CN106902828A - 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
- Publication number
- CN106902828A CN106902828A CN201710149793.7A CN201710149793A CN106902828A CN 106902828 A CN106902828 A CN 106902828A CN 201710149793 A CN201710149793 A CN 201710149793A CN 106902828 A CN106902828 A CN 106902828A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- carbon quantum
- waste water
- acetyl spiramycin
- nickel titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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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 52
- 229950006796 spiramycin ii Drugs 0.000 title claims abstract description 52
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 32
- 238000003672 processing method Methods 0.000 title claims abstract description 20
- 230000015556 catabolic process Effects 0.000 claims abstract description 44
- 238000006731 degradation reaction Methods 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- DGXKDBWJDQHNCI-UHFFFAOYSA-N dioxido(oxo)titanium nickel(2+) Chemical compound [Ni++].[O-][Ti]([O-])=O DGXKDBWJDQHNCI-UHFFFAOYSA-N 0.000 claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 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 10
- 239000000243 solution Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 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
- 239000001509 sodium citrate Substances 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- 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 5
- 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
- 238000012805 post-processing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 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 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- -1 Carbon quantum dot nickel titanate compound Chemical class 0.000 abstract 3
- 239000003054 catalyst Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000011083 sodium citrates Nutrition 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 238000005286 illumination Methods 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
- 238000005516 engineering process Methods 0.000 description 3
- 239000010842 industrial wastewater 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 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
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 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
- 230000003197 catalytic effect 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
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002171 ethylene diamines Chemical class 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
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method 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
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Physical Water Treatments (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of processing method of acetyl spiramycin antibiotic waste water, comprise the following steps：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, complete the degraded to acetyl spiramycin；The carbon quantum dot nickel titanate compound degradation agent is obtained by following methods：(1) nickel titanate precursor solution is prepared；(2) carbon quantum dot solution is prepared；(3) nickel titanate precursor solution and carbon quantum dot solution are mixed into water-filling thermal response, precipitated product is post-processed, obtain carbon quantum dot nickel titanate compound degradation agent.The processing method has the advantages 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 water
Processing method.
Background technology
Antibiotics production process include microbial fermentation, filtering, extraction, crystallization, refinement, refine etc. process, generation give up
The features such as water has organic concentration high, complicated component, there is bio-toxicity material, colourity high, big pH fluctuations, intermittent discharge,
It is class industrial wastewater difficult to deal with.At present, the removal both at home and abroad to antibiotic in water it is main or rely on it is conventional it is aerobic,
Anaerobism or anaerobism add aerobic bioremediation, but the resistance to the action of a drug having 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 treatment.Therefore, find efficiently,
Practical antibiotic waste water processing method turns into the task of top priority of many enterprises.
Photocatalysis is that the luminous energy existed using nature is converted into the energy needed for chemically reacting to produce catalysis
The technology of effect, is decomposed to human body and the harmful organic substance of environment, while not resulting in the wave of resource by this means
Take the formation with additional pollution.Numerous studies show, almost all of organic pollution can be by effectively photocatalytic degradation, de-
Color, mineralising are inorganic molecules material, so that the pollution and harm to environment are eliminated, therefore, photocatalytic degradation progressively turns into
Organic Pollution administers one of the study hotspot in field, is expected to replace biological treatment, realizes especially thering is life to antibiotic
Efficient, the stabilization degraded of the antibiotic of thing toxicity.Most widely used at present is the TiO of ultraviolet excitation2Based photocatalyst, but
It is, due to its greater band gap (3.2eV), only have response in ultraviolet light range, in visible-range and without catalysis activity,
Thus TiO2Utilization rate of the based photocatalyst in use to sunshine is relatively low, which greatly limits the reality of this kind of catalyst
Apply on border.Sight has been turned to Recent study personnel the exploitation of novel visible active photocatalyst one after another, exploitation at present
Visible light catalyst has the narrower semi-conducting material of band gap, such as bismuth tungstate, nickel titanate, zinc ferrite.Under the irradiation of visible ray,
Electronics in the narrower semi-conducting material valence band of this kind of band gap is excited to and electron-hole pair is formed on conduction band, and oxygen is caused respectively
