CN111995169A - Novel treatment device and treatment method for pharmaceutical wastewater - Google Patents

Abstract

The invention discloses a novel treatment device and a novel treatment method for pharmaceutical wastewater, and belongs to the technical field of sewage treatment. The method comprises the steps of firstly directly carrying out oxidative degradation on pharmaceutical wastewater to be treated by using peroxymonosulfate, then flocculating and settling the wastewater in a sedimentation tank under the action of a coagulant aid, and then sequentially enabling the wastewater to enter an anaerobic bioreactor and an MBR (membrane bioreactor) coupled with an algae system for treatment.

Description

A novel treatment device and treatment method for pharmaceutical wastewater

technical field

The invention relates to a novel treatment device and treatment method for pharmaceutical wastewater, belonging to the technical field of sewage treatment.

Background technique

With the increasing aging of my country's population and the people's emphasis on the concept of health, people's demand for rehabilitation health care and medical treatment is increasing, and the pharmaceutical industry has developed rapidly. At present, my country has become one of the world's largest producers and exporters of chemical raw materials and one of the world's largest producers of pharmaceutical preparations. At the same time, pharmaceutical wastewater is produced in large quantities. According to the 2016 China Environmental Statistical Yearbook, as of 2015, there were 3,874 pharmaceutical manufacturing enterprises in my country, and the total amount of wastewater discharged from the pharmaceutical industry reached 532.59 million tons, accounting for 2.93% of the total industrial wastewater discharge. The pharmaceutical industry has a wide variety of products and complex processes. As a result, pharmaceutical wastewater has complex composition, strong toxicity, high organic concentration, high chroma, large pH fluctuation, high nitrogen and phosphorus content, large water quality fluctuation and difficult to biodegrade. If it is not handled properly and discharged into natural water bodies, it will not only cause serious water pollution problems, destroy the ecological balance of water bodies, and affect the self-purification function of water bodies, but also continuously accumulate into organisms and human bodies through food chains and food webs, which is harmful to aquatic plants, animals and human health. bring immeasurable harm. Therefore, pharmaceutical wastewater is one of the most polluted and difficult industrial wastewaters in China.

In the 1940s, the United States was the first to use physical and chemical methods such as neutralization, precipitation, and oxidation to simply treat the wastewater of the pharmaceutical industry; in the 1950s, aerobic biological advanced treatment gradually emerged; from the 1960s to the 1970s, pure oxygen Biochemical treatment technologies such as aeration and tower biofilters have become a development trend; after the 1970s, research on wastewater treatment in the pharmaceutical industry has developed rapidly in developing countries. At present, various methods are usually used in combination at home and abroad or the traditional process is strengthened to treat pharmaceutical wastewater. However, the current commonly used treatment methods face the problems of complicated operation, high cost, unstable and unsatisfactory effluent effect. Therefore, it is necessary to seek a pharmaceutical wastewater treatment method with simple operation, low cost and good effluent effect.

SUMMARY OF THE INVENTION

In view of the problems in the prior art, the present invention provides a novel treatment device and treatment method for pharmaceutical wastewater. The method of the present invention firstly uses peroxymonosulfate to directly carry out oxidative degradation of the pharmaceutical wastewater to be treated, and then under the action of a coagulant The waste water is flocculated and settled in the sedimentation tank, and then the waste water enters the anaerobic bioreactor and the MBR membrane bioreactor coupled with the algae system for treatment. Treatment to obtain high-quality effluent.

For realizing the above technical purpose, the technical scheme of the present invention is:

A novel treatment device for pharmaceutical wastewater, comprising a peroxymonosulfate oxidation tank, a sedimentation tank, a UASB anaerobic bioreactor and an MBR membrane bioreactor, which are sequentially arranged in series from upstream to downstream; a light source is installed in the MBR membrane bioreactor and aeration device, microalgae are evenly distributed in the activated sludge in the MBR membrane reactor.

