CN107029801A - A kind of mimetic enzyme catalyst for catalytic degradation phenol - Google Patents
A kind of mimetic enzyme catalyst for catalytic degradation phenol Download PDFInfo
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- CN107029801A CN107029801A CN201710315224.5A CN201710315224A CN107029801A CN 107029801 A CN107029801 A CN 107029801A CN 201710315224 A CN201710315224 A CN 201710315224A CN 107029801 A CN107029801 A CN 107029801A
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 36
- 230000015556 catabolic process Effects 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 11
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 claims abstract description 5
- 239000001509 sodium citrate Substances 0.000 claims abstract description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000002351 wastewater Substances 0.000 claims description 24
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 19
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000000593 degrading effect Effects 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 230000033228 biological regulation Effects 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000008118 PEG 6000 Substances 0.000 claims description 3
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052961 molybdenite Inorganic materials 0.000 abstract description 17
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 238000011160 research Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
Abstract
Catalytic degradation method Degradation of Phenol associated with a kind of light-advanced oxidation of present invention research, to imitate enzyme MoS2/(PVP、PEG、CTAB、Na2SiO3·9H2O and sodium citrate) material be catalyst, H2O2For oxidant, the Photocatalytic Degradation of Phenol aqueous solution.Method for preparing catalyst of the present invention is simple, and synthesis condition is gentle, and cost of material is more cheap.Workable, technique of the invention is simple, cost is low, processing time is short and obvious processing effect.The clearance of catalyst treatment phenol reaches more than 90%, while COD clearance is 60% or so.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to imitative enzyme materials application is urged in absorption-light of phenol in wastewater
Change oxidation degradation method.
Background technology
Phenol (phenol) also known as carbolic acid, relative molecular mass is 94.11, and density is 1.071, and boiling point is 182 DEG C, is melted
Point is 42-43 DEG C, and phenol is colourless acicular crystal and carries penetrating odor, is soluble in organic solvent, such as：Chloroform, ether, wine
The organic solvents such as essence, carbon disulfide, mainly for the production of synthetic resin, dyestuff, bactericide, preservative and agricultural chemicals etc., are also answered
For sterilize surgical instruments, skin sterilization and excreta processing in terms of.
Aldehydes matter is the intermediate of important dyestuff and medicine, and phenol wastewater is fine from petrochemical industry, synthesis extensively
The industries such as dimension, medicine are class toxicity height and are difficult to biodegradable organic wastewater, and traditional biochemical process has processing time
Long, the low shortcoming for the treatment of effeciency, it is difficult to meet the demand of enterprise's production.In the processing method of phenol wastewater, absorption, multiphase are urged
Change the processing methods such as oxidation largely to report.Absorption method is the porous property absorption Pollutants in Wastewater using adsorbent, is made
For a kind of traditional wastewater processing technology, it can effectively be removed, and effluent quality after multiple pollutant in waste water, processing is good and ratio
Relatively stablize.Adsorbent typically has larger specific surface area and stronger adsorption capacity, the common active charcoal of adsorbent, activity
Carbon fibe, resin, molecular sieve etc..For the absorption of phenol in wastewater, NACF is a kind of adsorbent of function admirable, tool
There are treatment conditions gentle, the advantages of rate of adsorption is fast, adsorption capacity is big, NACF can make again after desorption and regeneration
With.The method heated in Application No. CN02133116.2 technology using electric current is regenerated to NACF, Xu Zhida etc.（It is living
Property Carbon fibe Refinery Wastewater prospect, Treatment of Industrial Water 1998,18 (2)）Using 200 DEG C~500 DEG C superheated steams to work
Property Carbon fibe carry out desorption and regeneration, the above method haves the shortcomings that energy consumption is higher, and solvent desorbing method can introduce new change
Material is learned, therefore the regeneration of NACF is the subject matter for perplexing its application.In addition, the organic pollution after desorption is still
Need processing.
