CN113354220A - Recycling treatment method for amantadine wastewater - Google Patents
Recycling treatment method for amantadine wastewater Download PDFInfo
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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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- C02F1/722—Oxidation by peroxides
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- 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: adjusting the pH of the process wastewater, controlling a certain pH value to carry out carrier gas extraction concentration, and directly returning the concentrated solution to the production recovery process for treatment; pumping carrier gas extraction fresh water into a biochemical system, and adopting a salt-tolerant anaerobic and salt-tolerant aerobic treatment process; and (3) carrying out flocculation precipitation sludge-water separation on biochemical effluent, concentrating the sludge, carrying out external treatment, carrying out Advanced Oxidation (AOP) advanced treatment on supernatant, and discharging the supernatant after reaching the standard. The invention carries out process design aiming at the amantadine production wastewater, solves the technical problem that the amantadine is difficult to treat after the treatment by the technology of the invention, and can realize the reclamation of the wastewater.
Description
Technical Field
The invention relates to the technical field of treatment processes for production wastewater containing oil and having high COD (chemical oxygen demand), in particular to a recycling treatment method for amantadine wastewater.
Background
Amantadine, also known as amantadine and tricyclodecylamine, is an anti-influenza drug widely used in recent years, and is widely used for preventing and treating influenza virus A infectious diseases clinically. The amination wastewater and the bromination wastewater are refractory wastewater generated in the production process of amantadine, have high organic matter content and poor biodegradability and contain a large amount of amantadine substances.
Amantadine is a saturated tricyclodecanoamino derivative, a highly symmetric, very stable caged hydrocarbon. Data show that the content of amantadine in the inlet water 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. Biological processes are not ideal for the removal of amantadine from domestic wastewater. Therefore, the rational treatment and resource utilization of the amantadine production wastewater are problems to be solved at present, and the process and technical method innovation are urgently needed for the treatment of the amantadine production wastewater.
The main problems of the prior art are as follows: the waste water from the production of amantadine contains amantadine and its derivatives with high concentration, which have strong antibacterial activity, extremely poor biodegradability and great treatment difficulty, and finally enter the natural environment along with the waste water and excess sludge, accumulate in the environment, harm human health and have toxic action on the growth of soil organisms, aquatic organisms and the like.
Disclosure of Invention
Aiming at solving the technical problems, the invention provides an amantadine wastewater treatment method, which is characterized in that the process design is carried out on the amantadine production wastewater by adopting the processes of pH adjustment, carrier gas extraction, biochemical treatment, flocculation precipitation, advanced oxidation and the like aiming at the defects in the prior art. After technical treatment, the technical problem that amantadine is difficult to treat is solved, and the resource recycling of wastewater can be realized.
The invention is realized by the following steps:
the method for recycling amantadine wastewater 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-level oxidation section, and the specific design scheme is as follows:
(1) adjusting the pH of the process wastewater to be 6-9, adjusting the pH of the wastewater, and controlling the pH of carrier gas extraction inlet water according to related indexes such as COD (chemical oxygen demand) or ammonia nitrogen;
(2) introducing the process wastewater with the adjusted pH into a carrier gas extraction device, adopting a continuous water inlet mode, a continuous water outlet mode and an intermittent concentrated solution discharge mode, and returning the concentrated solution to the production recovery process after collection; the carrier gas extraction technology is a brand new water treatment method for desalting high salinity wastewater by using carrier gas, and realizes wastewater desalination by humidifying and dehumidifying air.
(3) Adjusting the pH of carrier gas extraction fresh water to be 7-8, controlling the TDS of the waste water to be 10000-30000 mg/L, and carrying out anaerobic reaction in a biochemical system treatment process, wherein the temperature is controlled to be 25-35 ℃, and the reaction time is 24-48 hours; the anaerobic reaction adopts an ABR baffling reaction device inoculated with LBQ salt-tolerant composite bacteria, LBQ salt-tolerant composite bacteria are immobilized on 1-6-mesh biological activated carbon, and the concentration of organic matters in the wastewater is further reduced through the treatment of a biochemical system; after the wastewater enters anaerobic state through carrier gas extraction, LBQ salt-tolerant complex bacteria are fully mixed with the wastewater under the stirring of a submersible stirrer, and the indissolvability of macromolecules is converted into substances which are easy to biodegrade and are small molecules and soluble; decomposing small molecular organic matter into CO2、H2O and H2And the like.
