CN108855083A - A method of sulfa drugs in water removal is removed with modified zeolite activation Peracetic acid - Google Patents
A method of sulfa drugs in water removal is removed with modified zeolite activation Peracetic acid Download PDFInfo
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- CN108855083A CN108855083A CN201810731624.9A CN201810731624A CN108855083A CN 108855083 A CN108855083 A CN 108855083A CN 201810731624 A CN201810731624 A CN 201810731624A CN 108855083 A CN108855083 A CN 108855083A
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- peracetic acid
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- reaction
- water removal
- sulfa drugs
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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
- B01J23/70—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
- B01J23/745—Iron
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- 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
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- 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
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- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention discloses a kind of methods for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid, including step：S1. catalyst preparation：Artificial zeolite is worn into fine powder, after pickling, washing, drying, is placed in ferrous sulfate solution and is soaked for a period of time, is centrifugated, obtained solid is washed with deionized and dries；S2. oxidation reaction：Prepared peracetic acid soln is added in sulfamethoxazole waste water, initial pH on wastewater is adjusted, proper catalyst is added, oxidation reaction is carried out under normal temperature and pressure, stirring condition.The catalysis material preparation that the present invention uses is simple, and easy to maintain, activation efficiency is high, and active component dissolution rate is low；Activation Peracetic acid system oxidisability is strong and treatment process has both sterilizing function, realize the advanced treating of waste water and the combination of disinfection treatment function, it is stronger with Modern sewage treatment plant processing compatibility, sulfamethoxazole degradation efficiency is high and reaction condition is mild, it is at low cost, be suitable for industrializing extensive wastewater treatment.
Description
Technical field
It is specifically a kind of to utilize Fe the present invention relates to a kind of advanced oxidization method based on activation Peracetic acid2+/ artificial boiling
The method that stone activation Peracetic acid removes sulfa antibiotics in water removal.
Background technique
Sulfa antibiotics are mainly used in the fields such as medical treatment, cultivation, have stronger transfer ability in the environment, are water environments
In one of main antibiotic pollutant.Currently, sulfa antibiotics have reached ng/L level in China's surface water.Especially sulphur
Amine first oxazole, the content in the water body of part are even more than ng/L up to a hundred.In sewage treatment plant inflow, sulfa antibiotics
Concentration is higher.Since presence of this pollutant in water body has seriously threatened the existence and human health of aquatic animals and plants, have
The technology of necessity research and development efficiently, environmentally friendly effectively administers it.
Currently, there is the method for sulfa antibiotics in removal water body：Coagulation floatation, active carbon adsorption, activated sludge
Method, biofilm, advanced oxidation processes etc..It can be generally divided into biology, physical chemistry and chemical treatment method three categories.However object
Change processing technique is selectively poor, and treatment process is the process of simple transfer, concentration pollutant, and there are secondary pollutions；Though
So existing document report biodegrade is also a kind of approach for removing sulfa antibiotics, but strain culturing process is longer, application
In may be subjected to the inhibition of other mushrooms, be difficult to reach requirement on industrial application at this stage.It is compared to the above, advanced oxygen
Change technology has the characteristics that applied widely, treatment effeciency is high, and treatment process changes the chemical structure of pollutant, makes its turn
The small organic molecule for turning to harmless inorganic matter or being easily biodegradable has significant advantage.