Urged using multiphases such as photocatalysis, O3 catalytic oxidation, catalytic wet air oxidation, catalytic wet hydrogen peroxide oxidations
Change the research of oxidative treatment phenol wastewater it has been reported that wherein catalytic wet hydrogen peroxide oxidation method uses hydrogen peroxide for oxygen
Agent, with equipment is simple, operating condition gentle, non-secondary pollution the features such as, but lot of documents is reported in the method and is catalyzed
The optimum activity temperature of agent is more more than 50 DEG C, if whole waste water of factory are heated into more than 50 DEG C reprocessing, energy consumption
It is also to influence the subject matter of its application.As can be seen here, single processing method is difficult to realize effective degraded of phenol in wastewater,
Need to couple the phenol in the advantage processing waste water of multiple methods.Patent（Application number 200710015182.X）Using active carbon fibre
Phenolic compound in dimension-ozonisation Synergistic degradation water, obtains preferable phenol clearance, but do not refer to and containing in patent
The COD clearances of phenol waste water.A kind of cerium of mixing for air cleaning is disclosed in Application No. CN201210142480.6 to receive
Rice Titanium dioxide/active carbon fiber composite photochemical catalyst and preparation method thereof, improves the photocatalytic activity of nano titanium oxide,
But light-catalysed efficiency is not also high in the treatment of waste water.
The photochemical catalyst N-type metal-oxide semiconductor (MOS) for photocatalytic degradation environmental contaminants is studied at present, particularly
TiO2Because its is nontoxic, it is stable and cheap apply the most extensive, but be due to its big energy gap（More than 3eV）Cause pair
The absorption of sunshine is in ultraviolet light range, and the light of this part wavelength only accounts for 3% of sunshine or so, has a strong impact on it
Service efficiency.With TiO2Compare, MoS2Band gap width there was only 1.80eV or so, to sunshine include visible light part have very
Strong absorption, while it has good chemical stability, learns from other's strong points to offset one's weaknesses, therefore MoS2Equally have in photocatalysis field
Very big Research Significance and application potential.In addition, nanometer MoS2Material has porous bigger serface concurrently, big than surface companion
With the generation of many dangling bonds, it is easy to be combined with other atoms because of the unsaturated property that it has, therefore show very strong
Chemism, these features become the study hotspot in Photocatalitic Technique of Semiconductor.
The content of the invention
In order to solve the deficiencies in the prior art, catalytic degradation associated with a kind of light-advanced oxidation of present invention research
Method Degradation of Phenol, to imitate enzyme MoS2/(PVP、PEG、CTAB、Na2SiO3·9H2O and sodium citrate) material be catalyst,
H2O2For oxidant, the Photocatalytic Degradation of Phenol aqueous solution.
The preparation method of mimetic enzyme catalyst is as follows in the present invention:
（1）In molar ratio 1：1 ~ 5 weighs Na2MoO4·2H2O and NH2CSNH2, plus distilled water and the dissolving under ultrasonic wave added, note
For solution A；
（2）Polyvinylpyrrolidone is added into solution A（PVP）, polyethylene glycol（PEG）, cetyl trimethylammonium bromide
（CTAB）、Na2SiO3·9H2O, sodium citrate, polyethylene glycol PEG6000 one or more, addition account for the 5 ~ 30% of total amount,
To being completely dissolved, solution B is designated as；
（3）With hydrochloric acid regulation regulation solution B acidity, pH is to 6 for regulation, and 30 ~ 60min is stirred at room temperature, solution C is designated as；
（4）Solution C is poured into ptfe autoclave, 6 ~ 24h, preferably 180 DEG C reaction 12h are reacted in 150 ~ 300 DEG C；
（5）After the completion of reaction, sample is taken out after the cooling completely of question response kettle, is centrifuged repeatedly respectively with distilled water and absolute ethyl alcohol
Washing 2 ~ 5 times, is freeze-dried more than 24h in freeze drying box.
