CN103058346A - Wastewater treatment method - Google Patents
Wastewater treatment method Download PDFInfo
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- CN103058346A CN103058346A CN2011103171817A CN201110317181A CN103058346A CN 103058346 A CN103058346 A CN 103058346A CN 2011103171817 A CN2011103171817 A CN 2011103171817A CN 201110317181 A CN201110317181 A CN 201110317181A CN 103058346 A CN103058346 A CN 103058346A
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- waste water
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- oxygenant
- wastewater
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- 238000004065 wastewater treatment Methods 0.000 title abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 160
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 230000000694 effects Effects 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000008187 granular material Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- WQYVRQLZKVEZGA-UHFFFAOYSA-N Hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052803 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- 230000003197 catalytic Effects 0.000 abstract description 12
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000001590 oxidative Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 8
- 230000005672 electromagnetic field Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N Copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl radical Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002894 chemical waste Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007430 reference method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N Cobalt(II,III) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N Copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 229960004643 Cupric oxide Drugs 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L Iron(II) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L Manganese(II) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L Nickel(II) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M Silver chloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- -1 cobaltinitrite Chemical compound 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical group [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- LZMCUTZPLPUFMB-UHFFFAOYSA-L dihydroxy(oxo)manganese Chemical compound O[Mn](O)=O LZMCUTZPLPUFMB-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- LILHXQCLSOZSRO-UHFFFAOYSA-J dizinc;oxozinc;dicarbonate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[Zn+2].[Zn]=O.[Zn]=O.[Zn]=O.[O-]C([O-])=O.[O-]C([O-])=O LILHXQCLSOZSRO-UHFFFAOYSA-J 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000789 fastener Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N iron-sulfur Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
Abstract
The invention provides a wastewater treatment method. Specifically, the method includes: under the effect of a magnetic field, suspending magnetic catalyst particles in wastewater, and conducting a mixing treatment on the wastewater, the magnetic catalyst and an oxidant so as to make the B/C of the treated wastewater larger than equal to 0.3. The wastewater treatment method provided by the invention make the magnetic catalyst particles suspended in the wastewater in the presence of an external magnetic field, and performs catalytic oxidation treatment on the wastewater. With the method, the wastewater treatment effect can be improved significantly, the wastewater treatment effect is stable, and the biodegradability of wastewater can be effectively enhanced.
Description
Technical field
The present invention relates to a kind for the treatment of process of waste water.
Background technology
For a long time, the processing of the organic wastewater with difficult degradation thereby in the environment is the difficult point in the water technology always, also is the important problem of puzzlement countries in the world environment circle.
In recent years, the research of catalyzed oxidation technical finesse organic wastewater with difficult degradation thereby has obtained significant progress.The mechanism of catalyzed oxidation technology is to be combined with oxygenant with catalyzer, produces active extremely strong free radical (such as hydroxyl radical free radical) in reaction; By the adduction between free radical and the organic compound, replacement, transfer transport, scission of link etc., make the macromole hardly degraded organic substance oxidative degradation in the water body become to be easy to biodegradable small-molecule substance, even directly be degraded into CO again
2And H
2O is near permineralization.Be divided into again two kinds of homogeneous catalysis oxidation and heterogeneous catalytic oxidations by the form catalyzed oxidation technology of catalyzer in reaction.The heterogeneous catalytic oxidation technology since have simple to operate, adapt to pH value a wider range, need not frequent catalyzer etc. and more come to have obtained approximately everybody attention.
For example: CN201077792Y discloses a kind of ozone heterogenous catalysis oxygenize water treating device, and this treatment unit comprises ozone generation system (10), mixing wastewater with air system, heterogeneous catalytic oxidation post (8); Heterogeneous catalytic oxidation post (8) is airtight cavity, the lower end is provided with mixing wastewater with air layer (13), waste water jet orifice (7) gos deep in the mixing wastewater with air layer (13), mixing wastewater with air layer (13) upper end is provided with support water distribution board (15), heterogeneous catalytic oxidation packing layer (16), water outlet filter plate (17), effluent weir (18) and closure fange (19) successively, is provided with exhaust port (20) in closure fange (19) top.This device adopts Venturi tube to absorb ozone and guarantees the air water high-speed mixing, increases the solubleness of ozone in waste water by the waste water jet orifice again, guarantees the efficient treatment effect of ozone.This apparatus structure is simple, and can improve the oxidation efficiency of ozone, effectively reduces working cost.But, adopt still not ideal enough height of processing efficiency that this device carries out wastewater treatment, and the replacing of catalyzer trouble.
