CN218115223U - Treatment device for refractory pharmaceutical wastewater - Google Patents
Treatment device for refractory pharmaceutical wastewater Download PDFInfo
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- CN218115223U CN218115223U CN202222137435.3U CN202222137435U CN218115223U CN 218115223 U CN218115223 U CN 218115223U CN 202222137435 U CN202222137435 U CN 202222137435U CN 218115223 U CN218115223 U CN 218115223U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The utility model relates to a processing apparatus of difficult degradation pharmacy waste water. The method comprises the following steps: the pH adjusting tank is used for adjusting the pH value of the wastewater to be neutral; the pulse electrocoagulation reactor is connected with the pH adjusting tank and is used for carrying out pulse electrocoagulation reaction on the wastewater treated by the pH adjusting tank; the hydrolysis acidification pool is connected with the pulse electrocoagulation reactor and is used for carrying out hydrolysis acidification treatment on the wastewater obtained in the pulse electrocoagulation reactor; the aerobic reaction tank is connected with the hydrolysis acidification tank and is used for carrying out aerobic decomposition reaction on the wastewater treated in the hydrolysis acidification tank; the MBR membrane is connected to the aerobic reaction tank and is used for performing membrane biological reaction and filtration treatment on the wastewater obtained in the aerobic reaction tank; the system also comprises a first circulating pump and a second circulating pump, wherein the hydrolysis acidification tank, the first circulating pump, the aerobic reaction tank and the second circulating pump are sequentially connected in series to form a circulating pipeline. This patent is through carrying out cyclic processing back with hydrolytic acidification and aerobic reaction, has improved the efficiency of aerobic degradation process.
Description
Technical Field
The utility model relates to a processing apparatus of difficult degradation pharmacy waste water belongs to waste water treatment technical field.
Background
Pharmaceutical wastewater includes four types of wastewater, i.e., organic synthetic drug wastewater, inorganic synthetic drug wastewater, antibiotic wastewater, and Chinese herbal medicine production wastewater. Pharmaceutical wastewater, especially wastewater generated by chemical synthesis process in pharmaceutical industry, often has the following characteristics: the water quality has complex components, high content of pollutants in the wastewater, high COD value, a plurality of toxic and harmful substances, a plurality of substances which are difficult to be biologically degraded, and high salinity and chromaticity of partial wastewater.
Generally, in the case of pharmaceutical wastewater from synthetic drugs, biological treatment is used, including aerobic, anaerobic and anaerobic-aerobic combined treatment, which mainly decomposes the components of wastewater by the action of microorganisms, so that in some treatment systems the biological treatment is combined with other treatment steps. For example, chinese patent medicineThe CN109111019B discloses a method for treating high-concentration and degradation-resistant chemical synthesis pharmaceutical wastewater, and the system comprises a pre-aeration adjusting tank, a coagulating sedimentation tank, a Fenton reactor, nano TiO which are connected in sequence 2 A photocatalytic reactor, a buffer sedimentation tank, a comprehensive adjusting tank, a forced hydrolysis tank, an IC distribution tank, an IC anaerobic reactor, a multifunctional biological purification tank, a secondary sedimentation tank and a clean water tank.
The problems in this processing system are: meanwhile, steps of coagulation, fenton reaction, photocatalysis, hydrolysis, anaerobic reaction and the like are used, so that the working procedure is too long, and the equipment investment cost and the operation cost are increased.
Disclosure of Invention
The utility model discloses the technical problem that will solve is: the prior art has the problems of more equipment flows, high investment cost and high operation cost when the pharmaceutical wastewater which is difficult to degrade is treated.
The patent solves the idea that the intermittent hydrolysis aerobic cycle process is utilized to carry out flow treatment, the treatment of the wastewater difficult to degrade is realized in a short flow mode, the equipment investment and the operation cost are reduced, and the treatment effect and the water quality can both meet the technical requirements.
