CN115215490B

CN115215490B - Pretreatment method of antibiotic production wastewater

Info

Publication number: CN115215490B
Application number: CN202211149614.7A
Authority: CN
Inventors: 王啸; 田野; 田哲; 于勇; 王运
Original assignee: Shijiazhuang Secco Environmental Protection Research Institute; Hebei Wangxiao Environmental Protection Engineering Co ltd
Current assignee: Shijiazhuang Secco Environmental Protection Research Institute; Hebei Wangxiao Environmental Protection Engineering Co ltd
Priority date: 2022-09-21
Filing date: 2022-09-21
Publication date: 2023-02-07
Anticipated expiration: 2042-09-21
Also published as: CN115215490A

Abstract

The invention relates to the technical field of wastewater treatment, and provides a pretreatment method of antibiotic production wastewater, which comprises the following steps of S1, adjusting the pH value of antibiotic wastewater to 7.5-10 to obtain a mixture A; s2, adding a catalyst into the mixture A, and uniformly stirring to obtain a mixture B; s3, heating the mixture B to 110-160 ℃ to obtain a mixture C; s4, allowing the mixture C to enter a membrane module to separate ammonia gas, and finishing pretreatment; the catalyst comprises one or more of CaO-NiO, mgO-NiO, caO-CoO and MgO-CoO. Through the technical scheme, the problem that in the prior art, the additive amount of the medicament is large in the process of strengthening hydrolysis treatment of antibiotic wastewater, and synchronous removal of antibiotic and ammonia nitrogen cannot be realized, so that anaerobic biological treatment cannot be stably carried out is solved.

Description

Pretreatment method of antibiotic production wastewater

Technical Field

The invention relates to the technical field of wastewater treatment, in particular to a pretreatment technology of antibiotic production wastewater.

Background

China is a main production base of the fermented antibiotics in the world, and the production of the fermented antibiotics plays an important role in the economy of China. The production of the fermentation antibiotics mainly comprises the steps of fermentation, filtration, extraction, refining and the like, and the pharmaceutical wastewater has high Chemical Oxygen Demand (COD), high ammonia nitrogen, high biological concentration and complex composition and is typical high-concentration refractory organic wastewater. From the characteristics of COD and ammonia nitrogen, the wastewater is suitable for biological treatment, such as removing COD through anaerobic biological treatment and removing ammonia nitrogen through a nitrification-denitrification biological process, which is a mature and low-cost treatment technology. However, high concentrations of antibiotics are also present in the wastewater, which severely inhibit the functional microorganisms of the wastewater treatment, resulting in failure of the biological treatment. Therefore, the addition of a pretreatment process before biological treatment to remove antibiotic inhibition is the key to realizing the biological treatment of the wastewater.

Only antibiotics in the pharmaceutical wastewater can be removed by singly using the intensified hydrolysis pretreatment technology, and ammonia nitrogen cannot be removed. That is, for pharmaceutical wastewater with low ammonia nitrogen concentration, only intensified hydrolysis can be used as a pretreatment process, and then subsequent anaerobic biological treatment can be performed. For the pharmaceutical wastewater with high ammonia nitrogen concentration, ammonia nitrogen is removed in other pretreatment modes after the enhanced hydrolysis, and then the pharmaceutical wastewater enters anaerobic biological treatment. Thus, the treatment cost is high and the process flow is long. For the physicochemical removal of ammonia nitrogen, the traditional ammonia distillation method is influenced by blowing-off and foaming, the foam is not foam understood in the traditional sense, but foam similar to sponge, as shown in figure 1, and the application of the ammonia distillation method is severely limited. The hydrophobic membrane denitrification method does not require stripping, but is affected by organic matters in wastewater to cause membrane penetration, and cannot be used continuously.

In the ammonia nitrogen recovery process, whatever the technology is used, the pH needs to be adjusted to be alkaline, generally 9-11. The pH value of the inlet water of the anaerobic treatment is generally controlled to be 6-7, so that the treatment requirement can be met by adding alkali first and then adding acid, the salt content of the wastewater is increased, and the medicament cost is increased. In the process of intensified hydrolysis, the hydrolysis speed of the antibiotic is slower, and the denitrification speed is faster, so that the situation that ammonia nitrogen is recovered but the antibiotic is not completely hydrolyzed can occur, and the hydrolysis speed of the antibiotic needs to be improved, so that the two processes are completed in a similar time. Application No. 201410185329.X, a pretreatment method for removing antibiotics in fermentation antibiotic pharmaceutical wastewater, and the reinforced hydrolysis pretreatment can only realize the destruction of antibiotics and cannot simultaneously remove ammonia nitrogen.