However, also there is processing cost height or be difficult to the problems such as industrializing in advanced oxidation.Especially for sulfa antibiotics
This kind of novel PPCPs pollutant, conventional sewage plants are difficult to merge to have in existing treatment process targetedly to purify work
Skill.Therefore, application cost is low, secondary pollution is small and agrees with the strong advanced oxygen of ability with Modern sewage treatment plant water-purifying process for selection
Change technology is to remove one of the key breakthrough points of sulfa antibiotics in water removal at present.So far, high-level oxidation technology uses
Mainstream oxidant is hydrogen peroxide, and the hydroxyl radical free radical generated can be by the quick mineralising of organic pollutant, and itself is changed into H2O
And O2, secondary pollution is minimum.But the transport of hydrogen peroxide and preservation condition are more harsh, and reaction process is vulnerable to environment temperature
It with the influence of reaction pH, usually need to can just be shown compared with strong oxidizing property in acidic atmosphere, increase operating cost and management is difficult
Degree.In recent years, Peracetic acid (PAA) as it is a kind of kill it is high-efficient, do not generate toxic disinfection by-products, preference temperature scope
Wide efficient germicide has been widely used in water process, and has the tendency that gradually replacing traditional chlorination, but be used for
The research of advanced oxidation processing sewage is also rarely reported.Peracetic acid structure is close with hydrogen peroxide, containing O -- O bond, with dioxygen
H in water is compared, CH3The electron-withdrawing ability of COO- group is stronger, therefore the O -- O bond in Peracetic acid is slightly better than in hydrogen peroxide
O -- O bond, high stability, low concentration solution easily store.According to the oxidability of proper technology enhancing Peracetic acid system, knot
Its stronger sterilizing function is closed, there can be preferable development prospect with Modern sewage treatment plant technique good coupling.
The O -- O bond of Peracetic acid, which is broken, using suitable activation method generates CH3COO·、CH3CO3It is free with HO etc.
Base can substantially enhance system oxidability.Currently used activation method includes thermal activation, photoactivation, transition metal activation etc..Phase
Specific energy activation, Fe2+Activating technology application cost is low, activation efficiency is high, it is easier to industrial applications.However, Fe2+It is easily molten
Solution oxygen etc. is aoxidized and is failed, Fe2+Utilization efficiency is low, therefore is based on Fe2+The usual demand acidic atmosphere of homogeneous activation technology.This
Outside, Fe2+The preservation difficulty of solution is larger, generally requires and is using preceding Extemporaneous.In contrast, in heterogeneous catalysis, iron
Source is stable in the presence of material internal structure, lower by limited degrees such as pH, and also rare hydroxide precipitating generates for reaction, and metal is molten
Extracting rate is low, and material reusing is good, and practicability is stronger.The core of heterogeneous activating technology is to prepare efficient, cheap catalysis
Agent.
Artificial zeolite is the nonmetallic mineral that a kind of source is wide, resource reserve is big, because having loose, porous Large ratio surface
Product, the application in materialization field are further extensive.It is easily prepared using artificial zeolite, easily modified, reproducible feature, prepares peroxide
The heterogeneous activated catalyst of acetic acid is a kind of effective mode.Using load Fe2+Artificial zeolite (Fe2+/ artificial
Zeolite) activation Peracetic acid processing sulfa antibiotics waste water, economy and environmental benefit will be increased substantially, mitigates the ring of society
Packing pressure.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, provides a kind of using Fe2+/ artificial zeolite activates peroxide second
The method that acid removes sulfa antibiotics in water removal is easy industrially scalable to reach treatment process simple process, mild condition
The effect of implementation.
The purpose of the present invention is achieved through the following technical solutions：It is a kind of to be gone in water removal with modified zeolite activation Peracetic acid
From a wealth of sources, cheap, preparation method is utilized simply and the higher Fe of activity in the method for sulfa drugs, screening2+/ artificial
Zeolite catalyst, and utilize the work of its heterogeneous priming reaction generation strong oxidizing property occurred in a mild condition with Peracetic acid
Property species, and then degrade to the representative sulfa antibiotics-sulfamethoxazole filtered out, step includes：
S1. catalyst preparation：Artificial zeolite is ground into uniform fine powder, certain mass is weighed and is added in dilute sulfuric acid, stirring
Uniformly and after standing a period of time being washed with deionized water to pH is near neutral (6.8~7.2), and 100 are heated in Muffle furnace
DEG C drying.Fine powder after a certain amount of drying is added in ferrous sulfate solution, after being soaked for a period of time, cleans 3 with deionized water
~4 times, Fe is made in solid drying by centrifuge separation2+/ artificial zeolite catalyst；
S2. oxidation reaction：Prepared peracetic acid soln is added in the waste water containing sulfamethoxazole, with sulfuric acid and
Sodium hydroxide solution adjusts initial pH on wastewater, and appropriate Fe is added2+/ artificial zeolite catalyst, in proper temperature, at the uniform velocity stirring condition
Lower carry out oxidation reaction.