The technical scheme is as follows:
a treatment device for refractory pharmaceutical wastewater comprises:
the pH adjusting tank is used for adjusting the pH value of the wastewater to be neutral;
the pulse electrocoagulation reactor is connected with the pH adjusting tank and is used for carrying out pulse electrocoagulation reaction on the wastewater treated by the pH adjusting tank;
the hydrolysis acidification pool is connected with the pulse electric flocculation reactor and is used for carrying out hydrolysis acidification treatment on the wastewater obtained in the pulse electric flocculation reactor;
the aerobic reaction tank is connected with the hydrolysis acidification tank and is used for carrying out aerobic decomposition reaction on the wastewater treated in the hydrolysis acidification tank;
the MBR membrane is connected to the aerobic reaction tank and is used for performing membrane biological reaction and filtration treatment on the wastewater obtained in the aerobic reaction tank;
the system also comprises a first circulating pump and a second circulating pump, and a circulating pipeline is formed by sequentially connecting the hydrolysis acidification tank, the first circulating pump, the aerobic reaction tank and the second circulating pump in series.
Further comprising: and the acid liquid tank is connected with the pH adjusting tank and is used for adding acid liquid into the pH adjusting tank.
Further comprising: and the grid is connected to the pH adjusting tank and used for preliminarily filtering the wastewater entering the pH adjusting tank to remove suspended matters.
The pulse electrocoagulation reactor is provided with polar plates, wherein the anode polar plate is made of iron, and the cathode polar plate is made of titanium.
A stirrer and a sheet type filler are arranged in the hydrolysis acidification tank, the diameter of a plastic ring sheet of the filler is 10-50mm, the sheet interval is 20-60mm, and the filling amount is 1000-3000 sheets/m 3 。
The bottom of the aerobic reaction tank is provided with an aeration pipe.
The MBR membrane is provided with a hollow fiber membrane with the aperture of 0.1-0.5 um.
Advantageous effects
In the process of treating the pharmaceutical wastewater difficult to degrade, after hydrolytic acidification and aerobic reaction are circularly treated, degradation products in a hydrolytic reactor enter an aerobic reactor through circulation, the inhibition effect of the intermediate products is reduced, and the efficiency of the hydrolytic degradation process is improved.
Drawings
Fig. 1 is a flow chart of the present patent.
Fig. 2 is a diagram of the apparatus of this patent.
FIG. 3 is a graph showing the effect of COD treatment in a hydrolytic acidification tank.
FIG. 4 is a graph showing the effect of COD treatment in the aerobic reaction tank.
Wherein, 1, a grid; 2. a pH adjusting tank; 3. an acid liquor tank; 4. a pulse electrocoagulation reactor; 5. a hydrolysis acidification pool; 6. an aerobic reaction tank; 7. an aeration pipe; 8. MBR membrane; 9. a first circulation pump; 10. and a second circulation pump.
Detailed Description
The refractory pharmaceutical wastewater to be treated in the following examples is exemplified by synthetic wastewater of an ethoxybenzoic acid intermediate, ethoxybenzoic acid is an important pharmaceutical intermediate, and the synthetic steps are mainly obtained by reacting salicylic acid with diethyl sulfate, and the reaction flow is as follows:
the basic water quality condition of the waste water is as follows: the COD is 3700 to 4100mg/L, the pH value is 11.0 to 12.0, the chroma is 280 to 310, the transparency is realized, and the B/C is 0.18 to 0.20.
When catalytic decomposition is carried out on waste water generated in the reaction process and aerobic treatment is continuously carried out, molecules such as ethoxybenzoic acid and the like simultaneously generate intermediate products such as acetaldehyde and acetic acid during the aerobic treatment, small molecules are difficult to metabolize in a hydrolysis system, and the accumulated larger acetaldehyde and the like also inhibit the activity of microorganisms.
