CN102936077B - Treatment method of polyacrylonitrile fiber production sewage - Google Patents
Treatment method of polyacrylonitrile fiber production sewage Download PDFInfo
- Publication number
- CN102936077B CN102936077B CN201110233438.0A CN201110233438A CN102936077B CN 102936077 B CN102936077 B CN 102936077B CN 201110233438 A CN201110233438 A CN 201110233438A CN 102936077 B CN102936077 B CN 102936077B
- Authority
- CN
- China
- Prior art keywords
- waste water
- polyacrylonitrile
- anaerobic
- treatment
- fiber production
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a treatment method of polyacrylonitrile fiber production sewage. The method comprises the steps of: under the conditions of a pH value of 8-12, a pressure of 0.5-3MPa, and a temperature of 100-260DEG C, hydrolyzing the wastewater A generated in a polymerization process during polyacrylonitrile fiber production, mixing the hydrolysis product with the wastewater B generated by at least one process among other processes except the polymerization process during polyacrylonitrile fiber production, subjecting the mixture to settling separation, and then conducting biochemical treatment on the separated supernatant. The method provided in the invention can treat the polyacrylonitrile fiber production sewage till meeting the discharge standards, and can significantly reduce the consumption of an additional flocculant in the treatment process.
Description
Technical field
The present invention relates to a kind for the treatment of process of polyacrylonitrile fiber production sewage.
Background technology
Polyacrylonitrile fibre (commodity are called acrylic fibers) is one of principal item of synthon, and 1-10 month polyacrylonitrile fibre cumulative production in 2009 58.63 ten thousand tons, accounts for 2.89% of the synthon ultimate production same period, be only second to terylene and polyamide fibre according to statistics.
Polyacrylonitrile fiber production sewage mainly produces the process procedures such as auto-polymerization, spinning and solvent recuperation, and water quality is complicated, and the organonitrogen often containing low-molecular(weight)polymer, high density and vitriol also have the material of quite a few difficult for biological degradation.Wherein low-molecular(weight)polymer, exists with suspension colloidal form usually, and be difficult to natural subsidence and remove, these low-molecular(weight)polymers not only affect the normal operation of biochemical system after entering biochemical system, and increase the load of organic matter degradation; These low-molecular(weight)polymers easily block filler simultaneously, reduce the specific surface area of filler, add wastewater biochemical intractability.Prior art adopts usually first carries out flocculating with except low-molecular(weight)polymer, then carries out the method process polyacrylonitrile fiber production sewage of biochemical treatment.Such as, CN 1293159A discloses a kind of bioremediation of acrylic fibers waste water by dry process, and the method comprises: the composite flocculation agent that (1) adopts polymerize aluminum chloride and quaternary ammonium salt cation flocculation agent to form removes oligopolymer colloid; (2) tandem phase-splitting anaerobic digestion; (3) Anoxybiotic-aerobic biologic denitrogenation, adds water-soluble carboxylate as co-substrate at aerobic section; (4) sand filtration; (5) charcoal absorption.CN1539766A discloses a kind of method of two-step approach acrylic fibre wet spinning technique trade effluent for the treatment of taking Sodium Thiocyanate 99 as solvent, the method comprises successively: the oligopolymer in micro-electrolysis method degraded polymerization workshop section waste water, then add flocculation agent alum, be separated by coagulant precipitation; Polymerization workshop section waste water mixes homogeneous with the cyanide wastewater of spinning and solvent recuperation workshop section; Then being hydrolyzed successively, acidifying, carbonization are nitrated, denitrification, aeration are separated with sludge settling.But the method for above-mentioned existing process polyacrylonitrile fiber production sewage all needs to use relatively large flocculation agent.
Summary of the invention
The object of this invention is to provide a kind for the treatment of process of new polyacrylonitrile fiber production sewage, the method has higher processing efficiency, and obviously can reduce the amount of additional flocculating agents, even can completely without additional flocculating agents.
