CN110217951A - A kind of deep treatment method of antibiotic pharmaceutical wastewater - Google Patents

Abstract

The invention provides an advanced treatment method for antibiotic pharmaceutical wastewater, which belongs to the field of pharmaceutical wastewater treatment. In the present invention, the magnetic zeolite catalyst is used as the catalyst for ozone oxidation treatment, which can effectively oxidize the refractory macromolecular organic matter in wastewater into biodegradable small molecular organic matter. At the same time, the catalyst is magnetic and easy to separate; The residual ozone in the wastewater after oxidation treatment is removed to avoid the poisonous effect of ozone on the microorganisms in the subsequent biological aerated filter; the wastewater after ozone removal passes through the biological aerated filter to obtain standard wastewater, which can be directly discharged. In addition, the advanced treatment method has the advantages of simple process and easy implementation.

Description

A kind of advanced treatment method of antibiotic pharmaceutical wastewater

technical field

The invention relates to the technical field of pharmaceutical wastewater treatment, in particular to an advanced treatment method for antibiotic pharmaceutical wastewater.

Background technique

For a long time, antibiotics have been widely used in the treatment of human and animal diseases, and are added to animal feed in sub-therapeutic doses to prevent animal diseases and promote growth. Antibiotic pharmaceutical wastewater mainly comes from domestic and industrial sewage discharge, hospital and pharmaceutical factory wastewater discharge, aquaculture wastewater and landfills, etc. also contain a large amount of antibiotic drugs. Wastewater contains a large amount of organic matter, dissolved solids, suspended The waste water has strong biological toxicity, poor biodegradability and difficult treatment. The effective treatment and up-to-standard discharge of antibiotic pharmaceutical wastewater has been a long-term focus of antibiotic manufacturers and researchers. At present, scholars at home and abroad have carried out a lot of technical research on antibiotic pharmaceutical wastewater, mainly using advanced oxidation method, enhanced biological treatment method, adsorption method, membrane separation method and coagulation sedimentation method. However, none of the above methods can effectively degrade the antibiotics to meet the discharge standards.

Contents of the invention

The purpose of the present invention is to provide an advanced treatment method for antibiotic pharmaceutical wastewater, which can effectively degrade antibiotics, and the effluent quality can stably meet the national discharge standard (GB 21903-2008).

In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

A method for advanced treatment of antibiotic pharmaceutical wastewater, comprising the steps of:

The antibiotic pharmaceutical wastewater is sequentially subjected to ozonation treatment and ozone removal to obtain biochemically treatable wastewater; the catalyst for the ozonation treatment is a magnetic zeolite catalyst;

passing the biochemically treatable waste water through a biological aerated filter to obtain standard waste water;

The magnetic zeolite catalyst includes modified natural zeolite, ferric oxide and active components, and the ferric oxide and active components are distributed on the internal pore surface and outer surface of the modified natural zeolite, and the active components are Ceria;

The preparation method of the modified natural zeolite comprises the following steps: sequentially impregnating the natural zeolite in nitric acid solution and ammonium nitrate solution to obtain the modified natural zeolite.

Preferably, the particle size of the magnetic zeolite catalyst is 180-220 mesh.

Preferably, based on the mass percentage of cerium in the modified natural zeolite, the loading amount of the active component is 1-8 wt%.

Preferably, based on the mass percentage of ferric ferric oxide in the modified natural zeolite, the loaded amount of ferric ferric oxide is 10-15 wt%.

Preferably, the amount of the magnetic zeolite catalyst is 0.5-4g/L, the concentration of ozone in the gas used for the ozone oxidation treatment is 40-60mg/L, and the flow rate of the gas used for the ozone oxidation treatment is 300-900mL/min , the time of the ozone oxidation treatment is 30-120min.

Preferably, the ozone removal catalyst is a modified natural zeolite, and the particle size of the modified natural zeolite is 1-2 cm.

Preferably, the ozone removal time is 20-40 minutes.

Preferably, the filler in the biological aerated filter includes a zeolite filler layer and a volcanic rock filler layer; the zeolite filler layer is located at the lower part of the volcanic rock filler layer; the thickness ratio of the zeolite filler layer and the volcanic rock filler layer is 0.1 to 0.5: 1.

