CN108772096A - The advanced oxidation processes of lavo-ofloxacin hydrochloride are handled in a kind of heterogeneous reaction system - Google Patents
The advanced oxidation processes of lavo-ofloxacin hydrochloride are handled in a kind of heterogeneous reaction system Download PDFInfo
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- CN108772096A CN108772096A CN201810477439.1A CN201810477439A CN108772096A CN 108772096 A CN108772096 A CN 108772096A CN 201810477439 A CN201810477439 A CN 201810477439A CN 108772096 A CN108772096 A CN 108772096A
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- Prior art keywords
- lavo
- reaction system
- ofloxacin hydrochloride
- heterogeneous reaction
- oxidation processes
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- C02F2101/305—Endocrine disruptive agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
Abstract
The present invention provides the advanced oxidation processes that lavo-ofloxacin hydrochloride is handled in a kind of heterogeneous reaction system, belongs to processing technology field containing antibiotic waste water.This method uses Fe first2+Composite catalyst is prepared on graphene oxide composite load to MCM-41 molecular sieve carriers, sodium peroxydisulfate is as oxidant, then catalyst and oxidant are added jointly in the waste water of hydrochloric lavo-ofloxacin, form heterogeneous reaction system, finally, the free radical generated by catalyst suction-operated itself and activation of catalyst oxidant jointly removes the lavo-ofloxacin hydrochloride in waste water.This method is simple and practicable, and removal effect is notable.
Description
Technical field
The present invention relates to processing technology field containing antibiotic waste water, particularly relate to handle salt in a kind of heterogeneous reaction system
The advanced oxidation processes of sour lavo-ofloxacin.
Background technology
Antibiotic is currently used antibacterial or sterilization class drug, is widely used in the row such as medicine, herding and aquaculture
In industry.The antibiotic overwhelming majority cannot directly be absorbed by body metabolism, generally go through after the circulatory system in the mankind with active compound and
The form of metabolite is excreted in environment.The antibiotic that agricultural breeding, aquaculture and industrial wastewater etc. use also can be direct
Or it is indirectly discharged into environment.In recent years, the adjoint adverse effect of the extensive use of antibiotic is also gradually burst, including induction
Bacterium generates drug resistance, genetoxic, aquatic toxicity and disturbance endocrine object activity etc., and the ground in many areas of world wide
Antibiotic is all detected in table water and drinking water, therefore, the ecological risk of antibiotic causes the extensive concern of people.Fluorine quinoline promise
Ketone drug was widely used by people so far since research and development in 1962, in use can be by suctions such as human body and livestocks
A part is received, but it has been found that there is abundant residues antibiotic to be discharged into water environment in sewage disposal process, and hydrochloric acid is left
Ofloxacin is typical third generation fluoroquinolone antibiotics, most representative.
In recent years, the Processing Technology Research of antibiotic waste water is the hot subject of field of environment protection.Currently, at antibiotic waste water
Reason method includes conventional method (bioanalysis, Physical, chemical method) and advanced oxidation processes.Conventional method such as bioanalysis, due to anti-
Raw element has microorganism certain toxicity inhibition, so bioanalysis is caused to be subject to certain restrictions the processing of antibiotic waste water,
And not only process cycle is longer for bioanalysis, and it is relatively low to the mineralization rate of antibiotic；Absorption, coagulation in Physical and UF membrane
Although even depth treatment effect is preferable, be not suitable for extensive antibiotic water process, and processing cost is higher；And traditional chemistry
Although method is known as antibiosis certain removal effect, removal is not thorough；There are pH value to be applicable in model for homogeneous advanced oxidation processes
The shortcomings of leading to wastage of material cannot be recycled by enclosing narrow, catalyst, so needing a kind of efficient, environmentally protective place at present
Reason method.
Invention content
The technical problem to be solved in the present invention is to provide lavo-ofloxacin hydrochloride is handled in a kind of heterogeneous reaction system
Advanced oxidation processes.
