CN111470724A - Deep purification treatment method for spandex industrial production wastewater - Google Patents
Deep purification treatment method for spandex industrial production wastewater Download PDFInfo
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Abstract
The invention discloses a deep purification treatment method of spandex industrial production wastewater. The method comprises the following steps: firstly, adding a coagulant into the industrial wastewater of spandex, naturally settling, and filtering out the precipitate; secondly, adding a decomposition accelerator to decompose DMF; thirdly, separating and recovering dimethylamine by using a gas stripping method; fourthly, adding a coagulant, and separating filtrate and filter residue after sedimentation; soaking the filter residue in ethanol to fully dissolve polyether in the filter residue in the ethanol, naturally settling, and distilling the obtained supernatant to separate polyether and ethanol; and sixthly, conveying the filtrate to the combined biological reaction tank. The method is suitable for the characteristics of complex wastewater components, high total nitrogen content, poor biodegradability, large water quality difference and high toxicity in the industrial production of spandex, has mild operation conditions, high treatment efficiency, excellent treatment effect and excellent shock load resistance, can recover polyether with high price in the wastewater and dimethylamine generated in the wastewater treatment process, and realizes the resource utilization of the wastewater to a higher degree.
Description
Technical Field
The invention relates to a deep purification treatment method of spandex industrial production wastewater, belonging to the technical field of sewage treatment.
Background
The spandex is a synthetic fiber obtained by polymerizing aromatic diisocyanate and a polyester segment or a polyether segment containing hydroxyl groups and then spinning. The industrial wastewater of spandex has the characteristics of complex components, high total nitrogen content, poor biodegradability, large water quality difference, high toxicity and the like. From the analysis of the components of the wastewater, the wastewater from the spandex industry contains organic solvent, dihydric alcohol, dimethylamine, hybrid amine, oil agent and the like. Among them, Dimethylformamide (DMF) is the most commonly used organic solvent in the production process of spandex, and is also one of the main pollutants in the industrial wastewater of spandex; the dihydric alcohol is a main raw material in the production process of spandex, takes polyether glycol as a main raw material, and the polyether glycol with the largest consumption in the current market is polytetramethylene ether glycol (PTMEG), so that the polyurethane elastomer has good hydrolysis resistance, poor water solubility, high market price and high recovery value. Because of the high solubility of polyether glycol (particularly PTMEG) in DMF, attempts have been made to adequately remove DMF from waste water in spandex industry for recovery of polyether glycol from waste water. Hydrolysis under strong acid or strong alkaline environment is one of the DMF removing methods commonly used at present, but the method needs to heat the wastewater to high temperature, the decomposition efficiency is not ideal, so that more DMF remains in the wastewater, and the residual DMF still causes the subsequent recovery and treatment of the polyether glycol to be difficult. In addition, the residual DMF in the wastewater causes the total nitrogen value of the treated wastewater to be higher.
At present, the main methods for treating the industrial wastewater of spandex industry at home and abroad comprise a chemical method (comprising catalytic oxidation, alkaline hydrolysis, supercritical oxidation and the like), a physical and chemical method (comprising rectification, extraction and the like) and a biological method, and the common methods have obvious defects. Wherein, the chemical method needs to add special reagents, so the investment and operation cost is high; the extraction, rectification and other methods are more effective in treating wastewater with extremely high concentration and low impurity content, and are not suitable for spandex industrial wastewater in the actual production process; the biochemical method has lower treatment cost, but the final treatment effect is difficult to reach the standard due to factors such as the toxicity of the wastewater and the like. The novel spandex wastewater treatment process with practical application value is developed, pollutants such as COD (chemical oxygen demand) and total nitrogen in spandex industrial production wastewater can be removed with low cost and high efficiency, the wastewater is recycled to a certain extent, the economic benefit of production enterprises is improved, and the spandex wastewater treatment process has remarkable application and popularization values in the spandex industrial field.
