CN110201719A - A kind of pharmacy sewage administering method - Google Patents

A kind of pharmacy sewage administering method Download PDF

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Publication number
CN110201719A
CN110201719A CN201910491280.3A CN201910491280A CN110201719A CN 110201719 A CN110201719 A CN 110201719A CN 201910491280 A CN201910491280 A CN 201910491280A CN 110201719 A CN110201719 A CN 110201719A
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nano silica
immobilized
quinoline
sewage
metal complex
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CN110201719B (en
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黄裕娥
张东海
仓理
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Beijing Xingyoutong Technology Co ltd
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Nanjing Polytechnic Institute
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    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
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    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/38—Lanthanides other than lanthanum
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

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Abstract

The invention belongs to technical field of sewage, and in particular to a kind of pharmacy sewage processing method.The present invention uses nano silica for carrier, and the 8-hydroxyquinoline derivative containing carbon-carbon double bond is aggregated to carrier surface, then forms the immobilized quinoline metal complex of nano silica by molecular self-assembling with metal ion.The immobilized quinoline metal complex of nano silica of the present invention can be catalyzed hydrogen peroxide degradation high concentration penicillin sewage, and penicillin degradation rate reaches 98% or more, COD removal rate and is up to 85%-90%；In addition, performance is stablized, and recycling is facilitated since metal complex of the present invention is organic (8-hydroxyquinoline derivative) inorganic (silica) hybrid systems, recovery is supported.

Description

A kind of pharmacy sewage administering method
Technical field
The invention belongs to technical field of sewage, and in particular to a kind of pharmacy sewage processing method more specifically relates to A kind of and method of the quinoline metal complex catalytic wet oxidation that nano silica is immobilized processing penicillin production sewage.
Background technique
Penicillin belongs to the antibiotic of beta-lactam, is one of most popular a kind of antibacterials of the mankind.It is such Antibiotic in conjunction with the penicillin binding protein of bacterium surface by interfering the synthesis of cell wall, to generate antibacterial action, has Have that antibacterial activity is strong, toxicity is low, low-cost advantage.Since penicillin bacteriostasis property is good, sewage can give birth to during processing It is poor to change performance.
There are many deficiencies for processing of the water treatment technology to antibiotic in currently available technology, if the bioanalysis period is long, And since microorganism is by the inhibiting effect of antibiotic, the effect for removing antibiotic is undesirable；Physical method (such as absorption-film filtering) Secondary pollution can be generated, can not achieve removal truly；Ozone and liquid chlorine oxidizing process higher cost, stability is poor, And since the reaction of chlorine oxygen can also generate the very strong chlorite by-product of toxicity in chlorination method；Ultraviolet light rule will be by water The influence of other organic matters, and the penetration power difference of ultraviolet light is also a problem.
(Yellow River Conservancy Technical Institute's journal, the 1st phase in 2017,51-54 pages, bismuth oxyiodide is visible by Chen Xiliang et al. Photocatalytic degradation penicillin research) at a lower temperature, using solvent structure bismuth oxyiodide nanometer sheet assembling Micro-structure, the bismuth oxyiodide photocatalytic degradation penicillin under visible optical drive.This method degradation condition is mild and can be by mould The degradation of element is extended under visible light by ultraviolet light, but the degradation rate of its penicillin is lower (degradation rate is only 60% or so).
Li Peng et al. (CN 105585102A) handles the side of penicillin production sewage using low-temperature catalyzed wet oxidation process Method, using one or more of copper sulphate, ferrous sulfate, manganese chloride, zinc sulfate mixture as catalyst, using 0.5~ The air of 3MPa as oxygen source, 130~170 DEG C the reaction time 1~2 hour.Final COD removal rate > 60%, color removal Big 99%, the B/C of rate rises to 0.8 by 0.35.This method has industrial applications prospect, and biochemistry is conducive to after processing；But in the technique With water base Cheng Junxiang in pyroreaction system, the later period can not recycle catalyst, and the catalytic component of introducing further increases The difficulty of subsequent sewage treatment；It is needed in the degradation rate and degradation process of penicillin in high temperature in addition, not referred in the patent It is carried out under high pressure, energy consumption and equipment requirement are higher.