Further, artificial zeolite described in step S1 is ground to 200~300 mesh, the sulfuric acid concentration that pickling uses for
0.05~0.1 mol/L, pickling time be 19~for 24 hours；
Further, when ferrous sulfate solution described in step S1 is prepared, deionized water pH is adjusted to 2.0 with sulfuric acid
~3.0, green vitriol is added, is configured to Fe2+Molar concentration is the solution of 0.2~0.4mol/L；
Further, when catalyst preparation described in step S1, artificial zeolite and Fe2+Mass ratio is 55:1~65:1,
Load time 20~for 24 hours；
Further, catalyst drying temperature described in step S1 is 70~100 DEG C；
Further, prepared peroxyacetic acid concentration described in step S2 is 10~12g/L；
Further, concentration of the Peracetic acid in reaction solution described in step S2 is 50mg/L~100mg/L；
Further, the catalytic amount added described in step S2 into reaction solution is 1.0~2.0g/L；
Further, sulfamethoxazole concentration is 0.1mg/L~3.0mg/L in waste water described in step S2；
Further, the initial pH of peak optimization reaction described in step S2 is 6.0~8.0, be suitable for the initial pH of reaction be 2.0~
9.0, reaction temperature is 25~35 DEG C, and mixing speed is 400~500rpm, and the reaction time is 20~30min.
The principle of the present invention is：The tetrahedron that artificial zeolite is made of tri- kinds of elements of Si, Al, O, due to silicon oxygen therein
Tetrahedron and aluminum-oxygen tetrahedron can construct the three-dimensional space rack-like of infinite expanding, therefore zeolite has very strong absorption and ion
Exchange capacity can efficiently trap Fe in liquid phase2+, form Fe2+/ artificial zeolite composite material.Using Fe2+/ artificial zeolite activated
When fluoroacetic acid, the Fe of reference state and loss out2+The activation for having both participated in Peracetic acid makes it be rapidly converted into activity stronger
The free radicals such as HO.Wherein, reference state Fe2+The active specy (mainly HO free radical) that activation Peracetic acid generates exists
Material surface generates in situ, and reacts with sulfamethoxazole, and by free state Fe2+The active specy that activation generates is scattered in
In liquid phase, homogeneous oxidizing pollutant.Due to Fe2+/ artificial zeolite large specific surface area, the probability with sulfamethoxazole molecule contacts
Height, therefore Heterogeneous oxidation reaction plays an important role during contaminant degradation.The conclusion is obtained also through homogeneous check experiment
To confirmation (being detailed in 5 table 1 of case study on implementation).
In addition, Fe2+/ artificial zeolite can by the effects of electrostatical binding, Van der Waals force adsorb fraction sulfamethoxazole, but
Absorption check experiment proves that the pollutants removal rate of this contribution is only 5.6% (being detailed in 5 table 1 of case study on implementation).Reaction principle
As shown in Fig. 1.
The present invention has the following advantages that：
1, the present invention provides a kind of efficient sulfa antibiotics advanced oxidations based on Peracetic acid system to remove skill
Art, in a short time, under mild reaction conditions, contaminant removal efficiency is up to 99% or more, and application cost is low, governance process is simultaneous
Has bacteria-eliminating efficacy.The present invention realizes the advanced treating of waste water and the combination of disinfection treatment function, with Modern sewage treatment plant work
The compatibility of skill is stronger.
2, the present invention uses novel Fe2+/ artificial zeolite is as Peracetic acid activator, on solid phase surface and in liquid phase
Activation Peracetic acid generates free radicals, and activation efficiency is much higher than homogeneous Fe2+Activation.
3, present invention employs from a wealth of sources, cheap, environmental-friendly artificial zeolites as catalyst carrier, the material
Expect that specific surface is big, hole is more, the high-efficient carriers such as ion exchange and Van der Waals force Fe can be passed through2+.In catalyst preparation process
Fe is coated with aluminum oxide2+, reduce Fe using skeleton structure2+Contact with air increases stability of material；Reaction terminates
Afterwards, separation of solid and liquid property is strong, and structure will not change catalyst in the process, and not introduce heteroion into liquid phase, Fe2+The amount of dissolution
It is low, largely avoid secondary pollution.
