CN106902828B - A kind of processing method of acetyl spiramycin antibiotic waste water - Google Patents
A kind of processing method of acetyl spiramycin antibiotic waste water Download PDFInfo
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- CN106902828B CN106902828B CN201710149793.7A CN201710149793A CN106902828B CN 106902828 B CN106902828 B CN 106902828B CN 201710149793 A CN201710149793 A CN 201710149793A CN 106902828 B CN106902828 B CN 106902828B
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- quantum dot
- carbon quantum
- nickel titanate
- acetyl spiramycin
- waste water
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- ZPCCSZFPOXBNDL-RSMXASMKSA-N spiramycin II Chemical compound O([C@H]1/C=C/C=C/C[C@@H](C)OC(=O)C[C@H]([C@@H]([C@H]([C@@H](CC=O)C[C@H]1C)O[C@H]1[C@@H]([C@H]([C@H](O[C@@H]2O[C@@H](C)[C@H](O)[C@](C)(O)C2)[C@@H](C)O1)N(C)C)O)OC)OC(C)=O)[C@H]1CC[C@H](N(C)C)[C@H](C)O1 ZPCCSZFPOXBNDL-RSMXASMKSA-N 0.000 title claims abstract description 50
- 229950006796 spiramycin ii Drugs 0.000 title claims abstract description 50
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 30
- 238000003672 processing method Methods 0.000 title claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 50
- 238000006731 degradation reaction Methods 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 13
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 229940078494 nickel acetate Drugs 0.000 claims description 7
- 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 description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 1
- -1 Nickel titanate compound Chemical class 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Abstract
The invention discloses a kind of processing methods of acetyl spiramycin antibiotic waste water, the following steps are included: carbon quantum dot-nickel titanate compound degradation agent is added in the acetyl spiramycin antibiotic waste water that concentration is 10mg/L~15mg/L, light-catalyzed reaction is carried out under the xenon lamp of 400W~600W, completes the degradation to acetyl spiramycin；The carbon quantum dot-nickel titanate compound degradation agent is made by following methods: (1) preparing nickel titanate precursor solution；(2) carbon quantum dot solution is prepared；(3) nickel titanate precursor solution and carbon quantum dot solution are mixed and carries out hydro-thermal reaction, precipitated product is post-processed, carbon quantum dot-nickel titanate compound degradation agent is obtained.The processing method has many advantages, such as that manufacturing cost is low, high treating effect.
Description
Technical field
The present invention relates to antibiotic waste water processing technology field more particularly to a kind of acetyl spiramycin antibiotic waste waters
Processing method.
Background technique
Antibiotics production process includes the processes such as microbial fermentation, filtering, extraction, crystallization, refinement, purification, and generation is given up
Water has the characteristics that organic concentration height, complicated component, there are bio-toxicity substance, coloration height, pH fluctuations greatly, intermittent discharge,
It is a kind of industrial wastewater difficult to deal with.Currently, it is main to the removal of antibiotic in water both at home and abroad or rely on it is conventional it is aerobic,
Anaerobism or anaerobism add aerobic bioremediation, but the drug resistance as possessed by antibiotic so that biological treatment mode without
Method normally plays a role, and pharmaceuticals industry Wastewater Pollutant discharge standard can not be fully achieved after processing.Therefore, find efficiently,
Practical antibiotic waste water processing method becomes the task of top priority of many enterprises.