Change reaction.However, still the recombination rate in its light induced electron and hole is too fast, so as to reduce its photocatalytic activity, it is therefore desirable to
The recombination rate in a kind of this kind of semi-conducting material light induced electron of effective method reduction and hole is found, this kind of semi-conducting material is improved
To the photocatalytic degradation capability of organic pollution especially antibiotic.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided it is a kind of it is simple to operate, with low cost,
The processing method of the acetyl spiramycin antibiotic waste water of high treating effect, solves existing nickel titanate based photocatalyst light and urges
Change activity not high so as to the problem for causing photocatalytic degradation antibiotic efficiency low.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of processing method of acetyl spiramycin antibiotic waste water, comprises the following steps：
Carbon quantum dot-nickel titanate compound degradation agent is added into the acetyl spiramycin that concentration is 10mg/L~15mg/L to resist
In raw element waste water, carbon quantum dot-nickel titanate compound degradation agent is 10g with the mass volume ratio of acetyl spiramycin antibiotic waste water
~20g: 100L, light-catalyzed reaction is carried out under the xenon lamp of 400W~600W, xenon lamp is useless with the acetyl spiramycin antibiotic
The liquid level distance of water is 18cm~22cm, completes the degraded to acetyl spiramycin；
The carbon quantum dot-nickel titanate compound degradation agent is obtained by following methods：
(1) nickel acetate, butyl titanate and sodium citrate are added in organic solvent, mixing and stirring obtains 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 stirring, the time is
3h~8h, obtains carbon quantum dot solution；
(3) the carbon quantum dot solution obtained by the nickel titanate precursor solution obtained by step (1) and step (2) is mixed, is stirred
Hydro-thermal reaction is carried out after mixing uniformly at 120 DEG C~150 DEG C, the time is 18h~24h, is centrifuged after completion of the reaction, to precipitated product
Post-processed, obtained carbon quantum dot-nickel titanate compound degradation agent.
Preferably, in the step (1), the mol 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 methyl alcohol, ethanol, 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 for 25~
50: 2.5~5.
Preferably, in the step (3), the post processing is：Precipitated product is entered using deionized water and ethanol successively
Row washing, 6h~10h is dried in the environment of being 45 DEG C~65 DEG C in temperature.
The principle of the processing method of acetyl spiramycin antibiotic waste water of the present invention is：
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, so as to suppress the compound of electric charge, thus more electronics can be with
Along the conduction band network transmission of carbon quantum dot, and then promote the electron-hole life of bismuth molybdate, improve light induced electron
Utilization rate, so that the catalysis activity of catalyst is improved, oxidant or the reducing agent hair in more electron hole pairs and solution
Raw reaction generation living radical, acetyl spiramycin molecule of degrading.
Compared with prior art, the advantage of the invention is that：
1st, the processing method of acetyl spiramycin antibiotic waste water of the invention, using the compound drop of carbon quantum dot-nickel titanate
Solution agent, degrades under the visible ray 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 electric charge, improves the catalysis activity of metatitanic acid Raney nickel.In addition, the present invention with glucose be raw water heat seal
Into carbon quantum dot, synthesized carbon quantum dot it is small-sized, can under visible light absorb lower energy photon, and discharge high energy light
Son, so as to excite nickel titanate to form electron hole pair, further increases the photocatalytic activity of nickel titanate, thus place of the invention
Reason method is high to the clearance of acetyl spiramycin in industrial wastewater, up to more than 88%.
2nd, processing method of the invention is simple to operate, easy control of reaction conditions, with low cost, with potential industrialization
Application prospect.
Brief description of the drawings
Fig. 1 is the carbon quantum dot-nickel titanate compound degradation agent of embodiment 1 and the nickel titanate photochemical catalyst light of comparative example 1
The graph of a relation of m- degradation efficiency when corresponding of the acetyl spiramycin in catalytic degradation waste water.
Fig. 2 is bent for the Photocatalytic Degradation Property of the carbon quantum dot-nickel titanate compound degradation agent circular response five times of embodiment 1
Line chart.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection domain.
Embodiment 1：
A kind of processing method of photocatalytic degradation acetyl spiramycin antibiotic waste water, comprises the following steps：
A. it is the acetyl spiramycin solution of 10mg/L 100ml concentration to be 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, in the dark one hour of magnetic agitation reach
Adsorption equilibrium.With UV, visible light spectrophotometric determination concentration, represent initial liquid concentration to be degraded and be designated as C0。
B. by the acetyl spiramycin solution of the addition carbon quantum dot-nickel titanate compound degradation agent of step a in visible ray light
Light-catalyzed reaction being carried out under the xenon lamp irradiation of source 500W and starting timing, light source is 20cm with liquid level distance.Every 10min from every
It is each in the reaction system of group to draw 5ml solution, after 5min is centrifuged under the rotating speed of 5000r/min, Aspirate supernatant, with it is ultraviolet can
See in spectrophotometric determination supernatant acetyl spiramycin residual concentration and be designated as C.After after illumination reaction 60min, xenon is closed
Lamp.
