CN102139992A - Process and equipment for treating high-concentration pyridine waste water - Google Patents
Process and equipment for treating high-concentration pyridine waste water Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 58
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 52
- 230000003647 oxidation Effects 0.000 claims abstract description 48
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010865 sewage Substances 0.000 claims abstract description 25
- 230000001112 coagulant Effects 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 238000004062 sedimentation Methods 0.000 claims abstract description 16
- 230000001105 regulatory Effects 0.000 claims abstract description 7
- 150000003222 pyridines Chemical class 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 230000014759 maintenance of location Effects 0.000 claims description 18
- 230000003197 catalytic Effects 0.000 claims description 17
- 238000004065 wastewater treatment Methods 0.000 claims description 14
- 238000005273 aeration Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- -1 iron-carbon Chemical compound 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 241000894006 Bacteria Species 0.000 claims description 5
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- 239000003513 alkali Substances 0.000 claims description 4
- 238000000247 postprecipitation Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
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- 238000011068 load Methods 0.000 abstract description 3
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- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 230000002378 acidificating Effects 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing Effects 0.000 abstract 1
- 241000276438 Gadus morhua Species 0.000 description 17
- 235000019516 cod Nutrition 0.000 description 17
- 230000037250 Clearance Effects 0.000 description 10
- 230000035512 clearance Effects 0.000 description 10
- 239000003905 agrochemical Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 230000004059 degradation Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl radical Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N Potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- DNDPLEAVNVOOQZ-UHFFFAOYSA-N 2,3,4,5,6-pentachloropyridine Chemical compound ClC1=NC(Cl)=C(Cl)C(Cl)=C1Cl DNDPLEAVNVOOQZ-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-Aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- KCDNYRPDKSGQCM-UHFFFAOYSA-N 4-[4-(3-chlorophenyl)-4-(pyrrolidine-1-carbonyl)piperidin-1-yl]-1-(4-fluorophenyl)butan-1-one Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCC(C=2C=C(Cl)C=CC=2)(C(=O)N2CCCC2)CC1 KCDNYRPDKSGQCM-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 210000004087 Cornea Anatomy 0.000 description 1
- 210000000887 Face Anatomy 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 229940069002 Potassium Dichromate Drugs 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000002070 germicidal Effects 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000749 insecticidal Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000002673 intoxicating Effects 0.000 description 1
- 238000009114 investigational therapy Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- INFDPOAKFNIJBF-UHFFFAOYSA-N paraquat Chemical compound C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 INFDPOAKFNIJBF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000007781 pre-processing Methods 0.000 description 1
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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Abstract
The invention relates to a process for treating high-concentration pyridine waste water, which comprises the following steps of: regulating raw water of waste water to be acidic, and treating the raw water in electro-catalytic oxidation equipment; leading effluent to a micro-electrolysis device for treatment under the condition of maintaining the acidity and oxygen enrichment of the waste water; regulating the effluent to be meta-alkalescent, and adding chemicals to perform coagulating sedimentation; and controlling the salinity of the waste water to be below 2 percent, and performing biochemical treatment in an anaerobic hydrolyzing device and a pressurizing biological contact oxidation device, so that the effluent reaches the conventional first-level standards for sewage discharge. Due to the adoption of a physico-chemical treatment process serving electro-catalytic oxidation as a core, pyridine pollutants can be decomposed effectively, the toxicity of the waste water can be reduced, and the biodegradability of the waste water can be improved; for biochemical treatment is realized by a combination process of anaerobic hydrolysis and pressurizing biological contact oxidation, the organic loads, treatment efficiency and salt-tolerant capacity of the biochemical treatment are improved; and the process has the characteristics of high impact load resistant capacity, good treatment effect and low operating cost, and the treated high-concentration pyridine waste water can reach the standard stably before discharge.
Description
Technical field
The invention belongs to the environmental engineering field of waste water treatment, is a kind of treatment process and equipment that is applicable to fine chemistry industry industry high-purity pyridine class waste water such as agricultural chemicals, fodder additives, pharmacy, dyestuff.