Disclosure of Invention
The invention relates to a deep purification treatment method of spandex industrial production wastewater, aiming at providing a novel wastewater treatment process which realizes the resource utilization of wastewater while treating the spandex industrial production wastewater with low cost and high efficiency under mild conditions. The invention starts from the components of the wastewater of spandex industry production, firstly treats DMF in the wastewater by a catalytic decomposition method, improves the biodegradability of the wastewater, recovers dimethylamine in the treatment process, simultaneously sharply reduces the solubility of polytetramethylene ether glycol (PTMEG) in the wastewater due to the removal of DMF, realizes the recovery and utilization of the PTMEG by the processes of agglutination-dissolution-evaporation, and finally realizes the deep purification treatment of the spandex wastewater by a biological treatment technology. The wastewater treatment process has high treatment efficiency and excellent treatment effect, realizes the resource utilization of wastewater to a higher degree, and has remarkable economic value.
The method for deeply purifying the wastewater generated in the spandex industry comprises the following specific steps:
step one, conveying the industrial production wastewater of spandex to a primary sedimentation tank, adding a coagulant, uniformly mixing and stirring at room temperature for 5-30min, naturally settling for 15-30 min, and filtering out the precipitate;
step two, conveying the wastewater obtained in the step one to a DMF decomposition pool, adding alkali, adjusting the pH value of the solution to 7-10, adding a zeolite molecular sieve, reacting at 10-30 ℃ for 1-12 h, and decomposing DMF to generate dimethylamine;
step three, separating the dimethylamine in the wastewater obtained in the step two by using a gas stripping method, and recovering the dimethylamine;
step four, conveying the wastewater obtained in the step three to a polyether separation pool, adding a coagulant, uniformly mixing and stirring for 5-30min, naturally settling for 15-30 min, and separating filtrate and filter residue;
step five, soaking the filter residue obtained in the step four in ethanol, stirring for 5-30min to fully dissolve polyether glycol in the filter residue in the ethanol, and naturally settling for 15-30 min; then, taking the supernatant fluid to distill and separate polyether glycol and ethanol at the temperature of 60-80 ℃ to realize the recovery of polyether glycol, and condensing the distilled ethanol in a heat exchanger for recycling;
and step six, conveying the filtrate obtained in the step four to a combined biological reaction tank for biodegradation to complete wastewater treatment.
Preferably, in the first step, the main initial water quality parameter ranges of the spandex industrial production wastewater are as follows: pH: 6-9, CODCr1000 mg/L-100000 mg/L, 50 mg/L-1000 mg/L suspended matter, 200 mg/L-10000 mg/L total nitrogen and 8000 chroma of 200-.
Preferably, in the first step, the coagulant is a combined coagulant and comprises a polyaluminium chloride solution and a polyacrylamide solution, wherein the mass fraction of the polyaluminium chloride in the polyaluminium chloride solution is 5-20%, the mass fraction of the polyacrylamide in the polyacrylamide solution is 0.05-0.2%, when the coagulant is added, the polyaluminium chloride solution is added firstly, the dosage of the polyaluminium chloride solution is 0.1-1 g/L, and after 20s, the polyacrylamide solution is added, and the dosage of the polyacrylamide solution is 0.1 g/L-1 g/L.
Preferably, in the second step, the alkali is one or two of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide.
Preferably, in the second step, the dosage of the zeolite molecular sieve is 0.5 g/L-10 g/L.
Preferably, in the third step, the stripping gas adopted by the gas stripping method is air or water vapor, and the gas flow rate is 2L/min-20L/min.
Preferably, in step four, the coagulant is basic ferric chloride and is used in an amount of 0.1 g/L-1 g/L.
Preferably, in the fifth step, the ethanol is absolute ethanol.
Preferably, in the sixth step, the combined biological reaction tank comprises an anaerobic treatment unit, an anoxic treatment unit and an aerobic treatment unit which are sequentially communicated.
