CN102372402B - Method for treating polyether polyol wastewater - Google Patents
Method for treating polyether polyol wastewater Download PDFInfo
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- CN102372402B CN102372402B CN201110302707.4A CN201110302707A CN102372402B CN 102372402 B CN102372402 B CN 102372402B CN 201110302707 A CN201110302707 A CN 201110302707A CN 102372402 B CN102372402 B CN 102372402B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229920000570 polyether Polymers 0.000 title claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 31
- 229920005862 polyol Polymers 0.000 title abstract 6
- 150000003077 polyols Chemical class 0.000 title abstract 6
- 238000005728 strengthening Methods 0.000 claims abstract description 28
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- 238000004062 sedimentation Methods 0.000 claims description 27
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- 239000010802 sludge Substances 0.000 claims description 21
- 238000012545 processing Methods 0.000 claims description 20
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- 238000002203 pretreatment Methods 0.000 claims description 16
- 239000011573 trace mineral Substances 0.000 claims description 15
- 235000013619 trace mineral Nutrition 0.000 claims description 15
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- 239000007788 liquid Substances 0.000 claims description 14
- 235000016709 nutrition Nutrition 0.000 claims description 14
- 230000035764 nutrition Effects 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
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- 238000000926 separation method Methods 0.000 claims description 11
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005273 aeration Methods 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 23
- 238000007254 oxidation reaction Methods 0.000 abstract description 23
- 239000002574 poison Substances 0.000 abstract description 7
- 231100000614 poison Toxicity 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 23
- 239000000126 substance Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000009279 wet oxidation reaction Methods 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 239000013530 defoamer Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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Abstract
The invention provides a method for treating polyether polyol wastewater and relates to the technical field of treatment of refractory organic wastewater. The method particularly comprises the following steps of: carrying out high-efficiency catalytic oxidation pretreatment on the polyether polyol wastewater; and entering the polyether polyol wastewater to enter a biochemical stage, wherein the biochemical stage is divided into a biochemical strengthening stage and an aerobic treatment stage. Most dissolved micromolecule organic poisons in the polyether polyol wastewater are removed by high-efficiency catalytic oxidation; the biotoxicity of the polyether polyol wastewater is greatly reduced; a B/C ratio (the B/C ratio is improved to the range of 0.42 to 0.65) of high-efficiency catalytic oxidation pretreatment effluent is obviously improved; the biochemical treatment load is reduced; and the biochemical treatment effluent is ensured stable and is ensured to reach the standard. The treatment method disclosed by the invention has the characteristics that the treatment method is efficient and rapid, has low cost, is safe and reliable, is easy to realize the large-scale industrial application and the like.
Description
Technical field
The present invention relates to a kind for the treatment of process of organic chemical industry's used water difficult to degradate, especially relate to a kind for the treatment of process of polyether glycol waste water.
Background technology
Polyether glycol is a kind of important industrial chemicals, the purposes of this product is very extensive, mainly for the production of urethane foam, also as paper industry defoamer, crude oil demulsifier, lubricant, quenching medium, emulsion foaming agent, rubber lubricant and dedicated solvent etc.Because polyether glycol itself and most of raw materials for production thereof are all the organism of difficult degradation, cause that in factory effluent, organic constituents is complicated, concentration is high, strong toxicity, biodegradability be poor.
In view of the pertinent literature report to polyether glycol wastewater treatment is few both at home and abroad, existing treatment process mainly adopts physico-chemical pretreatment to add the technological line of follow-up biochemical treatment.Conventional treatment process mainly contains following several:
Materialization treatment technology
(1) coagulant sedimentation, absorption method
< < coagulating sedimentation～acidication～biological adsorption～UBF～catalytic oxidation～oxidation ditch that Zhai builds～absorbing process is processed in polyether glycol waste water > > and is mentioned and utilize coagulating sedimentation to carry out pre-treatment polyether glycol waste water, and then by absorption etc. processing method further process.