4, entire treatment process simple process, reaction condition are mild, can efficient degradation under pH neutrality, normal temperature and pressure conditions
Sulfanilamide (SN) pollutant is easy industrial scale and implements.
5, this law advantageous pH range is wide, can be applied to the direct processing of strong acid, alkaline waste water, does not introduce additional acid, alkali
Cost is added, is had a wide range of application.
Detailed description of the invention
Fig. 1 is mechanism schematic diagram of the present invention.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and protection scope of the present invention is not limited to following institute
It states：
Embodiment 1：It is a kind of to utilize Fe2+The method that/artificial zeolite activation Peracetic acid removes sulfa antibiotics in water removal, it
Include the following steps：
S1. catalyst preparation：Artificial zeolite is ground into the uniform fine powder of 200 mesh, weighing certain mass addition concentration is
In the dilute sulfuric acid of 0.05mol/L, acid solution is made just to submerge powder, stir evenly and stood for 24 hours.It is washed with deionized water to pH
It is 6.8,100 DEG C of drying is heated in Muffle furnace.According to zeolite, Fe2+Mass ratio is 60:1 ratio will be after a certain amount of drying
Fine powder be added concentration be 0.2mol/L ferrous sulfate solution in, impregnate 20h after, clean 3~4 times with deionized water, centrifugation
Solid is placed in drying in 100 DEG C of baking ovens and catalyst is made by separation.
S2. oxidation reaction：Peracetic acid soln 0.4mL to the 50mL 0.1mg/L sulfalene that concentration is 10g/L is added to dislike
In azoles waste water, adjusting initial pH on wastewater with sulfuric acid and sodium hydroxide solution is 6.0, then 0.05g catalysis is added into mixed solution
Agent is 25 DEG C in temperature, and mixing speed reacts 30min under the conditions of being 500rpm.
Sulfamethoxazole concentration is 0mg/L after surveying reaction, corresponding removal rate 100%, iron dissolution rate 0.07%.
(note：Sulfamethoxazole detection method：It is measured using high performance liquid chromatograph (Waters 2695, USA).)
Embodiment 2：It is a kind of to utilize Fe2+The method that/artificial zeolite activation Peracetic acid removes sulfa antibiotics in water removal, it
Include the following steps：
S1. catalyst preparation：Artificial zeolite is ground into the uniform fine powder of 200 mesh, weighing certain mass addition concentration is
In the dilute sulfuric acid of 0.1mol/L, acid solution is made just to submerge powder, stir evenly and stands 19h.It is washed with deionized water to pH and is
7.0,100 DEG C of drying are heated in Muffle furnace.According to zeolite, Fe2+Mass ratio is 55:1 ratio will be after a certain amount of drying
Fine powder is added in the ferrous sulfate solution that concentration is 0.2mol/L, after impregnating for 24 hours, is cleaned 3~4 times with deionized water, centrifugation point
From solid being placed in 70 DEG C of baking ovens drying, catalyst is made.
S2. oxidation reaction：Peracetic acid soln 0.5mL to the 100mL 0.5mg/L sulfalene that concentration is 10g/L is added to dislike
In azoles waste water, adjusting initial pH on wastewater with sulfuric acid and sodium hydroxide solution is 7.0, then 0.15g catalyst is added into mixed liquor,
It is 35 DEG C in temperature, mixing speed reacts 20min under the conditions of being 450rpm.
Sulfamethoxazole concentration is 0mg/L after surveying reaction, corresponding removal rate 100%, iron dissolution rate 0.05%.
(note：Sulfamethoxazole detection method：It is measured using high performance liquid chromatograph (Waters 2695, USA).)