Background technology
Pyridine is one of Application and Development kind widest in area in the present heterogeneous ring compound, is a kind of important fine chemical material, and its derivative mainly contains alkyl pyridine, haloperidid, aminopyridine etc.According to statistics, have 70% agricultural chemicals, medicine, veterinary drug and organic chemical industry's product needed to use pyridine approximately, so it is called as chemical intermediate " chip ", wherein agricultural chemicals accounts for about 50% of pyridine series product total quantity consumed, fodder additives is about 30%, and medicine and other fields account for 20%.In recent years, the pesticide intermediate development is rapid, and the agricultural chemicals development that contains the pyridine group is very fast, Insecticides (tech) ﹠ Herbicides (tech) is efficiently not only arranged, and develop efficient germicide, and form the distinctive agricultural chemicals series of a big class gradually.
Pyridine normal temperature is down colourless liquid, can any ratio dissolve each other fully as alcohol, ether, sherwood oil, ketone, benzene and other multiple solvent with water or most of organic liquid of using always.The pyridine foul smelling has the intoxicating effect to nerve, and cornea is had infringement.Pyridine is the strongly inhibited effect to microorganism, and is difficult to oxidizedly, thereby causes difficulty for the self-cleaning of the surface water and the innocent treatment procedure of sewage.In the derivative of pyridine, has high biomagnification as Perchloropyridine.The principal feature of pyridines waste water: (1) pyridine is difficult to by potassium dichromate oxidation, therefore can not truly reflect its pollution level with COD index evaluation pyridines waste water; (2) pyridine has very strong inhibition or toxicity to the biological bacteria of biological process, causes biochemical treatment not carry out, because the pyridines material in the waste water can not be biochemical, makes mud death, the biochemical treatment system paralysis; (3) substance classes of band pyridine ring is various, but all has a common characteristic ring texture, and degraded is stablized, is difficult to material, and pyridine and derivative thereof are more stable than benzene.
Processing to the high-purity pyridine class generally has Coagulation Method, absorption method, chemical oxidization method, Fenton oxidation style, photocatalytic oxidation, direct burning method etc.Coagulation Method and absorption method can not be removed the pyridines pollutent effectively, and be not high to the degradation efficiency of pyridine though chemical oxidization method has certain clearance to COD, and according to the difference of oxygenant and the difference of processing wastewater property, easily produce secondary pollution.He Qihuan etc. discover that the use of metal oxide and noble metal catalyst can improve oxidation efficiency, and are cutting down COD
CrThe time, improved BOD
5/ COD
CrValue, for condition has been created in follow-up biochemical treatment, but cl content is too high in the water after should noting avoiding handling when adopting oxychlorination, can the microorganism of biochemical treatment be damaged like this.It should be noted that simultaneously: as a kind of reactive material, the normal and aromatic compounds generation oxidizing reaction of oxychlorination reagent and generate the chlorinated aromatic hydrocarbons analog derivative, these compounds are difficult to biological degradation, have further increased the difficulty of biochemical treatment.The organic waste water that Fenton oxidation style energy oxidation difficult for biological degradation or general chemical oxidation are difficult to prove effective, greatly, easily cause secondary pollution problems but Fenton reagent method exists the reagent cost height, need carry out subsequent disposal, flow process complexity, waste residue generation, these problems have restricted the development of Fenton method.ME Moctezuma etc. utilizes nano-TiO
2Though the photocatalytic degradation herbicides paraquat has all been obtained effect preferably, the photochemical catalytic oxidation fado is based on ultraviolet radiation, and equipment is relatively complicated, is subject to the influence of chroma in waste water, turbidity, and power consumption is big, processing costs is higher.Photocatalytic oxidation substantially also rests on theoretical investigation and experimental stage now as the recent studies on field that the nearest more than ten years grow up, and the industrial applications example is less.
Pyridine compounds and their is persistent organism (POPs), its Stability Analysis of Structures, and microorganism had restraining effect, so pyridines waste water is difficult to usually by biological degradation, the pyridines wastewater treatment is the difficult problem that field of waste water treatment faces.At present, less to the biochemical processing research of pyridines waste water.In the actual treatment engineering, owing to lack effective preprocessing means, all be that biochemical treatment is carried out in the lump with other waste water in pyridines waste water vast scale dilution back usually, tend to have influence on the treatment effect of whole biochemical treatment system.