Preferably, the air-water ratio in the biological aerated filter is 3-5:1, and the hydraulic retention time of the biochemically treatable wastewater in the biological aerated filter is 3.5-5 hours.

The invention provides a method for advanced treatment of antibiotic pharmaceutical wastewater, comprising the following steps: sequentially subject antibiotic pharmaceutical wastewater to ozone oxidation treatment and ozone removal to obtain biochemically treatable wastewater; the catalyst for the ozone oxidation treatment is a magnetic zeolite catalyst; Pass the biochemically treatable wastewater through a biological aerated filter to obtain standard wastewater; the magnetic zeolite catalyst includes modified natural zeolite, ferric oxide and active components, and the ferric oxide and active components are distributed On the internal channel surface and the external surface of the modified natural zeolite, the active component is cerium oxide; the preparation method of the modified natural zeolite comprises the following steps: sequentially impregnating the natural zeolite in nitric acid solution and ammonium nitrate solution, A modified natural zeolite is obtained.

In the present invention, the magnetic zeolite catalyst is used as the catalyst for ozone oxidation treatment, which can effectively oxidize the refractory macromolecular organic matter in wastewater into biodegradable small molecular organic matter. At the same time, the catalyst is magnetic and easy to separate; The residual ozone in the wastewater after oxidation treatment is removed to avoid the poisonous effect of ozone on the microorganisms in the subsequent biological aerated filter; the wastewater after ozone removal passes through the biological aerated filter to obtain standard wastewater, which can be directly discharged. In addition, the advanced treatment method has the advantages of simple process and easy implementation.

Detailed ways

The invention provides a kind of advanced treatment method of antibiotic pharmaceutical wastewater, comprising the following steps:

The antibiotic pharmaceutical wastewater is sequentially subjected to ozonation treatment and ozone removal to obtain biochemically treatable wastewater; the catalyst for the ozonation treatment is a magnetic zeolite catalyst;

passing the biochemically treatable waste water through a biological aerated filter to obtain standard waste water;

The magnetic zeolite catalyst includes modified natural zeolite, ferric oxide and active components, and the ferric oxide and active components are distributed on the internal pore surface and outer surface of the modified natural zeolite, and the active components are Ceria;

The preparation method of the modified natural zeolite comprises the following steps: sequentially impregnating the natural zeolite in nitric acid solution and ammonium nitrate solution to obtain the modified natural zeolite.

In the invention, the antibiotic pharmaceutical wastewater is sequentially subjected to ozone oxidation treatment and ozone removal to obtain biochemically treatable wastewater; the catalyst for the ozone oxidation treatment is a magnetic zeolite catalyst.

In the present invention, the antibiotic pharmaceutical wastewater is preferably the pharmaceutical tail water of an antibiotic pharmaceutical factory. The present invention has no special limitation on the source of the antibiotic pharmaceutical wastewater, any pharmaceutical tail water produced by antibiotic pharmaceutical factories can be used.

In the present invention, the magnetic zeolite catalyst includes modified natural zeolite, ferric iron tetroxide and active components, and the ferric ferric oxide and active components are distributed on the inner pore surface and outer surface of the modified natural zeolite, so The active component is cerium oxide; the preparation method of the modified natural zeolite comprises the following steps: sequentially impregnating the natural zeolite in nitric acid solution and ammonium nitrate solution to obtain the modified natural zeolite.

In the present invention, the particle size of the magnetic zeolite catalyst is preferably 180-220 mesh, more preferably 200 mesh. In the present invention, the magnetic zeolite catalyst with the above particle size is a powder catalyst with a large contact area with waste liquid, high catalytic efficiency, magnetic properties and easy separation.

In the present invention, based on the mass percentage of cerium in the modified natural zeolite, the loading amount of the active component is preferably 1-8 wt%.

In the present invention, based on the mass percentage of ferric oxide in the modified natural zeolite, the loaded amount of ferric oxide is preferably 10-15 wt%.

In the present invention, the preparation method of the magnetic zeolite catalyst preferably comprises the following steps:

The natural zeolite is sequentially impregnated in nitric acid solution and ammonium nitrate solution to obtain the modified natural zeolite;

Dispersing the modified natural zeolite in a mixed solution of ferrous ions and ferric ions, adding lye dropwise until the pH value is 9-11, and then aging to obtain magnetic zeolite; the ferrous ions and ferric ions The molar ratio is 1:2;

The magnetic zeolite is impregnated in the aqueous solution of cerium salt, then dried and calcined in sequence to obtain the magnetic zeolite catalyst.

