CN113354220B - Method for recycling amantadine wastewater - Google Patents
Method for recycling amantadine wastewater Download PDFInfo
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- CN113354220B CN113354220B CN202110835601.4A CN202110835601A CN113354220B CN 113354220 B CN113354220 B CN 113354220B CN 202110835601 A CN202110835601 A CN 202110835601A CN 113354220 B CN113354220 B CN 113354220B
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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Abstract
The invention provides a method for recycling amantadine wastewater, which belongs to the field of sewage treatment methods and comprises the following steps: regulating the pH value of the process wastewater, controlling a certain pH value to carry out carrier gas extraction concentration, and directly recycling the concentrated solution to the production and recovery process treatment; the carrier gas extraction fresh water is pumped into a biochemical system, and a salt-tolerant anaerobic treatment process and a salt-tolerant aerobic treatment process are adopted; the biochemical effluent is subjected to flocculation precipitation mud-water separation, sludge is subjected to concentration and then subjected to external treatment, and supernatant fluid is subjected to Advanced Oxidation (AOP) advanced treatment and then discharged after reaching standards. The invention aims at the technical design of the amantadine production wastewater, solves the technical problem that the amantadine is difficult to treat after the technical treatment of the invention, and can realize the recycling of the wastewater.
Description
Technical Field
The invention relates to the technical field of treatment processes of oily and high-COD production wastewater, in particular to a method for recycling amantadine wastewater.
Background
Amantadine, also known as amantadine, tricyclosunflower amine, is an anti-influenza drug widely used in recent years, and is widely used clinically for the prevention and treatment of influenza virus type a infectious diseases. The amination wastewater and the bromination wastewater are degradation-resistant wastewater generated in the production process of the amantadine, have high organic matter content and poor biodegradability, and contain a large amount of amantadine substances.
Amantadine is a saturated tricyclodecane amino derivative, which is a highly symmetrical, very stable cage hydrocarbon. The data show that the content of amantadine in the water inlet of the sewage treatment plant reaches 184-538 ng/L, 6.7-17.4% of amantadine can be removed by primary treatment, and the removal rate of amantadine is still below 50% after biological treatment. The biological process is not ideal for the removal of amantadine from domestic sewage. Therefore, the rationalization treatment and the resource utilization of the amantadine production wastewater are the problems to be solved urgently at present, and the innovation of the process and the technical method for treating the amantadine production wastewater is urgently needed.
The main problems of the prior art are: the amantadine production wastewater contains high-concentration amantadine and derivatives thereof, and the substances have strong antibacterial activity, extremely poor biodegradability and high treatment difficulty, and finally accumulate in the environment along with the wastewater and residual sludge entering the natural environment, so that the human health is endangered, and the substances have toxic effects on growth of earthworms, aquatic organisms and the like.
Disclosure of Invention
In order to solve the technical problems, the invention improves the method for treating the amantadine wastewater, and aims at overcoming the defects in the prior art, the process design is carried out on the amantadine production wastewater, and the processes of pH adjustment, carrier gas extraction, biochemical treatment, flocculation precipitation, advanced oxidation and the like are adopted. After technical treatment, the technical problem that amantadine is difficult to treat is solved, and the recycling of wastewater can be realized.
The invention is realized in the following way:
the method is characterized in that the wastewater in the treatment method sequentially passes through a pH adjusting section, a carrier gas extraction section, a biochemical system section, a flocculation precipitation section and a high-grade oxidation section, and the specific design scheme is as follows:
(1) Adjusting the pH value of the process wastewater to be 6-9, adjusting the pH value of the wastewater, and controlling the pH value of the carrier gas extraction water inlet according to related indexes such as COD or ammonia nitrogen and the like;
(2) Introducing the process wastewater with the pH value adjusted into a carrier gas extraction device, adopting continuous water inlet, continuous water outlet and intermittent concentrated solution discharging modes, and recycling the concentrated solution after collection into production and recovery process treatment; the carrier gas extraction technology is a brand new water treatment method for desalting high-salinity wastewater by using carrier gas, and the wastewater desalination is realized by humidifying and dehumidifying air.