The method for treating pharmaceutical wastewater using the above-mentioned device comprises the following steps:

(1) pass into the peroxymonosulfate oxidation pond with the pharmaceutical waste water to be treated, then in the peroxymonosulfate oxidation pond, add the peroxymonosulfate reaction;

(2) adopt pH regulator to adjust the pH of peroxymonosulfate oxidation tank effluent to 7-8, then add coagulant aid to waste water, make waste water enter settling tank and settle for 20～30min after fully stirring;

(3) pass the sedimentation tank effluent into the UASB anaerobic bioreactor, and carry out anaerobic treatment under the condition that pH is 6.5～7.5 and temperature is 35°C;

(4) The effluent of the anaerobic bioreactor is passed into the MBR membrane bioreactor for treatment, and the effluent is directly discharged.

Preferably, the dosage of the peroxymonosulfate described in the step (1) is 100 to 1200 μmol/L, and the ratio of the dosage of the peroxymonosulfate to the initial concentration of the antibiotic in the pharmaceutical wastewater is 100 μmol/L: (2 ~3) mg/L.

Preferably, the pH adjusting agent in step (2) is HCl solution or Ca(OH) ₂ suspension.

Preferably, the coagulant aid described in step (2) is polyacrylamide, and the dosage of the coagulant aid is 3 mg/L.

Preferably, the UASB anaerobic bioreactor described in step (3) is filled with polyethylene plastic rings as microorganism carriers.

Preferably, the activated sludge concentration in the MBR membrane reactor described in step (4) is 6-8 g/L, and the mass ratio of microalgae and activated sludge is 10:1.

Preferably, the membrane flux of the MBR membrane reactor described in step (4) is 6-10 L/(m ² /h), the hydraulic retention time HRT of the MBR membrane reactor is 8-10 h, and the sludge retention time SRT is 15～25d.

Preferably, the aeration volume in the MBR membrane reactor described in step (4) is controlled at 2L/m ³ , the light intensity of the light source is 300 μmol/(m ² .s), and the light-dark ratio is 12h:12h.

Preferably, the device further comprises a pretreatment device, the pretreatment device is a grid or a primary sedimentation tank, and the pharmaceutical wastewater to be treated is first processed by the pretreatment device and then passed through a sulfate oxidation tank.

As can be seen from the above description, the present invention has the following advantages:

(1) the method of the present invention first adopts peroxymonosulfate to directly carry out oxidative degradation of the pharmaceutical waste water to be treated, which can remove the antibiotic substances in the pharmaceutical waste water, improve the biodegradability of the waste water, and then make the waste water in the waste water under the action of the coagulant. The flocculation and sedimentation are carried out in the sedimentation tank, and then the waste water enters the anaerobic bioreactor and the MBR membrane bioreactor coupled with the algae system for treatment. High quality water.

(2) The present invention can realize the coupling between the algae system and the existing MBR membrane bioreactor by arranging the microalgae and the light source in the MBR. Under appropriate conditions, the microalgae and the activated sludge can form a symbiotic system, so that not only can the water body be affected by The deep degradation of organic carbon in water can also greatly improve the removal effect of nitrogen, phosphorus and other nutrients in water.

(3) Compared with the traditional Fenton oxidation treatment process, the use of unactivated peroxymonosulfate to oxidize pharmaceutical wastewater does not need to adjust the pH of the wastewater, which reduces the cost of wastewater treatment, and the peroxymonosulfate oxidation is selective and does not require It will be affected by the organic matter in the wastewater, and the reaction is efficient.

Detailed ways

Below by embodiment, further illustrate the characteristics of the present invention, but do not make any limitation to the claims of the present invention.

Example 1

A novel treatment device for pharmaceutical wastewater, comprising a grid, a peroxymonosulfate oxidation tank, a sedimentation tank, a UASB anaerobic bioreactor and an MBR membrane bioreactor, which are sequentially arranged in series from upstream to downstream; UASB anaerobic bioreactor A polyethylene plastic ring is filled as a microbial carrier in the MBR membrane bioreactor, a light source and an aeration device are installed in the MBR membrane bioreactor, and microalgae are evenly distributed in the activated sludge in the MBR membrane bioreactor.