In the invention, the natural zeolite is sequentially impregnated in the nitric acid solution and the ammonium nitrate solution to obtain the modified natural zeolite. In the present invention, immersion in nitric acid solution can remove impurities on the surface of zeolite, and immersion in ammonium nitrate solution can play a role in cleaning and expanding zeolite pores, and finally obtain zeolite with mesoporous pore structure.

In the present invention, the particle size of the natural zeolite used to prepare the magnetic zeolite catalyst is preferably 180-220 mesh, more preferably 200 mesh.

In the present invention, the concentration of the nitric acid solution is preferably 0.8-1.2 mol/L, more preferably 1 mol/L; the soaking time in the nitric acid solution is preferably 3-5 hours, more preferably 4 hours; the natural The dosage ratio of zeolite to nitric acid solution is preferably 1 g:2.5-3.5 mL.

After the immersion in the nitric acid solution is completed, the present invention preferably centrifuges and washes the obtained zeolite in sequence, and then immerses in the ammonium nitrate solution; the rotational speed of the centrifugation is preferably 2500-3500r/min, and the centrifugation time is preferably 5-10min The lotion for washing is preferably ultrapure water, and the number of times of washing is preferably 2 to 3 times; the method of washing is not particularly limited in the present invention, and conventional washing methods can be used.

In the present invention, the concentration of the ammonium nitrate solution is preferably 0.08-0.12mol/L, more preferably 0.1mol/L; the time of immersion in the ammonium nitrate solution is preferably 3-5h, more preferably 4h; The dosage ratio of the natural zeolite to the nitric acid solution is preferably 1g:2.5-3.5mL. After the immersion in the ammonium nitrate solution is completed, the present invention preferably carries out centrifugation, washing and drying of the gained zeolite in sequence, and the centrifugation and washing methods are the same as the centrifugation and washing methods carried out after immersion in the nitric acid solution, and are not mentioned here. To repeat; the drying temperature is preferably 100-110° C., and the drying time is preferably 9-12 hours.

In the present invention, it is preferable to maintain a stirring state during the impregnation.

After the modified natural zeolite is obtained, the present invention disperses the modified natural zeolite in a mixed solution of ferrous ions and ferric ions, drops alkaline solution until the pH value is 9-11, and then ages to obtain the magnetic zeolite; The molar ratio of the ferrous ion to the ferric ion is 1:2. In the present invention, after the lye is added dropwise, ferric oxide is gradually generated in the solution, and the color of the solution gradually changes from orange red to black, and the color of the solution remains unchanged after aging.

In the present invention, the ferrous ion is preferably provided by ferrous salt, and the ferrous salt is preferably at least one of ferrous sulfate, ferrous chloride and ferrous nitrate; It is provided that the iron salt is preferably at least one of ferric nitrate, ferric sulfate and ferric chloride; the concentration of the ferrous ion is preferably 0.04-0.18 mol/L.

In the present invention, the dosage ratio of the mixed solution of the modified natural zeolite to ferrous ions and ferric ions is preferably 1 g:8-12 mL.

In the present invention, the lye is preferably ammonia water or sodium hydroxide aqueous solution; the ammonia water is preferably concentrated ammonia water, and the mass concentration of the ammonia water is preferably 25% to 28%; the concentration of the sodium hydroxide aqueous solution is preferably 0.2 ~0.4mol/L.

In the present invention, the dropping speed is preferably 0.3-0.6 mL/s. In the present invention, rapid dropwise addition can reduce the exposure time with oxygen, so as to reduce the formation of by-product iron oxide.

In the present invention, after the lye is added dropwise until the pH value is 9-11, the present invention preferably stirs for 15-25 minutes, and then heats up to the temperature required for aging for aging. In the present invention, stirring for 15-25 minutes can prevent the agglomeration of ferric oxide particles and improve the uniformity of product particles.

In the present invention, the aging temperature is preferably 60-80° C., more preferably 70° C., and the aging time is preferably 2-3 hours, more preferably 2 hours.