The invention provides a kind for the treatment of process of polyacrylonitrile fiber production sewage, the method comprises: pH value be 8 ~ 12, under pressure is 0.5 ~ 3MPa, temperature is the condition of 100 ~ 260 DEG C, the waste water A that polymerization process in the production process of polyacrylonitrile fibre produces is hydrolyzed, the waste water B that the hydrolysate obtained and at least one operation in other operation in the production process of polyacrylonitrile fibre except polymerization process produce is mixed, and the mixture obtained is carried out settlement separate, then isolated supernatant liquid is carried out biochemical treatment.
Method according to the present invention, be hydrolyzed under given conditions by the waste water that the polymerization process in the production process of polyacrylonitrile fibre is produced, then the waste water that the hydrolysate obtained and at least one operation in other operation in the production process of polyacrylonitrile fibre except polymerization process produce is mixed, carry out settlement separate, the amount of additional flocculating agents can be reduced, even can completely without additional flocculating agents; And can by polyacrylonitrile fiber production sewage process to meeting emission standard by follow-up biochemical treatment process.
Embodiment
The treatment process of polyacrylonitrile fiber production sewage according to the present invention comprises: be 8 ~ 12 in pH value, pressure is 0.5 ~ 3MPa, temperature is under the condition of 100 ~ 260 DEG C, the waste water A (being called for short " waste water A ") produced by polymerization process in the production process of polyacrylonitrile fibre is hydrolyzed, the waste water B (being called for short " waste water B ") produced with at least one operation in other operation in the production process of polyacrylonitrile fibre except polymerization process by the hydrolysate obtained mixes, and the mixture obtained is carried out settlement separate, then isolated supernatant liquid is carried out biochemical treatment.
In the preferred case, the condition that described waste water A is hydrolyzed comprised: pH value is 10 ~ 11, pressure is 1 ~ 2MPa, and temperature is 170 ~ 200 DEG C, and the time is 1 ~ 10h.In the present invention, described pressure refers to absolute pressure.
According to described method provided by the invention, the principal pollutant in described waste water A are polyacrylonitrile, and the content of polyacrylonitrile can be 0.001 ~ 0.01 quality %.
According to described method provided by the invention, the production process of described polyacrylonitrile fibre mainly comprises polymerization process, spinning process and solvent recuperation operation usually.Therefore, in the present invention, other operation in the production process of described polyacrylonitrile fibre except polymerization process mainly comprises spinning process and solvent recuperation operation.
According to described method provided by the invention, the COD of described waste water B can be 500 ~ 1200mg/L, BOD
5can be 100 ~ 400mg/L, NH
3-N can be 20 ~ 100mg/L.Usually, the pollutent in described waste water B is mainly selected from the solvent that uses in methyl acrylate (MA), methyl methacrylate (MMA), vinyl acetate (VA), spinning process (as NaSCN, dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), acetone and HNO
3deng) and additive (as adding blue agent, defoamer etc.) in one or more.
According to described method provided by the invention, described hydrolysate (product by obtaining after described waste water A hydrolysis) can be 1: 0.1 ~ 10 with the mixing quality ratio of described waste water B, is preferably 1: 0.2 ~ 5.
In the present invention, described method can also be included in and add flocculation agent by the process mixed with described waste water B by the hydrolysate obtained after described waste water A hydrolysis.In this case, relative to the described hydrolysate of 100 mass parts and the total mass of described waste water B, the add-on of described flocculation agent can be 0.001 ~ 0.07 mass parts.
In the present invention, described flocculation agent can be the various flocculation agents that this area routine uses, can be such as at least one in Tai-Ace S 150, alum, the hydrate of iron trichloride, the hydrate of ferrous sulfate, polyaluminium sulfate, polymerize aluminum chloride, aluminium iron polychloride, polymeric aluminum sulfate silicate, polyacrylamide, sodium polyacrylate, polyvinyl pyridine and polymine, be preferably polymerize aluminum chloride and/or polyacrylamide.
According to described method provided by the invention, the method of described biochemical treatment can be the conventional biochemical processing method used in sewage treatment area, such as, can comprise at least one in activated sludge process, biological contact oxidation process, Gas biological filter, sequencing batch reactor, anaerobic biofilter method, anaerobic contact method, anaerobic-anoxic-oxic method and anoxic-anaerobic-aerobic process.
