CN108543532A - Wolframic acid bismuth catalyst and preparation method thereof and application of the combining ultrasonic in catalytic degradation antibiotic - Google Patents
Wolframic acid bismuth catalyst and preparation method thereof and application of the combining ultrasonic in catalytic degradation antibiotic Download PDFInfo
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- CN108543532A CN108543532A CN201810443014.9A CN201810443014A CN108543532A CN 108543532 A CN108543532 A CN 108543532A CN 201810443014 A CN201810443014 A CN 201810443014A CN 108543532 A CN108543532 A CN 108543532A
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- China
- Prior art keywords
- wolframic acid
- bismuth
- degradation
- ciprofloxacin hydrochloride
- acid bismuth
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Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—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
- C02F2103/003—Wastewater from hospitals, laboratories and the like, heavily contaminated by pathogenic microorganisms
Abstract
The invention discloses wolframic acid bismuth catalysts and preparation method thereof and application of the combining ultrasonic in catalytic degradation antibiotic.The present invention uses hydrothermal synthesis method, and the wolframic acid bismuth catalyst of square piece shape crystal form is synthesized under the conditions of pH=5.The present invention, process for synthetic catalyst is easy, safe, easy post-processing.And catalyst and combination of ultrasound sound catalytic degradation Ciprofloxacin Hydrochloride aqueous solution degradation rate are individually degraded the degradation rate of Ciprofloxacin Hydrochloride aqueous solution higher than bismuth tungstate, bismuth tungstate has better sound catalytic activity.The present invention is catalyzed ultrasonotomography Ciprofloxacin Hydrochloride aqueous solution using bismuth tungstate, its degradation efficiency is made to improve, and has directive significance for synthesizing more effective sound catalytic nanometer material.
Description
Technical field
The present invention relates to the process fields of medical waste liquid, are specifically related to a kind of preparation side of the bismuth tungstate of square piece shape crystal form
Method and the application in handling Ciprofloxacin Hydrochloride aqueous solution.
Background technology
With the development of medical technology, the use of a large amount of antibiotic so that remain a large amount of antibiotic in the sewage of discharge.
This not only causes environmental pollution, while can also induce the generation of drug-resistant bacteria, and is enriched with food chain, further to human health
It causes to seriously threaten.However, conventional biologic process for treating sewage is difficult to effectively remove for antibiotics pollution.Ultrasound
Wave because of its exclusive cavitation effect, have in terms of contaminant degradation removal efficiency is high, degradation condition is mild, degradation speed is fast,
Applied widely, the features such as facility is simple, receive the concern of domestic and foreign scholars.In recent years, in catalytic degradation organic contamination object space
Face, ultrasound is combined with semi-conducting material shows high degradation rate, environmentally protective, method relative ease and the feasibility advantages such as by force,
As the important research direction of degradable organic pollutant.
Invention content
The object of the present invention is to provide a kind of preparation method is simple, the bismuth tungstate of the high square piece shape crystal form of catalytic degradation efficiency
The application of catalyst and its combination ultrasound in catalytic degradation Ciprofloxacin Hydrochloride.
To achieve the goals above, the technical solution adopted by the present invention is：Wolframic acid bismuth catalyst, preparation method include as follows
Step：After citric acid, bismuth nitrate and sodium tungstate are dissolved in distilled water respectively, mixing adjusts the pH of mixed liquor, magnetic agitation
Afterwards, it is then sonicated, mixed liquor moves into reaction kettle, and in 180 DEG C of hydro-thermal reaction 20-24h, cooled to room temperature, suction filtration stays filter
Slag, it is constant that washing, alcohol are washed till pH, dry, obtains wolframic acid bismuth catalyst.
Preferably, in molar ratio, citric acid:Bismuth nitrate:Sodium tungstate=1:2:1.
Preferably, the pH for adjusting mixed liquor is 5.
Preferably, after magnetic agitation 30min, it is being ultrasonically treated 30min.
Preferably, the bismuth tungstate is square piece shape crystal form, and grain size mean size is 500nm or so.
Application of the above-mentioned wolframic acid bismuth catalyst combining ultrasonic in catalytic degradation antibiotic.Method is as follows：It will be above-mentioned
Bismuth tungstate is added in the waste water containing antibiotic, ultrasound under the conditions of room temperature is protected from light, ultrasonic power 200W, catalytic degradation 1-
3h。
Preferably, the antibiotic is Ciprofloxacin Hydrochloride.
Preferably, the initial concentration for adjusting Ciprofloxacin Hydrochloride is 10mg/L, bismuth tungstate and contains Ciprofloxacin Hydrochloride
The solid-liquid ratio of waste water is (1g~5g):1L.