After the aging is completed, the present invention preferably filters the reaction liquid obtained through aging, and washes and dries the filtered solid in sequence to obtain the magnetic zeolite.

After the magnetic zeolite is obtained, the present invention impregnates the magnetic zeolite in an aqueous solution of cerium salt, and then performs drying and roasting in sequence to obtain the magnetic zeolite catalyst.

In the present invention, the cerium salt is preferably at least one of cerium nitrate, cerium chloride and cerium sulfate, and the concentration of cerium ions in the aqueous solution of the cerium salt is preferably 0.05-0.1mol/L, more preferably 0.086 mol/L; the pH value of the aqueous solution of the cerium salt is preferably 7 to 10, more preferably 7 to 8. In the present invention, it is preferred to use ammonia water to adjust the pH value of the aqueous solution of the cerium salt, and the ammonia water is preferably concentrated ammonia water , the mass concentration of the concentrated ammonia water is preferably 25-28%; the amount ratio of the magnetic zeolite to the aqueous solution of the cerium salt is preferably 25-35g:100mL.

In the present invention, the impregnation is preferably carried out under ultrasonic conditions, and the intensity of the ultrasound is preferably 40-70 W/m ² ; the impregnation time is preferably 5-7 hours, more preferably 6 hours.

After impregnation is complete, the present invention preferably filters and the resulting solids are dried.

In the present invention, the drying temperature is preferably 55-70° C., more preferably 60° C.; the drying time is preferably 10-14 hours, more preferably 12 hours.

After drying, the present invention preferably cools the obtained solid to room temperature, grinds it, and then roasts it. In the present invention, the particle size of the grinding product is preferably 180-220 mesh. In the present invention, there is no special limitation on the grinding, as long as the dry obtained lumpy product can be dispersed.

In the present invention, the calcination is preferably carried out in an inert gas flow or a nitrogen gas flow; the flow rate of the inert gas flow or nitrogen gas flow is preferably 200-250 mL/min; the temperature of the calcination is preferably 420-480 ° C, more preferably 450 °C; the roasting time is preferably 4-5 hours, more preferably 4 hours; the heating rate to the temperature required for roasting is preferably 4-6 °C/min, more preferably 5 °C/min. In the present invention, roasting plays a role in dehydration, and simultaneously removes impurities such as anions (such as nitrate ions), and enhances the mechanical strength of the catalyst; slowly raising the temperature helps to obtain a better crystal form of the active component and improve the activity of the catalyst.

In the present invention, the amount of the magnetic zeolite catalyst is preferably 0.5-4 g/L, more preferably 1 g/L, and the concentration of ozone in the gas used for the ozone oxidation treatment is preferably 40-60 mg/L, more preferably 50 mg /; The flow rate of the gas used in the ozone oxidation treatment is preferably 300-900mL/min; the time of the ozone oxidation treatment is preferably 100-150min, more preferably 120-130min. In the present invention, during the ozone oxidation treatment process, under the catalysis of the magnetic zeolite catalyst, the refractory macromolecular organic matter is oxidized by the ozone into biodegradable small molecular organic matter.

After the ozone oxidation treatment is completed, the present invention preferably separates the wastewater after the ozone oxidation treatment from the magnetic zeolite catalyst, and then removes the ozone from the wastewater to obtain biochemically treatable wastewater.

In the present invention, the catalyst for ozone removal is preferably a modified natural zeolite, and the particle size of the modified natural zeolite is preferably 1 to 2 cm; the preparation method of the modified natural zeolite as a catalyst for ozone removal and the preparation of magnetic zeolite The method of modifying the natural zeolite in the catalyst is the same, only the particle size of the raw material natural zeolite used is different, which will not be repeated here. In the present invention, during the ozone removal process, under the catalysis of the modified natural zeolite, the ozone is decomposed, so that the concentration of dissolved ozone remaining in the water is greatly reduced, effectively reducing the impact on the microorganisms in the subsequent biological aerated filter (Excessive ozone concentration has a toxic effect on microorganisms). At the same time, the modified natural zeolite can further degrade the organic matter in the water during the process of catalyzing the decomposition of ozone, and improve the effect of advanced treatment.