It is as follows that catalyst of the present invention is applied to phenol processes in degrading waste water：
（1）Reactor is fixed bed, preferred jacket glass reaction container；
（2）Reaction condition：Reaction temperature is 20-60 DEG C, 1 ~ 12h of reaction time, [catalyst]=0.5 ~ 3.5g.L-1, pH value is
2 ~ 12, it is used as simulated solar light source from 300W ~ 1000W xenon lamps;Preferable reaction temperature is 40 DEG C, reaction time 2h, [catalysis
Agent] concentration=1.5g.L-1, pH=8.0,500W xenon lamps；
（3）50mg/L rhodamine Bs (RhB), 50mg/L methylene blues (MB) are added into the waste water containing phenol, [phenol] is dense
Degree is not higher than 1500mg.L-1, it is made into phenol solution P；
（4）Phenol solution P must react 40min in the dark before radiation of visible light, unrelated with molecular degradation dense to overcome
Degree reduction, reaches that adsorption equilibrium begins to irradiation；
（5）Electronics capturing agent is added, is combined to suppress electron-hole, preferably H2O2It is used as electronics capturing agent, H2O2Concentration
During for 2 ~ 10mmol/L, preferably H2O2Concentration be 8mmol/L, add H2O2MoS can not only effectively be suppressed2Electron-hole
It is compound, and more OH free radicals increase light-catalyzed reaction speed can be produced.
Light/H in the case of radiation of visible light2O2System phenol photocatalytic degradation clearance is about 6%.MoS2/ PVP is urged
The addition of agent promotes phenol degrading, this demonstrate that effectively degradation reaction needs visible ray and mimetic enzyme catalyst.
Hydrogen peroxide is added as electronics scavenger and receives the light induced electron from conduction band, suppresses the restructuring of electronics hole and increases
Plus OH concentration.The combination of photochemical catalyst and hydrogen peroxide is that degradation of phenol is largely effective under visible light illumination.It is preferred that in light
According to and H2O2Degradation of phenol under the conditions of simultaneous.
The advantage of the invention is that：
（1）Method for preparing catalyst of the present invention is simple, and synthesis condition is gentle, and cost of material is more cheap, and obtained catalyst is
Nanoscale, XRD analysis catalyst peak type and peak intensity are good；Composition is easily controllable, and pattern is in lamella overlapping mesh；Synthetic catalyst
Main active component MoS2There is relatively large number of S atom to be exposed to molecular surface in molecular structure, with higher surface-active, because
This has good light and imitative enzymatic characteristic；
（2）Catalyst does not introduce other metal ions, such as Co2+、Co3+、Fe2+Deng metal ion and noble metal, the poly- second of addition
Alkene pyrrolidone（PVP）, polyethylene glycol（PEG）, cetyl trimethylammonium bromide（CTAB）、Na2SiO3·9H2O, citric acid
The catalyst that sodium, polyethylene glycol PEG6000 are synthesized, can by fluorimetric analysis during catalytic degradation organic molecule
Know there is the generation of strong oxidizer OH free radicals, effectively increases catalyst performance.One side MoS2Excited easily by photon
Electron hole pair is produced, electron hole pair occurs to be combined, and is released energy in the way of light and heat；Hole in one side valence band
Occur the electronics in reduction reaction, conduction band and the O on surface with the water at atomic surface2Generation oxidation reaction, so free radical with
Oxidative decomposition occurs for organic matter.During this, the electronics on catalyst material surface and the concentration in hole are modified, and are had
Effect extends the life-span of carrier, and accelerates propagation of the carrier at interface, promotes and improve the quantum effect of photocatalysis
Rate；
（3）The present invention adds certain density electronics capturing agent H in catalytic degradation reaction2O2, effectively inhibit MoS2Electricity
Son-hole it is compound, and more OH free radicals increase light-catalyzed reaction speed can be produced, improve catalytic performance；
（4）Workable, technique of the invention is simple, cost is low, processing time is short and obvious processing effect.Catalyst treatment benzene
The clearance of phenol reaches more than 90%, while COD clearance is 60% or so；
（5）Catalyst of the present invention is solid catalyst, and not solution-off, and be easily isolated reuse, drops significantly in aqueous phase reactions
Low catalyst use cost.Catalyst recycles experiment and understood, after four times reuse, and reclaims catalyst sample to it
XRD tests are carried out, structure shows not finding that crystallinity has declined after any other impurity peaks, circulation in XRD spectrum, test number
There is certain decline according to the catalytic degradation of display composite, but fall is less, remains to be maintained at 80%.Illustrate repeatedly to follow
Ring catalysis rear catalyst can keep greater activity.