(4) Carrying out aerobic reaction on the anaerobic effluent, controlling the temperature to be 25-35 ℃, controlling the dissolved oxygen to be 2-4 mg/L, and controlling the reaction time to be 24-48 hours; the aerobic reaction is beneficial to deeply reducing the concentration of organic matters in the wastewater; the waste water is subjected to aerobic treatment after anaerobic treatment, and the organic matters in the waste water are greatly reduced by utilizing the metabolism of microorganisms under the conditions of proper carbon-nitrogen ratio, moisture content, oxygen and the like;
(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 after coagulation to enter an advanced oxidation process, performing plate-frame filter pressing on a mud-water mixture, and carrying out sludge outward; the flocculant is one or a combination of more of ferrous sulfate, polyaluminium chloride, polyaluminium sulfate, polyferric chloride and polyferric sulfate, and the coagulant aid is polyacrylamide; the effluent of the flocculation precipitation passes through O3/H2O2Advanced oxidation process for deep treatment, namely, oxidizing the residual nonbiodegradable organic matters by using oxidant under the action of catalystA compound (I) is provided.
(6) Carrying out advanced oxidation advanced treatment on the coagulating sedimentation effluent, carrying out catalytic oxidation on the residual organic matters by using an oxidant under the action of a catalyst, and directly discharging after the treatment reaches the standard; the oxidant is one or a combination of ozone, hydrogen peroxide and ultraviolet light, and the residual organic matters are degraded by utilizing the strong oxidizing property of hydroxyl radicals.
Further, the LBQ halotolerant complex bacteria is a combination of gluconobacter oxydans, lactobacillus fermentum, lactobacillus brevis, micrococcus luteus, micrococcus halonae, pseudomonas alcaligenes, pseudomonas aureofaciens, pseudomonas aeruginosa, pseudomonas nitrate reductans, 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 value, 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 and the prior art are as follows:
1. according to the invention, an LBQ salt-tolerant composite bacteria biochemical treatment process is adopted, LBQ salt-tolerant composite bacteria are utilized to carry out biochemical treatment on the mixed wastewater, high-multiple dilution is not required, and the operation cost is reduced; in addition, under the anaerobic condition, the biodegradability of the wastewater is improved, and in the aerobic section, under the action of the metabolism of aerobic bacteria, the biodegradability substances in the wastewater are degraded, the COD 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, and can oxidize most of organic matters which are difficult to be biochemically generated in the wastewater; meanwhile, the problem of regeneration of the adsorbing material and the extracting agent caused by an adsorption method and an extraction method is solved, and energy consumption is reduced.
3. The invention effectively solves the problem of amantadine wastewater treatment, has high product resource recovery rate and low solid waste generation amount, realizes the resource utilization of wastewater in production engineering of enterprises, and has important environmental significance.
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FIG. 1 is a schematic flow chart of a recycling treatment method of amantadine wastewater.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention more clear, the present invention is further described in detail by the following examples. It should be noted that the specific embodiments described herein are merely illustrative of the invention and are 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 value of amantadine wastewater, controlling the pH value to be between 6 and 9, carrying out carrier gas extraction concentration after the adjustment is finished, directly returning a concentrated solution to production and recovery, and carrying out carrier gas extraction fresh water to progress the next step; 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.
Pumping carrier gas extraction fresh water into a biochemical system, and further treating by adopting salt-tolerant anaerobic and salt-tolerant aerobic processes;
2.1, introducing carrier gas extracted fresh water into an anaerobic reaction tank, adjusting the pH to be 7-8, adding LBQ salt-tolerant composite 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 the anaerobic effluent obtained in the step 2.1 into an aerobic reaction tank, adding LBQ salt-tolerant composite bacteria and aerobic biological filler into a water body, controlling the temperature to be 25-35 ℃, controlling the dissolved oxygen to be 2-4 mg/L, and controlling the reaction time to be 48-72 hours;
2.3, adjusting the pH of the aerobic effluent obtained in the step 2.2 to 9-10, adding a flocculating agent and a coagulant aid for coagulation, feeding the coagulated supernatant into a high-grade oxidation system, performing plate-frame filter pressing on the mud-water mixture, and transporting the sludge outside. The flocculating agent is one or a combination of a plurality of ferrous sulfate, polyaluminium chloride polyaluminium 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 ozone, hydrogen peroxide and ultraviolet light.
