash distilled water diluting, suction filtration 3-10 times to neutral, be aged in aging reactor after drying
Crystallization 7-9h at 12-24h, 100-140 DEG C, obtains modified coal ash Zeolite support；
(3) doped by rare-earths TiO2The preparation of photochemical catalyst：Described modified coal ash Zeolite support is crushed to 300-400
Mesh, with 50-70 parts of titanate esters as predecessor, adds 40-60 parts of glacial acetic acid, 8-10 parts of concentrated nitric acid, 120-240 parts of alcoholic solution, makes
30-40min is mixed with magnetic stirring apparatus, mixing speed is 800-900r/min, obtains sol solution, by 150-200 parts
Described p-type coal ash zeolite is added in the sol solution, and 2-2.5h is stirred with 500-600r/min speed, is obtained gel and is mixed
Compound, loads reflux, continues to stir in 80-85 DEG C of water bath with thermostatic control, with acid buret by mischmetal salt/alcoholic solution
It is slowly added in described gel mixture from return duct top, continues to stir to be obstructed to magnetic stir bar stop automatically, is removed
Reflux, places 1-2h in 80-85 DEG C of water bath with thermostatic control, vapors away ethanol, and 20-24h is dried at 100-110 DEG C, crushes
To 200-300 mesh, that is, obtain doped by rare-earths TiO2Photochemical catalyst；
(4) photochemical catalyst absorption degradation anthracene：It is 1 with solid-liquid ratio in entering to make by oneself apparatus for photoreaction by the water drainage containing anthracene:200-
600 add the doped by rare-earths TiO2Photochemical catalyst, stirs 5-15min, standing adsorption 30-40min, opens self-control light anti-
Answering the illumination lamp source in device carries out catalytic degradation 20-60min；
(5) anthracene photolytic efficiency analysis test：Water sample centrifugation after light reaction is degraded, taking supernatant carries out liquid-liquid extraction, rotation
Steam, nitrogen such as blows at a series of pretreatment, the concentration of anthracene is finally determined with GC-MS, solid catalyst discharge is filtered out if up to standard
Water after catalytic degradation, repeat step (4) is continued until anthracene content is up to standard in water if below standard.
2. a kind of zeolite-loaded doped by rare-earths TiO of modified coal ash as claimed in claim 12Catalytic degradation removal anthracene
Method, it is characterised in that the mixed alkali described in step (2) is NaOH and KOH with mol ratio 1:0.5-1 proportionings are formed.
3. a kind of zeolite-loaded doped by rare-earths TiO2 catalytic degradations of modified coal ash as claimed in claim 1 remove anthracene
Method, it is characterised in that the titanate esters described in step (3) are butyl titanate or isopropyl titanate.
4. a kind of zeolite-loaded doped by rare-earths TiO2 catalytic degradations of modified coal ash as claimed in claim 1 remove anthracene
Method, it is characterised in that step (3) described alcoholic solution is one or two the mixture in methyl alcohol, ethanol or isopropanol.
5. a kind of zeolite-loaded doped by rare-earths TiO2 catalytic degradations of modified coal ash as claimed in claim 1 remove anthracene
Method, it is characterised in that the mischmetal salt described in step (3) extract from radioactive Rare Earth Mine rock ballast is free of
The product of rare earth oxide and nitric acid, described rare earth oxide is lanthanide oxide, and wherein Ce elements content is not less than
40%.
6. a kind of zeolite-loaded doped by rare-earths TiO2 catalytic degradations of modified coal ash as claimed in claim 1 remove anthracene
Method, it is characterised in that the self-control apparatus for photoreaction described in step (4) includes constant temperature digital-display magnetic stirrer (1), magnetic agitation
Sub (2), internal layer reaction tank (3), outer layer cooling bay (4), xenon lamp (5), outer reaction pond (4) upper end is connected to cooling
The water inlet pipe (6) and outlet pipe (7) of water, the internal layer reaction tank upper end are connected with the water inlet pipe (8) of reaction solution, and bottom is connected with
The outlet pipe (9) of reaction solution, the outlet pipe (9) of the reaction solution is connected with filter (10) through outer layer cooling bay (4), described
The water inlet pipe (8) and outlet pipe (9) middle setting of reaction solution have valve (11), and xenon lamp (5) is being arranged on internal layer reaction tank (3) just
Top, the inside front of internal layer reaction tank (3) is provided with temperature sensor (12), and the magnetic stir bar (2) is reacted in internal layer
The bottom in pond (3), lower section of the constant temperature digital-display magnetic stirrer (1) in outer layer cooling bay (4).
7. a kind of zeolite-loaded doped by rare-earths TiO2 catalytic degradations of modified coal ash as claimed in claim 1 remove anthracene
Method, it is characterised in that the illumination lamp source described in step (4) is hernia lamp, and intensity of illumination is 0.7-1.1mW/m2, and wavelength is
350-450nm。
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| CN110510627A (en) * | 2019-09-20 | 2019-11-29 | 神华准能资源综合开发有限公司 | The preparation method of P type zeolite molecular sieve and resulting P type zeolite molecular sieve |
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