Preferably, reflux devices are arranged between the anaerobic treatment unit and the anoxic treatment unit and between the anoxic treatment unit and the aerobic treatment unit, the residence time of the anaerobic treatment unit is 6-24 h, the reaction temperature range is 20-40 ℃, the dissolved oxygen range is 0-2.0 mg/L, the residence time of the anoxic treatment unit is 4-12 h, the reaction temperature range is 25-35 ℃, the dissolved oxygen range is 1.0 mg/L-2.0 mg/L, the residence time of the aerobic treatment unit is 6-24 h, the reaction temperature range is 20-40 ℃, and the dissolved oxygen range is 2.0 mg/L-10.0 mg/L.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1. the invention provides a method for deeply purifying and treating wastewater produced in spandex industry by comprehensively applying chemical, physical and biological combined technologies, which is based on the components of the wastewater produced in the spandex industry and comprises the following steps: the zeolite molecular sieve is used for catalytically decomposing DMF at normal temperature, thereby improving the biodegradability of the wastewater and reducing the toxicity of the wastewater; meanwhile, the full removal of DMF in the wastewater greatly reduces the solubility of polyether glycol in the wastewater, and provides convenience for the subsequent recovery and use of polyether glycol PTMEG; and finally, realizing the deep purification treatment of the wastewater of the spandex industry through a biological treatment technology.
2. The technical scheme provided by the invention has the advantages of mild operation conditions, high treatment efficiency and excellent treatment effect, and can recover expensive polyether glycol in the wastewater and dimethylamine generated by decomposing DMF in the wastewater treatment process, thereby realizing the resource utilization of the wastewater to a higher degree; and the ethanol used in the treatment process can be recycled, so that the recovery cost is reduced, and the whole treatment process has obvious economic value.
3. In consideration of the characteristic of great water quality fluctuation of the spandex industrial production wastewater generated in different production links, the invention removes a large amount of COD (chemical oxygen demand) and total nitrogen in water by the primary precipitation, DMF (dimethyl formamide) decomposition and polyether glycol recovery processes at the front end, lightens the load of a rear-end combined biological treatment unit and ensures that the wastewater treatment reaches the standard and is discharged. The whole treatment system is suitable for the characteristics of complex components, high total nitrogen content, poor biodegradability, large water quality difference and high toxicity of the wastewater generated in the spandex industry, and has excellent impact load resistance.
4. The advanced purification treatment method for the wastewater produced in the spandex industry provided by the invention enables the water quality indexes such as COD (chemical oxygen demand) and total nitrogen of the effluent to reach the first-class A discharge standard specified in discharge Standard of pollutants for municipal wastewater treatment plants (GB18918-2002), and can be directly discharged.
Detailed Description
The technical solutions in the present invention will be described clearly and completely below, and it should be apparent 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 creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment relates to a deep purification treatment method of spandex industrial production wastewater, which comprises the following steps:
step one, setting the initial water quality parameter of 5L as pH 7 and CODCrConveying spandex industrial production wastewater with the chemical oxygen demand of 3000 mg/L (suspended matters) of 250 mg/L, the total nitrogen of 500 mg/L and the chroma of 700 to a primary sedimentation tank, firstly adding a polyaluminum chloride solution with the mass fraction of 10 percent, the dosage of the polyaluminum chloride solution is 0.5 g/L, after 20s, adding a polyacrylamide solution with the mass fraction of 0.1 percent, the dosage of the polyacrylamide solution is 0.4 g/L, uniformly mixing and stirring at room temperature for 10min, naturally settling for 15min, and filtering out precipitates;
step two, conveying the wastewater obtained in the step one to a DMF decomposition pool, adding potassium carbonate, adjusting the pH value of the solution to 9, adding a zeolite molecular sieve with the dosage of 1.5 g/L, and reacting for 2 hours at 25 ℃;
step three, separating the dimethylamine in the wastewater obtained in the step two by using a gas stripping method, wherein the stripping gas is air, the gas flow rate is 10L/min, and the dimethylamine is recovered by an elution tower;
step four, conveying the wastewater obtained in the step three to a polyether separation tank, adding basic ferric chloride with the dosage of 0.2 g/L, uniformly mixing and stirring for 10min, naturally settling for 15min, and separating filtrate and filter residue;
step five, soaking the filter residue obtained in the step four in ethanol of 500m L, stirring for 10min to fully dissolve the polyether glycol in the filter residue in the ethanol, naturally settling for 15min, conveying the obtained supernatant to a distillation kettle, separating the polyether glycol and the ethanol at 75 ℃, condensing the evaporated ethanol in a heat exchanger and recycling, and collecting the polyether glycol in the distillation kettle after distillation is finished;
and step six, enabling the filtrate obtained in the step four to sequentially pass through an anaerobic treatment unit, an anoxic treatment unit and an aerobic treatment unit, wherein the residence time of the anaerobic treatment unit is 6 hours, the reaction temperature range is 30 ℃, the dissolved oxygen range is 0.6 mg/L, the residence time of the anoxic treatment unit is 6 hours, the reaction temperature range is 35 ℃, the dissolved oxygen range is 1.5 mg/L, the residence time of the aerobic treatment unit is 12 hours, the reaction temperature range is 30 ℃, the dissolved oxygen range is 2.0 mg/L, and anaerobic bacteria, facultative bacteria and aerobic bacteria are respectively arranged in the anaerobic treatment unit, the anoxic treatment unit and the aerobic treatment unit and are used for performing biodegradation on organic matters in the filtrate and reducing the COD value and the total nitrogen in water.