In the present invention, the ozone removal time is preferably 20-40 minutes. In the present invention, the ozone removal is preferably carried out in a contact retention tank, and the filling ratio of the modified natural zeolite in the contact retention tank is preferably 60 to 80%, more preferably 70%, and the ozone removal time is is the residence time of wastewater in the contact retention tank.

After the biochemically treatable wastewater is obtained, the present invention passes the biochemically treatable wastewater through a biological aerated filter to obtain standard wastewater.

In the present invention, the filler in the biological aerated filter preferably includes a zeolite filler layer and a volcanic rock filler layer; the zeolite filler layer is located at the lower part of the volcanic rock filler layer; the thickness ratio of the zeolite filler layer and the volcanic rock filler layer is preferably 0.1-0.5:1; the filler particle size of the zeolite filler layer is preferably 1-2 cm; the filler particle size of the volcanic rock filler layer is preferably 1-2 cm. In the present invention, the design of the above-mentioned filler has a decomposing effect on dissolved ozone, which can further protect microorganisms from the influence of residual ozone and play a further protective role; at the same time, both the zeolite filler in the lower layer and the volcanic rock filler in the upper layer can be used as biological Membrane carrier.

In the present invention, the air-water ratio in the biological aerated filter is preferably 3 to 5:1, more preferably 4:1; the hydraulic retention time of the biochemically treatable wastewater in the biological aerated filter Preferably it is 3.5-5h, more preferably 4h.

In the present invention, the biofilm in the biological aerated filter is preferably prepared by the following method:

After the activated sludge is mixed with the filler of the volcanic rock filler layer, it is filled into the biological aerated filter, and the continuous water inflow mode of the biological aerated filter is turned on, and the continuous operation is 13 to 20 days to complete the film formation.

In the present invention, the activated sludge is preferably taken from the aerobic tank of the wastewater biochemical treatment unit in a pharmaceutical factory that produces antibiotic pharmaceutical wastewater.

The advanced treatment method of an antibiotic pharmaceutical wastewater provided by the present invention will be described in detail below in conjunction with the examples, but they should not be interpreted as limiting the protection scope of the present invention.

Example 1

The effluent water from the biochemical treatment unit of the sewage treatment station of an antibiotic pharmaceutical factory in a pharmaceutical park in North China is taken. The water quality is as follows: COD is 203-262 mg·L ^-1 , BOD ₅ is 23-43 mg·L ^-1 , TOC is 79-101 mg·L ^-1 , NH ₄ ⁺ -N is 9~14mg·L ^-1 , pH is 6.5~7.5, DO is 5~6mg·L ^-1 , chroma is 70~90, SS is 80~110mg L ^-1 , TN is 20 ～32mg L ^-1 , total phosphorus is 2.3mg L ^-1 .

Preparation of magnetic zeolite catalyst:

Add 30 g of 200-mesh natural zeolite to 90 mL of HNO ₃ solution with a concentration of 1.0 mol/L and stir for 4 hours, then centrifuge at 3000 r/min for 5 minutes, wash the centrifuged solid with ultrapure water twice; then add it to 90 mL Stir in _NH4NO3 solution with a concentration _of 0.1mol/L for 4h, then centrifuge at a speed of 3000r/min for 5min, wash the centrifuged solid with ultrapure water twice, put it in an oven at 105°C for 6h, and cool To room temperature, obtain modified natural zeolite;

Weigh 3.60g FeSO ₄ 7H ₂ O and 10.44g Fe(NO ₃ ) ₃ 9H ₂ O and dissolve them in 300mL of anaerobic water, take 30g of modified natural zeolite and place them in the prepared solution, and stir at room temperature Quickly add concentrated ammonia water dropwise to the suspension system to make the pH value reach 11, then stir for 20 minutes, then age in a constant temperature water bath at 70°C for 2 hours, filter, wash the obtained solid 2 to 3 times, filter again, and place in Dry in an oven at 80°C for 2 hours to obtain magnetic zeolite;