(3) Adjusting the pH value of carrier gas extracted fresh water to 7-8, controlling the TDS of wastewater to 10000-30000 mg/L, performing biochemical system treatment anaerobic reaction, controlling the temperature to 25-35 ℃ and the reaction time to 24-48 hours; the anaerobic reaction adopts an ABR baffling reaction device inoculated with LBQ salt-tolerant complex bacteria, LBQ salt-tolerant complex bacteria are fixedly carried on 1-6 meshes of biological activated carbon, and the concentration of organic matters in the wastewater is further reduced through biochemical system treatment; after the wastewater is extracted by carrier gas and enters anaerobic, LBQ salt-tolerant complex bacteria are fully mixed with the wastewater under the stirring of a submersible stirrer, so that the macromolecule insoluble substances are converted into micromolecules which are easy to biodegrade and soluble substances; decomposing small molecular organic matters into CO 2 、H 2 O and H 2 Etc.
(4) Carrying out aerobic reaction on the anaerobic effluent, controlling the temperature to be 25-35 ℃, and controlling the dissolved oxygen to be 2-4 mg/L, wherein the reaction time is 24-48 hours; the aerobic reaction is helpful for deeply reducing the concentration of organic matters in the wastewater; the waste water is subjected to anaerobic treatment and then is subjected to aerobic treatment, and under the conditions of proper carbon-nitrogen ratio, water content, oxygen and the like, the metabolism of microorganisms is utilized, so that the organic matters in the waste water are greatly reduced;
(5) Adjusting the pH value of the biochemical effluent to 9-10, adding a flocculating agent and a coagulant aid for coagulation, allowing the supernatant to enter a high-grade oxidation process after coagulation, allowing a mud water mixture to enter a plate frame for filter pressing, and carrying out sludge outward; the flocculant is one or a combination of more of ferrous sulfate, polyaluminum chloride, polyaluminum sulfate, polyferric chloride and polyferric sulfate, and the coagulant aid is polyacrylamide; flocculation precipitation of effluent through O 3 /H 2 O 2 Advanced oxidation process advanced treatment, which utilizes oxidant to catalyze and oxidize the residual organic matters difficult to biodegrade under the action of catalyst.
(6) Advanced oxidation advanced treatment is carried out on the coagulating sedimentation effluent, the residual organic matters are catalyzed and oxidized by using an oxidant under the action of a catalyst, and the treatment reaches the standard and is directly discharged; the oxidant is one or a combination of more of ozone, hydrogen peroxide and ultraviolet light, and the residual organic matters are degraded by utilizing the strong oxidizing property of hydroxyl free radicals.
Further, the LBQ salt-tolerant complex bacteria are various combinations of gluconobacter oxydans, lactobacillus fermentum, lactobacillus brevis, micrococcus luteus, micrococcus carsicki, pseudomonas alcaligenes, pseudomonas aurogena, pseudomonas green leaf, pseudomonas reduction by nitric acid, pseudomonas riboflavin, pseudomonas putida and pseudomonas agilis; the anaerobic biological filler uses biological activated carbon, and the aerobic biological filler uses polyurethane sponge filler.
Further, an acidic reagent or an alkaline reagent is adopted to adjust the pH, wherein the acidic reagent is sulfuric acid or hydrochloric acid, and the alkaline reagent is sodium hydroxide or calcium hydroxide.
The beneficial effects of the invention compared with the prior art are as follows:
1. according to the invention, a LBQ salt-tolerant composite bacterium biochemical treatment process is adopted, and LBQ salt-tolerant composite bacterium is used for biochemical treatment of mixed wastewater, so that high-multiple dilution of the mixed wastewater is not required, and the running cost is reduced; in addition, under anaerobic conditions, the biodegradability of the wastewater is improved, and under the metabolism of aerobic bacteria in an aerobic section, substances with biodegradability in the wastewater are degraded, so that COD (chemical oxygen demand) is greatly reduced, and the investment cost and the operation cost of the rear-end advanced oxidation organic load are further reduced.
2. The invention adopts an advanced oxidation process, so that most of difficult biochemical organic matters in the wastewater can be oxidized; meanwhile, the method solves the problem of regeneration of the adsorption material and the extractant caused by an adsorption method and an extraction method, and reduces energy consumption.
3. The method effectively solves the problem of treatment of the amantadine wastewater, has high recovery rate of product recycling and small solid waste production, realizes the recycling of the wastewater in the production engineering of enterprises, and has important environmental significance.
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FIG. 1 is a schematic flow chart of a method for recycling amantadine wastewater.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions, and effects of the present invention more apparent. It should be noted that the detailed description herein is for purposes of illustration only and is not intended to limit the invention.