The pH value of the effluent after treatment is 7 and the COD isCr22 mg/L is 0 mg/L, total nitrogen is 6 mg/L, chroma is 7, and all water quality parameters meet the first-class A emission standard specified in pollutant emission Standard of municipal wastewater treatment plant (GB18918-2002), and can directly reach the standard for emission.
The preliminary precipitation, DMF decomposition and dimethylamine recovery, polyether separation and recovery and combined biological treatment are synergistic, so that various indexes of treated spandex industrial production wastewater can meet the requirement of direct discharge, and certain parameters of effluent can not reach the standard in the absence of the treatment. To illustrate this problem, the following comparative examples were carried out:
comparative example 1
Compared with the embodiment 1, the method has the advantages that the step one is omitted, and other processing steps are the same as the embodiment 1.
The SS of the final effluent is 43 mg/L, and exceeds the standard meeting requirement of SS <10 mg/L in the first class A discharge standard specified in pollutant discharge Standard of municipal wastewater treatment plant (GB18918-2002), which indicates that the step one of removing the suspended matters in the wastewater by adding the polyaluminium chloride and polyacrylamide combined coagulant is effective and necessary.
Comparative example 2-1
Step two was omitted compared to example 1, and the other processing steps were the same as example 1.
COD of final effluentCr272 mg/L and 104 mg/L of total nitrogen, which greatly exceed the standard reaching requirements corresponding to the first-class A emission standard specified in the pollutant emission Standard of municipal wastewater treatment plant (GB18918-2002), indicate that the biological treatment unit cannot work efficiently under high DMF concentration, which leads to serious high index of effluent quality, and in addition, polyether glycol PTMEG cannot be successfully recovered in the process, because the existence of DMF improves the solubility of polyether glycol in wastewater, which leads to the fact that polyether glycol cannot be separated from the wastewater under the action of basic ferric chloride in the step four, the comparative example 2-1 illustrates that the catalytic decomposition treatment of DMF in the step two is beneficial to the recovery and use of PTMEG and the efficient subsequent biological treatment.
Comparative examples 2 to 2
Compared with example 1, no zeolite molecular sieve as decomposition promoter was added in step two, and the other treatment steps were the same as in example 1.
COD of final effluentCrCompared with the example 1 and the comparative example 2-1, the comparative example 2-2 shows that the decomposition of DMF is not sufficient without the zeolite molecular sieve, namely the addition of the zeolite molecular sieve can promote the decomposition of DMF, improve the treatment effect, realize the recovery of polyether glycol and improve the recovery amount of dimethylamine.
Comparative example 3
Step three was omitted compared to example 1, and the other processing steps were the same as example 1.
The total nitrogen content of the final effluent is 67 mg/L, which exceeds the standard reaching requirement corresponding to the first grade A emission standard specified in pollutant emission Standard of municipal wastewater treatment plant (GB18918-2002), and the exceeding of the total nitrogen content is caused by the large amount of dimethylamine in the wastewater.
Comparative example 4
Step four was omitted compared to example 1, and the other processing steps were the same as example 1.
COD of final effluentCrAnd the total nitrogen can reach the standard, but the polyether glycol PTMEG can not be recovered in the process, thereby greatly reducing the economic benefit.
Comparative example 5
Step five is omitted compared to example 1, and the other processing steps are the same as example 1.
COD of final effluentCrAnd total nitrogen can reach the standard, but the polyether glycol PTMEG can not be recovered in the process.
Comparative examples 1 to 7
Step six is missing compared to example 1 and the other processing steps are the same as example 1.