Solid metallic-organic backbone complex is formed using organic micromolecule ligand and metal, it is wet as catalyst Formula hydrogen peroxide oxidation process solves the problems, such as that catalyst is difficult to recycle.Southeast China University Xu Yang (is based on wet type in its Master's thesis The copper-containing metal of catalytic oxidation technologies-organic framework catalyst research, Southeast China University's master thesis, 01 month 2016) with Copper nitrate is copper source, with 1,3,5- trimesic acid (H3BTC) or 1,4- terephthalic acid (TPA) is that ligand is prepared copper-containing metal-and had Machine skeleton catalysis material, catalysis hydrogen peroxide degradation of phenol have preferable phenol removal rate and COD degradation rate.But the test system It is to use pure phenol system, and phenol itself has oxidizable property, removal is relatively easy.
So exploitation is suitble to the catalysis material of the practical penicillin sewage of catalysis, provide a kind of degradation condition mildly, degradation rate High penicillin processing method is current industry urgent problem to be solved.
Summary of the invention
The purpose of the present invention is overcoming in penicillin sewage in the prior art, penicillin degradation rate is low, degradation condition is harsh Defect, the invention proposes a kind of pharmacy sewage processing methods.The present invention uses nano silica for carrier, will contain carbon carbon The 8-hydroxyquinoline derivative of double bond is aggregated to carrier surface, then forms nanometer two by molecular self-assembling with metal ion The immobilized quinoline metal complex of silica；Type by adjusting organic ligand and metal ion adjusts catalytic wet oxidation Performance filters out the complex for having efficient catalytic degradation penicillin sewage.The degradable high concentration penicillin sewage of the present invention, it is green Mycin degradation rate reaches 98% or more, COD removal rate and is up to 85%-90%；In addition, since metal complex of the present invention is organic (8-hydroxyquinoline derivative) inorganic (silica) hybrid systems, performance are stablized, and recycling is facilitated, and support recovery.
According to the first aspect of the invention, the present invention provides a kind of cooperations of quinoline metal that nano silica is immobilized The preparation method of object, including nano silica successively to be passed through to methane sulfonic acid acidification, using the silane idol containing carbon-carbon double bond Join agent surface treatmentization the modified nano silica in surface, then under the action of radical initiator with contain carbon carbon pair The 8-hydroxyquinoline derivative of key carries out graft polymerization reaction, and the aqueous solution for being eventually adding metal salt is formed by molecular self-assembling The immobilized quinoline metal complex of nano silica.
The preparation method, specifically comprises the following steps:
1) nano silica is placed in the aqueous solution of methanesulfonic of 0.5mol/L the ultrasound 2-4h at 30-50 DEG C, so Filtration drying obtains hydroxylating nano silica afterwards；Nano silica is handled using under acid condition, increases dioxy The hydroxy radical content on SiClx surface；
2) hydroxylating nano silica is dispersed in 80V% methanol aqueous solution and is stirred evenly, be then added dropwise and contain carbon The methanol solution of the silane coupling agent of carbon double bond is warming up to 40-60 DEG C of stirring 2-8h after completion of dropwise addition, be cooled to room temperature, filtering, subtract Press dry the dry nano silica for obtaining surface and being modified；The silane coupling agent additional amount containing carbon-carbon double bond is hydroxylating nanometer The 1-5% of silica weight；The present invention using the silane coupling agent containing carbon-carbon double bond to hydroxylating nano silica into Row surface is modified, on the one hand avoids the reunion between Nano particles of silicon dioxide, on the other hand passes through silane coupling agent for double bond It is introduced into nano-silica surface, provides reaction site for subsequent organic polymer；
3) nano silica for taking the surface 10g modified, which is placed in dehydrated alcohol, to stir evenly, and free radical is then added and draws Hair agent and 5-10mmol contain the 8-hydroxyquinoline derivative of carbon-carbon double bond, are warming up to reflux polymerization reaction 2-3h；Then it is added The aqueous solution of the metal salt of 5-10mmol, back flow reaction 10-24h carries out molecular self-assembling after completion of dropwise addition, is cooled to room temperature, mistake Filter, dry the immobilized quinoline metal complex of nano silica after anhydrous methanol elution.