As shown in fig. 1, the technical scheme of the invention comprises the following steps:
step one, adjusting the pH of amantadine wastewater, controlling the pH to be between 6 and 9, carrying out carrier gas extraction and concentration after the adjustment, directly recycling concentrated solution into production and recovery treatment, and carrying out carrier gas extraction and fresh water further; the system in the carrier gas extraction process comprises a blower, a humidifying tower, a dehumidifying tower, a steam-water separator, a process pump and a condensate water tank; adopts the modes of continuous water inlet, continuous water outlet and intermittent concentrated liquid discharge.
Step two, the carrier gas extraction fresh water in the step one is pumped into a biochemical system, and further treatment is carried out by adopting salt-tolerant anaerobism and salt-tolerant aerobics;
2.1, introducing carrier gas extraction fresh water into an anaerobic reaction tank, adjusting pH=7-8, adding LBQ salt-tolerant complex bacteria and anaerobic biological filler into a water body, controlling the temperature to be 25-35 ℃ and the anaerobic reaction time to be 48-72 hours;
2.2, introducing anaerobic effluent obtained in the step 2.1 into an aerobic reaction tank, adding LBQ salt-tolerant complex bacteria and aerobic biological filler into the water body, controlling the temperature to be 25-35 ℃, and controlling the dissolved oxygen to be 2-4 mg/L, wherein the reaction time is 48-72 hours;
2.3, adjusting the pH value of the aerobic effluent in the step 2.2 to 9-10, adding a flocculating agent and a coagulant aid for coagulation, allowing the coagulated supernatant to enter a high-grade oxidation system, allowing a mud water mixture to enter a plate frame for filter pressing, and carrying out sludge outward. The flocculant is one or a combination of more of ferrous sulfate, polyaluminum chloride, polyaluminum sulfate, polyferric chloride and polyferric sulfate, and the coagulant aid is polyacrylamide. The oxidant used in the advanced oxidation system is one or a combination of more of ozone, hydrogen peroxide and ultraviolet light.
And thirdly, separating mud and water from biochemical effluent through flocculation precipitation, concentrating the sludge, performing external treatment, and performing advanced oxidation on supernatant fluid, namely performing advanced AOP treatment and discharging the supernatant fluid after reaching the standard. Flocculation precipitation of effluent through O 3 /H 2 O 2 Advanced oxidation process advanced treatment, which utilizes oxidant to catalyze and oxidize the residual organic matters difficult to biodegrade under the action of catalyst.
The invention is described in further detail by specific embodiments below with industrial wastewater of a certain enterprise as a research object, and the feasibility and accuracy of the method of the invention are verified.
The main body of the enterprise operates amantadine series, and the wastewater contains a large amount of amantadine substances and a small amount of organic matters such as tetrabutylammonium bromide, and the main characteristics are as follows: ph=10, cod cr =11500 mg/L，Cl - =3500 mg/L, total salts 7000 mg/L.
Adjusting the pH=6 of the amantadine wastewater into a carrier gas extraction device; the carrier gas extraction treatment capacity is 10t/d, a continuous water inlet mode, a continuous water outlet mode and an intermittent concentrated solution discharge mode are adopted, the concentrated solution is recovered as a product, the material of the circulating pump is ETFE/PVDF, and the material of the heat exchanger is titanium alloy material; the carrier gas extraction water is pumped into a baffle plate anaerobic device, the water temperature is controlled to 25 ℃, 1-6 meshes of biological activated carbon which is fixedly loaded with LBQ salt-tolerant compound bacteria is added into the water body as a filler, the stay time in the anaerobic stage is 72 h, and the biodegradability of the wastewater is improved; continuously introducing anaerobic effluent into an aerobic system, regulating the pH value to about 7 by using 98% concentrated sulfuric acid or 30% sodium hydroxide aqueous solution, controlling the water temperature to 25 ℃, adding polyurethane loaded with LBQ salt-tolerant compound bacteria as a filler, performing aerobic reaction for 72 hours, and controlling the aerobic dissolved oxygen to be 2 mg/L; adjusting pH=10 of biochemical effluent by using NaOH solution, adding PAC and PAM for coagulation, connecting supernatant to a rear-end advanced oxidation device, and carrying out additional outward treatment on sludge; advanced oxidation systems use O 3 /H 2 O 2 Adding 0.5mL of 27.5% hydrogen peroxide and O into each 1L of supernatant by using the combination process 3 The adding amount is 3 times of the residual COD value, and the residence time is 8 hours; COD of the effluent after advanced oxidation is less than 50 mg/L, NH 3 N is less than 5 mg/L, TN is less than 15 mg/L, and the national first-grade A emission standard is achieved.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications could be made by those skilled in the art without departing from the principles of the invention, which modifications would also be considered to be within the scope of the invention.