Step three, performing flocculation sedimentation on biochemical effluentSeparating sludge from water, concentrating the sludge, performing external treatment, and performing advanced oxidation on supernatant, namely performing AOP advanced treatment and discharging the sludge after reaching the standard. The effluent of the flocculation precipitation passes through O3/H2O2Advanced oxidation process advanced treatment, and residual organic matters which are difficult to biodegrade are catalyzed and oxidized by using an oxidant under the action of a catalyst.
The invention is further described in detail by specific implementation mode by taking the industrial wastewater of a certain enterprise as a research object, and the feasibility and the accuracy of the method are verified.
The main body of the enterprise operates the amantadine series, the waste water 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, CODcr =11500 mg/L，Cl-=3500 mg/L, 7000 mg/L total salt.
Adjusting the pH =6 of the amantadine wastewater, and allowing the amantadine wastewater to enter a carrier gas extraction device; the carrier gas extraction treatment capacity is 10t/d, a continuous water inlet, continuous water outlet and intermittent concentrated liquid discharge mode is adopted, concentrated liquid is recovered as a product, the material of a circulating pump is ETFE/PVDF, and the material of a heat exchanger is titanium alloy; pumping carrier gas extraction effluent into a baffle plate anaerobic device, controlling the water temperature to be 25 ℃, adding 1-6 meshes of biological activated carbon immobilized with LBQ salt-tolerant complex bacteria into a water body as a filler, and increasing the biodegradability of wastewater, wherein the retention time in an anaerobic stage is 72 hours; continuously introducing anaerobic effluent into an aerobic system, adjusting the pH to be about =7 by using 98% concentrated sulfuric acid or 30% sodium hydroxide aqueous solution, controlling the water temperature to be 25 ℃, adding polyurethane immobilized LBQ salt-tolerant composite bacteria as a filler, and carrying out aerobic reaction for 72 hours, wherein the aerobic dissolved oxygen is controlled to be 2 mg/L; adjusting the pH of biochemical effluent to be =10 by using NaOH solution, adding PAC and PAM for coagulation, connecting supernate to a rear-end advanced oxidation device, and carrying out external treatment on sludge; advanced oxidation system using O3/H2O2In the combined process, 0.5mL of 27.5% hydrogen peroxide and O are added into each 1L of supernatant3The adding amount is 3 times of the residual COD value, and the retention time is 8 hours; after advanced oxidation, the COD of the effluent is less than 50 mg/L and NH3N is less than 5 mg/L, TN is less than 15 mg/L, and the national first-class A emission standard is achieved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the present invention, and these modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The method for recycling amantadine wastewater is characterized by comprising the following steps:
step one, adjusting the pH value of amantadine wastewater, carrying out carrier gas extraction concentration after the pH value is adjusted, directly recycling a concentrated solution for production, and carrying out carrier gas extraction on fresh water to enter the next step;
pumping carrier gas extraction fresh water into a biochemical system in the step one, and performing biochemical treatment by adopting LBQ salt-tolerant composite bacteria;
and step three, performing flocculation precipitation on biochemical effluent to realize sludge-water separation, concentrating the sludge, performing external treatment, and performing advanced oxidation on supernatant, namely performing advanced treatment by using the AOP technology and then discharging the supernatant after reaching the standard.
2. The method as claimed in claim 1, wherein in the first step, the pH of the wastewater is adjusted to control the pH = 6-9.
3. The method for recycling amantadine wastewater according to claim 1, characterized in that the system in the carrier gas extraction process 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.