CN1872730A discloses a kind of technique of coking wastewater deep treatment, this technology utilization solid catalyst and the secondary oxidizer that does not produce secondary pollution carry out advanced treatment to coking chemical waste water, the preparation method of described solid catalyst be with the support of the catalyst aluminium sesquioxide take out after with steeping fluid cupric nitrate dipping, dry, roasting is for subsequent use; Coking chemical waste water behind the equalizing tank homogeneous, is carried out catalytic oxidation with sump pump in the water-in fastener driving device on catalyzer adsorption column top, purify up to standard after by catalyzer adsorption column water outlet discharging, the water outlet bottom is susceptor; The homogeneous pH value of sewage water is 3-7, oxygenant H
2O
2Dosage 0.1-0.5ml/100ml waste water, reaction times 45-90 minute.
But prior art remains at treatment effect not high, the shortcomings such as catalyst change trouble, thereby be necessary to develop more effective, method is processed waste water more easily.
Summary of the invention
The treatment effect of waste water that the object of the invention is to overcome prior art is not good, treatment effect is unstable, and the defective of the replacing of catalyzer trouble and a kind of can be effectively also stable waste water be processed is provided, and the method for biodegradability that can Effective Raise waste water.
To achieve these goals, the invention provides a kind for the treatment of process of waste water, wherein, the method is included under the effect in magnetic field, the magnetic granules of catalyst of tool is suspended in the waste water, and waste water and the magnetic catalyzer of tool and oxygenant carried out combination treatment, so that the B/C of the waste water after processing is 〉=0.3.
The present inventor finds, under the effect of externally-applied magnetic field, the magnetic granules of catalyst of tool is suspended in the waste water, and make waste water and the magnetic catalyzer of tool and oxygenant carry out combination treatment, and waste water is carried out catalytic oxidation treatment, can significantly improve the treatment effect of waste water, also be, treatment effect to waste water is better, and is more stable, and biodegradability that can Effective Raise waste water; Moreover described method can avoid catalyst change trouble and the granules of catalyst can be with problems such as water outlet losses well, and method is more simple.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below will be elaborated to the specific embodiment of the present invention.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the treatment process of described waste water is included under the effect in magnetic field, the magnetic granules of catalyst of tool is suspended in the waste water, and waste water and the magnetic catalyzer of tool and oxygenant are carried out combination treatment, so that the B/C of the waste water after processing is 〉=0.3.
According to the present invention, under the effect in magnetic field, the magnetic granules of catalyst of tool is suspended in the waste water, make waste water carry out catalyzed oxidation with oxygenant and catalyzer, waste water being carried out in the process of catalyzed oxidation, the size in described magnetic field can guarantee to make the magnetic granules of catalyst of tool to be suspended in the waste water, and it is fully contacted with waste water, as long as and the condition of described combination treatment can guarantee to make the B/C of processed waste water to get final product for 〉=0.3 (that is, improving the value of the B/C of waste water).
According to the present invention, the selectable range of the magneticstrength in described magnetic field is wider, as long as the magnetic granules of catalyst of tool is suspended in the waste water, under the preferable case, described magneticstrength can be the 10-2000 oersted, and more preferably in the situation, described magneticstrength is the 100-1000 oersted.In the present invention, described magnetic field can be various magnetic fields, the magnetic field that produces such as electromagnetic field and/or magneticsubstance etc.The producing method in described magnetic field can adopt and well known to a person skilled in the art that ordinary method produces magnetic field.For example, can twine at the outer wall of reactor conspicuous nurse hertz coil, make itself and reactor coaxial, and in coil, pass into certain electric current, so that even, stable externally-applied magnetic field to be provided.Wherein, the winding number of turns of coil, the spacing between coil and the size that passes into the electric current in the coil can suitably be adjusted, as long as guarantee to make the magneticstrength of generation to be enough to satisfy the magnetic granules of catalyst of tool are suspended in the waste water.