Claims (7)
1. The method for recycling the amantadine wastewater is characterized by comprising the following steps of:
step one, adjusting the pH value of amantadine wastewater to be less than 6, carrying out carrier gas extraction concentration after adjusting the pH value, directly recycling concentrated solution to production, and carrying out carrier gas extraction fresh water to enter the next step;
step two, introducing carrier gas extraction fresh water into an anaerobic reaction tank, adjusting pH=7-8, adding LBQ salt-tolerant complex bacteria and anaerobic biological filler into the wastewater, controlling the temperature to be 25-35 ℃ and the anaerobic reaction time to be 48-72 hours; the anaerobic reaction adopts an ABR baffling reaction device inoculated with LBQ salt-tolerant complex bacteria, and LBQ salt-tolerant complex bacteria are immobilized on 1-6 meshes of biological activated carbon; after the wastewater is extracted by carrier gas and enters an anaerobic reaction tank, LBQ salt-tolerant complex bacteria and the wastewater are fully mixed under the stirring of a submersible stirrer, insoluble macromolecules are converted into small molecules and soluble substances which are easy to biodegrade under the action of LBQ salt-tolerant complex bacteria, and then small molecular organic substances are decomposed into CO 2 、H 2 O and H 2 The method comprises the steps of carrying out a first treatment on the surface of the LBQ the salt-tolerant complex bacteria are various combinations of Gluconobacter oxydans, lactobacillus fermentum, lactobacillus brevis, micrococcus luteus, micrococcus caryophyllus, pseudomonas alcaligenes, pseudomonas aurogena, pseudomonas green leaf, pseudomonas reduction by nitric acid, pseudomonas riboflavin, pseudomonas putida and Pseudomonas agilis;
introducing anaerobic effluent from the step two into an aerobic reaction tank, adding LBQ salt-tolerant complex bacteria and aerobic biological filler into the wastewater, controlling the temperature to be 25-35 ℃, and controlling the dissolved oxygen to be 2-4 mg/L, wherein the reaction time is 48-72 hours; the waste water is subjected to anaerobic treatment and then is subjected to aerobic treatment, and organic matters in the waste water are reduced by utilizing the metabolism of microorganisms;
and fourthly, adjusting the pH value of the aerobic effluent in the third step to 9-10, adding a flocculating agent and a coagulant aid for coagulation, allowing the supernatant to enter an advanced oxidation system after coagulation, allowing a mud water mixture to enter a plate frame for filter pressing, and carrying out outward transportation treatment on filter pressed mud.
2. The method for recycling amantadine wastewater according to claim 1, wherein the system in the carrier gas extraction in the first step comprises a blower, a humidifying tower, a dehumidifying tower, a steam-water separator, a process pump and a condensate water tank; adopts the modes of continuous water inlet, continuous water outlet and intermittent concentrated liquid discharge.
3. The method for recycling amantadine wastewater according to claim 1, wherein the anaerobic bio-filler is bioactive carbon, and the aerobic bio-filler is polyurethane sponge filler.
4. The method for recycling amantadine wastewater according to claim 1, wherein the flocculant in the fourth step is one or a combination of more of ferrous sulfate, polyaluminum chloride, polyaluminum sulfate, polyferric chloride and polyferric sulfate, and the coagulant aid is polyacrylamide.
5. The method for recycling amantadine wastewater according to claim 1, wherein the first step is to adjust the pH with sulfuric acid or hydrochloric acid.
6. The method for recycling amantadine wastewater according to claim 1, wherein the oxidant used in the advanced oxidation system in the fourth step is one or a combination of ozone, hydrogen peroxide and ultraviolet light.
7. The method for recycling amantadine wastewater according to claim 6, wherein the advanced oxidation system in the fourth step adopts O 3 /H 2 O 2 The combined process utilizes an oxidant to catalyze and oxidize the residual refractory organics under the action of a catalyst.
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| CN107176759A (en) * | 2017-06-21 | 2017-09-19 | 江苏蓝必盛化工环保股份有限公司 | A kind of method for handling fluorescent whitening agent waste water from dyestuff |
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