Summary of the invention
The present invention wants the technical solution problem to be: at the big problem of high-purity pyridine class treatment of Organic Wastewater difficulty, set up a kind of high-purity pyridine class waste water treatment process, make processing back water outlet reach " integrated wastewater discharge standard " (GB8978-1996) primary standard.
In order to solve above technical problem, high-purity pyridine class waste water treatment process provided by the invention is characterized in that waste water passes through following several process sections successively and handles:
The catalytic oxidation process section---the pH value of pyridines waste water is adjusted to 3.0～4.0, and sends into electric catalysis reactor and carry out the catalytic oxidation processing; Further, the current density of electric catalysis reactor is 10～20mA/cm in this process section
2, retention time of sewage 0.5～1.5 hour; In this process section, strong oxidizing substance such as the hydroxyl radical free radical that the electrocatalytic reaction process produces can be opened pyridine ring, is the small organic molecules such as lower aliphatic hydrocarbon of easily degrading with the pyridine oxygenolysis;
Little electrolysis process section---the waste water after catalytic oxidation is handled is sent into micro-electrolysis reactor and is handled, iron-carbon micro-electrolysis reactor bottom aeration aerating, and reaction process adds acid in right amount, and the pH value that keeps waste water is acid; Further, the acid that adds in this process section is hydrochloric acid and/or sulfuric acid, and the pH value of waste water remains on that retention time of sewage is 0.5～2.0 hour in 3.0～5.0 the scope; Micro-electrolysis reactor is the iron-carbon micro-electrolysis reactor, and its inner iron, carbon volume ratio are 1: 1;
The water outlet of coagulation-settlement process section---micro-electrolysis reactor enters the coagulating sedimentation processing unit, and the pH value that adds alkali adjusting waste water in the coagulating sedimentation processing unit adds PAM again to weakly alkaline (PH=8.0～9.0), carries out coagulating, through the post precipitation water outlet; In this process section, little electrolysis combines the COD in the degrading waste water significantly with the coagulation-settlement process section.
Water outlet after anaerobic hydrolysis process section---coagulating sedimentation is handled enters anaerobic hydrolysis equipment after salinity is regulated, by the anaerobe bacterium organism in the waste water is further degraded; Further, in this process section, salinity is regulated and is made the waste water salinity less than 2%; Retention time of sewage was at least 24 hours;
Pressurization contact oxidation technology section---the anaerobic hydrolysis water outlet enters the pressurization contact oxidation reactor, by the aerobe bacterium organism in the waste water is degraded; Further, in this process section, the aeration rate of pressurization contact oxidation reactor is 25～30: 1, and working pressure 0.1～0.5MPa, retention time of sewage are 5～10 hours.The water outlet of this process section finally reaches " integrated wastewater discharge standard " (GB8978-1996) primary standard.
In addition, the present invention also provides a kind of high-purity pyridine class sewage treatment equipment, it is characterized in that: comprise the electric catalysis reactor, micro-electrolysis reactor, coagulating sedimentation processing unit, anaerobic hydrolysis equipment, the pressurization contact oxidation reactor that connect successively, the current density of described electric catalysis reactor is 10～20mA/cm
2, described micro-electrolysis reactor is the iron-carbon micro-electrolysis reactor, and its inner iron, carbon volume ratio are 1: 1, and the aeration rate of pressurization contact oxidation reactor is 25～30: 1, and working pressure is 0.1～0.5MPa.
The present invention is with the combination that combines with biochemical processing process of materialization treatment process, it turns to the materialization treatment process of core with electrocatalytic oxidation, can effectively decompose the pyridines pollutent, reduce the toxicity of waste water, improve the biodegradability of waste water, it preferentially carries out catalytic oxidation handles, and the strong oxidizing substance that utilizes electrocatalysis oxidation reaction equipment to produce decomposes pyridines organism in the water, improves the unitary processing efficiency of follow-up little electrolysis treatment; Anaerobic hydrolysis+pressurization bio-contact oxidation combination process is adopted in biochemical treatment, improves organic loading, processing efficiency and the salt resistance ability of biochemical treatment.This treatment process has the advantages that the anti impulsion load ability is strong, treatment effect good, working cost is lower, can guarantee the stably reaching standard discharging after treatment of high-purity pyridine waste water.