Preferably, the silane coupling agent containing carbon-carbon double bond described in step 2) includes (vinyl three of silane coupling A -151 Ethoxysilane), silane coupling A -171 (vinyltrimethoxysilane), the ((β-first of vinyl three of silane coupling A -172 Oxygroup ethyoxyl) silane), silane coupling agent KH-560 (γ-glycidyl ether oxygen propyl trimethoxy silicane) or silane coupled The combination of one of agent KH-570 (γ-methacryloxypropyl trimethoxy silane) or arbitrary proportion；
Preferably, the 8-hydroxyquinoline derivative containing carbon-carbon double bond described in step 3) be 7- allyl -8-hydroxyquinoline, 2- [2- (2- aminophenyl) vinyl] -8-hydroxyquinoline, 2- vinyl-8-hydroxyquinoline, further preferably 2- vinyl - 8-hydroxyquinoline；The present invention is drawn with the carbon-carbon double bond in silane coupling agent in free radical using the carbon-carbon double bond contained in ligand It is polymerize under the action of hair agent, so that organic micromolecule ligand is grafted to nanometer silicon dioxide surface, while utilizing organic The hydroxyl oxygen of 8-hydroxyquinoline and nitrogen and metal ion are self-assembly of complex in smaller ligand skeleton, are had using different Machine smaller ligand and metal ion adjust the activity of complex-catalyzed oxidation.
Preferably, the step 3) metal salt is CoCl2、CuCl2, manganese acetate (III), MnSO4、Ce(NO3)3Or its correspondence Any one in hydrate；Those skilled in the art can also be carried out using other cobalt salt, mantoquita, manganese salt or cerium salts of equal value Substitution.
Preferably, the 8-hydroxyquinoline derivative containing carbon-carbon double bond described in step 3) is 2- vinyl-8-hydroxyquinoline, The metal salt is CuCl2Or Ce (NO3)3.2- vinyl-8-hydroxyquinoline and CuCl2Or Ce (NO3)3The gold being self-assembly of Metal complex catalytic oxidation activity is high, and cost is compared with 7- allyl -8-hydroxyquinoline, 2- [2- (2- aminophenyl) ethylene Base] -8-hydroxyquinoline is low.
According to another aspect of the present invention, the present invention provides a kind of cooperations of quinoline metal that nano silica is immobilized The purposes of object is used for catalytic degradation penicillin sewage in the presence of oxidant.
Preferably, described in the presence of oxidant, it is used for catalytic degradation penicillin sewage, is specifically comprised the following steps:
1) penicillin sewage is obtained into filtrate using plate and frame filter press filter and remove suspended substances, alkali tune is then used into filtrate Section system pH to 4-7；The filtrate is at rufous, pH=3-4, CODcr=16000-17650mg/L, B/C=0.31-0.34, Penicillin Content=620-650mg/L；
2) the immobilized quinoline metal complex of the nano silica and oxidant are added into sewage at 20-80 DEG C Stop reaction after reacting 1-6h, the immobilized quinoline metal complex of filtering removal nano silica obtains water purification.
Preferably, the oxidant is sodium hypochlorite, H2O2, further preferably H2O2；Relative to sodium hypochlorite hydrogen peroxide It is more environmentally-friendly, sodium chloride can be generated after hypochlorite oxidation, and sewage salt content is caused to increase.
Preferably, the oxidant is H2O2, going described in every 1L oil removal to obtain, that nano silica is added in filtrate is immobilized Quinoline metal complex 300-500mg, H2O2Dosage be 60-100ml concentration be 30wt%.
Preferably, step 2) reacts 1-6h at 20-50 DEG C；In wet-type oxidation degradation, as temperature increases, penicillin and The removal rate of COD increases, and especially degradation rate is accelerated, and basic 40min can be completed；Temperature is more than penicillin drop after 50 DEG C Solution rate is substantially unchanged, but COD removal rate can decline, and reason is under high temperature that hydrogen peroxide can thermally decompose, and be changed into water And oxygen, cause the hydroxyl radical free radical generated to reduce, and the quinoline metal cooperation that nano silica prepared by the present invention is immobilized Object can not efficiently use active oxygen, so that the organic matter comprising penicillin is rested on oxidation intermediate state, can not make organic matter mine completely Change, COD removal rate is caused to decline.