Disclosure of Invention

The invention provides a pretreatment method of antibiotic production wastewater, which solves the problem that anaerobic biological treatment cannot be stably carried out due to the fact that in the prior art, the additive amount of a medicament is large in the process of strengthening hydrolysis treatment of antibiotic wastewater, and synchronous removal of antibiotic and ammonia nitrogen cannot be realized.

The technical scheme of the invention is as follows:

a pretreatment method of antibiotic production wastewater comprises the following steps:

s1, adjusting the pH value of antibiotic wastewater to 7.5-10 to obtain a mixture A;

s2, adding a catalyst into the mixture A, and uniformly stirring to obtain a mixture B;

s3, heating the mixture B to 110-160 ℃ to obtain a mixture C;

s4, allowing the mixture C to enter a membrane module to separate ammonia gas, and finishing pretreatment;

the catalyst comprises one or more of CaO-NiO, mgO-NiO, caO-CoO and MgO-CoO.

As a further technical scheme, after the pH value of the pretreatment substance is adjusted to 6-7, anaerobic biological treatment can be carried out.

As a further technical scheme, the water quality of the antibiotic wastewater is characterized in that 100-2000 mg/L of antibiotic and 500-3000 mg/L of ammonia nitrogen.

As a further technical scheme, the water quality of the antibiotic wastewater is characterized in that the antibiotic is 800-2000 mg/L, and the ammonia nitrogen is 800-2000 mg/L.

As a further technical scheme, the fermentation pharmaceutical wastewater comprises organic wastewater generated after beta-lactams, tetracyclines, macrolides, aminoglycosides, polypeptides or other antibiotics are produced by a fermentation method.

As a further technical scheme, the antibiotics comprise one or more of terramycin, penicillin, cefamycin, erythromycin, spiramycin, streptomycin, gentamicin and colistin.

As a further technical scheme, the pH value in the step S1 is 8-9.

As a further technical scheme, the input amount of the catalyst in the step S2 is 0.01-0.1g/L.

As a further technical scheme, the membrane component in the step S4 is a tubular membrane, and the pore diameter is 0.1-0.3 μm.

As a further technical scheme, the membrane assembly in the step S4 includes a gaseous membrane, and the gaseous membrane is made of polytetrafluoroethylene.

As a further technical scheme, the residence time of the membrane component entering in the step S4 is 10-30min.

As a further technical scheme, the residence time of the membrane component entering in the step S4 is 15-20min.

As a further technical scheme, the absorption liquid of the membrane module in the step S4 is 2-3mol/L sulfuric acid.

As a further technical scheme, the anaerobic treatment comprises one of an anaerobic biological filter, an upflow granular sludge bed, a granular sludge expanded bed, an internal circulation anaerobic reactor and an anaerobic membrane bioreactor.

The working principle and the beneficial effects of the invention are as follows:

1. the invention provides a pretreatment method of antibiotic production wastewater, aiming at the technical problems that in the prior art, ammonia nitrogen can not be removed in the process of treating antibiotic wastewater by adopting reinforced hydrolysis, so that when the high ammonia nitrogen pharmaceutical wastewater is treated, subsequent anaerobic sludge organisms are inhibited by ammonia nitrogen, particularly free ammonia, the treatment capacity is obviously reduced, the anaerobic biological treatment can not stably run, and even the treatment capacity is lost, and the principle of the method is shown in figure 2. First, catalytic hydrolysis of antibiotics. At high temperature, the pharmacodynamic functional group of the antibiotic can react with hydrogen ions and hydroxyl in water, and is quickly inactivated under the promotion action of micro-electrolysis and a novel catalyst. Secondly, at the same time, under the high temperature and the lower pH value, more than 90 percent of ammonia nitrogen still can be ensured to exist in the form of free ammonia, and under the action of pressure difference between two sides, the ammonia nitrogen selectively permeates the hydrophobic membrane and is absorbed by acid solution (such as sulfuric acid) on the other side. The whole process is very quick, and the reaction can be completed within about 15-20min. Compared with the traditional treatment mode, the method has the advantages of simple operation, low energy consumption, high reaction speed, small medicament addition and low operation cost.