Based on the water quality condition, the process route adopted by the patent is as follows:
the waste water is processed by a grille well, larger suspended matters or floating matters are intercepted, and the waste water is lifted to a regulating tank through a lifting pump; homogenizing water quality and water quantity in an adjusting tank, and adjusting the pH value to be neutral by using hydrochloric acid; the effluent of the regulating reservoir is pumped to a pulse electrocoagulation reaction tank by a lift pump, wherein the pulse electrocoagulation adopts a power supply mode of 'power supply-power off-power supply' which is repeated continuously, and a pulse signal is applied in the pulse electrocoagulation process, so that the reaction on the electrode is intermittent, and the diffusion of solution ions on the surface of the electrode is facilitated. In normal operation, the electrode (for example, an iron anode) mainly reacts as follows:
anodic oxidation:
Fe-3e→Fe 3+
2H 2 O-4e→O 2 ↑+4H +
cathode reduction:
2H + +2e→H 2 ↑
the total reaction is as follows:
Fe 3+ +3H 2 O→Fe(OH) 3 +3H + fe produced at the anode 3+ Provides a metal source for flocculation, and simultaneously generates oxygen with strong oxidizability, which can directly oxidize organic matters. The hydrogen generated by the cathode floats suspended matters and flocculates in the wastewater to the water surface through the air flotation effect, so that the removal is facilitated. Application of a pulse signal to cause Fe produced at the anode 3+ Can be sufficiently diffused into the solution to be uniform. In the operation process, the current intensity is controlled to be 0.01-0.05A/cm 2 The pulse frequency is 0.5-2KHz, and the hydraulic retention time is 40-100min.
After pulse electric flocculation treatment, bigger organic matters in the wastewater can be further decomposed into micromolecular organic matters, the wastewater is sent into a hydrolysis acidification-aerobic cycle process for treatment, the hydrolysis process comprises a hydrolysis acidification reactor and an aerobic reactor for an aerobic reaction process, and in the reaction process, a part of the wastewater obtained from the aerobic reactor flows back to the hydrolysis acidification reactor to realize cycle treatment. A stirrer and a combined fiber filler are arranged in the hydrolysis acidification tank, the diameter of a plastic ring sheet of the filler is 35mm, the sheet interval is 40mm, and the filling amount is 2300 sheets/m 3 And 6 porous sand core aeration heads are uniformly distributed at the bottom of the aerobic reactor. In the hydrolysis acidification process, firstly, sludge is added according to 4-6g/L of MLSS for starting, and after the operation is carried out for 3-5d, wastewater treatment can be carried out; meanwhile, aerating in an aerobic reactor to ensure that the dissolved oxygen reaches more than 3mg/L, wherein the hydraulic retention time in the hydrolysis acidification process is 6-8d, the retention time in the aerobic reaction operation process is 4-6d, and in the operation process, part of wastewater in the aerobic reaction is refluxed in the hydrolysis acidification process through a circulating pump for circular treatment, and the volume ratio of the wastewater in a hydrolysis acidification pool to the wastewater in an aerobic reaction pool is 1.2-1.5 by adjusting the flow rate: 1.
after the treatment, the wastewater is sent into an MBR reactor for advanced treatment, COD in the wastewater is further degraded by aerobic bacteria in an MBR tank, water and activated sludge are subjected to solid-liquid separation through an MBR membrane, the separated excess sludge is discharged into a sludge treatment system, and the produced water can be directly discharged to reach the first-level A standard of the industry. The MBR reactor is of a negative pressure suction type, wherein a hollow fiber membrane with the aperture of 0.1-0.5um is filled in the MBR reactor, and the negative pressure range is-0.05 to-0.08 MPa.