(2) heat pre-treatment method
Li Pinjuan has used the method for heating to remove the larger molecular organics in polyether glycol waste water in < < Design of polyhydric alcohol conjugated polyether wastewater treatment engineering > >.
But these two kinds of pretreatment processs are owing to lacking specific aim, coagulant sedimentation to COD clearance only 5%～10% less than, thereby cause technical process complicated operation, processing cost high.
Therefore, for a large amount of solvability organic poisons to follow-up biochemical treatment important again that exist in polyether glycol waste water, the physico-chemical pretreatment technology of research and development efficient economy.
(3) high-level oxidation technology
At present conventional have methods such as wet oxidation, photochemical catalytic oxidation, Fenton reagent oxidation method, efficiently catalyzing and oxidizing.These treatment technology performance characteristics are as shown in table 1 below:
The Performance Ratio of several high-level oxidation technologies of table 1
Wet Oxidation Process can be processed complicated organic waste water, but Wet Oxidation Process need to carry out under the condition of high temperature (125 ℃～320 ℃) and high pressure (0.5MPa～20MPa) condition, so exist processing safety poor, the shortcomings such as facility investment is large, running cost is high, thus be difficult to carry out practical application; There are two main shortcomings in Fenton reagent oxidation method: one when practical application, abundant mineralising organism, in reaction process, usually have partial organic substances and change into some intermediate product, these intermediate products or form complex compound with Fe3+, or compete with OH generation route, thereby its processing efficiency is reduced; Its two, Fe
2+and H
2o
2add that concentration is higher, utilization ratio is lower, thereby cause processing cost higher; Photochemical catalysis, electrocatalysis are subject to the restrictions such as turbidity of wastewater, energy consumption, and processing efficiency is low, and amplification is difficult, running cost is high.
Therefore, apply new and effective catalyzed oxidation technology, can under polynary synergy, produce high-density hydroxyl radical free radical, carry out oxidative degradation complicated difficult degraded dissolved organic matter, significantly reduce waste water bio-toxicity, improve its biodegradability, thereby for the efficient stable operation of follow-up biochemical treatment facility provides strong technical guarantee, this is the key problem in technology of processing polyether glycol waste water.
Summary of the invention
The object of the invention is to change prior art processing cost high, processing safety is poor, the catalyzed reaction time provides a kind for the treatment of process of polyether glycol waste water compared with long feature, can effectively reduce polyether glycol bio-toxicity, and the organism in degrading waste water, makes the COD after processing be reduced to 60～80mg/L.
Technical solution of the present invention is: a kind of method of polyether glycol wastewater treatment, and its concrete steps are as follows:
(1) with acid solution, regulating polyether glycol waste water ph is 2～6, and after control pre-treatment, water outlet B/C ratio is 0.42～0.65;
(2) after with alkaline solution adjusting, after step (1) pre-treatment, the pH value of waste water is 7～8, enter in the biochemistry strengthening pond that adds biological reinforced mud, control dissolved oxygen concentration, pH value, ORP value and hydraulic detention time in biochemical strengthening pond, and add nitrogen phosphorus nutrition liquid and trace element, stir or plug-flow operation, make this pond mud carry out bioselection;
(3) water outlet of processing through biochemical strain enters preliminary sedimentation tank, and the sludge reflux after mud-water separation acts on biochemical strengthening pond; Supernatant liquor enters Aerobic Pond, carries out aeration operation, controls dissolved oxygen concentration, pH value, ORP value and hydraulic detention time in Aerobic Pond, and adds nitrogen phosphorus nutrition liquid and trace element, for the aerobic sludge in pond provides good growing environment and benefits wastewater treatment; Carry out wastewater treatment;
(5) waste water through aerobic treatment enters second pond, and supernatant liquor is discharged, and sludge reflux enters Aerobic Pond.