According to the present invention, as long as the particle diameter of the magnetic granules of catalyst of described tool can satisfy and can suspend in water and fully contact with waste water, under the preferable case, the particle diameter of the magnetic granules of catalyst of described tool can be the 0.1-2000 micron, more preferably in the situation, the particle diameter of the magnetic granules of catalyst of described tool is the 2-1000 micron, and further under the preferable case, the particle diameter of the magnetic granules of catalyst of described tool is the 50-300 micron.The selectable range of the kind of the magnetic catalyzer of described tool is wider, thereby and can be for various tools magnetic and can play catalytic oxidant the oxidation of waste water is generated the stronger free radical of oxidisability, such as the catalyzer of hydroxyl radical free radical.Under the preferable case, the magnetic catalyzer chosen from Fe of described tool, cobalt, nickel, they insoluble hydroxide of metal and their insoluble metal salt at least a; Perhaps chosen from Fe, cobalt, nickel, they metal oxide, they insoluble hydroxide of metal and their insoluble metal salt at least a be selected from manganese, copper, zinc, titanium, silver, aluminium, their metal oxide, their insoluble hydroxide of metal and at least a mixture in their the insoluble metal salt.Wherein, insoluble hydroxide of metal recited above under a normal atmosphere, 20 ℃ the solubleness in water less than 0.1g/100cm
3Insoluble metal salt recited above under a normal atmosphere, 20 ℃ the solubleness in water less than 0.1g/100cm
3Specifically, described insoluble hydroxide of metal can be selected from ferrous hydroxide, ironic hydroxide, aluminium hydroxide and manganous hydroxide (Mn (OH)
2) in one or more; Described insoluble metal salt can be selected from one or more in Iron sulfuret, iron protocarbonate, cupric sulfide, cuprous sulfide, cobaltinitrite, nickelous carbonate, manganous carbonate, zinc carbonate, zinc sulphide and the silver chloride.In addition, the magnetic granules of catalyst of described tool can be commercially available, and perhaps also can adopt the method for well known to a person skilled in the art to prepare.
Among the present invention, described oxygenant can carry out oxidation with the impurity such as organism in the water, and therefore, the oxygenizement of described oxygenant can be decomposed into larger molecular organics the biodegradability that small organic molecule improves waste water.Wherein, the magnetic granules of catalyst of described tool can be under the effect in magnetic field, and further catalytic oxidant produces the stronger free radical of oxidisability, and for example, hydroxyl radical free radical, thereby oxidation that can more effective accelerating oxidation agent further improve the biodegradability of waste water.
According to the present invention, described oxygenant can be this area various oxygenants that the organism in the water etc. can be carried out oxidation commonly used, under the preferable case, described oxygenant can be selected from one or more in hydrogen peroxide (mass percent concentration of hydrogen peroxide can be 27.5%-50% usually), ozone, persulphate, hypochlorite, dioxide peroxide and the chlorine, more preferably hydrogen peroxide.
According to the present invention, as long as the consumption of the method for described combination treatment, condition and oxygenant and the magnetic catalyzer of tool can satisfy the B/C that makes the waste water after the processing that obtains 〉=0.3.Therefore, the selectable range of the amount of described oxygenant and the magnetic catalyzer of tool is wider, and can suitably regulate according to the COD value of waste water, as long as can play so that the bacterium in the waste water and the abundant oxygenolysis of the impurity such as organism and oily substance, and the requirement of satisfying the B/C of processed waste water gets final product.Under the preferable case, organic mass ratio is 0.01-10 in described oxygenant and the waste water: 1; More preferably in the situation, organic mass ratio is 0.1-5 in described oxygenant and the waste water: 1, and under the most preferred case, organic mass ratio is 0.1-2 in described oxygenant and the waste water: 1.
In order more to be beneficial to the abundant contact reacts of waste water and oxygenant and the magnetic granules of catalyst of tool, and considering cost and effect, under the preferable case, the method of described combination treatment comprises: under the effect of externally-applied magnetic field, with waste water and the continuous magnetic granules of catalyst contact reacts of tool with suspending of oxygenant.The described catalytic time is not particularly limited, as long as the magnetic granules of catalyst of waste water and tool is contacted with the requirement of the catalytic organism oxidation in the waste water with the B/C value that satisfies waste water.Wherein, can be according to the different consumptions of suitably selecting the magnetic granules of catalyst of tool and oxygenant of the water quality of pending waste water; The selectable range of the residence time of described waste water is wider, also can carry out suitable adjusting according to the difference of the size of the consumption of the magnetic granules of catalyst of water quality, tool of waste water and oxygenant and device, under the preferable case, the residence time of described waste water (reaction times in reactor) can be 2-600 minute, further under the preferable case, the residence time of described waste water is 5-300 minute, more preferably 10-180 minute.In hour the residence time be equivalent to the inverse of liquid hourly space velocity (the magnetic granules of catalyst of unit volume tool is per hour processed the volume of waste water), therefore, the liquid hourly space velocity that namely is equivalent to described waste water can be 0.1-50h
-1, 0.5-10h more preferably
-1, most preferably be 2-8h
-1In addition, the magnetic catalyzer of described tool can account for the 40-95% of reactor volume usually; Under the preferable case, the magnetic catalyzer of described tool accounts for the 60-85% of reactor volume.