Based on the above method, the apparatus adopted in this patent, as shown in fig. 2, includes:
the pH adjusting tank 2 is used for adjusting the pH value of the wastewater to be neutral;
the pulse electrocoagulation reactor 4 is connected with the pH adjusting tank 2 and is used for carrying out pulse electrocoagulation reaction on the wastewater treated by the pH adjusting tank 2;
the hydrolysis acidification pool 5 is connected with the pulse electrocoagulation reactor 4 and is used for carrying out hydrolysis acidification treatment on the wastewater obtained in the pulse electrocoagulation reactor 4;
the aerobic reaction tank 6 is connected with the hydrolysis acidification tank 5 and is used for carrying out aerobic decomposition reaction on the wastewater treated in the hydrolysis acidification tank 5;
the MBR membrane 8 is connected to the aerobic reaction tank 6 and is used for performing membrane biological reaction and filtration treatment on the wastewater obtained in the aerobic reaction tank 6;
wherein, still include first circulating pump 9 and second circulating pump 10, and form a circulation pipeline through hydrolysis-acidification tank 5, first circulating pump 9, aerobic reaction pond 6 and second circulating pump 10 series connection in proper order.
Further comprising: and the acid liquor tank 3 is connected to the pH adjusting tank 2 and is used for adding acid liquor into the pH adjusting tank 2.
Further comprising: and the grid 1 is connected to the pH adjusting tank 2 and is used for preliminarily filtering the wastewater entering the pH adjusting tank 2 to remove suspended matters.
The pulse electrocoagulation reactor 4 is provided with polar plates, wherein the anode polar plate is made of iron, and the cathode polar plate is made of titanium.
A stirrer and a combined fiber filler are arranged in the hydrolysis acidification tank, the diameter of a plastic ring sheet of the filler is 10-50mm, the sheet interval is 20-60mm, and the filling amount is 1000-3000 sheets/m 3 ，
The bottom of the aerobic reaction tank 6 is provided with an aeration pipe.
The MBR membrane is provided with a hollow fiber membrane with the aperture of 0.1-0.5 um.
The basic water quality condition of the ethoxybenzoic acid intermediate wastewater treated in the following examples is as follows: the COD is 3700 to 4100mg/L, the pH value is 11.0 to 12.0, the chroma is 280 to 310, the transparency is realized, and the B/C is 0.18 to 0.20.
Example 1
Firstly, pre-filtering the wastewater by a grid, then adjusting the pH to be about neutral by adding hydrochloric acid, and performing electrocoagulation treatment by a pulse electrocoagulation reactor, wherein iron is used as an anode, titanium is used as a cathode, and the current intensity is controlled to be 0.02A/cm 2 The pulse frequency is 1KHz, the hydraulic retention time is 60min, then the wastewater is treated in a centralized way through a hydrolysis acidification tank and an aerobic reaction tank which are started and completed, the dissolved oxygen in the hydrolysis acidification tank is controlled to be below 0.5mg/L, the retention time is controlled to be about 7d, the dissolved oxygen in the aerobic reaction tank is more than 3mg/L, the bottom aeration treatment is carried out, the retention time is controlled to be 5d, and the wastewater in the aerobic reaction tank is treated by refluxing through a circulating pump in the process, so that the volume ratio of the wastewater in the overall hydrolysis acidification tank to the wastewater in the aerobic reaction tank is 1.3:1; and (4) feeding the treated wastewater into an MBR membrane reactor for deep decomposition and purification treatment.
The quality of produced water:
comparative example 1
The difference from example 1 is that: and no circular treatment is carried out between the hydrolysis acidification tank and the aerobic reaction tank.
Firstly, the wastewater is pre-filtered by a grid, then the pH is adjusted to be about neutral by adding hydrochloric acid, the electric flocculation treatment is carried out by a pulse electric flocculation reactor, iron is used as an anode in the pulse electric flocculation reactor, titanium is used as a cathode, and the current intensity is controlled to be 0.02A/cm 2 Pulse frequency is 1KHz, hydraulic retention time is 60min, then the waste is treatedWater is treated in a centralized way through a hydrolysis acidification tank and an aerobic reaction tank which are started and finished, the dissolved oxygen in the hydrolysis acidification tank is controlled below 0.5mg/L, so that the retention time is controlled to be about 7d, the dissolved oxygen in the aerobic reaction tank is more than 3mg/L, and the bottom aeration treatment is carried out, so that the retention time is controlled to be 5d; and (4) feeding the treated wastewater into an MBR membrane reactor for deep decomposition and purification treatment.