In the present invention, described activated sludge process can be the activated sludge process that this area routine uses, refer in the aeration tank of artificial oxygenation, utilize the organism in active sludge removal sewage, then mud is made to be separated with water, major part mud is back to aeration tank again, and by the method for remainder mud discharge.Described active sludge is the flock formed by the organic and inorganic nitrogen solids coagulation in multiple aerobic microbiological and amphimicrobe (can contain a small amount of anaerobion) and sewage.The operational condition of described activated sludge process can comprise: temperature is 25 ~ 35 DEG C, and mud age is 3 ~ 5d, and sludge loading is 0.2 ~ 0.4kg BOD
5/ (kg MLSSd), volume load is 0.3-0.6kg BOD
5/ (M
3d), suspended solids (MLSS) concentration is 1500 ~ 3000mg/L, and the treatment time is 4 ~ 8h, and reflux ratio is 0.25 ~ 0.5.In the present invention, BOD
5refer to 5 days biochemical oxygen demand (BOD)s.
In the present invention, described biological contact oxidation process can be the biological contact oxidation process that this area routine uses, load filler in biological contact oxidation pond, utilize the oxygen of microbial film and the ample supply be adsorbed on filler, pass through biological oxidation, the pollutant oxidations such as the organic amine in described filtrate are decomposed, thus reaches the method for the object of purification.The operational condition of described biological contact oxidation process can comprise: temperature is 25 ~ 35 DEG C, and volume load is 1.0 ~ 1.8kgBOD
5/ (M
3d), the treatment time is 2 ~ 8h.
In the present invention, described Gas biological filter can be the Gas biological filter that this area routine uses, refer to the granule filter material in the in-built raising specific surface area of bio-reactor, the carrier grown to provide microbial film, and it is lower to stream or upward flow to being divided into according to the various flows of sewage, sewage flows through filter material layer from top to bottom or from bottom to top, at filter material layer blowing air down aeration, air is reverse with sewage or contact in the same way, makes the method that the organism in sewage is removed by carrying out biochemical reaction with filling surface microbial film.The operational condition of described Gas biological filter can comprise: temperature is 25 ~ 35 DEG C, and volume load is 3 ~ 6kgCOD/ (M
3d), air water volume ratio is 1 ~ 5: 1, and the treatment time is 2 ~ 10h.In the present invention, COD refers to chemical oxygen demand (COD).
In the present invention, described sequencing batch reactor can be the sequencing batch reactor that this area routine uses, and is a kind of active sludge water technology run by intermittent aeration mode, also known as sequencing batch active sludge.The operational condition of described sequencing batch reactor can comprise: temperature is 25 ~ 35 DEG C, mud age is 5 ~ 15d, the concentration of suspended solids (MLSS) is 2000 ~ 5000mg/L, filling time is 1 ~ 4h, reaction times 2 ~ 8h, sedimentation and drawing time 2 ~ 4h, time of repose 1 ~ 3h.
In the present invention, described anaerobic biofilter method can be the anaerobic biofilter method that this area routine uses, and is a kind of anaerobic biological treatment method, in the sealing pond of placing filler, sewage enters at the bottom of pond, discharges from Chi Ding, thus the process of organics removal.The operational condition of described anaerobic biofilter method can comprise: temperature is 25 ~ 35 DEG C, and volume load is 3 ~ 6kg COD/ (M
3d), treatment time 12 ~ 96h.
In the present invention, described anaerobic contact method can be the anaerobic contact method that this area routine uses, and be also a kind of anaerobic biological treatment method, form class is similar to activated sludge process, after digester, establish settling tank, and precipitating sludge is back to digester.The operational condition of described anaerobic contact method can comprise: temperature is 25 ~ 35 DEG C, and volume load is 3 ~ 5kg COD/ (M
3d), treatment time 12 ~ 48h.
In the present invention, described anaerobic-anoxic-oxic method can be the anaerobic-anoxic-oxic method that this area routine uses, refer to technique anaerobism, anoxic, aerobic method combined, sewage, successively through anaerobic pond, anoxic pond and Aerobic Pond, carries out the technical process processed.The operational condition of described anaerobic-anoxic-oxic method can comprise: temperature is 25 ~ 35 DEG C, and volume load is 3 ~ 8kg COD/ (M
3d), the anaerobic treatment time is 12 ~ 48h, and the anaerobic treatment time is 12 ~ 48h, and the aerobic treatment time is 4 ~ 16h.