Described pre-treatment, in waste water, add and pass into efficiently catalyzing and oxidizing reactor after catalyzer and oxygenant and carry out pre-treatment, the patent that wherein said efficiently catalyzing and oxidizing reactor is applied for by the inventor: a kind of oxidation strengthening technique and device (publication number: CN101148287) of processing organic poison waste water, first polyether glycol waste water is carried out the removal of part COD, and reduce its bio-toxicity (from the poisoning micro-poison or nontoxic that is reduced to), improve B/C than (B/C is than bringing up to 0.42～0.65 from very low), improve biodegradability, after pre-treatment, again it is carried out to biochemistry combination process processing.Described pretreatment process, is characterized in that described preconditioning technique can reduce the bio-toxicity of polyethers waste water greatly, for follow-up biochemical treatment stable water outlet is up to standard and the further resource utilization of final tail water provides strong technical guarantee.
The acid solution of above-mentioned adjusting pH value is generally nitric acid or hydrochloric acid, and concentration is general 1-5mol/L; The alkaline solution of above-mentioned adjusting pH value is potassium hydroxide or sodium hydroxide; Concentration is generally 1-5mol/L.
The mud that above-mentioned biological reinforced pond adds is general optional with aerobic sludge, anaerobic sludge or amphimicrobian mud.The mud adding in Aerobic Pond is generally aerobic sludge.
Described preliminary sedimentation tank and second pond all adopt traditional vertical sedimentation tank or radial-flow sedimentation tank; Control surface load 0.5～2.0m/h.
Catalyzer described in preferred pretreatment is Fe, Al, Al
2o
3or one or more compositions in gac; Oxygenant is dioxide peroxide or Textone, and wherein the concentration that adds of dioxide peroxide is 2000～5000mg/L, and it is 2500～5500mg/L that Textone adds concentration.
Preferably controlling dissolved oxygen concentration in biochemical strengthening pond is 0.1～1.0mg/L; PH value is 6～8; ORP value-400～0mV; Hydraulic detention time is 1～10d; The ratio that adds of nitrogen phosphorus nutrition liquid is according to C: N: P=(100～300): (5～7): 1 is equipped with and adds (wherein said C is in the COD value of waste water in biochemistry strengthening pond); Trace element is iron, cobalt, nickel, and the dosage of trace element is 0.001～0.01mg/L (in muddy water cumulative volume in biochemistry strengthening pond).
Preferably controlling dissolved oxygen concentration in Aerobic Pond is 1～4mg/L; PH value is 6～8; ORP value 100～250mV; Hydraulic detention time is 1～10d; The ratio that adds of nitrogen phosphorus nutrition liquid is according to C: N: P=(100～300): (5～7): 1 is equipped with and adds (wherein said C is in the COD value of waste water in Aerobic Pond); Trace element is for being iron, cobalt, nickel, and the dosage of trace element is 0.001～0.01mg/L (in muddy water cumulative volume in Aerobic Pond).
In nitrogen phosphorus nutrition liquid preferably, that nitrogen nutrition liquid is ammonium chloride (NH
4cl) or ammonium nitrate (NH
4nO
3); Phosphorus nutrition liquid is potassium primary phosphate (KH
2pO
4) or SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
4).
Beneficial effect:
1. pair polyether glycol waste water carries out respectively Fenton catalyzed oxidation, coagulating sedimentation, and micro-electrolysis, efficiently catalyzing and oxidizing method is carried out pre-treatment.Through overtesting, find, efficiently catalyzing and oxidizing method to the treatment effect of this waste water far away higher than other three kinds for the treatment of process, this method is to the COD clearance of Aethoxy Sklerol waste water up to 40%～60%, and waste water B/C ratio is increased to 0.42～0.65, and the biodegradability of waste water can improve greatly.
2. biochemical strengthening combination process is reasonable in design, and the pretreated waste water of catalyzed oxidation is had to good treatment effect, and COD is had significantly and reduced.Biochemical method processing cost is low, adopts the economical rationality of biochemical strengthening combination process, effectively reduces costs.