The quality of produced water:
through the comparison, after the hydrolytic acidification and the aerobic reaction are circularly processed, degradation products in the hydrolytic reactor enter the aerobic reactor through circulation, the inhibition effect of the intermediate products is reduced, and the efficiency of the hydrolytic degradation process is improved.
Claims (10)
1. A treatment device for refractory pharmaceutical wastewater, comprising:
the pH adjusting tank (2) is used for adjusting the pH value of the wastewater to be neutral;
the pulse electrocoagulation reactor (4) is connected with the pH adjusting tank (2) and is used for carrying out pulse electrocoagulation reaction on the wastewater treated by the pH adjusting tank (2);
the hydrolysis acidification pool (5) is connected with the pulse electric flocculation reactor (4) and is used for carrying out hydrolysis acidification treatment on the wastewater obtained in the pulse electric flocculation reactor (4);
the aerobic reaction tank (6) is connected with the hydrolytic acidification tank (5) and is used for carrying out aerobic decomposition reaction on the wastewater treated in the hydrolytic acidification tank (5);
the MBR membrane (8) is connected to the aerobic reaction tank (6) and is used for performing membrane biological reaction and filtration treatment on the wastewater obtained in the aerobic reaction tank (6);
the system also comprises a first circulating pump (9) and a second circulating pump (10), and a circulating pipeline is formed by sequentially connecting the hydrolysis acidification tank (5), the first circulating pump (9), the aerobic reaction tank (6) and the second circulating pump (10) in series.
2. The apparatus for treating refractory pharmaceutical wastewater as set forth in claim 1, further comprising: and the acid liquor tank (3) is connected to the pH adjusting tank (2) and is used for adding acid liquor into the pH adjusting tank (2).
3. The apparatus for treating refractory pharmaceutical wastewater as set forth in claim 1, further comprising: and the grid (1) is connected to the pH adjusting tank (2) and is used for preliminarily filtering the wastewater entering the pH adjusting tank (2) to remove suspended matters.
4. The apparatus for treating refractory pharmaceutical wastewater as defined in claim 1, wherein the pulse electrocoagulation reactor (4) is installed with anode plate and cathode plate.
5. The apparatus for treating pharmaceutical wastewater difficult to degrade according to claim 4, wherein the anode plate is made of iron.
6. The apparatus for treating pharmaceutical wastewater difficult to degrade according to claim 4, wherein the cathode plate is made of titanium.
7. The apparatus for treating pharmaceutical wastewater difficult to degrade according to claim 1, wherein a stirrer and a sheet filler are disposed in the hydrolysis acidification tank.
8. The apparatus for treating pharmaceutical wastewater difficult to degrade according to claim 7, wherein the diameter of the plate-type filler is 10-50mm, the distance between plates is 20-60mm, and the filling amount is 1000-3000 plates/m 3 。
9. The apparatus for treating refractory pharmaceutical wastewater as defined in claim 1, wherein the bottom of the aerobic reaction tank (6) is provided with an aerator pipe.
10. The apparatus for treating refractory pharmaceutical wastewater according to claim 1, wherein the MBR membrane is provided with a hollow fiber membrane with a pore size of 0.1-0.5 um.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202222137435.3U CN218115223U (en) | 2022-08-15 | 2022-08-15 | Treatment device for refractory pharmaceutical wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202222137435.3U CN218115223U (en) | 2022-08-15 | 2022-08-15 | Treatment device for refractory pharmaceutical wastewater |
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| Publication Number | Publication Date |
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| CN218115223U true CN218115223U (en) | 2022-12-23 |
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| CN202222137435.3U Active CN218115223U (en) | 2022-08-15 | 2022-08-15 | Treatment device for refractory pharmaceutical wastewater |
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