2. The novel catalyst is added to treat the antibiotic production wastewater, so that the hydrolysis rate of the antibiotic is improved, the energy consumption is reduced, the membrane module is synchronously used for separating ammonia gas while the enhanced hydrolysis pretreatment is carried out, the removal of ammonia nitrogen is increased, multiple projects are realized in one step, and the process flow is saved.

3. The invention realizes the recovery of ammonia nitrogen at lower pH by utilizing the high temperature for carrying out the intensified hydrolysis treatment on the antibiotic wastewater, improves the utilization efficiency of energy and reduces the addition of medicaments.

4. The method removes ammonia nitrogen while performing hydrolysis treatment before anaerobic biological treatment, thereby not only removing the inhibition of ammonia nitrogen on the anaerobic treatment, but also reducing the operation cost of subsequent nitrification-denitrification. Aiming at the high-temperature and alkaline environment in the invention, the polytetrafluoroethylene gaseous membrane is selected to have the best separation effect.

5. The pretreatment of the invention hardly reduces the COD in the wastewater, which ensures that almost all organic matter can enter the anaerobic biological treatment unit and then the biologically usable part is converted into methane by anaerobic fermentation, thereby realizing the maximization of energy recovery.

Drawings

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

FIG. 1 is a diagram showing the appearance of foam overflow generated in a sewage treatment system of a pharmaceutical factory;

FIG. 2 is a schematic diagram of the pretreatment of antibiotic wastewater according to the present invention;

FIG. 3 is a diagram showing the operation effect of the oxytetracycline production wastewater pretreated by AnMBR.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.

Example 1

The wastewater quality is characterized by NH ₄ 1000 mg/L of N, 1000 mg/L of oxytetracycline and pH 6.5.

s1, adding 20% of sodium hydroxide to adjust the pH value of antibiotic wastewater to 8.5 to obtain a mixture A;

s3, heating the mixture B to 120 ℃ in an electric heating mode to obtain a mixture C;

s4, allowing the mixture C to enter a gaseous membrane module to separate ammonia gas, and finishing pretreatment;

wherein: the catalyst is CaO-NiO and MgO-NiO, and the mass ratio of the CaO-NiO to the MgO-NiO is 1; the input amount of the catalyst is 0.03g/L;

the gaseous membrane component is a tubular membrane, and the aperture is 0.2 mu m; the gaseous film is made of Polytetrafluoroethylene (PTFE) material; the retention time of the antibiotic wastewater in the membrane module is 20min; the absorption liquid of the membrane module is 2mol/L sulfuric acid.

Example 2

The wastewater quality is characterized by NH ₄ 1000 mg/L of N, 1000 mg/L of penicillin and pH 6.8.

s1, adding 20% of sodium hydroxide to adjust the pH value of antibiotic wastewater to 9 to obtain a mixture A;

s4, enabling the mixture C to enter a gaseous membrane module to separate ammonia gas, and finishing pretreatment;

wherein: the catalyst is MgO-NiO; the input amount of the catalyst is 0.03g/L;

the gaseous membrane component is a tubular membrane, the aperture is 0.3 mu m, and the gaseous membrane is made of Polytetrafluoroethylene (PTFE) material; the retention time of the antibiotic wastewater in the membrane module is 20min; the absorption liquid of the membrane module is 2mol/L sulfuric acid.

Example 3

The wastewater quality is characterized in that the oxytetracycline concentration is as follows: 1000 mg/L, NH ₄ The concentration of N was 1200 mg/L and the pH was 4.8.

s5, adjusting the pH value of the pretreatment liquid to 6.8, and then carrying out anaerobic biological treatment;

wherein: the catalyst is CaO-NiO; the input amount of the catalyst is 0.05g/L;

the gaseous membrane component is a tubular membrane, and the aperture is 0.3 mu m; the gaseous film is made of Polytetrafluoroethylene (PTFE) material; the retention time of the antibiotic wastewater in the membrane component is 20min; the absorption liquid of the membrane module is 3mol/L sulfuric acid.

Example 4

The wastewater quality characteristics are as follows: the pH was 6.0; penicillin concentration: 800 mg/L; NH ₄ -N concentration 1900 mg/L.

s1, adding 20% of sodium hydroxide to adjust the pH value of antibiotic wastewater to 8 to obtain a mixture A;

s3, heating the mixture B to 160 ℃ in an electric heating mode to obtain a mixture C;

wherein: the catalyst is CaO-NiO; the input amount of the catalyst is 0.03g/L;

the gaseous membrane component is a tubular membrane, and the aperture is 0.1 mu m; the gaseous film is made of Polytetrafluoroethylene (PTFE) material; the retention time of the antibiotic wastewater in the membrane module is 15min; the absorption liquid of the membrane module is 3mol/L sulfuric acid.