The method for treating pharmaceutical wastewater using the above-mentioned device comprises the following steps:

(1) pass the to-be-treated pharmaceutical waste water after grid interception and filtration into the peroxymonosulfate oxidation pond, then add the peroxymonosulfate reaction 10min to the peroxymonosulfate oxidation pond, wherein, the to-be-treated pharmaceutical waste water contains Tetracycline, the concentration of tetracycline is 10mg/L, and the dosage of peroxymonosulfate is 500μmol/L;

(2) The pH of the effluent from the peroxymonosulfate oxidation tank was adjusted to 7-8 by using Ca(OH) ₂ suspension, and then polyacrylamide was added to the waste water, and the dosage of polyacrylamide was 3 mg/L. After fully stirring Let the wastewater enter the sedimentation tank for 25min;

(3) The effluent of the sedimentation tank is passed into the UASB anaerobic bioreactor, and the anaerobic treatment is carried out under the conditions of pH of 6.5-7.5 and temperature of 35 °C; among which, the inoculation of anaerobic sludge in the UASB anaerobic bioreactor The ratio is 3:1;

(4) Pass the effluent of the anaerobic bioreactor into the MBR membrane bioreactor for treatment and then discharge the effluent directly, wherein the activated sludge concentration in the MBR membrane reactor is 7g/L, and the mass ratio of microalgae and activated sludge is 10:1; the membrane flux of the MBR membrane reactor is 8L/(m ² /h), the hydraulic retention time HRT of the MBR membrane reactor is 9h, and the sludge retention time SRT is 20d; the aeration volume in the MBR membrane reactor Controlled at 2L/m ³ , the light intensity of the light source was 300 μmol/(m ² .s), and the light-dark ratio was 12h:12h.

The wastewater in this embodiment adopts laboratory water distribution, and the water quality of the influent and effluent of each step in this embodiment is shown in Table 1:

Table 1

Example 2

The method for treating pharmaceutical wastewater using the same device as in Example 1, comprising the following steps:

(1) pass the to-be-treated pharmaceutical waste water after grid interception and filtration into the peroxymonosulfate oxidation pond, then add the peroxymonosulfate reaction 10min to the peroxymonosulfate oxidation pond, wherein, the to-be-treated pharmaceutical waste water contains beta-lactam, the concentration of beta-lactam is 30mg/L, and the dosage of peroxymonosulfate is 1000μmol/L;

(2) The pH of the effluent from the peroxymonosulfate oxidation tank was adjusted to 7-8 by using Ca(OH) ₂ suspension, and then polyacrylamide was added to the waste water, and the dosage of polyacrylamide was 3 mg/L. After fully stirring Let the wastewater enter the sedimentation tank for 25min;

(3) The effluent of the sedimentation tank is passed into the UASB anaerobic bioreactor, and the anaerobic treatment is carried out under the conditions of pH of 6.5-7.5 and temperature of 35 °C; among which, the inoculation of anaerobic sludge in the UASB anaerobic bioreactor The ratio is 3:1;

(4) Pass the effluent of the anaerobic bioreactor into the MBR membrane bioreactor for treatment and then discharge the effluent directly, wherein the activated sludge concentration in the MBR membrane reactor is 7g/L, and the mass ratio of microalgae and activated sludge is 10:1; the membrane flux of the MBR membrane reactor is 8L/(m ² /h), the hydraulic retention time HRT of the MBR membrane reactor is 9h, and the sludge retention time SRT is 20d; the aeration volume in the MBR membrane reactor Controlled at 2L/m ³ , the light intensity of the light source was 300 μmol/(m ² .s), and the light-dark ratio was 12h:12h.