In the technical process of the present invention, the catalytic oxidation process section adopts efficient multi-electrodes electrocatalysis reactor.The reactor positive plate is the titanium plate of the multiple catalytic specie of surface-coated, be filled with the surface between the cathode and anode pole plate and supported the granule electrode of multiple catalytic specie coating, pole plate and particle surface catalytic specie are by multiple oxide-metal combinations such as tin, antimony, iridium, tantalum, manganese, and coating sintering forms.Reactor under electric field and catalytic specie effect, the multiple strong oxidizing substance based on hydroxyl radical free radical (OH) of generation, oxidative degradation organism.Because reactor has multidimensional structure, mass-transfer efficiency improves, and water treatment effect is remarkable.
In the described micro-electrolysis reactor, 1: 1 by volume mixed packing of iron filings and carbon granules, iron are that anode, carbon are negative electrode, and iron and carbon constitute several small corrosion cells.During work, under acidity, excess oxygen, form little current response device between iron and the carbon, the organism in the waste water is reduced and oxidation under the effect of the little electric current of corrosion cell.
Described pressurization bio-contact oxidation treatment system is a sealing, have the aerobe reactor of certain operating pressure, its working pressure is 0.1-0.5MPa, because it has certain working pressure, the dissolved oxygen efficiency height, retention time of sewage shortens, can adapt to high salinity waste water, the COD clearance significantly improves.
Beneficial effect of the present invention is as follows:
(1) oxidation capacity is strong.The hydroxyl radical free radical (OH) that system produces has high oxidation potential (2.8V), can destroy and open pyridine ring effectively, and the macromole type organic of Stability Analysis of Structures, difficult degradation is degraded to small organic molecules such as lower aliphatic hydro carbons, organic acid.Two sections physicochemical techniques of electrocatalysis and little electrolysis are handled, and can efficiently decompose the pyridines material in the high-concentration waste water, and the clearance of materialization treating processes waste water TOC is reached more than 70%.
(2) the pressurization bio-contact oxidation can improve oxyty, shorten retention time of sewage, improve salt resistant character and the COD processing efficiency of microorganism, make the water outlet after the processing reach " integrated wastewater discharge standard " (GB8978-1996) primary standard, its leading indicator COD emission concentration is less than 100mg/L, and the ammonia nitrogen emission concentration is less than 15mg/L.
(3) the main process flow process is made of " materialization+biochemistry " treatment combination, the oxidative decomposition capacity of materialization and biochemical process section by by force to a little less than, configuration rationally, treatment process is connected well.
(4) less energy-consumption, low reagent consumption does not need to regulate pH repeatedly, and sludge quantity is few, and the overall craft flow process is short, and working cost is low.
As seen, ingenious conception of the present invention, effect is remarkable, can solve a difficult problem of handling high-purity pyridine waste water, has good market outlook.
Description of drawings
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is the schema of technology of the present invention.
Fig. 2 is the present device structured flowchart.
Embodiment
A kind of high-purity pyridine class of the present invention organic wastewater treatment process as shown in Figure 1, step comprises:
A, with the former water of high-purity pyridine class waste water pH regulator to 3.0～4.0, send into the multi-dimensional electro-catalytic reactor and carry out catalytic oxidation and handle, conditioned reaction device working current density is 10～20mA/cm
2, retention time of sewage 0.5～1.5 hour;
B, the waste water after catalytic oxidation is handled are sent into micro-electrolysis reactor and are handled, micro-electrolysis reactor bottom aeration aerating, an amount of additional hydrochloric acid is or/and sulfuric acid keeps reaction system acidity (pH is 3.0～5.0) in the reaction process, and retention time of sewage is 0.5～2.0 hour; In this process section, micro-electrolysis reactor is the iron-carbon micro-electrolysis reactor, and its inner iron, carbon volume ratio are 1: 1.