Comparative example 1

The same antibiotic production wastewater as in example 3 was used for pretreatment, comprising the following steps:

s1, adding 20% of sodium hydroxide to adjust the pH value of antibiotic wastewater to 10.5 to obtain a mixture A;

s2, feeding the mixture A into a gaseous membrane module to separate ammonia gas, and finishing pretreatment; the gaseous membrane module used was the same as in example 1.

Comparative example 2

s1, adding concentrated sodium hydroxide to adjust the pH value of the antibiotic wastewater to 6 to obtain a mixture A;

s2, heating the mixture A to 60 ℃ to obtain a mixture B;

and S3, heating the mixture B to 110 ℃, reacting for 1h, and then cooling to 35 ℃ through gradual heat exchange to finish pretreatment.

Comparative example 3

Comparative example 3, step S2 was electrically heated to 50 c as compared with example 1, and the rest was the same as example 1.

Comparative example 4

Comparative example 4 is similar to example 1 except that CaO-NiO and MgO-NiO are not added, as compared with example 1.

The effects of the above examples 1 to 4 and comparative examples 1 to 4 on the treatment effect of antibiotic wastewater were measured:

(1) examples 1-4 and comparative examples 1-4 on NH in antibiotic wastewater ₄ N, determination of the antibiotic removal rate.

And (3) ammonia nitrogen determination: measuring the ammonia nitrogen value of the wastewater by adopting a Nashin reagent method (HJ 535-2009 Nashin reagent spectrophotometry for measuring ammonia nitrogen in water quality);

and (3) measuring the contents of penicillin and oxytetracycline: the determination is carried out by adopting a liquid chromatography-tandem mass spectrometry method.

TABLE 1 results of measurement of removal rates of examples 1 to 4 and comparative examples 1 to 4

Compared with example 1, comparative example 3 reduces the hydrolysis temperature, and comparative example 4 does not add a catalyst, and as can be seen from table 1, the effects of comparative example 1, comparative example 3, and comparative example 4 on the pretreatment of antibiotic wastewater are lower than those of example 1. Comparative example 1 adopts a hydrophobic membrane method for treatment, does not add a catalyst, does not raise the temperature, increases the pH of the antibiotic wastewater to 10.5, finds that a hydrophobic membrane is penetrated, the process cannot be effectively operated, and the process can not treat NH in the wastewater ₄ N and antibiotics were hardly removed.

Comparative example 2 hydrolysis was performed by using a method of enhanced hydrolysis pretreatment and direct heating, and as can be seen from table 1, comparative example 2 only removed antibiotics and did not remove NH from wastewater ₄ -N is removed.

(2) The antibiotic wastewater after pretreatment of example 3 and comparative example 2 was treated by an anaerobic membrane bioreactor (AnMBR).

1) Continuously injecting water into the antibiotic wastewater pretreated in the embodiment 3 into an anaerobic membrane bioreactor (AnMBR) with the effective volume of 8L by using a peristaltic pump, wherein the effluent is intermittent effluent, and performing anaerobic biological treatment on the hydrolysis-enhanced wastewater;

wherein: adjusting the organic load entering the AnMBR by adjusting the water inlet flow, wherein the water inlet flow is 0.975L/d and 1.95/d respectively; the anaerobic biological treatment temperature is 35 ℃; the aeration flow of the biogas is kept at 1L/min; the flux of the membrane is controlled to be 12LMH; anMBR intermittently discharges water, namely the operation mode of the membrane is selected to be intermittent operation, the operation is carried out for 3 minutes, the rest time (the rest time is the time interval between two adjacent membrane operations) is changed along with the change of the inflow water flow, the membrane operation (membrane filtration) time is 3min and 3min, and the rest (filtration stopping) time is 88.63min and 44.31min. Determining the organic load of anaerobic biological treatment of the AnMBR to be 1.5g COD/L/d and 3g COD/L/d (corresponding to the R4 and R5 stages in the figure 3) respectively according to the inflow rate, wherein the organic load is calculated according to the following formula:

organic load = C Q/V

Wherein: c: COD concentration (g/L) of inlet water; q: flow rate (L/d); v: anMBR reactor effective volume (L); the unit is gCOD/L/d.