The waste water in the present embodiment comes from a certain pharmaceutical waste water in Shanghai, and the water quality of the inlet and outlet of each step of the present embodiment is as shown in Table 2:

Comparative Example 1

The same method as in Example 2 was adopted, except that the mass ratio of microalgae and activated sludge was 9:1. The water quality of the inlet and outlet of each step of the present embodiment is shown in Table 3:

Comparative Example 2

The same method as in Example 2 was adopted, except that the mass ratio of microalgae and activated sludge was 11:1. The inlet and outlet water quality of each step of the present embodiment is as shown in Table 4:

It can be understood that the above specific description of the present invention is only used to illustrate the present invention and is not limited to the technical solutions described in the embodiments of the present invention. It should be understood by those of ordinary skill in the art that the present invention can still be modified or equivalently replaced to achieve the same technical effect; as long as the use needs are met, it is within the protection scope of the present invention.

Claims (10)

1. A novel treatment device for pharmaceutical wastewater is characterized by comprising a peroxymonosulfate oxidation tank, a sedimentation tank, a UASB anaerobic bioreactor and an MBR membrane bioreactor which are sequentially connected in series from upstream to downstream; a light source and an aeration device are arranged in the MBR membrane bioreactor, and microalgae are uniformly distributed in the activated sludge in the MBR membrane bioreactor.

2. The method for treating pharmaceutical wastewater by using the device of claim 1, comprising the steps of:

(1) introducing the pharmaceutical wastewater to be treated into a peroxymonosulfate oxidation tank, and then adding peroxymonosulfate into the peroxymonosulfate oxidation tank for reaction;

(2) adjusting the pH of effluent of a peroxymonosulfate oxidation tank to 7-8 by adopting a pH regulator, then adding a coagulant aid into the wastewater, and after fully stirring, allowing the wastewater to enter a sedimentation tank for sedimentation for 20-30 min;

(3) introducing effluent of the sedimentation tank into a UASB anaerobic bioreactor, and carrying out anaerobic treatment under the conditions that the pH is 6.5-7.5 and the temperature is 35 ℃;

(4) and (3) introducing the effluent of the anaerobic bioreactor into an MBR (membrane bioreactor) for treatment, and directly discharging the effluent.

3. The method of claim 2, wherein the amount of the peroxymonosulfate added in step (1) is 100-1200 μmol/L, and the ratio of the amount of the peroxymonosulfate added to the initial concentration of the antibiotic in the pharmaceutical wastewater is 100 μmol/L (2-3) mg/L.

4. The method of claim 2, wherein the pH regulator in step (2) is HCl solution or Ca (OH)₂And (4) suspending the solution.

5. The method according to claim 2, wherein the coagulant aid used in step (2) is polyacrylamide, and the amount of the coagulant aid added is 3 mg/L.

6. The method as claimed in claim 2, wherein the UASB anaerobic bioreactor in step (3) is filled with polyethylene plastic rings as microbial carriers.

7. The method of claim 2, wherein the concentration of the activated sludge in the MBR membrane reactor in the step (4) is 6-8 g/L, and the mass ratio of the microalgae to the activated sludge is 10: 1.

8. The method of claim 2, wherein the MBR membrane reactor in step (4) has a membrane flux of 6-10L/(m)²H), HRT (hydraulic retention time) of the MBR (membrane bioreactor) membrane reactor is 8-10 h, and SRT (sludge retention time)Is 15 to 25 days.

9. The method of claim 2, wherein the aeration rate in the MBR membrane reactor in step (4) is controlled to be 2L/m³The illumination intensity of the light source is 300 mu mol/(m)²S), light-to-dark ratio of 12h: and (4) 12 h.

10. The method of claim 2, wherein the apparatus further comprises a pretreatment device, the pretreatment device is a grid or a primary sedimentation tank, and the pharmaceutical wastewater to be treated is treated by the pretreatment device and then passed through a sulfate oxidation tank.