3. efficiently catalyzing and oxidizing technology combines with biochemical strengthening combination process, has solved a processing difficult problem for polyether glycol waste water, has not only reduced wastewater toxicity and COD, has also reduced processing cost.
In a word, the present invention is a kind of economy, the method for processing efficiently polyether glycol, and the bio-toxicity that has realized polyethers waste water effectively reduces, and COD is had to very high clearance.Present method has economy, efficient, and system stability is good, safe, easy to operate, is convenient to the advantages such as industry amplification.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention; Wherein: 1-efficiently catalyzing and oxidizing reactor; The biochemical strengthening of 2-pond; 3-preliminary sedimentation tank; 4-Aerobic Pond; 5-second pond; A-water inlet: B-sludge reflux; C-sludge reflux; D-water outlet.
Embodiment
Embodiment below in conjunction with embodiment is described in further detail foregoing of the present invention again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following example.Do not departing under the above-mentioned technical matters state of mind, various replacements or the change according to ordinary skill knowledge and customary means, made, all should comprise within the scope of the invention.Process flow sheet of the present invention as shown in Figure 1.
Embodiment 1
(1). the polyether glycol factory effluent of certain petroleum chemical enterprise that is 3000mg/L by COD carries out catalyzed oxidation pre-treatment, with the sulphuric acid soln adjusting waste water ph of 2mol/L, is 3, and catalyzer adopts Al
2o
3catalyzer add-on and reaction column volume ratio are 1: 8, oxygenant adopts the dioxide peroxide of 2000mg/L, patent is shown in operating process: a kind of oxidation strengthening technique and device (publication number: CN101148287) of processing organic poison waste water, make waste water COD drop to 2500mg/L left and right, B/C ratio brings up to 0.47, then is 7.0 with the sodium hydroxide solution adjusting pH of 5mol/L.
(2). the water outlet after catalyzed oxidation is passed in biochemical strengthening pond, in pond, mud is aerobic sludge, control dissolved oxygen concentration 0.9mg/L, pH value 7.8, ORP value-100mV, hydraulic detention time 7d, C: N: P=300: be equipped with at 7: 1 and add, add nickelous chloride, nickel dosage is 0.01mg/L, make mud in pond carry out bioselection effect, its water outlet enters in vertical-flow preliminary sedimentation tank, and control overhead is 0.60m/h, and Sludge from primary sedimentation tank passes back in biochemical strengthening pond, preliminary sedimentation tank mud-water separation, now COD is 400～450mg/L.
(3). the supernatant liquor in preliminary sedimentation tank after mud-water separation enters (what in Aerobic Pond, add is aerobic sludge) in Aerobic Pond, control its dissolved oxygen concentration 3.8mg/L, pH value 6.0, ORP value 220mV, hydraulic detention time 7d, C: N: P=300: be equipped with at 7: 1 and add, trace element is nickelous chloride, and the dosage of nickel is 0.01mg/L.Control further degradation of organic substances, COD is further removed.Water outlet enters vertical-flow second pond, and control overhead is 1m/h, and in second pond, sludge reflux enters in Aerobic Pond, second pond mud-water separation, and supernatant C OD is at 60-80mg/L.
Embodiment 2
(1). the polyether glycol factory effluent that is certain petroleum chemical enterprise of 2300mg/L left and right by COD carries out catalyzed oxidation pre-treatment, with the hydrochloric acid soln adjusting polyether glycol waste water ph of 2mol/L, be 5.8, catalyzer adopts gac, catalyzer add-on and reaction column volume ratio are 1: 10, oxygenant adopts the Textone of 2500mg/L, patent is shown in operating process: a kind of oxidation strengthening technique and device (publication number: CN101148287) of processing organic poison waste water, make waste water COD drop to 1850mg/L, B/C ratio brings up to 0.62, with the potassium hydroxide solution adjusting pH of 2mol/L, be 8 again.