The water outlet of C, micro-electrolysis reactor enters coagulating sedimentation treatment process unit, and the pH value that adds alkali adjusting waste water adds PAM again to meta-alkalescence (pH is 8.0～9.0), carries out the coagulating sedimentation reaction;
Water outlet after D, coagulating sedimentation handle if salinity greater than 2%, then need to regulate, regulative mode can mix low salinity waste water, guarantees that the waste water salinity is less than 2%, waste water after the adjusting enters the anaerobic hydrolysis process section of biochemical treatment, and retention time of sewage is at least 24 hours in this step;
E, anaerobic hydrolysis treat effluent enter the pressurization contact oxidation reactor of aerobic treatment, and this section is regulated operating pressure 0.1-0.5MPa, aeration rate (25～30): 1, and retention time of sewage 5-10 hour.Final treat effluent can reach " integrated wastewater discharge standard " (GB8978-1996) primary standard.
Provide two below and handle example, effect of the present invention is described.
Embodiment 1
Certain agricultural chemicals enterprise high-purity pyridine waste water, principal pollutant are dichloropyridine and adjacent dichloropyridine between pyridine derivate.Adopt this technology to handle, former water pH transfers to 3.0, and multi-dimensional electro-catalytic oxidation panel working current density is controlled at 15mA/cm
2, 1 hour residence time; Enter micro-electrolysis reactor again and handle, keep acidity (about pH=4) and aeration aerating, reaction time 1.5 hours; Water outlet adds Ca (OH)
2Regulate wastewater pH to 9.0, and add PAM and carry out the coagulating sedimentation reaction.Water outlet to post precipitation detects a dichloropyridine clearance 99.82%, adjacent dichloropyridine clearance 99.93%, COD clearance 76%.Experiment shows that materialization processing section pyridine ring texture is opened, and pyridine is effectively decomposed, and waste water BOD/COD has guaranteed that than improving follow-up biological treatment becomes possibility.
Embodiment 2
Certain agricultural chemicals enterprise chlopyrifos pesticides production plant contains pyridines high density processing wastewater, and waste water is reddish-brown, and the strong impulse smell is arranged.Its main water-quality guideline: pH 5～6, COD 36705mg/L, TOC 6312mg/L, TP 1835mg/L, saltiness 16%.Adopt art breading of the present invention.Enter the electrocatalysis oxidation reaction device after pyridines waste water adds about acid for adjusting pH to 3, control current density is 14mA/cm
2, retention time of sewage is 60min, the water outlet gravity flow enters little electrolyzer; Fill cast iron filing and coke in little electrolyzer, iron carbon volume ratio is 1: 1, adds acid in right amount, controls wastewater pH between 3-5, retention time of sewage 60min; Water outlet directly enters coagulative precipitation tank, with Ca (OH)
2Regulate about pH to 8, and add coagulating agent and carry out coagulating sedimentation, water outlet enters " anaerobic hydrolysis+pressurization catalytic oxidation " biochemical treatment system.The operation result is as follows: materialization processing section COD clearance 55.6%, the organophosphorus clearance reaches 73.8%, TOC clearance 72.6%.Water outlet COD after materialization is handled because salinity is too high, can not directly carry out biochemical treatment about 16000mg/L, add about 8 times low concentration wastewater, and the control salinity is entering biochemical treatment system below 2%, and at this moment, the COD of waste water is about 1800mg/L.Anaerobic fixed film reactor adopts upflow type anaerobic reactor, 25 ℃ of controlled temperature, retention time of sewage control 36h, its COD clearance is 35%, and COD is below 1200mg/L in the anaerobic hydrolysis water outlet, squeezes into the pressurization biological contact oxidation tower by force (forcing) pump, about red-tape operati pressure 0.3Mpa, dissolved oxygen 4～7mg/L, retention time of sewage 8h, final treat effluent COD is below 100mg/L.