Compared with prior art, the present invention has following remarkable result
(1) present invention is for the first time using silica as carrier, using the 8-hydroxyquinoline derivative that contains carbon-carbon double bond as having Machine ligand forms the immobilized quinoline metal complex of nano silica with metal salt；Pass through selection organic ligand and metal salt Type adjust catalytic wet oxidation activity；
(2) the immobilized quinoline metal complex of nano silica of the present invention can be wet under the temperate condition of normal temperature and pressure Formula oxidative degradation penicillin；Air oxidation compared to high temperature and pressure is easier to operate to, and energy consumption is lower；
(3) present invention is using Ce as source metal, the nano silica prepared using 2- vinyl-8-hydroxyquinoline as ligand Immobilized quinoline metal complex, catalysis wet-type oxidation degradation penicillin can be degradable, and COD removal rate is in 85%-90% Between；
(4) the immobilized quinoline metal complex of nano silica of the present invention can be dirty with catalytic degradation high concentration penicillin Water has actual application prospect.
(5) the immobilized quinoline metal complex of nano silica of the present invention is convenient separates from system, being capable of recovery set With having certain cost advantage.
Explanation of nouns: CODcr- COD is measured using dichromate titration (GB11914-89)；BOD5It is biochemical Oxygen demand is measured using dilution and inocalation method (HJ505-2009)；B/C- sewage biochemical indicator, i.e. BOD5With CODCrRatio Value；Penicillin Content-uses high performance liquid chromatography.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the immobilized quinoline metal complex Si@Ce/Q of nano silica prepared by the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the immobilized quinoline metal complex Si@Ce/Q of nano silica prepared by the present invention.
Specific embodiment
Penicillin sewage comes from practical pharmacy sewage, and filter and remove suspended substances and gelling object obtain treatment sewage before testing, Specific condition of water quality is as follows after filtering: sewage is at rufous, pH=3-4, CODcr=16854mg/L, B/C=0.33, penicillin Content=650mg/L.
Nano silica is from Beijing Deco Dao Jin Science and Technology Ltd., average grain diameter: 30nm；Specific surface area: 600m2/g；Remaining raw materials and reagents is conventional commercial chemical industry rank raw material.
Embodiment 1
1) 100g nano silica is placed in the aqueous solution of methanesulfonic that 200ml concentration is 0.5mol/L in 30-50 Then ultrasound 2-4h at DEG C is filtered, is dried under reduced pressure to obtain hydroxylating nano silica at 35-40 DEG C；
2) 100g hydroxylating nano silica is dispersed in 200ml concentration is to stir evenly in 80V% methanol aqueous solution, Then the methanol solution (A-171 containing 5g) and 0.05ml acetic acid of 50ml silane coupling A -171 is added dropwise；It is warming up to after completion of dropwise addition 40-60 DEG C of stirring 6-8h is cooled to room temperature, filtering, is dried under reduced pressure to obtain the modified nano silica in surface；
3) nano silica for taking the surface 10g modified, which is placed in dehydrated alcohol, to stir evenly, and it is free that 0.5g is then added Base initiator A IBN and 10mmol organic ligand is warming up to reflux polymerization reaction 2-3h；Then the metal salt of 10mmol is added Aqueous solution, back flow reaction 18-24h carries out molecular self-assembling after completion of dropwise addition, room temperature, filtering is cooled to, after anhydrous methanol elution Dry the immobilized metal complex of nano silica.
In order to remove because complicated component influences the catalytic performance of complex in practical penicillin sewage, so as to more acurrate verifying The effect of different ligands and metal ion, use self-control 3000mg/L benzylpenicillin sodium solution carry out wet oxidation Performance Evaluation (with The North China pharmacy penicillin bulk pharmaceutical chemicals that purity is 99%, are formulated using purified water, with sulphur acid for adjusting pH to 4.6), with mould Plain degradation rate R% (being detected using HPLC, according to the concentration calculation of the penicillin of degradation front and back) and CODcr removal rate T% (according to The CODcr of degradation front and back is calculated) profile error object is screened for evaluation index.