COD of final effluentCr1280 mg/L, 85 mg/L of total nitrogen, which greatly exceed the standard reaching requirements corresponding to the first class A emission standard specified in the pollutant emission Standard of municipal wastewater treatment plant (GB18918-2002), which indicates that the combined biological reaction treatment process is an essential step for advanced purification treatment of wastewater produced in spandex industry.
Example 2
The embodiment relates to a deep purification treatment method of spandex industrial production wastewater, which comprises the following steps:
step one, setting the initial water quality parameter of 5L as pH 7 and CODCrConveying the spandex industrial production wastewater with 85000 mg/L-530 mg/L, total nitrogen-9200 mg/L and chromaticity-6200 to a primary sedimentation tank, adding a polyaluminium chloride solution with the mass fraction of 20 percent and the dosage of 1 g/L at first, adding a polyacrylamide solution with the mass fraction of 0.2 percent and the dosage of 1 g/L at last after 20s, uniformly mixing and stirring at room temperature for 25min, naturally settling for 30min, and filtering out precipitates;
step two, conveying the wastewater obtained in the step one to a DMF decomposition pool, adding sodium carbonate, adjusting the pH value of the solution to 9, adding a zeolite molecular sieve with the dosage of 8.5 g/L, and reacting for 2 hours at 25 ℃;
step three, separating the dimethylamine in the wastewater obtained in the step two by using a gas stripping method, wherein the stripping gas is air, the gas flow rate is 20L/min, and the dimethylamine is recovered by an elution tower;
step four, conveying the wastewater obtained in the step three to a polyether separation tank, adding basic ferric chloride with the dosage of 0.8 g/L, uniformly mixing and stirring for 30min, naturally settling for 30min, and separating filtrate and filter residue;
step five, soaking the filter residue obtained in the step four in ethanol of 500m L, stirring for 30min to fully dissolve polyether glycol in the filter residue in the ethanol, naturally settling for 30min, conveying the obtained supernatant to a distillation kettle, separating the polyether glycol and the ethanol at 78 ℃, condensing the evaporated ethanol in a heat exchanger and recycling, and collecting the polyether glycol in the distillation kettle after distillation is finished;
step six, enabling the filtrate obtained in the step four to sequentially pass through an anaerobic treatment unit, an anoxic treatment unit and an aerobic treatment unit, wherein the residence time of the anaerobic treatment unit is 24 hours, the reaction temperature range is 30 ℃, the dissolved oxygen range is 0.6 mg/L, the residence time of the anoxic treatment unit is 12 hours, the reaction temperature range is 35 ℃, the dissolved oxygen range is 1.5 mg/L, the residence time of the aerobic treatment unit is 24 hours, the reaction temperature range is 30 ℃, the dissolved oxygen range is 2.0 mg/L, carrying out reflux circulation treatment for three times under the above experimental conditions, the pH of treated effluent is 7, and the COD (chemical oxygen demand) isCr45 mg/L is 6 mg/L, total nitrogen is 13 mg/L, chroma is 19, and all water quality parameters meet the first-class A emission standard specified in pollutant emission Standard of municipal wastewater treatment plant (GB18918-2002), and the emission can reach the standard directly.
The wastewater in the embodiment mainly comes from the production process of a refining distillation section, the concentration of the wastewater is extremely high, the COD (chemical oxygen demand) and the total nitrogen value are dozens of times of those of the common wastewater, the wastewater can be directly treated by properly prolonging the treatment time, increasing the reagent dosage and the like until all water quality parameters reach the standard and then directly discharged, and the effectiveness of the method for deeply purifying and treating the wastewater in the spandex industry is further proved.