In the present invention, organic quality can represent with the chemical oxygen demand (COD) (COD) of waste water in the described waste water, COD refers under certain conditions, when adopting certain strong oxidizer to process water sample, the oxidant content that consumes, it is what a index of reducing substances (being mainly organism) in the expression water.Can be understood as so, is the waste water of 1mg/L corresponding to the COD value, and the consumption of oxygenant is 0.01-10mg, is preferably 0.1-5mg, more preferably 0.1-2mg.
According to a kind of preferred embodiment of the present invention, the mode that makes the magnetic catalyzer of waste water and tool and oxygenant carry out combination treatment is: under the effect of externally-applied magnetic field, the magnetic granules of catalyst of tool is suspended in (described reactor is made of the good material of magnetic permeability in the reactor, for example, stainless material), pending waste water and oxygenant passed into from reactor bottom (waste water and oxygenant can pass into respectively, pass into after also can mixing), waste water discharge after will processing gradually with the magnetic granules of catalyst contact reacts of tool that suspends, and from the top of reactor.
According to the present invention, the condition of described combination treatment generally also comprises temperature, pressure and time, and the present invention all was not particularly limited temperature, pressure and time of combination treatment, for example, described treatment temp can be normal temperature usually, for example, and 0-99 ℃, pressure can be 0-0.03MPa usually, is preferably normal pressure (0-0.01MPa).As long as the treatment time can guarantee to make the B/C value of waste water to reach requirement.
According to the present invention, better for the treatment effect that can make waste water, the pH value of the waste water of described pending processing can be 1-9, more preferably 2-7 usually.The method of described adjusting waste water ph can be the method for this area routine, for example, adds acid or alkali and regulates, and the concentration of acid or alkali and consumption can be adjusted according to actual needs, as long as guarantee the pH value of waste water is adjusted to 1-9, is preferably 2-7 and gets final product.
According to the present invention, described waste water can be various waste water, for example, printing and dyeing class waste water, paper waste, pharmacy waste water and petrochemical industry waste water etc., generally, the B/C of the described waste water of described waste water is＜0.3mg/L, for example, for more unmanageable waste water, its B/C can be 0-0.25mg/L; The COD value of described pending waste water is generally greater than 60mg/L, and for example, the COD value can be 200-1000mg/L.
The present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope of the present invention, can carry out multiple simple variant to technical scheme of the present invention, and these simple variant all belong to protection scope of the present invention.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode, for fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
The below will further describe in detail embodiments of the invention.
Among the following embodiment, the measuring method of the COD of waste water is dichromate titration (GB11914-89), and the measuring method of the BOD of waste water is dilution inoculation method (GB/T 7488-1987).
The volume for cylindrical reactor, reactor of the magnetically stabilized bed reactor that adopts among the following embodiment is 2L, and the material of reactor adopts the 316L stainless steel, and 5 coils are arranged in the reactor outside, the number of turn 350 circles of each coil, and the spacing of coil is 30mm.
Embodiment 1
Present embodiment is used for illustrating the treatment process of waste water provided by the invention.
The waste water that present embodiment is processed is the high-concentration waste water of certain refinery.
With aqueous sulfuric acid (mass percent concentration is 98%) the pH value of above-mentioned pending waste water is adjusted to 6, described waste water and oxidant hydrogen peroxide (mass percent concentration is 30%) (the hydrogen peroxide consumption is 400mg/L) introduced continuously from the bottom that the magnetic that ferriferrous oxide particles (particle diameter is 120 microns) is housed is stablized reactor (loadings of ferriferrous oxide particles is 65% of reactor volume the reactor, the residence time of waste water is 20 minutes), in the coil that is wrapped in described reactor periphery, pass into electric current, so that the magneticstrength of additional electromagnetic field is 300 oersteds, described ferriferrous oxide particles is suspended in the waste water, and the waste water after will processing is drawn the waste water after obtaining processing from described reactor head.Waste water quality index before and after processing is as shown in table 1.