As shown in Figure 2, structured flowchart for high-purity pyridine class sewage treatment equipment of the present invention, it comprises electric catalysis reactor, micro-electrolysis reactor, coagulating sedimentation processing unit, anaerobic hydrolysis equipment, the pressurization contact oxidation reactor that connects successively, and the current density of described electric catalysis reactor is 10～20mA/cm
2, described micro-electrolysis reactor is the iron-carbon micro-electrolysis reactor, and its inner iron, carbon volume ratio are 1: 1, and the aeration rate of pressurization contact oxidation reactor is 25～30: 1, and working pressure is 0.1～0.5MPa.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (10)
1. high-purity pyridine class waste water treatment process is characterized in that waste water handles through following several process sections successively:
The catalytic oxidation process section---the pH value of pyridines waste water is adjusted to 3.0～4.0, and sends into electric catalysis reactor and carry out the catalytic oxidation processing;
Little electrolysis process section---the waste water after catalytic oxidation is handled is sent into micro-electrolysis reactor and is handled, micro-electrolysis reactor bottom aeration aerating, and reaction process adds acid in right amount, and the pH value that keeps waste water is acid;
The water outlet of coagulation-settlement process section---micro-electrolysis reactor enters the coagulating sedimentation processing unit, and the pH value that adds alkali adjusting waste water in the coagulating sedimentation processing unit adds PAM again to weakly alkaline, carries out coagulating, through the post precipitation water outlet;
Water outlet after anaerobic hydrolysis process section---coagulating sedimentation is handled enters anaerobic hydrolysis equipment after salinity is regulated, by the anaerobe bacterium organism in the waste water is further degraded;
Pressurization contact oxidation technology section---the anaerobic hydrolysis water outlet enters the pressurization contact oxidation reactor, by the aerobe bacterium organism in the waste water is degraded.
2. high-purity pyridine class waste water treatment process according to claim 1 is characterized in that: in the described catalytic oxidation process section, the current density of electric catalysis reactor is 10～20mA/cm
2, retention time of sewage 0.5～1.5 hour.
3. high-purity pyridine class waste water treatment process according to claim 1, it is characterized in that: in described little electrolysis process section, the acid that adds is hydrochloric acid and/or sulfuric acid, and the pH value of waste water remains in 3.0～5.0 the scope, and retention time of sewage is 0.5～2.0 hour.
4. high-purity pyridine class waste water treatment process according to claim 3 is characterized in that: in described little electrolysis process section, described micro-electrolysis reactor is the iron-carbon micro-electrolysis reactor, and its inner iron, carbon volume ratio are 1: 1.
5. high-purity pyridine class waste water treatment process according to claim 1 is characterized in that: in the described coagulation-settlement process section, after adding alkali regulate pH value to 8.0～9.0 of waste water in the coagulating sedimentation processing unit, add PAM again.
6. high-purity pyridine class waste water treatment process according to claim 1 is characterized in that: in the described anaerobic hydrolysis process section, salinity is regulated and is made the waste water salinity less than 2%, and retention time of sewage was at least 24 hours.
7. high-purity pyridine class waste water treatment process according to claim 1, it is characterized in that: in the described pressurization contact oxidation technology section, the aeration rate of pressurization contact oxidation reactor is 25～30: 1, and operation of equipment pressure is 0.1～0.5MPa, and retention time of sewage is 5～10 hours.
8. a high-purity pyridine class sewage treatment equipment is characterized in that: comprise the electric catalysis reactor, micro-electrolysis reactor, coagulating sedimentation processing unit, anaerobic hydrolysis equipment, the pressurization contact oxidation reactor that connect successively.
9. high-purity pyridine class sewage treatment equipment according to claim 8 is characterized in that: described micro-electrolysis reactor is the iron-carbon micro-electrolysis reactor, and its inner iron, carbon volume ratio are 1: 1.
10. high-purity pyridine class sewage treatment equipment according to claim 8 is characterized in that: the current density of described electric catalysis reactor is 10～20mA/cm
2, the aeration rate of pressurization contact oxidation reactor is 25～30: 1, working pressure is 0.1～0.5MPa.
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| CN102417274A (en) * | 2011-10-14 | 2012-04-18 | 武汉凯瑞达环保工程有限公司 | Non-degradable industrial sewage treatment technology and equipment |
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| CN108706761B (en) * | 2018-04-26 | 2021-03-23 | 浙江奇彩环境科技股份有限公司 | Method for treating chloropyridine wastewater |
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| CN108892321B (en) * | 2018-07-27 | 2021-04-23 | 江苏南大华兴环保科技股份公司 | Method for treating pyridine pesticide wastewater by biological-electrochemical coupling technology |
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