Example 3
The embodiment relates to a deep purification treatment method of spandex industrial production wastewater, which comprises the following steps:
step one, setting the initial water quality parameter of 5L as pH 7 and CODCrConveying the spandex industrial production wastewater with the chroma of 1300 to a primary sedimentation tank, adding a polyaluminium chloride solution with the mass fraction of 10% and the dosage of 0.5 g/L at first, adding a polyacrylamide solution with the mass fraction of 0.1% and the dosage of 0.4 g/L at 20s later, uniformly mixing and stirring at room temperature for 10min, naturally settling for 15min, and filtering out precipitates;
step two, conveying the wastewater obtained in the step one to a DMF decomposition pool, adding potassium carbonate, adjusting the pH value of the solution to 9, adding a zeolite molecular sieve with the dosage of 5 g/L, and reacting for 2 hours at 25 ℃;
step three, separating the dimethylamine in the wastewater obtained in the step two by using a gas stripping method, wherein the stripping gas is air, the gas flow rate is 10L/min, and the dimethylamine is recovered by an elution tower;
step four, conveying the wastewater obtained in the step three to a polyether separation tank, adding basic ferric chloride with the dosage of 0.4 g/L, uniformly mixing and stirring for 10min, naturally settling for 15min, and separating filtrate and filter residue;
step five, soaking the filter residue obtained in the step four in ethanol of 500m L, stirring for 10min to fully dissolve the polyether glycol in the filter residue in the ethanol, naturally settling for 15min, conveying the obtained supernatant to a distillation kettle, separating the polyether glycol and the ethanol at 78 ℃, condensing the evaporated ethanol in a heat exchanger and recycling, and collecting the polyether glycol in the distillation kettle after distillation is finished;
step six, enabling the filtrate obtained in the step four to sequentially pass through an anaerobic treatment unit, an anoxic treatment unit and an aerobic treatment unit, wherein the residence time of the anaerobic treatment unit is 12 hours, the reaction temperature range is 30 ℃, the dissolved oxygen range is 0.6 mg/L, the residence time of the anoxic treatment unit is 12 hours, the reaction temperature range is 35 ℃, the dissolved oxygen range is 1.5 mg/L, the residence time of the aerobic treatment unit is 24 hours, the reaction temperature range is 30 ℃, the dissolved oxygen range is 2.0 mg/L, the pH of the treated effluent is 7, the COD isCr31 mg/L-5 mg/L, 12 mg/L of total nitrogen and 7 of chroma, and all the water quality parameters meet the pollutant discharge standard of urban sewage treatment plant (GB 18918-20)02) The first grade A discharge standard specified in the specification can directly reach the discharge standard.
Example 4
The embodiment relates to a deep purification treatment method of spandex industrial production wastewater, which comprises the following steps:
step one, setting the initial water quality parameter of 5L as pH 7 and CODCrConveying the spandex industrial production wastewater with the chroma of 280 to a primary sedimentation tank, adding a polyaluminium chloride solution with the mass fraction of 10% and the dosage of 0.5 g/L at first, adding a polyacrylamide solution with the mass fraction of 0.1% and the dosage of 0.4 g/L at 20s, uniformly mixing and stirring at room temperature for 10min, naturally settling for 15min, and filtering out precipitates;
step two, conveying the wastewater obtained in the step one to a DMF decomposition pool, adding sodium carbonate, adjusting the pH value of the solution to 9, adding a zeolite molecular sieve with the dosage of 1.5 g/L, and reacting for 2 hours at 10 ℃;
step three, separating the dimethylamine in the wastewater obtained in the step two by using a gas stripping method, wherein the stripping gas is air, the gas flow rate is 10L/min, and the dimethylamine is recovered by an elution tower;
step four, conveying the wastewater obtained in the step three to a polyether separation tank, adding basic ferric chloride with the dosage of 0.2 g/L, uniformly mixing and stirring for 10min, naturally settling for 15min, and separating filtrate and filter residue;
step five, soaking the filter residue obtained in the step four in ethanol of 500m L, stirring for 10min to fully dissolve the polyether glycol in the filter residue in the ethanol, naturally settling for 15min, conveying the obtained supernatant to a distillation kettle, separating the polyether glycol and the ethanol at 75 ℃, condensing the evaporated ethanol in a heat exchanger and recycling, and collecting the polyether glycol in the distillation kettle after distillation is finished;
step six, enabling the filtrate obtained in the step four to sequentially pass through an anaerobic treatment unit, an anoxic treatment unit and an aerobic treatment unit, wherein the residence time of the anaerobic treatment unit is 6 hours, the reaction temperature range is 30 ℃, the dissolved oxygen range is 0.6 mg/L, the residence time of the anoxic treatment unit is 6 hours, the reaction temperature range is 35 ℃, the dissolved oxygen range is 1.5 mg/L, and the residence time of the aerobic treatment unit is 12h, the reaction temperature range is 30 ℃, the dissolved oxygen range is 2.0 mg/L, the pH of the effluent is 7, and the COD isCr14 mg/L is 0 mg/L, total nitrogen is 4 mg/L, chroma is 5, and all water quality parameters meet the first grade A emission standard specified in pollutant emission Standard of municipal wastewater treatment plant (GB18918-2002), and can directly reach the standard for emission.