Weigh 3.72g Ce(NO ₃ ) ₃ 6H ₂ O and add it into 100.0mL of pure water to prepare a Ce(NO ₃ ) ₃ solution with a concentration of 0.086mol/L, put 30.0g of the above-mentioned magnetic zeolite in it, and use Adjust the pH value to 7 with concentrated ammonia water, ultrasonically impregnate at 60W/ ^m2 for 6h, dry in an oven at 60°C for 12h, take it out, cool to room temperature, grind it into powder, put it in a tube furnace, in a nitrogen stream , heated up to 450°C at a rate of 5°C/min, roasted at a constant temperature for 4 hours, and the flow rate of the nitrogen gas flow was 200.0mL/min; after the roasting was completed, cooled to obtain a magnetic zeolite catalyst; the magnetic zeolite catalyst was obtained by X-ray energy spectrometer analysis. The loading amount of ferric oxide is 10wt%, and the loading amount of cerium is 3.6wt%.

Pass 1L of the above-mentioned waste water into the reactor for ozone oxidation treatment for ozone oxidation treatment; the amount of magnetic zeolite catalyst used in the ozone oxidation treatment process is 1g/L, the concentration of gas used for ozone oxidation treatment is 50mg/L, and the flow rate is 600mL/min , the time of ozone oxidation treatment is 60min. After the ozone oxidation treatment is completed, the magnet is placed at the bottom of the reactor for ozone oxidation treatment, the magnetic zeolite catalyst is adsorbed at the bottom of the reactor, and then the wastewater after ozone oxidation treatment is discharged to the contact retention tank Carry out ozone removal; The modified natural zeolite is placed in the contact retention tank, the modified natural zeolite is prepared according to the preparation method of the modified natural zeolite in the preparation process of the magnetic zeolite catalyst, and the particle size of the modified natural zeolite is The filling ratio of the modified natural zeolite is 70%, and the residence time of the wastewater in the contact retention tank is 30 minutes; the wastewater that can be biochemically treated is obtained after ozone removal;

Pass the biochemically treatable wastewater through a biological aerated filter to obtain standard wastewater; the fillers in the biological aerated filter are zeolite fillers in the lower layer and volcanic rock fillers in the upper layer, the particle size of the zeolite fillers is 1 to 2 cm, and the volcanic rock fillers The particle size is 1-2cm, the thickness ratio of zeolite filler and volcanic rock filler is 0.2:1, and the biological aerated filter should be film-coated before use. Specifically, it is best to take the biochemical treatment unit of the sewage treatment station of an antibiotic pharmaceutical factory in a pharmaceutical park. Activated sludge in the oxygen tank, after mixing the activated sludge with volcanic rock filler, fill it on the zeolite filler layer of the biological aerated filter, turn on the continuous water inlet mode of the biological aerated filter, and run continuously for 20 days, complete Membrane hanging, biochemically treated wastewater is passed through, and the air-water ratio is 4:1 during the process of passing through the biological aerated filter, and the hydraulic retention time is 4h.

Example 2

According to the method of Example 1, the advanced treatment of biopharmaceutical wastewater was carried out, the difference being that the addition of FeSO ₄ 7H ₂ O was 3.60 g, and the addition of Fe(NO ₃ ) ₃ 9H ₂ O was 10.44 g, The concentration of the Ce(NO ₃ ) ₃ solution is 0.043mol/L, the loading amount of ferric oxide in the magnetic zeolite catalyst is 10wt%, and the loading amount of cerium is 1.8wt%.

Example 3

According to the method of Example 1, the advanced treatment of biopharmaceutical wastewater was carried out, the difference being that the addition of FeSO ₄ 7H ₂ O was 3.60 g, and the addition of Fe(NO ₃ ) ₃ 9H ₂ O was 10.44 g, The concentration of the Ce(NO ₃ ) ₃ solution is 0.172 mol/L, the loading amount of ferric oxide in the magnetic zeolite catalyst is 10wt%, and the loading amount of cerium is 7.9wt%.

Example 4

Advanced treatment of antibiotic pharmaceutical wastewater was carried out according to the method of Example 1, the difference being that no catalyst was added to the contact retention tank, the residence time was 1 h, and the residual ozone in the sewage was naturally decomposed in the contact retention tank.

Example 5

Advanced treatment of antibiotic pharmaceutical wastewater was carried out according to the method of Example 1, except that the filler in the biological aerated filter was only volcanic rock filler.