In the present invention, described anoxic-anaerobic-aerobic process can be anoxic-anaerobic-aerobic process that this area routine uses, refer to technique anaerobism, anoxic, aerobic method combined, sewage, successively through anoxic pond, anaerobic pond and Aerobic Pond, carries out the technical process processed.The operational condition of described anoxic-anaerobic-aerobic process can comprise: temperature is 25 ~ 35 DEG C, and volume load is 3 ~ 8kg COD/ (M
3d), the anaerobic treatment time is 12 ~ 48h, and the anaerobic treatment time is 12 ~ 48h, and the aerobic treatment time is 4 ~ 16h.
The invention will be further described with comparative example by the following examples.
In the following Examples and Comparative Examples, the BOD in the reuse water obtained after treatment
5gB7488-87 dilution is adopted to measure with inoculation method; COD measures according to the catalysis Quick Oxidation method in " water and waste water method for monitoring and analyzing guide (middle volume) "; Ammonia nitrogen (NH
3-N) refer in water with free state (NH
3) or ammonium salt (NH
4 +) form exist nitrogenous compound, NH
3-N content adopts GB7479-87 Nessler's reagent photometer to measure; The water quality of the reuse water obtained after treatment is evaluated according to integrated wastewater discharge standard GB8978-1996, wherein, specifies in GB8978-1996: BOD
5first discharge standard be the primary standard of 20mg/L, COD be 100mg/L, NH
3the first discharge standard of-N is 15mg/L.
Embodiment 1
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.009 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 9 of the material in retort, it is 170 DEG C that temperature controls, pressure-controlling is 1MPa, and keeps at this temperature and pressure reacting about 3h.Then, (COD is 781mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 280mg/L, NH
3-N is 60mg/L) be to mix at 1: 1 with mass ratio, after Homogeneous phase mixing, the mixture obtained is left standstill 1h.Adopt activated sludge process that the supernatant liquid that obtains after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 35 DEG C, and mud age is 3 days, and sludge loading is 0.3kg BOD
5/ (kg MLSSd), volume load is 0.4kg BOD
5/ (M
3d), suspended solids (MLSS) concentration is 1500mg/L, and the treatment time is 8h, and reflux ratio is 0.40.Learn by measuring, the COD in the reuse water obtained after process is 80mg/L, BOD
5for 20mg/L, NH
3-N is 12mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Comparative example 1
(COD is 781mg/L, BOD for spinning process in the waste water (polyacrylonitrile containing 0.009 quality %) directly produced by the polymerization process in the production process of polyacrylonitrile fibre and the production process of polyacrylonitrile fibre and the waste water of solvent recuperation operation generation
5for 280mg/L, NH
3-N is 60mg/L) be to mix at 1: 1 with mass ratio, then according to the method for embodiment 1, biochemical treatment is carried out to the composite waste obtained.Learn by measuring, the COD in the reuse water obtained after process is 120mg/L, BOD
5for 30mg/L, NH
3-N is 20mg/L, does not meet the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Comparative example 2
(COD is 781mg/L, BOD for spinning process in the waste water (polyacrylonitrile containing 0.009 quality %) directly produced by the polymerization process in the production process of polyacrylonitrile fibre and the production process of polyacrylonitrile fibre and the waste water of solvent recuperation operation generation
5for 280mg/L, NH
3-N is 60mg/L) be to mix at 1: 1 with mass ratio, afterwards relative to the composite waste obtained of 100 mass parts, the polyacrylamide of 0.1 mass parts is added (purchased from company of Beijing Hengju Chemical Group Co., Ltd in described composite waste, trade mark HENGFLOC 70008), and leave standstill 1h, then according to the method for embodiment 1, biochemical treatment is carried out to the supernatant liquid obtained after leaving standstill.Learn by measuring, the COD in the reuse water obtained after process is 100mg/L, BOD
5for 20mg/L, NH
3-N is 15mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
By embodiment 1 and comparative example 1 are compared and can find out, directly biochemical treatment is carried out in the waste water mixing of the waste water of polymerization process generation in the production process of described polyacrylonitrile fibre and the spinning process in the production process of described polyacrylonitrile fibre and the generation of solvent recuperation operation, the reuse water obtained does not meet emission standard, and method according to the present invention, first be hydrolyzed under certain conditions by the waste water that the polymerization process in the production process of described polyacrylonitrile fibre is produced, then biochemical treatment is carried out after the waste water produced with the spinning process in the production process of described polyacrylonitrile fibre and solvent recuperation operation mixes, then can by wastewater treatment to meeting emission standard.