4. The method for recycling amantadine wastewater according to claim 1, characterized in that the second step is specifically:
2.1, introducing carrier gas extracted fresh water into an anaerobic reaction tank, adjusting the pH to be 7-8, adding LBQ salt-tolerant composite 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;
2.2, introducing the anaerobic effluent obtained in the step 2.1 into an aerobic reaction tank, adding LBQ salt-tolerant composite bacteria and aerobic biological filler into the wastewater, controlling the temperature to be 25-35 ℃, the dissolved oxygen to be 2-4 mg/L, and the reaction time to be 48-72 hours;
2.3, adjusting the pH of the aerobic effluent obtained in the step 2.2 to 9-10, adding a flocculating agent and a coagulant aid for coagulation, feeding the coagulated supernatant into a high-grade oxidation system, performing plate-frame filter pressing on the mud-water mixture, and transporting filter-pressed sludge outside.
5. The method as claimed in claim 4, wherein LBQ halotolerant complex bacteria is selected from the group consisting of gluconobacter oxydans, lactobacillus fermentum, lactobacillus brevis, micrococcus luteus, micrococcus coronarius, pseudomonas alcaligenes, pseudomonas aureofaciens, pseudomonas aeruginosa, pseudomonas nitrate reductants, pseudomonas riboflavin, pseudomonas putida, and pseudomonas agilis; the anaerobic biological filler uses biological activated carbon, and the aerobic biological filler uses polyurethane sponge filler.
6. The method for recycling amantadine wastewater as claimed in claim 4, characterized in that, in step 2.2, the anaerobic reaction adopts an ABR baffling reaction device inoculated with LBQ salt-tolerant complex bacteria, LBQ salt-tolerant complex bacteria are immobilized on 1-6 mesh biological activated carbon, and the concentration of organic matters in wastewater is further reduced through the treatment of a biochemical system; carrying out gas-carrying extraction on the wastewater, then introducing the wastewater into an anaerobic environment, fully mixing LBQ salt-tolerant complex bacteria and the wastewater under the stirring of a submersible stirrer, and converting the insolubility of macromolecules into biodegradable micromolecules and soluble substances under the action of LBQ salt-tolerant complex bacteria; then decomposing the small molecular organic matter into CO2、H2O and H2(ii) a The aerobic reaction can deeply reduce the concentration of organic matters in the wastewater; the waste water is treated by anaerobic treatment and then treated by aerobic treatment, and the organic matters in the waste water are reduced by utilizing the metabolism of microorganisms.
7. The method for recycling amantadine wastewater according to claim 4, characterized in that the flocculating agent in step 2.3 is one or a combination of ferrous sulfate, polyaluminum chloride, polyaluminum sulfate, polyferric chloride and polyferric sulfate, and the coagulant aid is polyacrylamide.
8. The method for recycling amantadine wastewater as claimed in claim 4, characterized in that the oxidant used in the advanced oxidation system in step 2.3 is one or a combination of ozone, hydrogen peroxide and ultraviolet light.
9. The method as claimed in claim 4, wherein pH is adjusted by using acidic reagent or alkaline reagent, the acidic reagent is sulfuric acid or hydrochloric acid, and the alkaline reagent is sodium hydroxide or calcium hydroxide.
10. The method as claimed in claim 1, wherein the effluent from the flocculation precipitation in step three is passed through O3/H2O2Advanced oxidation process advanced treatment, and residual organic matters which are difficult to biodegrade are catalyzed and oxidized by using an oxidant under the action of a catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823775A (en) * | 2010-05-11 | 2010-09-08 | 沈阳建筑大学 | Method for treating amantadine waste water through crystallization |
| 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 |
| CN110451596A (en) * | 2019-08-28 | 2019-11-15 | 黑珀（上海）工业技术有限公司 | A kind of carrier gas extraction HPE vapo(u)rization system |
| CN110803835A (en) * | 2019-12-02 | 2020-02-18 | 江苏蓝必盛化工环保股份有限公司 | Recycling treatment method for quaternary ammonium salt wastewater |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823775A (en) * | 2010-05-11 | 2010-09-08 | 沈阳建筑大学 | Method for treating amantadine waste water through crystallization |
| 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 |
| CN110451596A (en) * | 2019-08-28 | 2019-11-15 | 黑珀（上海）工业技术有限公司 | A kind of carrier gas extraction HPE vapo(u)rization system |
| CN110803835A (en) * | 2019-12-02 | 2020-02-18 | 江苏蓝必盛化工环保股份有限公司 | Recycling treatment method for quaternary ammonium salt wastewater |
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