(2). the water outlet after catalyzed oxidation is passed in biochemical strengthening pond, in pond, mud is anaerobic sludge, control dissolved oxygen 0.2mg/L, pH value 6, ORP value-380mV, hydraulic detention time 2d, C: N: P=100: be equipped with at 5: 1 and add, add ferric sesquichloride, the dosage of iron is 0.004mg/L, make mud in pond carry out bioselection effect, water outlet enters vertical-flow preliminary sedimentation tank, and control overhead is 2.0m/h, and Sludge from primary sedimentation tank passes back in biochemical strengthening pond, preliminary sedimentation tank mud-water separation, now COD is 300～380mg/L.
(3). the supernatant liquor in preliminary sedimentation tank after mud-water separation enters (what in Aerobic Pond, add is aerobic sludge) in Aerobic Pond, control dissolved oxygen concentration 2.0mg/L, pH value 7.0, ORP value 100mV, hydraulic detention time 2d, C: N: P=300: be equipped with at 7: 1 and add, trace element is ferric sesquichloride, and the dosage of iron is 0.01mg/L.Further degradation of organic substances, is further removed COD.Water outlet enters vertical-flow second pond, and control overhead is 1.8m/h, and in second pond, sludge reflux enters in Aerobic Pond, second pond mud-water separation, and OD is at 60-80mg/L for second pond supernatant C.
Embodiment 3
(1). the polyether glycol factory effluent of certain petroleum chemical enterprise that is 5000mg/L by COD carries out catalyzed oxidation pre-treatment, with the sulphuric acid soln adjusting waste water ph of 4mol/L, be 4.0, catalyzer adopts gac, catalyzer add-on and reaction column volume ratio are 1: 9, oxygenant adopts the dioxide peroxide of 4000mg/L, patent is shown in operating process: a kind of oxidation strengthening technique and device (publication number: CN101148287) of processing organic poison waste water, make waste water COD drop to 3860mg/L, B/C ratio brings up to 0.55, then is 7.5 with the sodium hydroxide solution adjusting pH of 2mol/L.
(2). the water outlet after catalyzed oxidation is passed in biochemical strengthening pond, in pond, mud is amphimicrobian mud, control dissolved oxygen concentration 0.5mg/L, pH value 7.0, ORP value 0mV, hydraulic detention time 5d, C: N: P=200: be equipped with at 6: 1 and add, add ferric sesquichloride, the dosage of iron is 0.005mg/L, make mud in pond carry out bioselection effect, its water outlet enters in radial-flow preliminary sedimentation tank, control overhead is 1.20m/h, Sludge from primary sedimentation tank passes back in biochemical strengthening pond, preliminary sedimentation tank mud-water separation, and now COD is 800～900mg/L.
(3). the supernatant liquor in preliminary sedimentation tank after mud-water separation enters (what in Aerobic Pond, add is aerobic sludge) in Aerobic Pond, control its dissolved oxygen concentration 3.0mg/L, pH value 8.0, ORP value 150mV, hydraulic detention time 5d, C: N: P=100: be equipped with at 5: 1 and add, trace element is cobalt chloride, and the dosage of cobalt is 0.002mg/L.Control further degradation of organic substances, COD is further removed.Water outlet enters Radial Flow Secondary Sedimentation Tank, and control overhead is 1.5m/h, and in second pond, sludge reflux enters in Aerobic Pond, second pond mud-water separation, and OD is at 60-80mg/L for second pond supernatant C.