Photocatalysis is one and is converted into the required energy of chemical reaction using luminous energy existing for nature, to generate catalysis
The technology of effect is decomposed to human body and the harmful organic substance of environment by this means, while not will cause the wave of resource
Take the formation with additional pollution.A large number of studies show that almost all of organic pollutant can be by effectively photocatalytic degradation, de-
Color, mineralising are inorganic molecules substance, to eliminate the pollution and harm to environment, therefore, photocatalytic degradation gradually becomes
Organic pollution administers one of the research hotspot in field, is expected to replace biological treatment, realization especially has life to antibiotic
Efficient, the stable degradation of the antibiotic of object toxicity.Most widely used at present is the TiO of ultraviolet excitation2Based photocatalyst, but
Only to have response in ultraviolet light range due to its greater band gap (3.2eV), in visible-range and do not have catalytic activity,
Thus TiO2Based photocatalyst is lower to the utilization rate of sunlight in use, and which greatly limits the realities of this kind of catalyst
Border application.Sight has been turned to the exploitation of novel visible active photocatalyst by Recent study personnel one after another, is developed at present
The semiconductor material that visible light catalyst has band gap relatively narrow, such as bismuth tungstate, nickel titanate, zinc ferrite.Under the irradiation of visible light,
Electronics in the relatively narrow semiconductor material valence band of this kind of band gap, which is excited on conduction band, forms electron-hole pair, causes oxygen respectively
Change reaction.However, still the recombination rate in its light induced electron and hole is too fast, to reduce its photocatalytic activity, it is therefore desirable to
Finding a kind of effective method reduces the recombination rate of this kind of semiconductor material light induced electron and hole, improves this kind of semiconductor material
To the photocatalytic degradation capability of organic pollutant especially antibiotic.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide it is a kind of it is easy to operate, low in cost,
The processing method of the acetyl spiramycin antibiotic waste water of high treating effect solves existing nickel titanate based photocatalyst light and urges
The problem of changing the active not high antibiotic low efficiency so as to cause photocatalytic degradation.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of processing method of acetyl spiramycin antibiotic waste water, comprising the following steps:
Carbon quantum dot-nickel titanate compound degradation agent is added to the acetyl spiramycin that concentration is 10mg/L~15mg/L to resist
In raw element waste water, the mass volume ratio of carbon quantum dot-nickel titanate compound degradation agent and acetyl spiramycin antibiotic waste water is 10g
~20g: 100L, light-catalyzed reaction is carried out under the xenon lamp of 400W~600W, xenon lamp and the acetyl spiramycin antibiotic are useless
The liquid level distance of water is 18cm~22cm, completes the degradation to acetyl spiramycin；
The carbon quantum dot-nickel titanate compound degradation agent is made by following methods:
(1) nickel acetate, butyl titanate and sodium citrate are added in organic solvent, are mixed evenly, obtain titanium
Sour nickel precursor solution；
(2) ethylenediamine is added in the aqueous solution of glucose, is reacted at 140 DEG C~220 DEG C after mixing evenly, the time is
3h~8h obtains carbon quantum dot solution；
(3) the resulting nickel titanate precursor solution of step (1) and the resulting carbon quantum dot solution of step (2) are mixed, is stirred
Hydro-thermal reaction is carried out at 120 DEG C~150 DEG C after mixing uniformly, and the time is 18h~for 24 hours, is centrifuged after completion of the reaction, to precipitated product
It is post-processed, obtains carbon quantum dot-nickel titanate compound degradation agent.
Preferably, in the step (1), the molar ratio of the nickel acetate, butyl titanate and sodium citrate is 1: 1: 0.5
~0.1.
Preferably, in the step (1), the organic solvent includes methanol, ethyl alcohol, ethylene glycol or glycerine.
Preferably, in the step (2), the ratio of the glucose, ethylenediamine and water is 5~6mol: 0.25~0.5L:
8~10L.
Preferably, in the step (3), the volume ratio of the nickel titanate precursor solution and carbon quantum dot solution is 25~
50: 2.5~5.
Preferably, in the step (3), the post-processing are as follows: successively using deionized water and ethyl alcohol to precipitated product into
Row washing, dry 6h~10h in the environment of temperature is 45 DEG C~65 DEG C.
The principle of the processing method of acetyl spiramycin antibiotic waste water of the present invention are as follows:
By hydrothermal synthesis method, carbon quantum dot can be made to be attached to the surface of nickel titanate, carbon quantum dot can receive metatitanic acid
Electronics in nickel conduction band, efficiently separates the photogenerated charge of nickel titanate, to inhibit the compound of charge, thus more electronics can be with
Along the conduction band network transmission of carbon quantum dot, and then the electron-hole service life of bismuth molybdate is promoted to extend, improves light induced electron
Utilization rate, so that the catalytic activity of catalyst is improved, oxidant or reducing agent hair in more electron hole pairs and solution
Raw reaction generates living radical, acetyl spiramycin molecule of degrading.
Compared with the prior art, the advantages of the present invention are as follows:
1, the processing method of acetyl spiramycin antibiotic waste water of the invention, using the compound drop of carbon quantum dot-nickel titanate
Agent is solved, is degraded under the visible light of 400W~600W to acetyl spiramycin, due to preparing carbon amounts using hydrothermal synthesis method
Sub- point-nickel titanate compound degradation agent can make carbon quantum dot be attached to the surface of nickel titanate, receive the electricity in nickel titanate conduction band
Son prevents the compound of charge, improves the catalytic activity of metatitanic acid Raney nickel.In addition, the present invention is using glucose as raw water heat seal
At carbon quantum dot, synthesized carbon quantum dot it is small-sized, lower energy photon can be absorbed under visible light, and release high energy light
Son further improves the photocatalytic activity of nickel titanate, thus place of the invention so that nickel titanate be excited to form electron hole pair
Reason method is high to the removal rate of acetyl spiramycin in industrial wastewater, up to 88% or more.