Example 5
The embodiment relates to a deep purification treatment method of spandex industrial production wastewater, which comprises the following steps:
step one, setting the initial water quality parameter of 5L as pH 7 and CODCr73000 mg/L-460 mg/L, 6500 mg/L of total nitrogen, 4900 of color of spandex industrial production wastewater is conveyed to a primary sedimentation tank, polyaluminum chloride solution with the mass fraction of 20 percent is added firstly, the dosage of the polyaluminum chloride solution is 1 g/L, polyacrylamide solution with the mass fraction of 0.2 percent is added after 20s, the dosage of the polyaluminum chloride solution is 1 g/L, the mixture is uniformly mixed and stirred at room temperature for 30min, natural sedimentation is carried out for 30min, and the sediment is filtered;
step two, conveying the wastewater obtained in the step one to a DMF decomposition pool, adding potassium carbonate, adjusting the pH value of the solution to 9, adding a zeolite molecular sieve with the dosage of 8 g/L, and reacting for 2 hours at 30 ℃;
step three, separating the dimethylamine in the wastewater obtained in the step two by using a gas stripping method, wherein the stripping gas is air, the gas flow rate is 15L/min, and the dimethylamine is recovered by an elution tower;
step four, conveying the wastewater obtained in the step three to a polyether separation tank, adding basic ferric chloride with the dosage of 0.6 g/L, uniformly mixing and stirring for 30min, naturally settling for 30min, and separating filtrate and filter residue;
step five, soaking the filter residue obtained in the step four in ethanol of 500m L, stirring for 30min to fully dissolve polyether glycol in the filter residue in the ethanol, naturally settling for 30min, conveying the obtained supernatant to a distillation kettle, separating the polyether glycol and the ethanol at 78 ℃, condensing the evaporated ethanol in a heat exchanger and recycling, and collecting the polyether glycol in the distillation kettle after distillation is finished;
step six, the filtrate obtained in the step four passes through an anaerobic treatment unit, an anoxic treatment unit and an aerobic treatment unit in turnThe anaerobic treatment unit has a residence time of 24h, a reaction temperature range of 30 ℃, a dissolved oxygen range of 0.6 mg/L, an anoxic treatment unit has a residence time of 12h, a reaction temperature range of 35 ℃, a dissolved oxygen range of 1.5 mg/L, an aerobic treatment unit has a residence time of 24h, a reaction temperature range of 30 ℃, a dissolved oxygen range of 2.0 mg/L, and the anaerobic treatment unit is subjected to reflux circulation treatment for three times under the above experimental conditions, wherein the pH of treated effluent is 7, and the COD isCr34 mg/L is 2 mg/L, total nitrogen is 9 mg/L, chroma is 17, and all water quality parameters meet the first-class A emission standard specified in pollutant emission Standard of municipal wastewater treatment plant (GB18918-2002), and can directly reach the standard for emission.
Analysis of economic benefits of polyether glycol PTMEG recovery: according to different waste water source sections, by applying the method for deeply purifying and treating the industrial wastewater of the spandex industry, 0.1 Kg-2 Kg of PTMEG can be recovered from each ton of wastewater, and the economic benefit of PTMEG recovery can reach 3-60 yuan/m according to the market price of the PTMEG which is about 3 ten thousand yuan/ton3. The daily average wastewater yield of spandex production enterprises is 500m3And calculating to create economic benefit as high as 0.15-3 ten thousand yuan/d.
The above description is only a preferred embodiment of the present invention, and therefore, the scope of the present invention should not be limited by the description of the preferred embodiment, and all equivalent changes and modifications made in the claims and the specification should be included in the scope of the present invention.