The beneficial effects of the invention are as follows：
1, the present invention uses sound catalysis technique, anti-in conjunction with bismuth tungstate catalyst degradation using the strong feature of ultrasonic penetration power
Raw element, ultrasonic wave penetrate solution, excite wolframic acid bismuth catalyst in solution, its surface generate active oxygen with strong oxidizing property and
Hole, can direct oxidation destroy antibiotic structure, make its resolve into innocuous substance in addition it is degradable be CO2And H2O。
2, of the invention, process for synthetic catalyst is easy, safe, easy post-processing.And after catalyst and combination of ultrasound, for
Ciprofloxacin Hydrochloride degradation rate illustrates that bismuth tungstate has good sound higher than bismuth tungstate is used alone to its degradation rate in aqueous solution
Catalytic activity.The present invention is catalyzed ultrasonotomography Ciprofloxacin Hydrochloride aqueous solution using bismuth tungstate, its degradation efficiency is made to improve, for
Synthesizing more effective sound catalytic nanometer material has directive significance.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of wolframic acid bismuth catalyst prepared by embodiment 1.
Fig. 2 is the XRD diagram of wolframic acid bismuth catalyst prepared by embodiment 1.
Fig. 3 is that not same amount is added, and bismuth tungstate is catalyzed ultrasonotomography Ciprofloxacin Hydrochloride and the independent absorption degradation salt of bismuth tungstate
The contrast curve of the degradation rate of sour Ciprofloxacin.
Fig. 4 is the differential responses time, and bismuth tungstate is catalyzed ultrasonotomography Ciprofloxacin Hydrochloride and the independent absorption degradation of bismuth tungstate
The relational graph in salt Ciprofloxacin corresponding reaction time and degradation rate.
Specific implementation mode
Technical scheme of the present invention is described in detail below by specific example.
1 wolframic acid bismuth catalyst of embodiment
(1) preparation method
Weigh citric acid 0.192g (0.5mmol), bismuth nitrate 0.970g (1.0mmol), sodium tungstate 0.330g (0.5mmol)
Respectively plus 20mL distills water dissolution, and above-mentioned 3 kinds of solution is mixed in 250mL conical flasks, and pH=is adjusted with sodium hydrate aqueous solution
5, magnetic agitation 30min, ultrasonic 30min (power 200W) move into 100mL reaction kettles, are placed in timing in 180 DEG C of baking ovens and heat
For 24 hours, stop cooled to room temperature after heating, suction filtration stays filter residue, discards filtrate, uses distilled water and washes of absolute alcohol number respectively
It is secondary, until filtrate pH constant (common pH test paper is measured, is in neutrality), is placed in timing in 80 DEG C of baking ovens by filter residue and dries 2.0h, obtain
Wolframic acid bismuth catalyst.
(2) gained wolframic acid bismuth catalyst, scanned Electronic Speculum detection, the results are shown in Figure 1, and bismuth tungstate is square piece shape crystal form
Structure, grain size mean size are 500nm or so.As Fig. 2 can determine that through XRD detection synthetic products as bismuth tungstate.
The method of 2 wolframic acid bismuth catalyst combining ultrasonic catalytic degradation Ciprofloxacin Hydrochloride of embodiment
(1) method is as follows
A concentration of 10mg/L for adjusting Ciprofloxacin Hydrochloride aqueous solution, wolframic acid bismuth catalyst prepared by embodiment 1 are added
Into Ciprofloxacin Hydrochloride aqueous solution, ultrasound under the conditions of room temperature is protected from light, ultrasonic power 200W, supersonic source is urged away from liquid level 30mm
Change degradation 1-3h.The solid-liquid ratio of wolframic acid bismuth catalyst and Ciprofloxacin Hydrochloride aqueous solution is (1g~5g):1L.
(2) influence of the bismuth tungstate catalyst charge to catalytic degradation Ciprofloxacin Hydrochloride degradation rate
The present invention：In the conical flask of 5 Ciprofloxacin Hydrochloride aqueous solutions equipped with a concentration of 10mg/L of 20mL, add respectively
Wolframic acid bismuth catalyst 10mg, 20mg, 30mg, 40mg, the 50mg for entering the preparation of embodiment 1, wrap up black film and are protected from light, by 5 tapers
Bottle is placed in ultrasonic instrument, (200W, control temperature are constant at 25 DEG C), and ultrasonic 2.0h negates solution supernatant 6mL after answering and is placed in
It jumps a queue in 10mL centrifuge tubes centrifugation (2000r/min, 20min), extracts centrifuged supernatant with 5mL syringes and cross miillpore filter
(discarding initial 5 drop) reserved filtrate in sample bottle, wraps up black film and is kept in dark place, and extinction is measured with ultraviolet-uisible spectrophotometer
Degree.Unreacted solution absorbance is A0, the solution absorbance after degradation is At, pass through formula：Degradation rate (%)=[(A0-At)/
A0] × 100% calculates degradation rate.As a result such as Fig. 3.