Brief description of the drawings
Fig. 1 is that, with the XRD spectrum of the catalyst of the synthesis at a temperature of differential responses, alphabetical a, b, c, d meaning is represented respectively
Reaction temperature is the synthetic catalyst XRD spectrum at 180 DEG C, 200 DEG C, 220 DEG C and 240 DEG C；Fig. 2 is existed with sodium molybdate and thiocarbamide
Different mol ratios (1:1、1:2、1:3、1:4、1:5) XRD spectrum of synthetic catalyst；Fig. 3 shows product MoS2- PVP's
SEM（SEM）Image；Fig. 4 be with the catalytic reaction activity figure under different pH value, pH value respectively 2.0,4.0,
6.0th, 8.0,10.0 and 12.0 catalytic degradation phenol is carried out；Fig. 5 is Catalyst Adsorption, directly catalysis and light-Fenton degraded benzene
The catalytic activity figure of phenol；Fig. 6 is MoS2The speed of degradation of phenol in each condition；Fig. 7 is catalyst concn Degradation of Phenol
Influence, alphabetical meaning be (a)：The influence of catalyst concn Degradation of Phenol,（b）：Pseudo- single order-ln (C/C0) to irradiation time
Linear graph, (c)：Catalyst concn and COD clearance Line Charts.
Embodiment
With reference to embodiment, the present invention will be further described, not to the limitation of its protection domain.
Embodiment 1
Using sodium molybdate as molybdenum source, thiocarbamide is sulphur source, passes through Hydrothermal Synthesiss catalyst.Weigh Na2MoO4·2H2O and NH2CSNH2Plus
Enter distilled water, be allowed to be completely dissolved under ultrasonic wave added；15%PVP additions are weighed, is completely dissolved and obtains clear solution；Use hydrochloric acid
Regulation regulation pH value of solution is about 6, and 30min is stirred at room temperature；）Reactant is poured into 100 mL reactors to react at a certain temperature；
Sample is taken out after the cooling completely of question response kettle after the completion of reaction, washing 2 times is centrifuged repeatedly with distilled water and absolute ethyl alcohol respectively,
24h is freeze-dried in freeze drying box.
Catalysis experiments at room temperature, catalytic reaction is in 200 mL jacketed glass container, and 0.1g catalyst is added
100 mL are respectively the target drop of 50 mg/L rhodamine Bs (RhB), 50 mg/L methylene blues (MB) and 200 mg/L phenol
Thing is solved, from 500W xenon lamps as simulated solar light source, after illumination starts, a sample is taken at regular intervals, its absorbance is surveyed.
Reaction temperature is very big to the particle size influences of sample, and as reaction of formation temperature is higher, the granularity of product substantially increases
Greatly.Fig. 1 is that reaction temperature is respectively 180 DEG C with the XRD spectrum of the catalyst of the synthesis at a temperature of differential responses, 200 DEG C, 220
DEG C and 240 DEG C, with the rise of reaction temperature, MoS2/ PVP crystal peak intensity enhancings.When reaction temperature is less than 180 DEG C, do not have
To form MoS2/ PVP crystal.When reaction temperature is higher than 180 DEG C, product particle size crystal formation increases with the rise of reaction temperature
By force, higher temperature means that the long period cools down, and is conducive to the formation of crystalline structure.
Fig. 2 is in different mol ratios (1 with sodium molybdate and thiocarbamide:1、1:2、1:3、1:4、1:5) XRD of synthetic catalyst
Collection of illustrative plates, it can be seen that sample proportioning is 1:When 4, peak intensity is maximum, most narrow, matches as 1:1、1:2、1:3 and 1:5 gradually subtract
Weak, crystal formation is preferable.It can be seen from the relation of half-peak breadth and crystallite dimension, half-peak breadth B is bigger, and nanometer particle size Dc is smaller, mole matches somebody with somebody
Than 1:4 sizes are maximum.
Pass through the size and aspect graph of SEM characterized by techniques samples.Fig. 3 shows product MoS2- PVP scanning electron microscopy
Mirror（SEM）Image.As can be seen that sample has highly interconnected porous network structure, the macropore with submicron-scale, and
The outward flange of network wall shows low contrast and obvious ripple, and excellent machine is made it have with several nanometers of wall of ultrathin
Tool is flexible.The catalyst MoS of addition is chosen in experiment2/PVP。
Embodiment 2
By mol ratio 1：4 weigh Na2MoO4·2H2O and NH2CSNH2, plus distilled water and the dissolving under ultrasonic wave added, it is designated as molten
Liquid A；Polyvinylpyrrolidone is added into solution A（PVP）Addition accounts for the 10% of total amount, to being completely dissolved, is designated as solution B；With
30min is stirred at room temperature to 6 in salt acid for adjusting pH, is designated as solution C；Solution C is poured into ptfe autoclave, it is anti-in 180 DEG C
Answer 12h；After the completion of reaction, sample is taken out after the cooling completely of question response kettle, is centrifuged repeatedly respectively with distilled water and absolute ethyl alcohol
Washing 5 times, is freeze-dried more than 24h in freeze drying box.
It is as follows that catalyst of the present invention is applied to phenol processes in degrading waste water：Reactor is jacketed glass container；Instead
It is 40 DEG C, reaction time 2h, [catalyst]=1.5g.L to answer temperature-1, pH value is certain value, from 500W xenon lamps as simulation too
Sunlight source;Into the waste water containing phenol add 50mg/L rhodamine Bs (RhB), 50mg/L methylene blues (MB), [phenol] no
Higher than 1500mg.L-1, it is made into phenol solution P；Phenol solution P must react 40min in the dark before radiation of visible light, with gram
The clothes concentration reduction unrelated with molecular degradation, reaches that adsorption equilibrium begins to irradiation.Add electronics capturing agent H2O2, H2O2It is dense
Spend for 8mmol/L.
Choose pH and carry out catalytic degradation phenol 2.0,4.0,6.0,8.0,10.0 and 12.0, as a result such as Fig. 4 c, certain model
As pH raises the degraded of phenol and COD removal efficiency increases in enclosing, when pH is 8, the degradation rate of phenol and COD clearance
Maximum is reached, pH further raises degradation rate and the reduction of COD removal effects of phenol；Meanwhile, understood from Fig. 4 b when pH is 8,
Observed rate constant Kapp is maximum, chooses degradation of phenol when pH is 8.Analyzed from the mechanistic point of phenol degrading, the degraded of phenol
Approach can be divided into phenol ionic reaction and decompose the radical reaction of the OH produced and phenol.Make benzene due to hydroxylation
Phenol molecule ortho position and the cloud density aligned are higher, and hydroxyl radical free radical directly attacks the ortho para of phenol molecule, carry out electrophilic
Substitution, generation catechol and hydroquinones.Due to Pka=9.45 of phenol, phenol shows faintly acid in water, with solution
PH rise, the hydrogen atom of Phenol in Aqueous Solution molecule easily generates phenol ion, and its resonant effect can further increase phenyl ring
Ortho para cloud density, be more beneficial for the electrophilic attack of hydroxyl radical free radical.It is worth noting that pH>When 8, COD's goes
Reduced on the contrary except effect does not increase, the solubility mainly due to oxidant increases and reduced with pH, causes OH free radicals
Response characteristic is reduced.
From figure 5 it can be seen that reaction condition [catalyst]=1.0g.L-1, [phenol]=50mg.L-1It is with pH value
8.0.Show MoS2/ PVP is present in dark, and phenol degrading increases slowly in 40min, is then held essentially constant.Therefore,
Phenol solution must react 40min in the dark before radiation of visible light, to overcome the concentration unrelated with molecular degradation to reduce, reach
Irradiation is begun to adsorption equilibrium.Light/H in the case of radiation of visible light2O2System phenol photocatalytic degradation clearance is about
6%.MoS2The addition of/PVP catalyst promotes phenol degrading, this demonstrate that effectively degradation reaction needs visible ray and photocatalysis
Agent.In addition, to light MoS2/ PVP systems add H2O2Increase phenol degrading.In fact, adding hydrogen peroxide is used as electronics scavenger
Receive the light induced electron from conduction band, suppress electronics hole restructuring increase OH concentration.Therefore, photochemical catalyst and hydrogen peroxide
Combination be degradation of phenol under visible light illumination most efficient method.From 6 it can be seen from the figure thats, enzyme MoS is imitated2/ PVP light
Catalytic rate is 1.4 times that its fenton-type reagent speed is, in illumination and H2O2Simultaneously under existence condition, MoS2Catalysis drop
Solution speed is greatly enhanced, so experimental selection is in illumination and H2O2Degradation of phenol under the conditions of simultaneous.