Claims (3)
1. a method for polyether glycol wastewater treatment, its concrete steps are as follows:
(1) by acid solution, regulating the value of polyether glycol wastewater pH is 2～6, then carries out pre-treatment, and after control pre-treatment, the B/C ratio of waste water is 0.42～0.65; Wherein pre-treatment passes into efficiently catalyzing and oxidizing reactor after catalyzer and oxygenant and carries out pre-treatment for adding in waste water; Wherein said catalyzer is Fe, Al, Al
2o
3or one or more compositions in gac; Oxygenant is dioxide peroxide or Textone;
(2) after with alkaline solution adjusting, after step (1) pre-treatment, the pH value of waste water is 7～8, enter in the biochemistry strengthening pond that adds biological reinforced mud, control dissolved oxygen concentration, pH value, ORP value and hydraulic detention time in biochemical strengthening pond, and add nitrogen phosphorus nutrition liquid and trace element, stir or plug-flow operation, make this pond mud carry out bioselection; Wherein controlling dissolved oxygen concentration in biochemical strengthening pond is 0.1～1.0mg/L; PH value is 6～8; ORP value-400～0mV; Hydraulic detention time is 1～10d; The ratio that adds of nitrogen phosphorus nutrition liquid is C:N:P=(100～300): (5～7): 1, wherein said C is in the COD value of waste water in biochemistry strengthening pond; Trace element is iron, cobalt, nickel; Wherein trace element adds quality and counts 0.001～0.01mg/L with muddy water cumulative volume in biochemistry strengthening pond;
(3) water outlet of processing through biochemical strengthening pond enters preliminary sedimentation tank, and the sludge reflux after mud-water separation acts on biochemical strengthening pond; Supernatant liquor enters Aerobic Pond, carries out aeration operation, controls dissolved oxygen concentration, pH value, ORP value and hydraulic detention time in Aerobic Pond, and adds nitrogen phosphorus nutrition liquid and trace element, carries out wastewater treatment; Controlling dissolved oxygen concentration in Aerobic Pond is 1～4mg/L; PH value is 6～8; ORP value 100～250mV; Hydraulic detention time is 1～10d; The ratio that adds of nitrogen phosphorus nutrition liquid is C:N:P=(100～300): (5～7): 1, wherein said C is in the COD value of waste water in Aerobic Pond; Trace element is for being iron, cobalt, nickel; Wherein the quality that adds of trace element is counted 0.001～0.01mg/L with muddy water cumulative volume in Aerobic Pond;
(4) waste water through aerobic treatment enters second pond, and supernatant liquor is discharged, and sludge reflux enters Aerobic Pond.
2. method according to claim 1, is characterized in that described preliminary sedimentation tank and second pond all adopt vertical sedimentation tank or radial-flow sedimentation tank; Control surface load 0.5～2.0m/h.
3. method according to claim 1, is characterized in that the nitrogen nutrition liquid in described nitrogen phosphorus nutrition liquid is ammonium chloride or ammonium nitrate; Phosphorus nutrition liquid is potassium primary phosphate or SODIUM PHOSPHATE, MONOBASIC.
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| CN103288292B (en) * | 2013-05-07 | 2015-03-25 | 江苏长华聚氨酯科技有限公司 | Processing method for polyether-containing wastewater |
| CN103288293B (en) * | 2013-05-07 | 2015-07-29 | 江苏长华聚氨酯科技有限公司 | Polyether wastewater treatment method |
| CN103288294B (en) * | 2013-05-07 | 2015-03-25 | 江苏长华聚氨酯科技有限公司 | Treatment method of polyether-containing wastewater |
| CN103449661B (en) * | 2013-05-07 | 2015-04-08 | 江苏长华聚氨酯科技有限公司 | Method for treating polyether wastewater |
| CN105417846B (en) * | 2015-11-13 | 2018-01-09 | 淄博正大聚氨酯有限公司 | The method for handling PPG technique waste water |
| CN107046135A (en) * | 2017-01-20 | 2017-08-15 | 常州大学 | Improve the method that microbiological fuel cell handles Polyester wastewater electricity production |
| CN107311273B (en) * | 2017-06-14 | 2020-11-06 | 中国石油化工股份有限公司 | Efficient pretreatment method of polyether wastewater |
| CN110872169A (en) * | 2018-09-04 | 2020-03-10 | 惠博普(武汉)生物环保科技有限公司 | Biological enhanced treatment method for high-COD acetic acid wastewater |
| CN113860587B (en) * | 2021-10-09 | 2023-05-09 | 南京大学 | Pretreatment method of styrene-containing wastewater |
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