Oxidation degradation method is as follows: 1L concentration is that the dioxygen that concentration is 30wt% is added in 3000mg/L benzylpenicillin sodium solution It is anti-to carry out wet oxidation under room temperature (25 DEG C) by the complex 500mg of water 15ml, above-mentioned different metal salt and organic ligand preparation It answers, monitors in aqueous solution (, the front and back twice change rate primary every 20min sampling and testing of CODcr removal rate T% when no longer changing It is considered as less than 1% and no longer changes), penicillin degradation rate R% and CODcr removal rate T% in each system is counted, as a result such as 1 institute of table Show:
The cooperation physical performance that different metal ions and ligand are prepared in 1 embodiment 1 of table
Sequence Metal ion Organic ligand R% T%
1 CuCl2 — 76.3 28.4
2 CuCl2 4-vinylpridine 92.1 39.4
3 CuCl2 2- vinyl-8-hydroxyquinoline 100 68.9
4 CoCl2 2- vinyl-8-hydroxyquinoline 98.2 36.6
5 Manganese acetate (III) 2- vinyl-8-hydroxyquinoline 100 50.7
6 MnSO4 2- vinyl-8-hydroxyquinoline 100 48.1
7 Ce(NO3)3 2- vinyl-8-hydroxyquinoline 100 88.2
8 Ce(NO3)3 7- allyl -8-hydroxyquinoline 100 86.2
9 Ce(NO3)3 2- [2- (2- aminophenyl) vinyl] -8-hydroxyquinoline 100 82.4
10 Ce(NO3)3 — 89.2 26.2
Note: sequence 1 indicates to use pure CuCl2Rather than complex form is used to wet oxidation；Sequence 10 is indicated using pure Ce (NO3)3Rather than complex form is used to wet oxidation.
Test result shows simple Ce (NO3)3Catalysis wet-type oxidation degradation ability is limited, and addition organic ligand can increase Strong activity；Using Ce (NO3)3The nanometer prepared as metal ion, 2- vinyl-8-hydroxyquinoline as organic ligand The immobilized quinoline cerium complexes of silica (being abbreviated as Si@Ce/Q) can effective catalysis wet-type oxidation degradation penicillin, penicillin Degradation rate R% up to 100% degradation, CODcr degradation rate T% is up to 88.2%.
Embodiment 2
To in embodiment 1 with Ce (NO3)3It is prepared as metal ion, 2- vinyl-8-hydroxyquinoline as organic ligand The immobilized quinoline cerium complexes of nano silica out (being abbreviated as Si@Ce/Q) carry out infrared and scanning electron microscope characterization, as a result It is as depicted in figs. 1 and 2:
Wave number is 1600cm in Fig. 1-1And 1556cm-1Peak can belong to C in the stretching vibration in quinoline ring and quinoline ring The stretching vibration of=N shows that 2- vinyl-8-hydroxyquinoline has loaded on silica.
Fig. 2 can be seen that the immobilized quinoline cerium complexes of the nano silica of preparation (being abbreviated as Si@Ce/Q) integral into Chondritic, partial size are nanoscale, at high degree of dispersion shape；Spherical nanostructure is capable of providing high-specific surface area, increase with The contact area of organic substance in sewage.
Embodiment 3
(Si@is abbreviated as to verify the immobilized quinoline cerium complexes of nano silica of the preparation of the embodiment of the present invention 1 Ce/Q) the wet oxidation ability in practical penicillin sewage, the present invention pass through filtering with microporous membrane to practical penicillin sewage Afterwards, using filtered sewage as evaluation object (water quality after processing: sewage is at rufous, pH=3-4, CODcr=16854mg/L, B/C=0.33, Penicillin Content=650mg/L) carry out catalytic wet oxidation, the method is as follows:
1L penicillin sewage is added sodium hydroxide and adjusts pH to 6-7, open stirring, 500mg Si@Ce/Q, 60ml is added The hydrogen peroxide that concentration is 30wt% carries out wet oxidation reaction under room temperature (25 DEG C), monitors CODcr removal rate T% in aqueous solution When no longer changing (primary every 20min sampling and testing, change rate is considered as no longer variation less than 1% twice for front and back), reached after 60min To balance, it is 72.8%, B/C=0.97 that statistics penicillin degradation rate R%, which is 100%, CODcr removal rate T%,.