It is as follows that the method comprising the steps of：
(1) prepared by composite catalyst：MCM-41 molecular sieves are weighed, pours into ethanol water and stirs evenly, it is molten to gained
Incorporation of concentration is the graphene oxide solution of 7.75g/L in liquid, is then ultrasonically treated, constant temperature whisks at 100-120 DEG C
And it is heated to reflux 3-5 hour, obtains hot solution；Ferrous sulfate heptahydrate is mixed in gained hot solution and is stirred to react 2-3
Hour, the color of mixing liquid becomes all black by brownish black at this time；Hot solution after stirring is filtered, is used in combination ethyl alcohol water-soluble
Liquid washs, and obtains black filter cake, filter cake is placed in freeze drier and is freeze-dried 12-18h, and finally taking-up is pulverized last
Obtain black powder catalyst；
(2) in heterogeneous reaction system lavo-ofloxacin hydrochloride removal：Lavo-ofloxacin hydrochloride solution is taken, is successively added
Obtained composite catalyst and oxidant in step (1), reaction temperature are 20-25 DEG C, are placed on magnetic stirring apparatus and carry out instead
It answers, reaction time 10-60min, you can complete the removal of lavo-ofloxacin hydrochloride.
Wherein, ethanol water volume ratio is 1 in step (1):1, MCM-41 molecular sieve is with graphene oxide mass ratio：
7:1~12:1.
Sonication treatment time is 15-30min in step (1).
The incorporation of ferrous sulfate heptahydrate is the 20%-30% of MCM-41 molecular sieve qualities in step (1).
The addition of catalyst is 4-6 times of lavo-ofloxacin hydrochloride quality in step (2).
Oxidant is Na in step (2)2S2O8, oxidant addition is 1.5-3 times of lavo-ofloxacin hydrochloride quality.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
This method reaches 98% or so to lavo-ofloxacin hydrochloride removal rate, is higher than the handling result of conventional method, catalysis
Agent can circulating repetition utilize, non-secondary pollution, when catalyst repeated utilization, still can reach lavo-ofloxacin hydrochloride removal
To good effect.
Specific implementation mode
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
The present invention provides the advanced oxidation processes that lavo-ofloxacin hydrochloride is handled in a kind of heterogeneous reaction system.
It is as follows that the method comprising the steps of：
(1) prepared by composite catalyst：MCM-41 molecular sieves are weighed, pours into ethanol water and stirs evenly, it is molten to gained
Incorporation of concentration is the graphene oxide solution of 7.75g/L in liquid, is then ultrasonically treated, constant temperature whisks at 100-120 DEG C
And it is heated to reflux 3-5 hour, obtains hot solution；Ferrous sulfate heptahydrate is mixed in gained hot solution and is stirred to react 2-3
Hour, the color of mixing liquid becomes all black by brownish black at this time；Hot solution after stirring is filtered, is used in combination ethyl alcohol water-soluble
Liquid washs, and obtains black filter cake, filter cake is placed in freeze drier and is freeze-dried 12-18h, and finally taking-up is pulverized last
Obtain black powder catalyst；
(2) in heterogeneous reaction system lavo-ofloxacin hydrochloride removal：Lavo-ofloxacin hydrochloride solution is taken, is successively added
Obtained composite catalyst and oxidant in step (1), reaction temperature are 20-25 DEG C, are placed on magnetic stirring apparatus and carry out instead
It answers, reaction time 10-60min, you can complete the removal of lavo-ofloxacin hydrochloride.
In specific implementation process, the preparation of composite catalyst is carried out first, the MCM-41 molecular sieves of 2-3g is weighed, pours into
It is stirred evenly in ethanol water, the graphene oxide solution of a concentration of 7.75g/L of 30-45ml is mixed into acquired solution, so
Ultrasound 15-30min is carried out afterwards, and constant temperature whisks and be heated to reflux 3-5 hour at 100-120 DEG C, obtains hot solution；It will
0.5-0.8g ferrous sulfate heptahydrate incorporation gained hot solution in be stirred to react 2-3 hour, at this time the color of mixing liquid by
Brownish black becomes all black；Hot solution after stirring is filtered, ethanol water is used in combination to wash, obtains black filter cake, will be filtered
Cake, which is placed in freeze drier, is freeze-dried 12-18h, finally takes out to pulverize and last obtains black powder catalyst；
Then the removal of lavo-ofloxacin hydrochloride in heterogeneous reaction system is carried out：Take a concentration of 100mg/L hydrochloric acid of 100mL
Catalyst 0.05g, oxidant (Na is successively added in the conical flask of 250mL in lavo-ofloxacin solution2S2O8) 0.02g, reaction
Temperature is 20-25 DEG C, is placed on magnetic stirring apparatus and is reacted, reaction time 60min.So far, heterogeneous reaction is completed
The removal of lavo-ofloxacin hydrochloride in system, the removal rate of lavo-ofloxacin hydrochloride reach 99%.