In the present embodiment, carbon quantum dot-nickel titanate compound degradation agent is adopted and prepared with the following method：
(1) 2.48g nickel acetates, 3.4g butyl titanates and 1.47g sodium citrates are added in 100mL ethylene glycol, are mixed
Conjunction stirs, and obtains nickel titanate precursor solution；
(2) glucose is dissolved in deionized water the glucose solution for being configured to that concentration is 0.6M；Take the 10mL glucose
Solution, adds 0.35mL ethylenediamines, and 6h is reacted at 180 DEG C after stirring, and obtains carbon quantum dot solution；
(3) by the 5mL carbon quantum dot solution obtained by the 50mL nickel titanates precursor solution obtained by step (1) and step (2)
Mixing, carries out hydro-thermal reaction at 150 DEG C after stirring, the time is 20h, is centrifuged after completion of the reaction, successively using deionization
Water and ethanol are washed to precipitated product, and 8h is dried in the environment of being 50 DEG C in temperature, are obtained carbon quantum dot-nickel titanate and are combined
Degradation agent.
Comparative example 1：
A kind of processing method of photocatalytic degradation acetyl spiramycin antibiotic waste water, comprises the following steps：
A. it is the acetyl spiramycin solution of 10mg/L 100ml concentration to be added in the conical flask of 200ml, by 10mg metatitanic acids
Nickel photochemical catalyst is added in above-mentioned acetyl spiramycin solution, in the dark one hour of magnetic agitation reach adsorption equilibrium.With
UV, visible light spectrophotometric determination concentration, represents initial liquid concentration to be degraded and is designated as C0。
B. step a is added into the acetyl spiramycin solution of nickel titanate photochemical catalyst in the xenon lamp of visible light source 500W
Light-catalyzed reaction is carried out under irradiation and starts timing, light source is 20cm with liquid level distance.Every 10min from every group of reaction system
Interior each absorption 5ml solution, after 5min is centrifuged under the rotating speed of 5000r/min, Aspirate supernatant uses UV, visible light spectrophotometer
Determine and acetyl spiramycin residual concentration and be designated as C in supernatant.After after illumination reaction 60min, xenon lamp is closed.
In the present embodiment, nickel titanate photochemical catalyst is adopted and prepared with the following method：
(1) 2.48g nickel acetates, 3.4g butyl titanates and 1.47g sodium citrates are added in 100mL ethylene glycol, are mixed
Conjunction stirs, and obtains nickel titanate precursor solution；
(2) the 50mL nickel titanates precursor solution obtained by step (1) is carried out into hydro-thermal reaction at 150 DEG C, the time is
20h, is centrifuged after completion of the reaction, and precipitated product is washed using deionized water and ethanol successively, in the ring that temperature is 50 DEG C
8h is dried under border, nickel titanate photochemical catalyst is obtained.
With C/C0It is ordinate, with light application time as abscissa, makees the nickel titanate photochemical catalyst and embodiment to ratio 1
M- degradation efficiency when acetyl spiramycin in 1 carbon quantum dot-nickel titanate compound degradation agent wastewater by photocatalysis is corresponding
Graph of a relation, as a result as shown in figure 1, as seen from the figure, it is seen that after light irradiation 30min, the carbon quantum dot-nickel titanate of embodiment 1 is multiple
Close 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 ray
Penetrate the degradation rate after 60min to acetyl spiramycin and be less than 80%, this shows, carbon quantum dot-nickel titanate of the invention is combined
The photocatalytic activity of degradation agent is far above 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 of 10mg embodiments 1 is weighed, is 10mg/L added to 100ml concentration
Acetyl spiramycin waste water in；The two phase anaerobic digestion system that with the addition of photochemical catalyst is placed on magnetic stirring apparatus,
Lucifuge stirs 1h to reach adsorption equilibrium, surveys its concentration with UV, visible light spectrophotometer, and be designated 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 is 20cm with liquid level distance.After after illumination reaction 60min, xenon lamp is closed.After reacting
Solution centrifugal separate, surveyed in supernatant with UV, visible light spectrophotometer and pollutant residual concentration C and calculate degradation efficiency.
C. the reacted carbon quantum dots of collection step b-nickel titanate compound degradation agent, 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.Degradation efficiency with acetyl spiramycin, as ordinate, is horizontal seat with cycle-index
Mark, draws the photocatalysis performance curve map of carbon quantum dot-nickel titanate compound degradation agent circular response five times, as shown in Fig. 2 by
After five circulations, carbon quantum dot-nickel titanate compound degradation agent still shows efficient photocatalysis performance, five degradeds of circulation
Efficiency is followed successively by 99.1%, 98.5%, 97.1%, 95.7% and 94.4%.Thus illustrate the present invention prepared by carbon quantum dot-
Nickel titanate compound degradation agent is a kind of stabilization and efficient new antibiotic composite photo-catalyst, with potential industrial applications
Prospect.