The result shows that it is dirty to can be used for catalysis wet-type oxidation degradation high concentration penicillin using Si@Ce/Q prepared by the present invention Water, can be degradable by penicillin molecule；Its CODcr removal rate T% be 72.8%, show can not by penicillin (or will Other organic matters in penicillin sewage) permineralization；But its biochemical indicator B/C is increased to by 0.33 before handling 0.97, it can be ensured that sewage passes through biochemical treatment qualified discharge.
Embodiment 4
In order to further increase penicillin sewage mineralization degree, the present invention is on the basis of embodiment 3, to wet oxidation PH, Si@Ce/Q dosage, temperature, H2O2Dosage is further optimized, the method is as follows:
(sewage is at rufous, pH=3-4, CODcr=16854mg/ for penicillin sewage of the 1L after filtering with microporous membrane L, B/C=0.33, Penicillin Content=650mg/L), sodium hydroxide is added and adjusts pH, opens stirring, 200-1000mg is added Si@Ce/Q, 40-200ml concentration is that the hydrogen peroxide of 30wt% (will lead to H because temperature is excessively high at 20-70 DEG C2O2It decomposes, so pole Limit temperature is set as 70 DEG C) under carry out wet oxidation reaction, when monitoring that CODcr removal rate T% no longer changes in aqueous solution (every 20min sampling and testing is primary, and change rate is considered as no longer variation less than 1% twice for front and back), it counts CODcr under different condition and removes Rate T%；The results are shown in Table 2:
Result under the different wet oxidation conditions of table 2
Test result shows that the pH in wet oxidation process has larger impact to the removal rate of COD, and strong acid and highly basic may The coordinate bond in Si@Ce/Q can be made to be destroyed, lead to the leaching of Ce, to make the removal rate of COD decline, for penicillin dirt The pH of water is easily adjusted between pH=5-6；Temperature is unsuitable excessively high in oxidation process, and temperature is excessively high to cause dioxygen dilutional hyponatremia to decompose, Hydroxyl radical free radical is reduced；In addition, CODcr removal rate T% declines instead when dioxygen water consumption is excessive, Southeast China University's Xu Yang (base It is studied in copper-containing metal-organic framework catalyst of wet raw noodles, Southeast China University's master thesis, 2016 01 Month) copper metal-organic framework catalyst degradation of phenol for using when there is also similar conclusions.
Embodiment 5
With optimal conditions in embodiment 4, (pH=6.0, temperature are 40 DEG C, and Si@Ce/Q is added in 1L penicillin sewage The hydrogen peroxide 60ml of 500mg, 30wt%) to penicillin sewage treatment after, filter to isolate Si@Ce/Q, used after being recovered by filtration Then 60V% methanol aqueous solution supersound washing 2-4h is dried under vacuum to constant weight, reuse after dry (insufficient using fresh Si@Ce/Q is supplied), performance is applied to investigate it；The results are shown in Table 3 for weight recovery and catalytic wet oxidation:
3 Si@Ce/Q recovery result of table
Cycle-index The rate of recovery/% T%
0 — 89.1
1 88.9 88.6
2 88.1 86.4
3 89.2 85.1
4 88.4 79.2
5 87.9 65.2
Test result shows that the weight recovery of Si@Ce/Q maintains 88% or so, due to Si@Ce/Q during test Dosage is only 500mg, and separation loss is larger, so later period rate of recovery in amplification production can improve to some extent；But its Active access times are more than after 3 times, and it is the project for needing to solve in subsequent further production process that appearance, which sharply declines,.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of preparation method for the quinoline metal complex that nano silica is immobilized, including nano silica is successively passed through Cross methane sulfonic acid acidification, using the silane coupling agent surface treatmentization containing carbon-carbon double bond surface modification nanometer titanium dioxide Silicon；
Then it carries out being graft-polymerized with the 8-hydroxyquinoline derivative containing carbon-carbon double bond under the action of radical initiator anti- It answers, the aqueous solution for being eventually adding metal salt forms the immobilized quinoline metal complex of nano silica by molecular self-assembling.