Contrast test：In the conical flask of 5 Ciprofloxacin Hydrochloride aqueous solutions equipped with a concentration of 10mg/L of 20mL, respectively
Wolframic acid bismuth catalyst 10mg, 20mg, 30mg, 40mg, 50mg prepared by embodiment 1 is added, wraps up black film and is protected from light, on shaking table
Shake 2.0h.It negates solution supernatant 6mL after answering and is placed in 10mL centrifuge tubes centrifugation (2000r/min, 20min) of jumping a queue, use 5mL
Syringe extraction centrifuged supernatant crosses miillpore filter (discarding initial 5 drop) reserved filtrate and in sample bottle, wraps up black film and be protected from light
It preserves, absorbance is measured with ultraviolet-uisible spectrophotometer.Degradation rate is calculated, as a result such as Fig. 3.
As seen from Figure 3, in the case where wolframic acid bismuth catalyst 10mg, 20mg, 30mg, 40mg, 50mg is added, the present invention,
Using wolframic acid bismuth catalyst combining ultrasonic catalytic degradation Ciprofloxacin Hydrochloride, degradation rate is respectively 43.1%, 70.9%,
77.2%, 86.2%, 91.9%.The degradation rate of contrast test is 32.8%, 56.6%, 67.8%, 75.2%, 80.8%.It is right
Under the conditions of same catalyst addition, bismuth tungstate combination ultrasonically catalyzing is high to the degradation rate of Ciprofloxacin Hydrochloride in aqueous solution
Degradation rate when bismuth tungstate is used alone, this shows that the bismuth tungstate of square piece shape crystal form has good sound catalytic activity, wolframic acid
Bismuth is catalyzed ultrasonotomography Ciprofloxacin Hydrochloride aqueous solution, so that its degradation efficiency is improved, it is seen then that method using the present invention, wolframic acid
Bismuth combines ultrasound apparent for the degradation effect of Ciloxan, has potential industrial prospect.
(3) influence of the catalytic degradation time to catalytic degradation Ciprofloxacin Hydrochloride degradation rate
The present invention：In the conical flask of 5 Ciprofloxacin Hydrochloride aqueous solutions equipped with a concentration of 10mg/L of 20mL, add respectively
The wolframic acid bismuth catalyst 20mg for entering the preparation of embodiment 1, wraps up black film and is protected from light, 5 conical flasks are placed in ultrasonic instrument,
(200W, control temperature are constant at 25 DEG C), ultrasound 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, negate solution supernatant after answering respectively
9mL is placed in 10mL centrifuge tubes centrifugation (2000r/min, 20min) of jumping a queue, and it is excessively micro- to extract centrifuged supernatant with 5mL syringes
Hole filter membrane (discarding initial 5 drop) reserved filtrate in sample bottle, wraps up black film and is kept in dark place, surveyed with ultraviolet-uisible spectrophotometer
Determine absorbance.Degradation rate is calculated, as a result such as Fig. 4.
Contrast test：In the conical flask of 5 Ciprofloxacin Hydrochloride aqueous solutions equipped with a concentration of 10mg/L of 20mL, respectively
Wolframic acid bismuth catalyst 20mg prepared by embodiment 1 is added, wraps up black film, shaken respectively on shaking table under the conditions of being protected from light 0.5h,
1.0h, 1.5h, 2.0h, 2.5h, negate should after solution supernatant 9mL be placed in 10mL centrifuge tubes centrifugation of jumping a queue (2000r/min,
20min), miillpore filter (discarding initial 5 drop) reserved filtrate is crossed with 5mL syringes extraction centrifuged supernatant in sample bottle, to wrap
It wraps up in black film to be kept in dark place, absorbance is measured with ultraviolet-uisible spectrophotometer.Degradation rate is calculated, as a result such as Fig. 4.