Embodiment 3：It is a kind of to utilize Fe2+The method that/artificial zeolite activation Peracetic acid removes sulfa antibiotics in water removal, it
Include the following steps：
S1. catalyst preparation：Artificial zeolite is ground into the uniform fine powder of 300 mesh, weighing certain mass addition concentration is
In the dilute sulfuric acid of 0.1mol/L, acid solution is made just to submerge powder, stir evenly and stood for 24 hours.It is washed with deionized water to pH and is
6.8,100 DEG C of drying are heated in Muffle furnace.According to zeolite, Fe2+Mass ratio is 65:1 ratio will be after a certain amount of drying
Fine powder is added in the ferrous sulfate solution that concentration is 0.4mol/L, after impregnating for 24 hours, is cleaned 3~4 times with deionized water, centrifugation point
From solid being placed in 90 DEG C of baking ovens drying, catalyst is made.
S2. oxidation reaction：Peracetic acid soln 2.0mL to the 200mL 1.5mg/L sulfalene that concentration is 10g/L is added to dislike
In azoles waste water, adjusting initial pH on wastewater with sulfuric acid and sodium hydroxide solution is 8.0, then 0.4g catalyst is added into mixed liquor,
It is 30 DEG C in temperature, mixing speed reacts 30min under the conditions of being 450rpm.
Sulfamethoxazole concentration is 0mg/L after surveying reaction, corresponding removal rate 100%, iron dissolution 0.05%.
(note：Sulfamethoxazole detection method：It is measured using high performance liquid chromatograph (Waters 2695, USA).)
Embodiment 4：It is a kind of to utilize Fe2+The method that/artificial zeolite activation Peracetic acid removes sulfa antibiotics in water removal, it
Include the following steps：
S1. catalyst preparation：Artificial zeolite is ground into the uniform fine powder of 200 mesh, weighing certain mass addition concentration is
In the dilute sulfuric acid of 0.1mol/L, acid solution is made just to submerge powder, stir evenly and stands 20h.It is washed with deionized water to pH and is
7.2,100 DEG C of drying are heated in Muffle furnace.According to zeolite, Fe2+Mass ratio is 55:1 ratio will be after a certain amount of drying
Fine powder is added in the ferrous sulfate solution that concentration is 0.3mol/L, after impregnating 20h, is cleaned 3~4 times with deionized water, centrifugation point
From solid being placed in 90 DEG C of baking ovens drying, catalyst is made.
S2. oxidation reaction：Peracetic acid soln 1.5mL to the 200mL 3.0mg/L sulfalene that concentration is 12g/L is added to dislike
In azoles waste water, adjusting initial pH on wastewater with sulfuric acid and sodium hydroxide solution is 8.0, then 0.3g catalyst is added into mixed liquor,
It is 25 DEG C in temperature, mixing speed reacts 25min under the conditions of being 450rpm.
Sulfamethoxazole concentration is 0.03mg/L after surveying reaction, corresponding removal rate 99.0%, iron dissolution 0.03%.
(note：Sulfamethoxazole detection method：It is measured using high performance liquid chromatograph (Waters 2695, USA).)
Embodiment 5：Single factor experiment research
(note：1, the method used when catalyst preparation in present case for：Artificial zeolite is ground into the uniform fine powder of 200 mesh,
It weighs certain mass to be added in the dilute sulfuric acid that concentration is 0.1mol/L, so that acid solution is just submerged powder, stir evenly and stand
20h.Being washed with deionized water to pH is 7.2, and 100 DEG C of drying are heated in Muffle furnace.According to zeolite, Fe2+Mass ratio is 55:1
Ratio by after a certain amount of drying fine powder be added concentration be 0.2mol/L ferrous sulfate solution in, impregnate 20h after, spend from
Sub- water cleans 3~4 times, centrifuge separation, solid is placed in drying in 90 DEG C of baking ovens, catalyst is made.2, sulfamethoxazole is degraded
The reaction solution volume that reaction uses is 100mL.3, sulfamethoxazole detection method：Using high performance liquid chromatograph (Waters
2695, USA) it measures.)
Oxidation system check experiment：,
Peracetic acid individually aoxidizes check experiment condition：Sulfamethoxazole concentration is 1.0mg/L, Peracetic acid dosage
For 100 mg/L, reacting initial pH is 7.0, and reaction time 30min, reaction temperature is 25 DEG C, and magnetic stirring speed is
450rpm。
Adsorbing check experiment condition is：Sulfamethoxazole concentration is 1.0mg/L, catalyst amounts 1.0g/L, reaction
Initial pH is 7.0, reaction time 30min, and reaction temperature is 25 DEG C, magnetic stirring speed 450rpm.