By embodiment 1 and comparative example 2 are compared and can find out, although also can by composite waste process to meeting emission standard in comparative example 2, but need in comparative example 2 additionally to use flocculation agent, and be better than the reuse water that obtains according to the method for comparative example 2 according to the water quality that the method for embodiment 1 obtains reuse water.As can be seen here, the method for embodiment 1 has the effect of process polyacrylonitrile fiber production sewage preferably, and saves the cost of additional flocculating agents relative to comparative example 2.
Embodiment 2
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.001 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 8 of the material in retort, it is 200 DEG C that temperature controls, pressure-controlling is 2MPa, and keeps at this temperature and pressure reacting about 5h.Then, (COD is 1030mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 370mg/L, NH
3-N is 50mg/L) be to mix at 1: 2 with mass ratio, and in the composite waste obtained after the described mixing of 100 mass parts, add the polymerize aluminum chloride (purchased from natural resources water-purifying material company limited of Gongyi City) of 0.05 mass parts, after Homogeneous phase mixing, the mixture obtained is left standstill 0.5h.Adopt biological contact oxidation process that the supernatant liquid that obtains after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 25 DEG C, and volume load is 1.5kg BOD
5/ (M
3d), the treatment time is 5h.Learn by measuring, the COD in the reuse water obtained after process is 70mg/L, BOD
5for 15mg/L, NH
3-N is 10mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Comparative example 3
(COD is 1030mg/L, BOD for spinning process in the waste water (polyacrylonitrile containing 0.001 quality %) directly produced by the polymerization process in the production process of polyacrylonitrile fibre and the production process of polyacrylonitrile fibre and the waste water of solvent recuperation operation generation
5for 370mg/L, NH
3-N is 50mg/L) be to mix at 1: 2 with mass ratio, afterwards relative to the composite waste obtained of 100 weight parts, the polymerize aluminum chloride (purchased from natural resources water-purifying material company limited of Gongyi City) of 0.1 mass parts is added in described composite waste, and leave standstill 0.5h, then according to the method for embodiment 2, biochemical treatment is carried out to the supernatant liquid obtained after leaving standstill.Learn by measuring, the COD in the reuse water obtained after process is 90mg/L, BOD
5for 20mg/L, NH
3-N is 14mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
By embodiment 2 and comparative example 3 are compared and can find out, although also can by composite waste process to meeting emission standard in comparative example 3, but the amount of the extra flocculation agent used obviously is greater than embodiment 2 in comparative example 3, and be better than the reuse water that obtains according to the method for comparative example 3 according to the water quality that the method for embodiment 2 obtains reuse water.As can be seen here, the method for embodiment 2 has the effect of process polyacrylonitrile fiber production sewage preferably, and significantly reduces the consumption of additional flocculating agents relative to comparative example 3.