2, processing method of the invention is easy to operate, easy control of reaction conditions, low in cost, has potential industrialization
Application prospect.
Detailed description of the invention
Fig. 1 is carbon quantum dot-nickel titanate compound degradation agent of embodiment 1 and the nickel titanate photochemical catalyst light of comparative example 1
The relational graph of acetyl spiramycin in catalytic degradation waste water m- degradation efficiency when corresponding.
Fig. 2 is that carbon quantum dot-nickel titanate compound degradation agent circular response five times Photocatalytic Degradation Property of embodiment 1 is bent
Line chart.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection scope.
Embodiment 1:
A kind of processing method of photocatalytic degradation acetyl spiramycin antibiotic waste water, comprising the following steps:
A. the acetyl spiramycin solution that 100ml concentration is 10mg/L is added in the conical flask of 200ml, by 10mg carbon amounts
Sub- point-nickel titanate compound degradation agent is added in above-mentioned acetyl spiramycin solution, and one hour of magnetic agitation reaches in the dark
Adsorption equilibrium.With UV, visible light spectrophotometric determination concentration, represents initial liquid concentration to be degraded and be denoted as C0。
B. by addition carbon quantum dot-nickel titanate compound degradation agent acetyl spiramycin solution of step a in visible light light
The xenon lamp irradiation of source 500W is lower to be carried out light-catalyzed reaction and starts timing, and light source and liquid level distance are 20cm.Every 10min from every
Group reaction system in respectively draw 5ml solution, under the revolving speed of 5000r/min be centrifuged 5min after, Aspirate supernatant, with it is ultraviolet can
See acetyl spiramycin residual concentration in spectrophotometric determination supernatant and is denoted as C.After illumination reaction 60min, xenon is closed
Lamp.
In the present embodiment, carbon quantum dot-nickel titanate compound degradation agent is prepared with the following method:
(1) 2.48g nickel acetate, 3.4g butyl titanate and 1.47g sodium citrate are added in 100mL ethylene glycol, are mixed
Conjunction stirs evenly, and obtains nickel titanate precursor solution；
(2) glucose is dissolved in the glucose solution for being configured to that concentration is 0.6M in deionized water；Take the 10mL glucose
Solution is added 0.35mL ethylenediamine, reacts 6h at 180 DEG C after mixing evenly, obtain carbon quantum dot solution；
(3) by the resulting 50mL nickel titanate precursor solution of step (1) and the resulting 5mL carbon quantum dot solution of step (2)
Mixing, carries out hydro-thermal reaction at 150 DEG C after mixing evenly, and time 20h is centrifuged after completion of the reaction, successively uses deionization
Water and ethyl alcohol wash precipitated product, and dry 8h, it is compound to obtain carbon quantum dot-nickel titanate in the environment of temperature is 50 DEG C
Degradation agent.
Comparative example 1:
A kind of processing method of photocatalytic degradation acetyl spiramycin antibiotic waste water, comprising the following steps:
A. the acetyl spiramycin solution that 100ml concentration is 10mg/L is added in the conical flask of 200ml, by 10mg metatitanic acid
Nickel photochemical catalyst is added in above-mentioned acetyl spiramycin solution, and one hour of magnetic agitation reaches adsorption equilibrium in the dark.With
UV, visible light spectrophotometric determination concentration represents initial liquid concentration to be degraded and is denoted as C0。
B. by step a addition nickel titanate photochemical catalyst acetyl spiramycin solution visible light source 500W xenon lamp
Irradiation is lower to be carried out light-catalyzed reaction and starts timing, and light source and liquid level distance are 20cm.Every 10min from every group of reaction system
Interior each absorption 5ml solution, after being centrifuged 5min under the revolving speed of 5000r/min, Aspirate supernatant, with UV, visible light spectrophotometer
It measures acetyl spiramycin residual concentration in supernatant and is denoted as C.After illumination reaction 60min, xenon lamp is closed.
In the present embodiment, nickel titanate photochemical catalyst is prepared with the following method:
(1) 2.48g nickel acetate, 3.4g butyl titanate and 1.47g sodium citrate are added in 100mL ethylene glycol, are mixed
Conjunction stirs evenly, and obtains nickel titanate precursor solution；
(2) the resulting 50mL nickel titanate precursor solution of step (1) is subjected to hydro-thermal reaction at 150 DEG C, the time is
20h is centrifuged after completion of the reaction, is successively washed using deionized water and ethyl alcohol to precipitated product, the ring for being 50 DEG C in temperature
Dry 8h, obtains nickel titanate photochemical catalyst under border.