Homogeneously check experiment condition is：Sulfamethoxazole concentration is 1.0mg/L, and green vitriol dosage is
80mg/L, Peracetic acid dosage are 100mg/L, and reacting initial pH is 7.0, reaction time 30min, reaction temperature 25
DEG C, magnetic stirring speed 450rpm.
Heterogeneous experimental condition is：Sulfamethoxazole concentration is 1.0mg/L, catalyst amounts 1.0g/L, peroxide second
Sour dosage is 100mg/L, and reacting initial pH is 7.0, reaction time 30min, and reaction temperature is 25 DEG C, magnetic stirring speed
For 450rpm.The results are shown in Table 1.
The removal effect of sulfamethoxazole in the different systems of table 1
| Serial number | Test group | Sulfamethoxazole removal rate (%) |
| 1 | Peracetic acid individually aoxidizes check experiment | 29.9 |
| 2 | Adsorb check experiment | 5.6 |
| 3 | Homogeneous check experiment | 32.8 |
| 4 | Heterogeneous test | 100.0 |
Degrading experiment under the conditions of different initial pH：
Experimental condition is：Sulfamethoxazole concentration is 1.0mg/L, catalyst amounts 1.0g/L, and Peracetic acid adds
Amount is 100mg/L, and reaction time 30min, reaction temperature is 25 DEG C, magnetic stirring speed 450rpm.As a result such as 2 institute of table
Show.
The removal effect of sulfamethoxazole under the conditions of the different initial pH of table 2
| Serial number | Initial pH value | Sulfamethoxazole removal rate (%) |
| 1 | 2.0 | 98.6 |
| 2 | 3.0 | 99.4 |
| 3 | 4.0 | 99.3 |
| 4 | 5.0 | 99.8 |
| 5 | 6.0 | 100.0 |
| 6 | 7.0 | 100.0 |
| 7 | 8.0 | 100.0 |
| 8 | 9.0 | 99.7 |
Degrading experiment under differential responses time conditions：
Experimental condition is：Sulfamethoxazole concentration is 1.0mg/L, catalyst amounts 1.0g/L, and Peracetic acid adds
Amount is 100mg/L, and reacting initial pH is 7.0, and reaction temperature is 25 DEG C, magnetic stirring speed 450rpm.As a result such as 3 institute of table
Show.
The removal effect of sulfamethoxazole under 3 differential responses time conditions of table
| Serial number | Time (min) | Sulfamethoxazole removal rate (%) |
| 1 | 0 | 0 |
| 2 | 0.5 | 54.2 |
| 3 | 1 | 67.5 |
| 4 | 3 | 81.6 |
| 5 | 5 | 91.6 |
| 6 | 7 | 96.2 |
| 7 | 10 | 98.9 |
| 8 | 20 | 99.3 |
| 9 | 30 | 100.0 |
The Degrading experiment of various concentration sulfamethoxazole：
Experimental condition is：Catalyst amounts are 1.0g/L, and Peracetic acid dosage is 100mg/L, and reacting initial pH is
7.0, reaction time 30min, reaction temperature are 25 DEG C, magnetic stirring speed 450rpm.The results are shown in Table 4.
The removal effect of 4 various concentration sulfamethoxazole of table
| Serial number | Sulfamethoxazole initial concentration (mg/L) | Sulfamethoxazole removal rate (%) |
| 1 | 0.1 | 99.0 |
| 2 | 0.3 | 100.0 |
| 3 | 0.5 | 100.0 |
| 4 | 1 | 100.0 |
| 5 | 2 | 100.0 |
| 6 | 3 | 99.6 |
| 7 | 4 | 96.3 |
| 8 | 5 | 95.5 |
Degrading experiment under the conditions of different catalysts dosage：
Experimental condition is：Sulfamethoxazole concentration is 1.0mg/L, and Peracetic acid dosage is 100mg/L, reacts initial pH
It is 7.0, reaction time 30min, reaction temperature is 25 DEG C, magnetic stirring speed 450rpm.The results are shown in Table 5.