Comparative example 1

Advanced treatment of antibiotic pharmaceutical wastewater was carried out according to the method of Example 1, the difference being that the catalyst used in the ozone oxidation treatment was LTA artificial zeolite with a particle size of 200 mesh.

The various indicators of the waste water obtained by the treatment of Examples 1 to 5 and Comparative Example 1 are analyzed, specifically: according to "State Environmental Protection Administration. Water and Waste Water Monitoring and Analysis Method" (4th Edition. Beijing: China Environmental Science Press, 2002) disclosed method tests COD, NH ₄ ⁺ -N, TN (total nitrogen), TP (total phosphorus), SS (suspended solids), BOD ₅ (biochemical oxygen demand) adopts 5 days culture method to measure; TOC (total Organic carbon) was measured by a TOC instrument (Analytik JenaMulti N/C 2100, Germany); the pH value of the solution was measured by a pH meter (OHAUS Starter 3C, Ohaus, USA). The results are shown in Table 1:

Table 1 embodiment 1～5 gained up to standard waste water and comparative example 1 every index of treated gained waste water

It can be seen from Table 1 that all indicators of the wastewater obtained in Examples 1-5 can meet the GB 21903-2008 standard, and can be directly discharged, and the biological oxygen demand and chemical oxygen demand of the wastewater obtained in Examples 1-5 are both low Compared with Comparative Example 1, it shows that the technical solution provided by the present invention can more fully degrade the organic matter in the wastewater. In addition, it can be seen from Table 1 that the biological oxygen demand and chemical oxygen demand of the wastewater obtained in Example 1 are lower than those in Examples 4-5, indicating that the addition of an ozonolysis catalyst is conducive to further deep degradation of organic matter. Zeolite filler and volcanic rock filler can further improve the wastewater treatment effect.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (9)

1. a kind of deep treatment method of antibiotic pharmaceutical wastewater, which comprises the steps of:

Antibiotic pharmaceutical wastewater is successively carried out to ozone Oxidation Treatment and ozone removal, obtains the waste water of biochemical processing；It is described The catalyst of ozone Oxidation Treatment is magnetic zeolite catalyst；

By the waste water of the biochemical processing by biological aerated filter, waste water up to standard is obtained；

The magnetic zeolite catalyst includes modified natural zeolite, ferroso-ferric oxide and active component, the ferroso-ferric oxide and Internal channel surfaces and outer surface of the Active components distribution in modified natural zeolite, the active component are cerium oxide；

The preparation method of the modified natural zeolite includes the following steps: natural zeolite is successively molten in nitric acid solution and ammonium nitrate It is impregnated in liquid, obtains modified natural zeolite.

2. deep treatment method according to claim 1, which is characterized in that the granularity of the magnetic zeolite catalyst is 180~220 mesh.

3. deep treatment method according to claim 1 or 2, which is characterized in that account for the quality of modified natural zeolite with cerium Percentages, the load capacity of the active component are 1~8wt%.

4. deep treatment method according to claim 1 or 2, which is characterized in that account for modified natural boiling with ferroso-ferric oxide The mass percent meter of stone, the load capacity of the ferroso-ferric oxide are 10~15wt%.

5. deep treatment method according to claim 1 or 2, which is characterized in that the dosage of the magnetic zeolite catalyst For 0.5~4g/L, the concentration of the gases used middle ozone of ozone Oxidation Treatment is 40~60mg/L, the ozone Oxidation Treatment Gases used flow is 300~900mL/min, and the time of the ozone Oxidation Treatment is 30~120min.

6. deep treatment method according to claim 1, which is characterized in that the catalyst of the ozone removal is modified day Right zeolite, the partial size of the modified natural zeolite are 1~2cm.

7. deep treatment method according to claim 1 or 6, which is characterized in that the time of ozone removal is 20~ 40min。

8. deep treatment method according to claim 1, which is characterized in that the filler in the biological aerated filter includes Zeolite filler layer and volcanic filling material layer；The zeolite filler layer is located at volcanic filling material layer lower part；The zeolite filler layer and The thickness ratio of volcanic filling material layer is 0.1~0.5:1.

9. deep treatment method according to claim 1, which is characterized in that the gas-water ratio in the biological aerated filter is 3~5:1, hydraulic detention time of the waste water of the biochemical processing in biological aerated filter are 3.5~5h.