Embodiment 3
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.002 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 10 of the material in retort, it is 190 DEG C that temperature controls, pressure-controlling is 0.5MPa, and keeps at this temperature and pressure reacting about 8h.Then, (COD is 568mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 150mg/L, NH
3-N is 34mg/L) be to mix at 1: 5 with mass ratio, and in the composite waste obtained after the described mixing of 100 mass parts, add the polyaluminium sulfate (purchased from flourishing age water-purifying material company limited of Gongyi City) of 0.03 mass parts, after Homogeneous phase mixing, the mixture obtained is left standstill 2h.Adopt anaerobic biofilter method that the supernatant liquid obtained after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 35 DEG C, and volume load is 4kg COD/ (M
3d), the treatment time is 72h.Learn by measuring, the COD in the reuse water obtained after process is 90mg/L, BOD
5for 20mg/L, NH
3-N is 12mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Embodiment 4
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.01 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 12 of the material in retort, it is 180 DEG C that temperature controls, pressure-controlling is 1.5MPa, and keeps at this temperature and pressure reacting about 10h.Then, (COD is 800mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 320mg/L, NH
3-N is 60mg/L) be to mix at 1: 0.5 with mass ratio, after Homogeneous phase mixing, the mixture obtained is left standstill 1.5h.Adopt Gas biological filter that the supernatant liquid that obtains after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 25 DEG C, and volume load is 3kg COD/ (M
3d), air water volume ratio is 3: 1, and the treatment time is 8h.Learn by measuring, the COD in the reuse water obtained after process is 70mg/L, BOD
5for 10mg/L, NH
3-N is 10mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Embodiment 5
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.002 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 11 of the material in retort, it is 100 DEG C that temperature controls, pressure-controlling is 2.5MPa, and keeps at this temperature and pressure reacting about 1h.Then, (COD is 905mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 380mg/L, NH
3-N is 80mg/L) be to mix at 1: 4 with mass ratio, and in the composite waste obtained after the described mixing of 100 mass parts, add the polymine (purchased from Shanghai Jin Maotai Chemical Co., Ltd.) of 0.07 mass parts, after Homogeneous phase mixing, the mixture obtained is left standstill 1h.Adopt anaerobic-anoxic-oxic method that the supernatant liquid obtained after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 35 DEG C, and volume load is 8kg COD/ (M
3d), the anaerobic treatment time is 36h, and the anaerobic treatment time is 24h, and the aerobic treatment time is 16h.Learn by measuring, the COD in the reuse water obtained after process is 75mg/L, BOD
5for 18mg/L, NH
3-N is 14mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Embodiment 6
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.007 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 10 of the material in retort, it is 200 DEG C that temperature controls, pressure-controlling is 2MPa, and keeps at this temperature and pressure reacting about 4h.Then, (COD is 630mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 260mg/L, NH
3-N is 50mg/L) be to mix at 1: 0.2 with mass ratio, after Homogeneous phase mixing, the mixture obtained is left standstill 2h.Adopt sequencing batch reactor that the supernatant liquid that obtains after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 35 DEG C, mud age is 10 days, suspended solids (MLSS) concentration is 3000mg/L, filling time 2h, reaction times is 6h, and the sedimentation and drawing time is 3h, and time of repose is 2h.Learn by measuring, the COD in the reuse water obtained after process is 95mg/L, BOD
5for 20mg/L, NH
3-N is 13mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Embodiment 7
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.005 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 9 of the material in retort, it is 260 DEG C that temperature controls, pressure-controlling is 1MPa, and keeps at this temperature and pressure reacting about 3h.Then, (COD is 550mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 170mg/L, NH
3-N is 30mg/L) be to mix at 1: 3 with mass ratio, and in the composite waste obtained after the described mixing of 100 mass parts, add the polymeric aluminum sulfate silicate (purchased from Vad, Jintan City dragon Chemical Co., Ltd.) of 0.01 mass parts, after Homogeneous phase mixing, the mixture obtained is left standstill 2h.Adopt anoxic-anaerobic-aerobic process that the supernatant liquid that obtains after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 30 DEG C, and volume load is 6kg COD/ (M
3d), the anaerobic treatment time is 40h, and the anaerobic treatment time is 32h, and the aerobic treatment time is 8h.Learn by measuring, the COD in the reuse water obtained after process is 60mg/L, BOD
5for 10mg/L, NH
3-N is 11mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
Embodiment 8
The present embodiment is for illustration of the treatment process of described polyacrylonitrile fiber production sewage of the present invention.
The waste water (polyacrylonitrile containing 0.004 quality %) that polymerization process in the production process of polyacrylonitrile fibre produces is passed in retort, by the pH regulator to 11 of the material in retort, it is 140 DEG C that temperature controls, pressure-controlling is 3MPa, and keeps at this temperature and pressure reacting about 5h.Then, (COD is 720mg/L, BOD to the waste water spinning process in the production process of the reaction product in retort and polyacrylonitrile fibre and solvent recuperation operation produced
5for 300mg/L, NH
3-N is 45mg/L) be to mix at 1: 0.7 with mass ratio, after Homogeneous phase mixing, the mixture obtained is left standstill 1.5h.Adopt anaerobic contact method that the supernatant liquid that obtains after leaving standstill is carried out biochemical treatment afterwards, concrete operational condition comprises: temperature is 30 DEG C, and volume load is 5kg COD/ (M
3d), the treatment time is 30h.Learn by measuring, the COD in the reuse water obtained after process is 70mg/L, BOD
5for 15mg/L, NH
3-N is 13mg/L, meets the first discharge standard specified in integrated wastewater discharge standard GB8978-1996.