Monitoring COD, pH and concentration of volatile fatty acid of AnMBR effluent during anaerobic biological treatment; measuring the methane yield in the anaerobic biological treatment process; calculating the COD removal rate of the wastewater treated by the AnMBR; measuring the concentration of the volatile fatty acid by adopting a titration method Q/YZJ10-03-02-2000 'determination of volatile fatty acid'; the amount of methane produced during the wastewater treatment was determined by gas chromatography.

AnMBR intakes: the pH is 7; the alkalinity of inlet water is 2500mg/L; the sludge concentration in the reactor is 20g/L;

AnMBR effluent: the pH values are all 6.8-8.5; the concentration of volatile fatty acid is less than 500mg/L.

2) The water after the intensive hydrolysis treatment of comparative example 2 was diluted three times (FIG. 3 R1), the water after the intensive hydrolysis treatment was diluted two times (FIG. 3 R2), and the water after the intensive hydrolysis treatment was not diluted (FIG. 3 R3), and the corresponding organic loads were 1g COD/L/d, 1.5g COD/L/d, and 1.5g COD/L/d, respectively. The rest is the same as in example 3.

The results of the anaerobic membrane bioreactor (AnMBR) treatment of the antibiotic wastewater after pretreatment in example 3 and comparative example 2 are shown in fig. 3.

The effect of the treatment of comparative example 2 is reflected in the periods R1 to R3 in fig. 3. It is known that AnMBR works well when dealing with diluted oxytetracycline spent mother liquor from the enhanced hydrolysis pretreatment, while the effect of dealing with undiluted oxytetracycline spent mother liquor becomes worse, manifested as an accumulation of Volatile Fatty Acids (VFA) of up to 1000 mg/L or more. At the same time, both biogas production and COD removal rate are reduced, which is a deterioration of the reactor due to free ammonia inhibition, which also limits the further increase of organic load. Subsequently, the R4 stage was changed to the pretreatment mode of example 3, and it was observed that at the same organic load (1.5 gCOD/L/d), the AnMBR treatment effect was increased, showing no accumulation of VFA, and the COD removal rate was restored to normal. On the basis, the organic load of the AnMBR is increased by increasing the inflow rate to reach 3g COD/L/d, as shown by R5. It was observed that there was VFA build-up in the early stages of the load-up, and over time the reactor could overcome this problem, again going into a steady and efficient state.

Based on the comparison, it can be found that example 3 can effectively overcome ammonia nitrogen inhibition faced by comparative example 2, effectively reduce accumulation of VFA, improve removal rate, and improve organic load of AnMBR treatment.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The pretreatment method for the antibiotic production wastewater is characterized by comprising the following steps:

s3, heating the mixture B to 110-160 ℃ to obtain a mixture C;

s4, the mixture C enters a membrane module to separate ammonia gas, and pretreatment is completed;

the catalyst comprises one or more of CaO-NiO, mgO-NiO, caO-CoO and MgO-CoO;

the input amount of the catalyst in the step S2 is 0.01-0.1g/L;

the antibiotic wastewater is fermentation pharmaceutical wastewater, and the water quality is characterized in that the antibiotic is 800-2000 mg/L, and the ammonia nitrogen is 800-2000 mg/L;

the pretreatment method for the antibiotic production wastewater is used for synchronously separating ammonia gas by the membrane module while performing the intensified hydrolysis pretreatment.

2. The method for pretreating antibiotic production wastewater according to claim 1, wherein the pH in step S1 is 8-9.

3. The method for pretreating antibiotic production wastewater according to claim 1, wherein the membrane module in step S4 is a tubular membrane with a pore size of 0.1-0.3 μm.

4. The method according to claim 1, wherein the membrane module in step S4 comprises a gaseous membrane made of polytetrafluoroethylene.

5. The pretreatment method of wastewater from antibiotic production according to claim 1, wherein the residence time of the wastewater entering the membrane module in step S4 is 10-30min.

6. The pretreatment method of wastewater from antibiotic production according to claim 1, wherein the residence time of the wastewater entering the membrane module in step S4 is 15-20min.

7. The method for pretreating antibiotic production wastewater according to claim 1, wherein the absorption liquid of the membrane module in step S4 is 2-3mol/L sulfuric acid.