2. preparation method according to claim 1, it is characterised in that: specifically comprise the following steps:
1) nano silica is placed in aqueous solution of methanesulfonic the ultrasound 2-4h at 30-50 DEG C, then filtration drying obtains hydroxyl Base nano silica；
2) hydroxylating nano silica is dispersed in methanol aqueous solution and is stirred evenly, the silicon containing carbon-carbon double bond is then added dropwise The methanol solution of alkane coupling agent is warming up to 40-60 DEG C of stirring 2-8h after completion of dropwise addition, be cooled to room temperature, filtering, be dried under reduced pressure to obtain table The modified nano silica in face；The silane coupling agent additional amount containing carbon-carbon double bond is hydroxylating nano silica weight The 1-5% of amount；
3) nano silica for taking the surface 10g modified, which is placed in dehydrated alcohol, to stir evenly, and radical initiator is then added The 8-hydroxyquinoline derivative for containing carbon-carbon double bond with 5-10mmol is warming up to reflux polymerization reaction 2-3h；Then 5- is added The aqueous solution of the metal salt of 10mmol, back flow reaction 10-24h carries out molecular self-assembling after completion of dropwise addition, is cooled to room temperature, mistake Filter, dry the immobilized quinoline metal complex of nano silica after anhydrous methanol elution.
3. preparation method according to claim 1 or 2, it is characterised in that: the silane containing carbon-carbon double bond described in step 2) Coupling agent include silane coupling A -151, silane coupling A -171, silane coupling A -172, silane coupling agent KH-560 or The combination of one of Silane coupling reagent KH-570 or arbitrary proportion.
4. preparation method according to claim 1 or 2, it is characterised in that: the 8- hydroxyl containing carbon-carbon double bond described in step 3) Base quinoline is 7- allyl -8-hydroxyquinoline, 2- [2- (2- aminophenyl) vinyl] -8-hydroxyquinoline, 2- ethylene Base -8-hydroxyquinoline.
5. preparation method according to claim 1 or 2, it is characterised in that: the step 3) metal salt is CoCl2、CuCl2、 Manganese acetate III, MnSO4、Ce(NO3)3Or it corresponds to any one in hydrate.
6. preparation method according to claim 5, it is characterised in that: the 8- hydroxyl quinoline containing carbon-carbon double bond described in step 3) Quinoline derivant is 2- vinyl-8-hydroxyquinoline, and the metal salt is CuCl2Or Ce (NO3)3。
7. a kind of purposes of the immobilized quinoline metal complex of the nano silica of the preparation of preparation method described in claim 1, It is characterized by: being used for catalytic degradation penicillin sewage in the presence of oxidant；Include the following steps:
1) penicillin sewage is obtained into filtrate using plate and frame filter press filter and remove suspended substances, body is then adjusted using alkali into filtrate It is pH to 4-7；The filtrate is at rufous, pH=3-4, CODcr=16000-17650mg/L, B/C=0.31-0.34, mould Cellulose content=620-650mg/L；
2) the immobilized quinoline metal complex of the nano silica is added into sewage and oxidant reacts at 20-80 DEG C Stop reaction after 1-6h, the immobilized quinoline metal complex of filtering removal nano silica obtains water purification.
8. purposes according to claim 7, it is characterised in that: the oxidant is sodium hypochlorite, H2O2。
9. purposes according to claim 8, it is characterised in that: the oxidant is H2O2, go oil removal to obtain described in every 1L Nano silica immobilized quinoline metal complex 300-500mg, H are added in filtrate2O2Dosage be concentration be 30wt% 60-100ml。
10. purposes according to claim 9, it is characterised in that: step 2) reacts 1-6h at 20-50 DEG C.
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