Comparative Examples 1
This Comparative Examples is used for the reference method of explanation wastewater treatment.
Process waste water according to the method for embodiment 1, different is, does not pass into electric current (namely not having additional electromagnetic field) to reactor, directly waste water and described oxygenant is passed in the reactor that ferriferrous oxide particles is housed.Waste water quality index before and after processing is as shown in table 1.
Table 1
| The waste water quality index | COD(mg/L) | BOD(mg/L) | B/C |
| Before the processing | 860 | 23 | 0.03 |
| Comparative Examples 1 | 480 | 28 | 0.06 |
| Embodiment 1 | 108 | 33 | 0.31 |
From the results shown in Table 1, method of the present invention can significantly improve the ratio of the B/C of processed waste water, adopt the B/C of the waste water after method of the present invention is processed to reach 0.31, and the B/C of Comparative Examples 1 only is 0.06, the biodegradability that processed waste water is described significantly improves, and treatment effect is stable, and in addition, the COD value of processed waste water also significantly reduces.
Embodiment 2
Present embodiment is used for illustrating the treatment process of waste water provided by the invention.
The waste water that present embodiment is processed is certain chemical plant wastewater.
Magnetic granules of catalyst preparation method is as follows for the tool that adopts in the present embodiment: obtaining particle diameter in 2 hours at 500 ℃ of sintering after the titanium dioxide (diameier is the 2-10 micron) of the cupric oxide (diameier is the 2-10 micron) of 70 % by weight iron powders (diameier is the 2-10 micron), 25 % by weight and 5 % by weight is mixed is 150 microns granules of catalyst.
With aqueous sulfuric acid (mass percent concentration is 98%) the pH value of above-mentioned pending waste water is adjusted to 6, described waste water and oxidant hydrogen peroxide (mass percent concentration is 30%) (the hydrogen peroxide consumption is 400mg/L) introduced continuously from the described bottom that the magnetically stabilized bed reactor of above-mentioned granules of catalyst is housed (the granules of catalyst loadings is 70% of reactor volume, the residence time of waste water is 15 minutes), in the coil that is wrapped in described reactor periphery, pass into electric current, so that the magneticstrength of additional electromagnetic field is 500 oersteds, described granules of catalyst is suspended in the waste water, and the waste water after will processing is drawn the waste water after obtaining processing from described reactor head.Waste water quality index before and after processing is as shown in table 2.
Comparative Examples 2
This Comparative Examples is used for the reference method of explanation wastewater treatment.
Process waste water according to the method for embodiment 1, different is, does not pass into electric current (namely not having additional electromagnetic field) to reactor, directly waste water and described oxygenant is passed in the reactor that embodiment 2 described granules of catalyst are housed.Waste water quality index before and after processing is as shown in table 2.
Table 2
| The waste water quality index | COD(mg/L) | BOD(mg/L) | B/C |
| Before the processing | 780 | 15 | 0.02 |
| Comparative Examples 2 | 360 | 24 | 0.07 |
| Embodiment 2 | 86 | 28 | 0.33 |
From the results shown in Table 2, method of the present invention can significantly improve the ratio of the B/C of processed waste water, adopt the B/C of the waste water after method of the present invention is processed to reach 0.33, and the B/C of Comparative Examples 1 only is 0.07, the biodegradability that processed waste water is described significantly improves, and treatment effect is stable, and in addition, the COD value of processed waste water also significantly reduces.
Embodiment 3
Present embodiment is used for illustrating the treatment process of waste water provided by the invention.
Method according to embodiment 1 is processed waste water, and different is that the magneticstrength of additional electromagnetic field is 800 oersteds; The COD value of processed waste water is 98mg/L, and the BOD value is 33mg/L, and B/C is 0.34.
Embodiment 4
Present embodiment is used for illustrating the treatment process of waste water provided by the invention.
Method according to embodiment 1 is processed waste water, and different is that the loadings of the magnetic granules of catalyst of tool is 75% of reactor volume.The COD value of processed waste water is 100mg/L, and the BOD value is 33mg/L, and B/C is 0.33.