Embodiment 3：
A kind of processing method of photocatalytic degradation acetyl spiramycin antibiotic waste water, comprises the following steps：
A. Henan Zhumadian pharmaceutical factory acetyl spiramycin production waste water, after testing, acetyl spiramycin concentration are chosen
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 two phase anaerobic digestion system of the ratio of 100L 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 designated 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 by 1: 1: 0.5 ratio of mol ratio
In, mixing and stirring obtains nickel titanate precursor solution；
(2) glucose is dissolved in deionized water the glucose solution for being configured to that concentration is 0.6M；Ethylenediamine is added to
The glucose solution, wherein ethylenediamine are 0.5: 10 with the volume ratio of glucose solution, are reacted at 200 DEG C after stirring
8h, obtains carbon quantum dot solution；
(3) the carbon quantum dot solution obtained by the nickel titanate precursor solution obtained by step (1) and step (2) is mixed, its
In, the volume ratio of nickel titanate precursor solution and carbon quantum dot solution is 30: 5, hydro-thermal is carried out at 150 DEG C after stirring anti-
Should, the time is that 4h is centrifuged after completion of the reaction, and precipitated product is washed using deionized water and ethanol successively, is in temperature
8h is dried in the environment of 50 DEG C, carbon quantum dot-nickel titanate compound degradation agent is obtained.
C. the two phase anaerobic digestion system of addition photochemical catalyst of the xenon lamp irradiating step b of visible light source 500W is used simultaneously
Start timing, light source is 20cm with liquid level distance.After after illumination reaction 60min, xenon lamp is closed.Aspirate supernatant after standing, uses
Acetyl spiramycin residual concentration and C is designated as in UV, visible light spectrophotometric determination supernatant.With C/C0It is degradation rate, as a result
Show, it is seen that after light irradiation 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%, and this shows, carbon quantum dot of the invention-nickel titanate compound degradation agent is in degraded acetyl
There is good industrial applications prospect in spiramvcin waste water.
Finally be necessary described herein be：Above example is served only for making further in detail technical scheme
Ground explanation, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art's the above of the invention
Some the nonessential modifications and adaptations made belong to protection scope of the present invention.Finally be necessary described herein be：With
Upper embodiment is served only for being described in more detail technical scheme, it is impossible to be interpreted as to the scope of the present invention
Limitation, some nonessential modifications and adaptations that those skilled in the art's the above of the invention is made belong to
Protection scope of the present invention.
Claims (6)
1. a kind of processing method of acetyl spiramycin antibiotic waste water, comprises 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 for 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 degraded to acetyl spiramycin；
The carbon quantum dot-nickel titanate compound degradation agent is obtained by following methods：
(1) nickel acetate, butyl titanate and sodium citrate are added in organic solvent, mixing and stirring obtains nickel titanate
Precursor solution；
(2) add ethylenediamine in the aqueous solution of glucose, after stirring at 140 DEG C~220 DEG C react, the time be 3h~
8h, obtains carbon quantum dot solution；
(3) the carbon quantum dot solution obtained by the nickel titanate precursor solution obtained by step (1) and step (2) is mixed, stirring is equal
Hydro-thermal reaction is carried out after even at 120 DEG C~150 DEG C, the time is 18h~24h, is centrifuged after completion of the reaction, and precipitated product is carried out
Post processing, obtains carbon quantum dot-nickel titanate compound degradation agent.
2. the processing method of acetyl spiramycin antibiotic waste water according to claim 1, it is characterised in that the step
(1) in, the mol ratio of the nickel acetate, butyl titanate and sodium citrate is 1: 1: 0.5~0.1.
3. the processing method of acetyl spiramycin antibiotic waste water according to claim 2, it is characterised in that the step
(1) in, the organic solvent includes methyl alcohol, ethanol, ethylene glycol or glycerine.
4. the processing method of acetyl spiramycin antibiotic waste water according to claim 1, it is characterised in that the step
(2) in, the ratio of the glucose, ethylenediamine and water is 5~6mol: 0.25~0.5L: 8~10L.
5. the processing method of acetyl spiramycin antibiotic waste water according to claim 1, it is characterised in that the step
(3) in, the nickel titanate precursor solution is 25~50: 2.5~5 with the volume ratio of carbon quantum dot solution.
6. the processing method of the acetyl spiramycin antibiotic waste water according to any one of Claims 1 to 4, its feature exists
In in the step (3), the post processing is：Precipitated product is washed using deionized water and ethanol successively, in temperature
To dry 6h~10h in the environment of 45 DEG C~65 DEG C.
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