As can be seen here, by polyacrylonitrile fiber production sewage process to meeting emission standard, and the consumption of additional flocculating agents in treating processes can significantly be reduced according to described method provided by the invention.
Claims (12)
1. the treatment process of a polyacrylonitrile fiber production sewage, the method comprises: pH value be 8 ~ 12, under pressure is 0.5 ~ 3MPa, temperature is the condition of 100 ~ 260 DEG C, the waste water A that polymerization process in the production process of polyacrylonitrile fibre produces is hydrolyzed, the waste water B that the hydrolysate obtained and at least one operation in other operation in the production process of polyacrylonitrile fibre except polymerization process produce is mixed, and the mixture obtained is carried out settlement separate, then isolated supernatant liquid is carried out biochemical treatment.
2. method according to claim 1, wherein, the condition of described hydrolysis comprises: pH value is 10 ~ 11, and pressure is 1 ~ 2MPa, and temperature is 170 ~ 200 DEG C, and the time is 1 ~ 10h.
3. method according to claim 1, wherein, described hydrolysate is 1:0.1 ~ 10 with the mixing quality ratio of described waste water B.
4. method according to claim 3, wherein, described hydrolysate is 1:0.2 ~ 5 with the mixing quality ratio of described waste water B.
5. the method according to claim 3 or 4, wherein, described method is also included in the process mixed with described waste water B by described hydrolysate and adds flocculation agent.
6. method according to claim 5, wherein, relative to the described hydrolysate of 100 mass parts and the total mass of waste water B, the add-on of described flocculation agent is 0.001 ~ 0.07 mass parts.
7. method according to claim 5, wherein, described flocculation agent is at least one in Tai-Ace S 150, alum, the hydrate of iron trichloride, the hydrate of ferrous sulfate, polyaluminium sulfate, polymerize aluminum chloride, aluminium iron polychloride, polymeric aluminum sulfate silicate, polyacrylamide, sodium polyacrylate, polyvinyl pyridine and polymine.
8. method according to claim 1, wherein, the method for described biochemical treatment is at least one in activated sludge process, biological contact oxidation process, Gas biological filter, anaerobic biofilter method, anaerobic contact method, anaerobic-anoxic-oxic method and anoxic-anaerobic-aerobic process.
9. method according to claim 1, wherein, the method for described biochemical treatment is sequencing batch reactor.
10. method according to claim 1, wherein, described waste water A contains the polyacrylonitrile of 0.001 ~ 0.1 quality %.
11. methods according to claim 1, wherein, other operation in the production process of described polyacrylonitrile fibre except polymerization process comprises spinning process and solvent recuperation operation.