With C/C0Make the nickel titanate photochemical catalyst and embodiment to ratio 1 using light application time as abscissa for ordinate
Acetyl spiramycin in 1 carbon quantum dot-nickel titanate compound degradation agent wastewater by photocatalysis m- degradation efficiency when corresponding
Relational graph, as a result as shown in Figure 1, as seen from the figure, it is seen that light irradiate 30min after, carbon quantum dot-nickel titanate of embodiment 1 is multiple
It closes degradation agent and 95.2% is up to the degradation rate of acetyl spiramycin, and the nickel titanate photochemical catalyst of comparative example 1 shines in visible light
It penetrates after 60min and 80% is less than to the degradation rate of acetyl spiramycin, this shows that carbon quantum dot-nickel titanate of the invention is compound
The photocatalytic activity of degradation agent is much higher than single nickel titanate photochemical catalyst.
Embodiment 2:
The carbon quantum dot of embodiment 1-nickel titanate compound degradation agent is steady during photocatalytic degradation acetyl spiramycin
Qualitative research:
A. carbon quantum dot-nickel titanate the compound degradation agent for weighing 10mg embodiment 1, being added to 100ml concentration is 10mg/L
Acetyl spiramycin waste water in；The two phase anaerobic digestion system for being added to photochemical catalyst is placed on magnetic stirring apparatus,
It is protected from light stirring 1h and surveys its concentration with UV, visible light spectrophotometer to reach adsorption equilibrium, and be denoted as C0。
B. the acetyl spiramycin solution of the addition photochemical catalyst of step a is carried out under the xenon lamp of visible light source 500W
Light-catalyzed reaction simultaneously starts timing, and light source and liquid level distance are 20cm.After illumination reaction 60min, xenon lamp is closed.After reacting
Solution centrifuge separation, surveyed in supernatant with UV, visible light spectrophotometer and pollutant residual concentration C and calculate degradation efficiency.
C. carbon quantum dot-nickel titanate compound degradation agent after collection step b reaction, and be added to 100ml concentration again and be
In the waste water of the acetyl spiramycin of 10mg/L, adsorption equilibrium-photocatalytic degradation-calculating degradation efficiency-collection carbon quantum is repeated
Point-nickel titanate compound degradation agent process five times.Using the degradation efficiency of acetyl spiramycin as ordinate, with cycle-index for horizontal seat
Mark draws carbon quantum dot-nickel titanate compound degradation agent circular response five times photocatalysis performance curve graph, as shown in Fig. 2, by
After five circulations, carbon quantum dot-nickel titanate compound degradation agent still shows efficient photocatalysis performance, the degradation of five circulations
Efficiency is followed successively by 99.1%, 98.5%, 97.1%, 95.7% and 94.4%.Thus illustrate carbon quantum dot-prepared by the present invention
Nickel titanate compound degradation agent is a kind of stabilization and efficient new antibiotic composite photo-catalyst, has potential industrial applications
Prospect.
Embodiment 3:
A kind of processing method of photocatalytic degradation acetyl spiramycin antibiotic waste water, comprising the following steps:
A. it chooses Henan Zhumadian pharmaceutical factory's acetyl spiramycin and produces waste water, through detecting, acetyl spiramycin concentration
It is 10mg/L by the wastewater dilution to acetyl spiramycin concentration more than 200mg/L.
B. it is 10g by the ratio of the two phase anaerobic digestion system after carbon quantum dot-nickel titanate compound degradation agent and dilution:
Carbon quantum dot-nickel titanate compound degradation agent is added in the ratio of 100L in the two phase anaerobic digestion system after above-mentioned dilution, dark
Place's one hour of magnetic agitation reaches adsorption equilibrium.With UV, visible light spectrophotometric determination acetyl spiramycin concentration, represent
Initial liquid concentration to be degraded simultaneously is denoted as C0。
Wherein, carbon quantum dot-nickel titanate compound degradation agent is prepared by following methods:
(1) nickel acetate, butyl titanate and sodium citrate are added to ethylene glycol with the ratio that molar ratio is 1: 1: 0.5
In, it is mixed evenly, obtains nickel titanate precursor solution；
(2) glucose is dissolved in the glucose solution for being configured to that concentration is 0.6M in deionized water；Ethylenediamine is added to
The glucose solution, wherein the volume ratio of ethylenediamine and glucose solution is 0.5: 10, is reacted at 200 DEG C after mixing evenly
8h obtains carbon quantum dot solution；
(3) the resulting nickel titanate precursor solution of step (1) and the resulting carbon quantum dot solution of step (2) are mixed,
In, the volume ratio of nickel titanate precursor solution and carbon quantum dot solution is 30: 5, and it is anti-to carry out hydro-thermal at 150 DEG C after mixing evenly
It answers, the time is that 4h is centrifuged after completion of the reaction, is successively washed using deionized water and ethyl alcohol to precipitated product, is in temperature
Dry 8h, obtains carbon quantum dot-nickel titanate compound degradation agent in the environment of 50 DEG C.