In another implementation process, the preparation process of composite catalyst is same as above, the hydrochloric acid in carrying out heterogeneous reaction system
When the removal of lavo-ofloxacin, the control magnetic agitation reaction time is 10min, the results show that the removal of lavo-ofloxacin hydrochloride
Rate reaches 97%.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (6)
1. handling the advanced oxidation processes of lavo-ofloxacin hydrochloride in a kind of heterogeneous reaction system, which is characterized in that including step
It is as follows：
(1) prepared by composite catalyst：MCM-41 molecular sieves are weighed, pours into ethanol water and stirs evenly, into acquired solution
Incorporation of concentration be 7.75g/L graphene oxide solution, be then ultrasonically treated, at 100-120 DEG C constant temperature whisk and
It is heated to reflux 3-5 hour, obtains hot solution；Ferrous sulfate heptahydrate is mixed in gained hot solution and is stirred to react 2-3 hour,
The color of mixing liquid becomes all black by brownish black at this time；Hot solution after stirring is filtered, ethanol aqueous wash is used in combination
It washs, obtains black filter cake, filter cake is placed in freeze drier and is freeze-dried 12-18h, finally take out last obtain of pulverizing
Black powder catalyst；
(2) in heterogeneous reaction system lavo-ofloxacin hydrochloride removal：Lavo-ofloxacin hydrochloride solution is taken, step is successively added
(1) obtained composite catalyst and oxidant in, reaction temperature are 20-25 DEG C, are placed on magnetic stirring apparatus and are reacted, instead
It is 10-60min between seasonable, you can complete the removal of lavo-ofloxacin hydrochloride.
2. the advanced oxidation processes of lavo-ofloxacin hydrochloride are handled in heterogeneous reaction system according to claim 1, it is special
Sign is that ethanol water volume ratio is 1 in the step (1):1, MCM-41 molecular sieve is with graphene oxide mass ratio：7:
1~12:1.
3. the advanced oxidation processes of lavo-ofloxacin hydrochloride are handled in heterogeneous reaction system according to claim 1, it is special
Sign is that sonication treatment time is 15-30min in the step (1).
4. the advanced oxidation processes of lavo-ofloxacin hydrochloride are handled in heterogeneous reaction system according to claim 1, it is special
Sign is that the incorporation of ferrous sulfate heptahydrate is the 20%-30% of MCM-41 molecular sieve qualities in the step (1).
5. the advanced oxidation processes of lavo-ofloxacin hydrochloride are handled in heterogeneous reaction system according to claim 1, it is special
Sign is, the addition of catalyst is 4-6 times of lavo-ofloxacin hydrochloride quality in the step (2).
6. the advanced oxidation processes of lavo-ofloxacin hydrochloride are handled in heterogeneous reaction system according to claim 1, it is special
Sign is that oxidant is Na in the step (2)2S2O8, oxidant addition is 1.5-3 times of lavo-ofloxacin hydrochloride quality.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810477439.1A CN108772096B (en) | 2018-05-18 | 2018-05-18 | Advanced oxidation method for treating levofloxacin hydrochloride in heterogeneous reaction system |
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| CN201810477439.1A CN108772096B (en) | 2018-05-18 | 2018-05-18 | Advanced oxidation method for treating levofloxacin hydrochloride in heterogeneous reaction system |
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| CN108772096A true CN108772096A (en) | 2018-11-09 |
| CN108772096B CN108772096B (en) | 2020-09-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553593A (en) * | 2012-01-10 | 2012-07-11 | 常州大学 | Method for preparing magnetic nanometer ferroferric oxide-graphene composite catalyst |
| CN105435829A (en) * | 2015-11-11 | 2016-03-30 | 华南师范大学 | Preparation method and application of Co-Mn-MCM-41 molecular sieve |
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2018
- 2018-05-18 CN CN201810477439.1A patent/CN108772096B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553593A (en) * | 2012-01-10 | 2012-07-11 | 常州大学 | Method for preparing magnetic nanometer ferroferric oxide-graphene composite catalyst |
| CN105435829A (en) * | 2015-11-11 | 2016-03-30 | 华南师范大学 | Preparation method and application of Co-Mn-MCM-41 molecular sieve |
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