Embodiment 5
Present embodiment is used for illustrating the treatment process of waste water provided by the invention.
Method according to embodiment 1 is processed waste water, and different is that the residence time of waste water is 50 minutes.The COD value of processed waste water is 105mg/L, and the BOD value is 35mg/L, and B/C is 0.33.
Embodiment 6
Present embodiment is used for illustrating the treatment process of waste water provided by the invention.
Process waste water according to the method for embodiment 1, different is, adopts Sodium Persulfate as oxygenant, and the oxygenant dosage is 1200mg/L, and the COD value of processed waste water is 112mg/L, and the BOD value is 36mg/L, and B/C is 0.32.
Embodiment 7
Present embodiment is used for illustrating the treatment process of waste water provided by the invention.
Method according to embodiment 1 is processed waste water, different is that magnetic granules of catalyst preparation method is as follows for the tool that adopts in the present embodiment: obtaining particle diameter in 2 hours at 550 ℃ of sintering after the ironic hydroxide powder (diameier is the 5-10 micron) of the nickel oxide (diameier is the 5-10 micron) of the cobalt oxide powder (diameier is the 5-10 micron) of 40 % by weight, 35 % by weight and 25 % by weight is mixed is 200 microns granules of catalyst.The residence time of waste water is 180 minutes, and the COD value of processed waste water is 85mg/L, and the BOD value is 35mg/L, and B/C is 0.41.
BOD/COD accounts for whole organic shares than biodegradable organism in the value representation waste water, and the biodegradable degree of this waste water.Can find out from the result of embodiment 1 to embodiment 7, adopt method of the present invention can significantly improve the ratio of the B/C of processed waste water, thereby can illustrate, adopt the biodegradability of the waste water after method of the present invention is processed to be significantly improved, and the treatment effect of waste water be more stable.
Claims (13)
1. the treatment process of a waste water, it is characterized in that the method is included under the effect in magnetic field, the magnetic granules of catalyst of tool is suspended in the waste water, and waste water and the magnetic catalyzer of tool and oxygenant carried out combination treatment, so that the B/C of the waste water after processing is 〉=0.3.
2. method according to claim 1, wherein, the magneticstrength in described magnetic field is the 10-2000 oersted.
3. method according to claim 2, wherein, described magneticstrength is the 100-1000 oersted.
4. method according to claim 1, wherein, the particle diameter of the magnetic catalyzer of described tool is the 0.1-2000 micron.
5. method according to claim 4, wherein, the particle diameter of the magnetic catalyzer of described tool is the 2-1000 micron.
6. method according to claim 1, wherein, the condition of described combination treatment comprises: organic mass ratio is 0.01-10 in oxygenant and the waste water: 1.
7. method according to claim 6, wherein, organic mass ratio is 0.1-5 in described oxygenant and the waste water: 1.
8. according to claim 1,6 or 7 described methods, wherein, the method of described combination treatment comprises: under the effect of externally-applied magnetic field, waste water is contacted with the magnetic granules of catalyst of tool that suspends continuously with oxygenant, the residence time of described waste water is 2-600 minute.
9. method according to claim 8, wherein, the residence time of described waste water is 5-300 minute.
10. according to claim 1,6 or 7 described methods, wherein, the magnetic catalyzer of described tool accounts for the 40-95% of reactor volume.
11. method according to claim 8, wherein, the magnetic catalyzer chosen from Fe of described tool, cobalt, nickel, they metal oxide, they insoluble hydroxide of metal and their insoluble metal salt at least a; Perhaps chosen from Fe, cobalt, nickel, they metal oxide, they insoluble hydroxide of metal and their insoluble metal salt at least a be selected from manganese, copper, zinc, titanium, silver, aluminium, their metal oxide, their insoluble hydroxide of metal and at least a mixture in their the insoluble metal salt.
12. method according to claim 8, wherein, described oxygenant is selected from one or more in hydrogen peroxide, ozone, persulphate, hypochlorite, dioxide peroxide and the chlorine.
13. method according to claim 1, wherein, the pH value of the waste water of pending processing is 1-9.
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| CN103936135A (en) * | 2014-05-07 | 2014-07-23 | 东华大学 | Method for oxidizing industrial wastewater with oxydol by using marmatite as catalyst |
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