Catalyst charge during catalytic degradation is the key factor of strong influence phenol photocatalytic degradation effect.
It is 50mg/L to simulate phenolic waste water concentration, and temperature is under the conditions of 40 DEG C, the addition of catalyst is carried out in fact from 0.0 to 1.5g/L
Test.Fig. 7 (a, c) shows that, with catalyst concn increase phenol degradation efficiency enhancing, COD removal also increases；Work as MoS2Catalysis
When the concentration of agent reaches 1.5g/L, the clearance that the degradation rate of simulation phenolic waste water is 96.5%, COD is about 60%.Due to catalysis
The increase of agent concentration causes the increase of the quantity of the photon and avtive spot absorbed on catalyst surface, and causes phenol degrading to increase
Strong and COD removes increase.Pseudo first-order reaction kinetics equation is to the applicability of the catalytic degradation of catechol by each catalyst
- ln (the C/C of concentration0) good linear between t figures confirms that Fig. 7 (b) is clearly illustrated, as catalyst concn increases, companion
With the observed rate constant Kapp increases of catalyst, observed rate constant Kapp values when catalyst concn is 1.5g/L are
0.1267, reach peak.Therefore, in order to avoid catalyst excess using and ensure effective photonic absorption, in our current research
Optimum catalyst concentration is used as using 1.5g/L.
Claims (3)
1. a kind of mimetic enzyme catalyst for catalytic degradation phenol, it is characterised in that the preparation method of the catalyst is：
（1）In molar ratio 1：1 ~ 5 weighs Na2MoO4·2H2O and NH2CSNH2, plus distilled water and the dissolving under ultrasonic wave added, it is designated as
Solution A；
（2）Polyvinylpyrrolidone is added into solution A（PVP）, polyethylene glycol（PEG）, cetyl trimethylammonium bromide
（CTAB）、Na2SiO3·9H2O, sodium citrate, polyethylene glycol PEG6000 one or more, addition account for the 5 ~ 30% of total amount,
To being completely dissolved, solution B is designated as；
（3）With hydrochloric acid regulation regulation solution B acidity, pH is to 6 for regulation, and 30 ~ 60min is stirred at room temperature, solution C is designated as；
（4）Solution C is poured into ptfe autoclave, 6 ~ 24h, preferably 180 DEG C reaction 12h are reacted in 150 ~ 300 DEG C；
（5）After the completion of reaction, sample is taken out after the cooling completely of question response kettle, is centrifuged repeatedly respectively with distilled water and absolute ethyl alcohol
Washing 2 ~ 5 times, is freeze-dried more than 24h in freeze drying box.
2. a kind of mimetic enzyme catalyst for catalytic degradation phenol according to claim 1, it is characterised in that the catalysis
Agent is applied to phenol processes in degrading waste water：
（1）Reactor is fixed bed, preferred jacket glass reaction container；
（2）50 mg/L rhodamine Bs (RhB), 50 mg/L methylene blues (MB) are added into the waste water containing phenol, phenol is dense
Degree is not higher than 1500 mg.L-1, it is made into phenol solution P；
（3）Phenol solution P must react 30 ~ 60min in the dark before radiation of visible light, unrelated with molecular degradation to overcome
Concentration is reduced, and reaches that adsorption equilibrium begins to irradiation；
（4）Add electronics capturing agent H2O2, H2O2Concentration be 2 ~ 10 mmol/L when；
（5）Reaction condition：Reaction temperature is 20-60 DEG C, 1 ~ 12h of reaction time, catalyst concn=0.5 ~ 3.5g.L-1, pH value
For 2 ~ 12, simulated solar light source is used as from 300W ~ 1000W xenon lamps.
3. a kind of mimetic enzyme catalyst for catalytic degradation phenol according to claim 2, it is characterised in that the catalysis
When agent is applied to phenol in degrading waste water, preferable reaction temperature is 40 DEG C, reaction time 2h, catalyst concn=1.5g.L-1、pH=
8.0,500W xenon lamps, preferably H2O2Concentration be 8mmol/L.
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