C. simultaneously using the two phase anaerobic digestion system of the addition photochemical catalyst of the xenon lamp irradiating step b of visible light source 500W
Start timing, light source and liquid level distance are 20cm.After illumination reaction 60min, xenon lamp is closed.Aspirate supernatant after standing is used
Acetyl spiramycin residual concentration and C is denoted as in UV, visible light spectrophotometric determination supernatant.With C/C0For degradation rate, as a result
Show, it is seen that after light irradiates 60min, the carbon quantum dot-nickel titanate compound degradation agent of the present embodiment is to the acetyl in industrial wastewater
Spiramvcin degradation efficiency reaches 88.2%, this shows carbon quantum dot of the invention-nickel titanate compound degradation agent in degradation acetyl
There is good industrial applications prospect in spiramvcin waste water.
Be it is necessary to described herein finally: above embodiments are served only for making technical solution of the present invention further detailed
Ground explanation, should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention
The some nonessential modifications and adaptations made all belong to the scope of protection of the present invention.It is it is necessary to described herein finally: with
Upper embodiment is served only for being described in more detail technical solution of the present invention, should not be understood as to the scope of the present invention
Limitation, some nonessential modifications and adaptations that those skilled in the art's above content according to the present invention is made belong to
Protection scope of the present invention.
Claims (4)
1. a kind of processing method of acetyl spiramycin antibiotic waste water, comprising the following steps:
Carbon quantum dot-nickel titanate compound degradation agent is added to the acetyl spiramycin antibiotic that concentration is 10mg/L~15mg/L
In waste water, the mass volume ratio of carbon quantum dot-nickel titanate compound degradation agent and acetyl spiramycin antibiotic waste water be 10g~
20g: 100L, light-catalyzed reaction, xenon lamp and the acetyl spiramycin antibiotic waste water are carried out under the xenon lamp of 400W~600W
Liquid level distance be 18cm~22cm, complete degradation to acetyl spiramycin；
The carbon quantum dot-nickel titanate compound degradation agent is made by following methods:
(1) nickel acetate, butyl titanate and sodium citrate are added in organic solvent, are mixed evenly, obtain nickel titanate
Precursor solution；In the step (1), the molar ratio of the nickel acetate, butyl titanate and sodium citrate is 1: 1: 0.5~
0.1；
(2) ethylenediamine is added in the aqueous solution of glucose, is reacted at 140 DEG C~220 DEG C after mixing evenly, the time be 3h~
8h obtains carbon quantum dot solution；
(3) the resulting nickel titanate precursor solution of step (1) and the resulting carbon quantum dot solution of step (2) are mixed, stirring is equal
Carry out hydro-thermal reaction after even at 120 DEG C~150 DEG C, the time is 18h~for 24 hours, is centrifuged, carries out after completion of the reaction to precipitated product
Post-processing, obtains carbon quantum dot-nickel titanate compound degradation agent；In the step (3), the nickel titanate precursor solution and carbon amounts
The volume ratio of son point solution is 25~50: 2.5~5.
2. the processing method of acetyl spiramycin antibiotic waste water according to claim 1, which is characterized in that the step
(1) in, the organic solvent includes methanol, ethyl alcohol, ethylene glycol or glycerine.
3. the processing method of acetyl spiramycin antibiotic waste water according to claim 1, which is characterized in that the step
(2) in, the ratio of the glucose, ethylenediamine and water is 5~6mol: 0.25~0.5L: 8~10L.
4. the processing method of described in any item acetyl spiramycin antibiotic waste waters, feature exist according to claim 1~3
In, in the step (3), the post-processing are as follows: successively precipitated product is washed using deionized water and ethyl alcohol, in temperature
Dry 6h~10h in the environment of being 45 DEG C~65 DEG C.
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