From fig. 4, it can be seen that in the case where being catalyzed 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, the present invention is urged using bismuth tungstate
Agent combining ultrasonic catalytic degradation Ciprofloxacin Hydrochloride, degradation rate is respectively 56.7%, 63.6%, 70.2%, 71.8%,
72.1%.The degradation rate of contrast test is respectively 53.2%, 54.7%, 56.9%, 57.4%, 58.8%.With ultrasonic time
Increase, the degradation rate of the two increases, it can be seen that 2.0h is the suitable reaction time.And no matter under which kind of in reaction time, this
Invention is above bismuth tungstate using the degradation rate of bismuth tungstate combination ultrasonic and catalytic degradation Ciprofloxacin Hydrochloride aqueous solution and individually adsorbs
The degradation rate of degradation, degradation effect improve, the sound catalytic activity for the bismuth tungstate that the present invention is shown, are urged for synthesizing more effective sound
Changing nano material has directive significance.
Claims (9)
1. wolframic acid bismuth catalyst, which is characterized in that preparation method includes the following steps：By citric acid, bismuth nitrate and sodium tungstate point
After not being dissolved in distilled water, mixing adjusts the pH of mixed liquor, after magnetic agitation, is then sonicated, and mixed liquor moves into reaction kettle,
In 180 DEG C of hydro-thermal reaction 20-24h, cooled to room temperature, suction filtration stays filter residue, and it is constant that washing, alcohol are washed till pH, dry, obtains wolframic acid
Bismuth catalyst.
2. wolframic acid bismuth catalyst according to claim 1, which is characterized in that in molar ratio, citric acid:Bismuth nitrate:Wolframic acid
Sodium=1:2:1.
3. wolframic acid bismuth catalyst according to claim 1, which is characterized in that the pH for adjusting mixed liquor is 5.
4. wolframic acid bismuth catalyst according to claim 1, which is characterized in that after magnetic agitation 30min, be ultrasonically treated
30min。
5. wolframic acid bismuth catalyst according to claim 1, which is characterized in that the bismuth tungstate is square piece shape crystal form.
6. application of the claim 1-5 any one of them wolframic acid bismuth catalyst combining ultrasonics in catalytic degradation antibiotic.
7. application according to claim 6, which is characterized in that method is as follows：Bismuth tungstate described in claim 1-5 is added
Enter into the waste water containing antibiotic, ultrasound under the conditions of room temperature is protected from light, ultrasonic power 200W, catalytic degradation 1-3h.
8. application according to claim 7, which is characterized in that the antibiotic is Ciprofloxacin Hydrochloride.
9. application according to claim 8, which is characterized in that the initial concentration for adjusting Ciprofloxacin Hydrochloride is 10mg/L,
The solid-liquid ratio of bismuth tungstate and the waste water containing Ciprofloxacin Hydrochloride is (1g~5g):1L.
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| CN201810443014.9A CN108543532A (en) | 2018-05-10 | 2018-05-10 | Wolframic acid bismuth catalyst and preparation method thereof and application of the combining ultrasonic in catalytic degradation antibiotic |
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| CN201810443014.9A CN108543532A (en) | 2018-05-10 | 2018-05-10 | Wolframic acid bismuth catalyst and preparation method thereof and application of the combining ultrasonic in catalytic degradation antibiotic |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058541A (en) * | 2021-04-23 | 2021-07-02 | 辽宁大学 | Ag2O/Bi2WO6Composite and preparation method and application thereof |
| CN113398946A (en) * | 2021-07-06 | 2021-09-17 | 辽宁大学 | Cobalt tungstate/bismuth composite acoustic catalyst and preparation method and application thereof |
| CN113713802A (en) * | 2021-09-15 | 2021-11-30 | 辽宁大学 | CoWO (cobalt oxide tungsten trioxide)4/Bi2WO6Composite acoustic catalyst and preparation method and application thereof |
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| CN106673121A (en) * | 2017-01-05 | 2017-05-17 | 北京师范大学 | Method for purifying tetracycline in sewage by photocatalysis method |
Non-Patent Citations (2)
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| AYDIN HASSANI ET AL.,: "Sonocatalytic degradation of ciprofloxacin using synthesized TiO2 nanoparticles on montmorillonite", 《ULTRASONICS SONOCHEMISTRY》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113058541A (en) * | 2021-04-23 | 2021-07-02 | 辽宁大学 | Ag2O/Bi2WO6Composite and preparation method and application thereof |
| CN113398946A (en) * | 2021-07-06 | 2021-09-17 | 辽宁大学 | Cobalt tungstate/bismuth composite acoustic catalyst and preparation method and application thereof |
| CN113713802A (en) * | 2021-09-15 | 2021-11-30 | 辽宁大学 | CoWO (cobalt oxide tungsten trioxide)4/Bi2WO6Composite acoustic catalyst and preparation method and application thereof |
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