Claims (10)
1. A deep purification treatment method of spandex industrial production wastewater is characterized in that:
step one, conveying the industrial production wastewater of spandex to a primary sedimentation tank, adding a coagulant, uniformly mixing and stirring at room temperature for 5-30min, naturally settling for 15-30 min, and filtering out the precipitate;
step two, conveying the wastewater obtained in the step one to a DMF decomposition pool, adding alkali, adjusting the pH value of the solution to 7-10, adding a zeolite molecular sieve, and reacting at 10-30 ℃ for 1-12 h;
step three, separating the dimethylamine in the wastewater obtained in the step two by using a gas stripping method, and recovering the dimethylamine;
step four, conveying the wastewater obtained in the step three to a polyether glycol separation tank, adding a coagulant, uniformly mixing and stirring for 5-30min, naturally settling for 15-30 min, and separating filtrate and filter residue;
step five, soaking the filter residue obtained in the step four in ethanol, stirring for 5-30min to fully dissolve polyether glycol in the filter residue in the ethanol, and naturally settling for 15-30 min; then, taking the supernatant fluid to distill and separate polyether glycol and ethanol at the temperature of 60-80 ℃ to realize the recovery of polyether glycol, and condensing the distilled ethanol in a heat exchanger for recycling;
and step six, conveying the filtrate obtained in the step four to a combined biological reaction tank for biodegradation to complete wastewater treatment.
2. The advanced purification treatment method of wastewater from spandex industry according to claim 1, characterized in that: in the first step, the main initial water quality parameter ranges of the spandex industrial production wastewater are as follows: pH: 6-9, CODCr1000 mg/L-100000 mg/L, 50 mg/L-1000 mg/L suspended matter, 200 mg/L-10000 mg/L total nitrogen and 8000 chroma of 200-.
3. The advanced purification treatment method of wastewater from spandex industry according to claim 1, characterized in that in step one, the coagulant is a combined coagulant composed of polyaluminum chloride solution and polyacrylamide solution, wherein the mass fraction of polyaluminum chloride in the polyaluminum chloride solution is 5% -20%, and the mass fraction of polyacrylamide in the polyacrylamide solution is 0.05% -0.2%, when the coagulant is added, the polyaluminum chloride solution is added in an amount of 0.1-1 g/L, and the polyacrylamide solution is added after 20s, and the amount of the polyacrylamide solution is 0.1 g/L-1 g/L.
4. The advanced purification treatment method of wastewater from spandex industry according to claim 1, characterized in that: in the second step, the alkali is one or two of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide.
5. The method for deeply purifying and treating the wastewater generated in the spandex industry according to claim 1, wherein in the second step, the dosage of the zeolite molecular sieve is 0.5 g/L-10 g/L.
6. The method for deeply purifying and treating the wastewater generated in the spandex industry according to claim 1, wherein in the third step, the stripping gas adopted by the gas stripping method is air or water vapor, and the gas flow rate is 2L/min to 20L/min.
7. The method for deeply purifying and treating the wastewater generated in the spandex industry according to claim 1, wherein in the fourth step, the coagulant is basic ferric chloride and the dosage of the basic ferric chloride is 0.1 g/L-1 g/L.
8. The advanced purification treatment method of wastewater from spandex industry according to claim 1, characterized in that: in the fifth step, the ethanol is absolute ethanol.
9. The advanced purification treatment method of wastewater from spandex industry according to claim 1, characterized in that: in the sixth step, the combined biological reaction tank comprises an anaerobic treatment unit, an anoxic treatment unit and an aerobic treatment unit which are sequentially communicated.
10. The advanced purification treatment method of wastewater from spandex industry according to claim 9, wherein reflux devices are respectively installed between the anaerobic treatment unit and the anoxic treatment unit and between the anoxic treatment unit and the aerobic treatment unit, the residence time of the anaerobic treatment unit is 6h-24h, the reaction temperature range is 20 ℃ -40 ℃, the dissolved oxygen range is 0-2.0 mg/L, the residence time of the anoxic treatment unit is 4h-12h, the reaction temperature range is 25 ℃ -35 ℃, the dissolved oxygen range is 1.0 mg/L-2.0 mg/L, the residence time of the aerobic treatment unit is 6h-24h, the reaction temperature range is 20 ℃ -40 ℃, and the dissolved oxygen range is 2.0 mg/L-10.0 mg/L.
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