The removal effect of sulfamethoxazole under the conditions of 5 different catalysts dosage of table
| Serial number | Catalyst amounts (g/L) | Sulfamethoxazole removal rate (%) |
| 1 | 0 | 29.9 |
| 2 | 0.1 | 75.5 |
| 3 | 0.2 | 89.2 |
| 4 | 0.5 | 92.0 |
| 5 | 1.0 | 97.3 |
| 6 | 1.5 | 98.3 |
| 7 | 2.0 | 100.0 |
Degrading experiment under the conditions of different Peracetic acid dosages：
Experimental condition is：Sulfamethoxazole concentration is 1.0mg/L, catalyst amounts 1.0g/L, and reacting initial pH is
7.0, reaction time 30min, reaction temperature are 25 DEG C, magnetic stirring speed 450rpm.The results are shown in Table 6.
The removal effect of sulfamethoxazole under the conditions of the different Peracetic acid dosages of table 6
Claims (10)
1. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid, which is characterized in that screening uses
From a wealth of sources, cheap, preparation method is simple and the higher Fe of activity2+/ artificial zeolite catalyst, and utilize itself and peroxide
The heterogeneous priming reaction that acetic acid occurs in a mild condition generates the active specy of strong oxidizing property, and then degradation of contaminant,
Step includes：
S1. catalyst preparation：Artificial zeolite is ground into uniform fine powder, certain mass is weighed and is added in dilute sulfuric acid, pickling, stirring
Uniformly and after standing a period of time being washed with deionized water to pH is neutrality, and it is dry that 100 DEG C of drying are heated in baking oven；It will be a certain amount of
Fine powder after drying is added in ferrous sulfate solution, after being soaked for a period of time, is cleaned 3~4 times with deionized water, is centrifugated,
Fe is made in solid drying2+/ artificial zeolite catalyst；
S2. oxidation reaction：Prepared peracetic acid soln is added in sulfa antibiotics waste water, with sulfuric acid and sodium hydroxide
Solution adjusts initial pH on wastewater in optimum range, adds into appropriate Fe2+/ artificial zeolite catalyst is at the uniform velocity stirred in proper temperature
Under the conditions of carry out oxidation reaction.
2. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：Artificial zeolite described in step S1 is ground to 200~300 mesh fine powders, the sulfuric acid concentration that pickling uses for
0.05~0.1mol/L, pickling time be 19~for 24 hours.
3. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：When ferrous sulfate solution described in step S1 is prepared, deionized water pH is adjusted to 2.0~3.0 with sulfuric acid,
Green vitriol is added, makes Fe2+Molar concentration is 0.2~0.4mol/L.
4. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：When catalyst preparation described in step S1, artificial zeolite and Fe2+Mass ratio is 55:1~65:1, zeolite leaching
Steep the time be 20~for 24 hours.
5. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：Catalyst drying temperature described in step S1 is 70~100 DEG C.
6. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：Prepared peroxyacetic acid concentration described in step S2 is 10~12g/L.
7. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：Concentration of the Peracetic acid described in step S2 in reaction solution is 50mg/L~100mg/L.
8. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：Fe described in step S22+/ artificial zeolite catalyst amounts are 1.0g/L~2.0g/L.
9. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：Sulfa antibiotics waste water described in step S2, wherein sulfamethoxazole concentration is 0.1mg/L~3.0mg/L.
10. a kind of method for removing sulfa drugs in water removal with modified zeolite activation Peracetic acid according to claim 1,
It is characterized in that：The initial pH of the peak optimization reaction of oxidation reaction described in step S2 is 6.0~8.0, and the suitable initial pH of reaction is 2.0
~9.0, reaction temperature is 25~35 DEG C, and mixing speed is 400~500rpm, and the reaction time is 20~30min.
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| CN111661911A (en) * | 2020-06-01 | 2020-09-15 | 五邑大学 | Method for removing organic pollutants in water |
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| CN114394642A (en) * | 2022-01-27 | 2022-04-26 | 江西农业大学 | Method for adsorbing nitrosodiethylamine in water based on modified zeolite |
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