12. methods according to claim 1 or 11, wherein, the COD of described waste water B is 500 ~ 1200mg/L, BOD
5be 100 ~ 400mg/L, NH
3-N is 20 ~ 100mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110233438.0A CN102936077B (en) | 2011-08-15 | 2011-08-15 | Treatment method of polyacrylonitrile fiber production sewage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110233438.0A CN102936077B (en) | 2011-08-15 | 2011-08-15 | Treatment method of polyacrylonitrile fiber production sewage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102936077A CN102936077A (en) | 2013-02-20 |
| CN102936077B true CN102936077B (en) | 2014-12-31 |
Family
ID=47695013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110233438.0A Active CN102936077B (en) | 2011-08-15 | 2011-08-15 | Treatment method of polyacrylonitrile fiber production sewage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102936077B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641277B (en) * | 2013-12-12 | 2015-05-27 | 中石化上海工程有限公司 | Acrylonitrile waste water treatment method |
| CN105557582A (en) * | 2015-12-24 | 2016-05-11 | 常州王者青城生态观光有限公司 | Green aquaculture method |
| CN106188359A (en) * | 2016-07-08 | 2016-12-07 | 中国石油化工股份有限公司 | The Application way of organic resource in a kind of Wastewater from Acrylonitrile Production |
| CN110498562B (en) * | 2019-08-08 | 2022-05-13 | 苏州苏净环保工程有限公司 | Treatment method of high-concentration stripping liquid wastewater |
| CN113562894B (en) * | 2021-08-20 | 2023-05-09 | 桂林南药股份有限公司 | DMF wastewater and DMSO wastewater treatment method and treatment system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385380A (en) * | 2001-05-11 | 2002-12-18 | 中国石油化工股份有限公司 | Method for treating acrylonitrile and acrylic waste water |
| CN1539766A (en) * | 2003-04-23 | 2004-10-27 | 中国石化上海石油化工股份有限公司 | Method for treating wastewater from industry of spinning acrylics thrugh two steps wet processes by using sodium thiocyanate as solvent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100541467B1 (en) * | 2004-04-27 | 2006-01-11 | 서희동 | Biological sewage and wastewater treatment method by the microclusterization of water molecules |
| CN101423312B (en) * | 2007-10-31 | 2012-05-30 | 中国石油化工股份有限公司 | Acrylon production waste water treatment method |
-
2011
- 2011-08-15 CN CN201110233438.0A patent/CN102936077B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385380A (en) * | 2001-05-11 | 2002-12-18 | 中国石油化工股份有限公司 | Method for treating acrylonitrile and acrylic waste water |
| CN1539766A (en) * | 2003-04-23 | 2004-10-27 | 中国石化上海石油化工股份有限公司 | Method for treating wastewater from industry of spinning acrylics thrugh two steps wet processes by using sodium thiocyanate as solvent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102936077A (en) | 2013-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10501355B2 (en) | Method for treating and recycling organic wastewater and apparatus | |
| US10647603B2 (en) | Method for treating waste water and recovering resources in acrylic fiber production | |
| CN102936077B (en) | Treatment method of polyacrylonitrile fiber production sewage | |
| CN104163539A (en) | Processing method of wastewater in coal chemistry industry | |
| CN103663840B (en) | Method for treating acrylonitrile and polymerization wastewater thereof | |
| CN107352757A (en) | A kind of microelectrolysis processing technique of dyeing waste water | |
| CN105565581B (en) | Coal ethylene wastewater integrated conduct method | |
| CN106219885B (en) | Coking waste water treatment method based on jet stream biochemical reactor | |
| CN104193119A (en) | Process for deeply treating printing and dyeing wastewater in presence of attapulgite catalyst | |
| CN110156249A (en) | A kind of pretreated integrated approach of high-concentration printing and dyeing wastewater based on tubular membrane | |
| CN111762965A (en) | Advanced treatment and recycling method for petrochemical wastewater | |
| CN113248060A (en) | Rare earth high-ammonium wastewater treatment system and method | |
| CN107935303B (en) | Process for recycling power plant boiler water from municipal secondary effluent | |
| CN107973488B (en) | Method for denitrification treatment of ammonia nitrogen wastewater | |
| CN109879538A (en) | A kind of high total nitrogen, high salinity antibiotics pharmacy waste water processing method | |
| CN117534240A (en) | Comprehensive sewage treatment process for brewing Maotai-flavor white spirit | |
| CN107055940B (en) | High-ammonia-nitrogen sewage advanced treatment process based on short-cut nitrification and denitrification | |
| CN112707601A (en) | Corn starch wastewater treatment system and method | |
| CN106587314A (en) | Efficient phosphorus removal agent and preparation method thereof | |
| CN110627314A (en) | Method for efficiently removing total nitrogen in printing and dyeing wastewater by multi-process combination | |
| CN104098221A (en) | Treating method for caprolactam sewage | |
| CN217103417U (en) | Treatment system for sewage of refuse landfill | |
| CN218435280U (en) | High ammonium effluent disposal system of tombarthite | |
| CN110194568A (en) | A kind of processing method of high ammonia-nitrogen wastewater | |
| CN111732291B (en) | Advanced treatment combined process for printing and dyeing wastewater by ozone oxidation and aerobic denitrification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |