CN203820583U - High concentration ammonia-nitrogen wastewater treatment device - Google Patents
High concentration ammonia-nitrogen wastewater treatment device Download PDFInfo
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- CN203820583U CN203820583U CN201420144633.5U CN201420144633U CN203820583U CN 203820583 U CN203820583 U CN 203820583U CN 201420144633 U CN201420144633 U CN 201420144633U CN 203820583 U CN203820583 U CN 203820583U
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- ammonia nitrogen
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title abstract description 74
- 238000004065 wastewater treatment Methods 0.000 title abstract description 4
- 230000000694 effects Effects 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 53
- 229910021529 ammonia Inorganic materials 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 210000001124 body fluid Anatomy 0.000 claims description 4
- 239000010839 body fluid Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 95
- 230000008569 process Effects 0.000 abstract description 44
- 239000002351 wastewater Substances 0.000 abstract description 44
- 238000011282 treatment Methods 0.000 abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 238000012545 processing Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000006396 nitration reaction Methods 0.000 description 9
- 238000011160 research Methods 0.000 description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 5
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 229910052567 struvite Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000009615 deamination Effects 0.000 description 4
- 238000006481 deamination reaction Methods 0.000 description 4
- 159000000003 magnesium salts Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 241001131796 Botaurus stellaris Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000001651 autotrophic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- IHTRHZMXELXCEJ-UHFFFAOYSA-N azane;helium Chemical compound [He].N IHTRHZMXELXCEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
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- Physical Water Treatments (AREA)
Abstract
The utility model relates to a high concentration ammonia-nitrogen wastewater treatment device, which solves the technical problems of high cost, complex treatment process, poor treatment effect and secondary pollution of an existing high concentration ammonia-nitrogen wastewater treatment method. The device comprises a water collecting pool, a settling pool, a middle pool, a four-effect evaporator, a slurry barrel, a centrifugal machine and a flash cooling crystallizing kettle, wherein the water collecting pool and the settling pool are connected through a pipeline, the settling pool and the middle pool are connected through a pump, the middle pool and the four-effect evaporator are connected through the pump, the four-effect evaporator is connected with the slurry barrel which is connected with the centrifugal machine, and the centrifugal machine is connected with the flash cooling crystallizing kettle through the pump. The device can be widely used for treatment of high concentration ammonia-nitrogen wastewater.
Description
Technical field
The utility model relates to a kind of water treatment device, particularly relates to a kind of device for treating high-concentration ammonia.
Background technology
At present, high-concentration ammonia nitrogenous wastewater treatment technology method mainly contains following several method:
1, blow-off method.
Under alkaline condition, utilize the phase concentrations of ammonia nitrogen and the vapor-liquid equilibrium relationship between liquid concentration to carry out a kind of separated method.It is generally acknowledged that stripping efficiency and temperature, pH, vapour-liquid ratio are relevant.
The ammonia nitrogen that domestic relevant expert removes in percolate blow-off method is studied, and the key factor of controlling stripping efficiency is temperature, vapour-liquid ratio and pH.In water temperature, be greater than 125 ℃, vapour-liquid ratio is controlled at 3500 left and right, and percolate pH is controlled at 10.5 left and right, the percolate for ammonia nitrogen concentration up to 2000～4000mg/L, and clearance can reach more than 90%.Blow-off method ammonia nitrogen removal efficiency when low temperature is not high.
Adopt ultrasonic wave stripping technology for example, to carry out Processing Test to fertilizer plant's high-concentration ammonia nitrogenous wastewater (882mg/L).Optimum process condition is pH=11, and the ultrasonic stripping time is 40min, and gas-water ratio is l000:1.Test-results shows, after waste water adopts Ultrasonic Radiation, the stripping successful of ammonia nitrogen increases, and compares with traditional stripping technology, and the clearance of ammonia nitrogen has increased by 17～16.4%, and more than 90%, after stripping, ammonia nitrogen is in 100mg/L.
For the cost with lower, pH regulator is extremely alkaline, need in waste water, add a certain amount of calcium hydroxide, but easily scale.Meanwhile, in order to prevent that the ammonia nitrogen that stripping goes out from causing secondary pollution, ammonia nitrogen absorption unit need to be set after stripping tower.
When processing through the pretreated percolate of UASB (2240mg/L), find at pH=11.5, the reaction times is 24h, only with the velocity slope of 120r/min, carries out mechanical stirring, and ammonia nitrogen removal frank just can reach 95%.And when pH=12, pass through aeration ammonia nitrogen removal, and at the 17th hour pH, starting to decline, ammonia nitrogen removal frank is only 85%.Think accordingly, the dominant mechanism of blow-off method denitrogenation should be that mechanical stirring rather than air diffuser stir.
Chemistry blow-off method denitride technology, except having high-efficiency sewage handling property, also has obvious energy-saving effect, and running cost is lower than traditional ammonia still process method, and effluent index is better than traditional ammonia still process method.
Technical process: waste water is sent into denitrification column top by fresh feed pump.In course of conveying with addition of denitrfying agent and alkali lye.From denitrification column bottom, blast air again.Air passes through tower body, the waste water counter current contact entering with tower top from bottom to top.At the bottom of tower, water outlet enters denitrogenation outlet sump.Tower top discharge gas contains a small amount of gaseous ammonia, through Ammonic washing tower, cuts back and prepares groove, circular treatment.Part water outlet can be used for washing ammonia after cooling.
Chemistry blow-off method nitrogen rejection facility also can be widely used in the sewage treatment area that chemical fertilizer, coal gas, percolate, papermaking, rare earth, electronics, metallurgy etc. contain ammonia nitrogen in high density.
CMBR is the novel process that the industrial sewage that combines of chemical blow-off method ammonia nitrogen removal and membrane bioreactor is processed.C shows chemical blow-off method denitrogenation, and MBR represents membrane bioreactor.First this method is applied to coking field, obtains good result.
CMBR technique can directly be processed high-concentration ammonia nitrogenous wastewater, and ammonia nitrogen concentration can high 5000mg/L.Water outlet can reach national grade one discharge standard does not have secondary pollution.Water outlet data fit national grade one discharge standard, contained ammonia nitrogen < 15mg/L, COD < 100mg/L, phenol < 0.5mg/L, cyanogen < 0.5mg/L, oils < 5mg/L, SS < 70mg/L, pH6～9.
CMBR technique can prevent microorganism loss, improves the volumetric loading of sludge concentration and biological process, guarantees stable effluent quality.
With the comparison of traditional ammonia still process method, the investment of CMBR method and running cost are low, and treatment efficiency is high, and energy-saving effect is remarkable, and occupied ground is little.
Denitrification column goes out after water cooling, enters biochemical system, first squeezes into air flotation slot, remove fine suspension and oil in water emulsion composition in water, then carry out successively anaerobism, the oxygen of holding concurrently, aerobic reaction, by nitration reaction, further remove other pollutents such as residue ammonia nitrogen in sewage and COD.External placed type tubular membrane component is entered in Aerobic Pond water outlet, and clean water basin are entered in tubular membrane component water outlet, can qualified discharge or reuse.Meanwhile, the water outlet of the tubular membrane the other end, is back to anaerobic pond.Regular spoil disposal is wanted in each pond, and the muddy water of discharge enters sludge drying pond, and sludge drying bed filtrate is got back to mud pond, through mud water pump, returns anaerobic pond, the mud outward transport after mummification.
2, zeolite deamination method.
Utilize positively charged ion in zeolite and the NH in waste water
4+exchange to reach the object of denitrogenation.The waste water that zeolite is generally used to process lower concentration ammonia-containing water or contains micro heavy.Yet the domestic scholar of having has inquired into effect and the feasibility of ammonia nitrogen in Activated Zeolite Adsorption removal percolate.Result of study shows, every gram of zeolite has the limit potentiality of absorption 15.5mg ammonia nitrogen, when zeolite particle diameter is 30～16 order, ammonia nitrogen removal frank has reached 78.5%, and in the situation that adsorption time, dosage and zeolite particle diameter are identical, influent ammonium concentration is larger, and adsorption rate is larger, and it is feasible that zeolite is removed Coal Gas Washing Cycling Water ammonia nitrogen as sorbent material.
Application zeolite deamination method must be considered the regeneration problem of zeolite, conventionally has regenerated liquid method and burning method.While adopting burning method, the ammonia of generation must be processed.
3, membrane separation technique.
Utilize the selection perviousness of film to carry out a kind of method of ammonia nitrogen removal.This method is easy to operate, and the ammonia nitrogen rate of recovery is high, non-secondary pollution.Adopt electroosmose process and polypropylene (PP) tubular fibre embrane method to process ammonia nitrogen in high density inorganic wastewater and can obtain good effect.Electroosmose process is processed ammonia nitrogen waste water 2000～3000mg/L, and clearance can, more than 85%, can obtain 8.9% strong aqua simultaneously.This method technical process simply, does not consume the electric weight consuming in medicament, operational process and is directly proportional to ammonia nitrogen concentration in waste water.PP tubular fibre embrane method deamination efficiency > 90%, the ammonium chloride concentration of recovery is in 25% left and right.Need in service add alkali, add alkali number and are directly proportional to ammonia nitrogen concentration in waste water.
Emulsion liquid membrane is that the liquid film existing with emulsion form has selection perviousness, can be used for liquid liquid separated.It is separating medium that emulsion liquid membrane (for example kerosene film) is normally take in sepn process, and concentration difference and diffusion in oil film both sides by NH3 are transmitted as impellent, NH3 is entered in film, thereby reach separated object.With liquid-film method, process the total discharge outlet waste water (ammonia nitrogen 1000～1200mg/L of certain hydrometallurgy factory, pH is 6～9), when adopting alkylolamide Soxylat A 25-7, be that dosage of surfactant is 4～6%, wastewater pH is adjusted to 10～11, ratio of milk and water is at 1:8～1:12, and oily internal ratio is 0.8～1.5.Sulfuric acid massfraction is 10%, and in waste water, ammonia nitrogen removal frank primary treatment can reach more than 97%.
4, the MAP precipitator method.
Mainly to utilize following chemical reaction:
Mg
2++NH
4++PO4
3-＝MgNH
4PO
4
With certain proportion, in the waste water that contains ammonia nitrogen in high density, add microcosmic salt and magnesium salts theoretically, as [Mg
2+] [NH
4+] [PO4
3-] > 2.5 * 10
– 13time can generate magnesium ammonium phosphate (MAP), remove the ammonia nitrogen in waste water.Employing adds MgCl in the higher trade effluent of ammonia nitrogen concentration
26H
2o and Na
2hPO
412H
2o generates the method for magnesium ammonium phosphate sediment, to remove ammonia nitrogen in high density wherein.Result shows, at pH, is 8.9l, Mg
2+, NH
4, P0
4 3-mol ratio be 1.25:1:1, temperature of reaction is 25 ℃, the reaction times is 20min, under the condition that sedimentation time is 20min, ammonia ammonia mass concentration can be reduced to 460mg/L by 9500mg/L, clearance reaches more than 95%.Because the content of magnesium salts in most waste water can be lower with respect to phosphoric acid salt and ammonia nitrogen, although the magnesium ammonium phosphate generating can be fertile and offset a part of cost as agriculture, the expense that adds magnesium salts still becomes the principal element that this method of restriction is carried out.Seawater is inexhaustible, and wherein contains a large amount of magnesium salts.With seawater as magnesium ion source experimental study ammoniomagnesium phosphate crystal process.Bittern is salt-making by-proudct, mainly containing MgCl
2with other mineral compound.Mg
2+be about 32g/L and be 27 times of seawater.Use MgCl
2, seawater, bittern be respectively as Mg
2+high-concentration ammonia nitrogenous wastewater is processed with ammoniomagnesium phosphate crystal method in source, and result shows, pH is most important control parameter, and when terminal pH ≈ 9.6, reaction can finish in 10min.Because the N/P in waste water is uneven, with other two kinds of Mg
2+source is compared, and the phosphor-removing effect of bittern is identical and denitrification effect is slightly poor.
5, chemical oxidization method.
Utilize strong oxidizer that ammonia nitrogen is direct oxidation into a kind of method that nitrogen removes.Break point chlorination is to utilize the ammonia in water to react generation ammonia deamination with chlorine, and this method can also play germicidal action, but the chlorine residue meeting producing has impact to fish, therefore must set up except chlorine residue facility.In the situation that bromide exists, can there is reacting of following similar break point chlorination with ammonia nitrogen in ozone:
Br
-+O
3+H
+→HBrO+O
2；
NH
3+HBrO→NH
2Br+H
2O；
NH
2Br+HBrO→NHBr
2+H
2O；
NH
2Br+NHBr
2→N
2+3Br
-+3H
+。
With the continuous aeration post of a useful volume 32L, to synthetic wastewater (ammonia nitrogen 600mg/L) research experiment, inquire into Br/N, pH and the impact of initial ammonia nitrogen concentration on reaction, to determine, remove maximum ammonia nitrogens and form minimum NO
3-optimum reaction condition.Find NFR (water outlet NO
3 -the ratio of-N and influent ammonia nitrogen) in logarithmic coordinates with Br
-the linear correlationship of/N, at Br
-/ N > 0.4, ammonia nitrogen loading is 3.6～4.0kg/ (m
3d), time, ammonia nitrogen loading reduces NFR and reduces.During water outlet pH=6.0, NFR and BrO
--Br (having toxic byproduct) is minimum.BrO
--Br can be by Na
2sO
3quantitatively decompose Na
2sO
3dosage can be controlled by ORP.
6, biochemical integrated process.
Physical chemistry method can not be restricted because ammonia nitrogen concentration is too high when processing high-concentration ammonia nitrogenous wastewater, but ammonia nitrogen concentration can not be dropped to enough low (as following in 100mg/L).And biological denitrificaion can be suppressed because of high density free ammonia or nitrite nitrogen.In practical application, adopt the method for biochemical associating, before biological treatment, first the waste water containing ammonia nitrogen in high density is carried out to materialization processing.
Adopt stripping-anoxic-aerobic process to process containing high-concentration ammonia nitrogenous wastewater.Result shows, when stripping condition is controlled at pH=9.5, stripping time and is 12h, stripping pre-treatment can be removed more than 60% ammonia nitrogen in waste water, then after anoxic-aerobe is processed the clearance >90% to ammonia nitrogen (being down to 19.4mg/L by 1400mg/L) and COD.
With biological activated carbon fluidized bed processing percolate (COD is 800～2700mg/L, and ammonia nitrogen is 220～800mg/L).Result of study shows, at ammonia nitrogen loading 0.71kg/ (m
3d)) time, nitrated clearance can reach more than 90%, and COD clearance reaches 70%, BOD and all removes.With lime flocculation precipitation+air stripping, as preprocessing means, improve the biodegradability of percolate, in aerobic treatment pond subsequently, add sorbent material (powdered active carbon and zeolite), find that sorbent material removal efficiency of COD and ammonia nitrogen when 0～5g/L all increases and improves with absorbent concentration.Removal effect zeolite for ammonia nitrogen is better than gac.
Film-bioreactor technology (MBR) is a kind of new and effective Sewage treatment systems that membrane separation technique and traditional wastewater biological reactor organic assembling are formed.MBR processing efficiency is high, and water outlet can direct reuse, and the few battlefield of equipment area is little, and surplus sludge volume is few.Its difficult point is the seepage that keeps film to have larger flux and prevent film.Domestic scholars utilizes integrated film bio-reactor to carry out the research of high-concentration ammonia nitrogenous wastewater Nitrification Characteristics.Result of study shows, when former water ammonia nitrogen concentration is 2000mg/L, the volumetric loading of the ammonia helium of intaking is 2.0kg/ (m
3d) time, the clearance of ammonia nitrogen can reach more than 99%, and systematic comparison is stable.In reactor, the specific nitrification rate of active sludge is basicly stable in 0.36/d left and right within the time of half a year.
7, short-cut nitrification and denitrification.
Biological nitrification and denitrification is most widely used denitrogenation mode.Owing to needing a large amount of oxygen, aeration expense to become the main spending of this denitrogenation mode in ammonia nitrogen oxidising process.Short-cut nitrification and denitrification (ammonia nitrogen is oxidizing to nitrite nitrogen and carries out denitrification), not only can save ammonia oxidation oxygen requirement but also can save the required charcoal of denitrification source.Foreign study person determines with synthetic wastewater (simulation is containing the trade effluent of ammonia nitrogen in high density) test the top condition that realizes nitrite accumulation.Want to realize nitrite accumulation, pH is not a crucial control parameter, because pH is at 6.45～8.95 o'clock, and whole nitrated generation nitrate, when pH < 6.45 or pH > 8.95, occur nitrated suppressed, ammonia nitrogen accumulation.When DO=0.7mg/L, can realize 65% ammonia nitrogen with the form accumulation of nitrite and mineralized nitrogen rate more than 98%.During DO < 0.5mg/L, there is ammonia nitrogen accumulation, whole nitrated generation nitrate during DO > 1.7mg/L.Domestic expert adopts the effect of nitrite type and the denitrogenation of nitric acid type to carry out comparative analysis to the high-concentration ammonia nitrogenous wastewater of low ratio of carbon to ammonium.Test-results shows, nitrite type denitrogenation can obviously improve total nitrogen removal efficiency, and ammonia nitrogen and nitric nitrogen load can improve nearly 1 times.In addition, the factor such as pH and ammonia nitrogen concentration has material impact to denitrogenation type.
8, Anammox (ANAMMOX) and whole process autotrophic denitrification (CANON).
Anammox refers to that ammonia nitrogen under anaerobic take nitrite and be directly oxidized to the process of nitrogen as electron acceptor(EA).The biochemical reaction formula of ANAMMOX is:
NH
4++NO
2 -→N
2↑+2H
2O
ANAMMOX bacterium is obligate anaerobic autotrophic bacteria, thereby is applicable to very much processing containing NO2
-, low C/N ammonia nitrogen waste water.Compare with traditional technology, the denitrogenation mode technical process based on Anammox is simple, does not need additional organic charcoal source, prevents secondary pollution, again good application prospect.The application of Anammox mainly contains two kinds: CANON technique and with SHARON (SHARON) combination, form SHARON-ANAMMOX process integration.
CANON technique is under the condition of limit oxygen, utilizes completely a kind of method of ammonia nitrogen and nitrite being removed simultaneously from the microorganism of nourishing one's nature, and from reaction formation, it is the combination of SHARON and ANAMMOX technique, in same reactor, carries out.Domestic research shows, dissolved oxygen is controlled at 1mg/L left and right, influent ammonia nitrogen < 800mg/L, ammonia nitrogen loading < 0.46kg/ (m
3d) under condition, can utilize sbr reactor device to realize CANON technique, the clearance > 95% of ammonia nitrogen, the clearance > 90% of total nitrogen.
External research shows that ANAMMOX and CANON process can run well in gas stripping type reactor, and reaches very high nitrogen transformation speed.Control dissolved oxygen in 0.5mg/L left and right, in gas stripping type reactor, the denitrification rates of ANAMMOX process reaches 8.9kg/ (m
3and CANON process can reach 1.5kg/ (m d),
3d).
9, aerobic denitrification.
Tradition denitrogenation theory thinks, denitrifying bacteria is facultative anaerobe, and its respiratory chain be take oxygen and under anoxia condition, be take nitrate radical as terminal electron acceptor as terminal electron acceptor under aerobic conditions.If so carry out anti-nitration reaction, must be under anaerobic environment.In recent years, Aerobic Denitrification Phenomenon is constantly found and reports, receives gradually people's concern.Some aerobic denitrifying bacterias are separated, and some can carry out aerobic denitrification and heterotrophic nitrification (as separated in Robertson etc., filter out Tpantotropha.LMD82.5) simultaneously.So just can in same reactor, realize synchronous nitration and denitrification truly, simplify technical process, save energy.
Domesticly with sequencing batch reactor, process ammonia nitrogen waste water, test-results has been verified the existence of aerobic denitrification, and aerobic denitrification denitrification ability reduces with the raising of mixed solution dissolved oxygen concentration, and when dissolved oxygen concentration is 0.5mg/L, nitrogen removal rate can reach 66.0%.
The continuous dynamic testing research of domestic scholars shows, for ammonia nitrogen in high density percolate, the nitrogen removal rate of the aerobic denitrification technique of ordinary activated sludge can reach more than 10%.Nitration reaction speed declines along with the reduction of dissolved oxygen concentration; Anti-nitration reaction speed rises along with the reduction of dissolved oxygen concentration.Nitrated and denitrifying dynamic analysis shows, there will be the synchronous nitration and denitrification phenomenon that rate of nitrification and denitrification rate are equal when dissolved oxygen is 0.14mg/L left and right.Its speed is 4.7mg/ (Lh), nitration reaction KN=0.37mg/L; Anti-nitration reaction KD=0.48mg/L.
In denitrification process, can produce N
2o is a kind of greenhouse gases, produces new pollution, and its related mechanism research is deep not enough, and much technique, still at laboratory stage, needs further research just can be effectively applied in Practical Project.In addition, also have techniques such as Full Autotrophic Ammonium Removal Process, synchronous nitration and denitrification to be still in the experimental study stage, have good application prospect.
Although it is multiple that the treatment process of processing high-concentration ammonia nitrogenous wastewater has, what process is all the waste water that some ammonia nitrogen concentrations are no more than 5000mg/L, and ammonia nitrogen concentration surpasses 5000mg/L, and treatment effect and cost are all undesirable.And also there is no at present a kind ofly can to take into account that flow process is simple, less investment, technology maturation, control is convenient and all respects such as non-secondary pollution.How to process cost-effectively high-concentration ammonia nitrogenous wastewater and be still a difficult problem of pendulum in face of the environmental engineering worker, how new and effective biological denitrification process is dropped into the emphasis that practical application and simple and practical biochemical process integration should become research work from now on.
AC whipping agent waste water index is: CODcr3000～5000mg/L;
Ammonia nitrogen 25000～35000mg/L;
pH＜4～5。
The treatment process that can be applicable at present AC whipping agent waste water mainly contains blow-off method and membrane separation technique, existing together mutually that both exist is to be all chemical process, all must add alkali is converted into free ammonia by ammonia and just can processes, this just needs very large cost, the processing cost of water per ton is between 120 yuan～150 yuan, cost is high, and maintenance of the equipment expense is high.If adopt above-mentioned two kinds of methods to process, AC whipping agent ton cost will increase the cost of 1500～2000 yuan, and this institute of ShiAC whipping agent manufacturer is unacceptable.
Summary of the invention
The utility model is exactly that existing device for treating high-concentration ammonia cost is high, treatment scheme is complicated in order to solve, the technical problem of poor processing effect, generation secondary pollution, provides that a kind of cost is low, treatment scheme is simple, treatment effect is good, do not produce the device for treating high-concentration ammonia of secondary pollution.
The utility model adopts the method for physics to process, first by waste water after sedimentation recycling, insoluble substance is almost nil, for water treatment project provides reliable raw material.Adopt four-effect countercurrent extraction evaporation technology, the charging of IV effect, I effect high temperature precipitated sodium chloride, after centrifugal sodium-chlor product; Adopt secondary shwoot technique, by an effect clear liquid, after secondary flash device, low temperature is separated out ammonium chloride, after centrifugal ammonium chloride product, recycling condensing water, in production system, is realized wastewater zero discharge.
The utility model provides a kind of device for treating high-concentration ammonia, comprise water collecting basin, settling tank, intermediate pool, quadruple effect evaporator, slurries bucket, whizzer and flash cooling crystallization kettle, between water collecting basin and settling tank, by pipeline, connect, between settling tank and intermediate pool, by pump, be connected, between intermediate pool and quadruple effect evaporator, by pump, be connected, quadruple effect evaporator is connected with slurries bucket, and slurries bucket is connected with whizzer, between whizzer and flash cooling crystallization kettle, by pump, is connected;
Quadruple effect evaporator comprises evaporator room and heating chamber, and evaporator room is connected by circulation tube with heating chamber; Circulation tube is connected with horizontal axial-flow pump; Evaporator room is provided with secondary vapor outlet, liquidometer mouth, liquidometer mouth and crosses material liquid outlet; Heating chamber is provided with heating vapor inlet, not condensing outlet, condensation-water drain, water of condensation import; Circulation tube is established effective body fluid inlet, drain;
Flash cooling crystallization kettle comprises evaporator room and crystallisation chamber, and the evaporator room of flash cooling crystallization kettle is provided with negative pressure system interface and liquidometer mouth, and crystallisation chamber is provided with fluid inlet, liquidometer mouth, slurry inlet, slurries outlet and drain.
The beneficial effects of the utility model are: cost is low, treatment scheme is simple, treatment effect is good, do not produce secondary pollution; Sodium-chlor >=95%, ammonium chloride (nitrogenous >=25%) (three grades of Agricultural Fertilizer standards that meet GB).
Accompanying drawing explanation
Fig. 1 is the structural representation of quadruple effect evaporator;
Fig. 2 is the structural representation of flash cooling crystallization kettle.
Nomenclature in accompanying drawing:
1. two vapor outlets; 2. heat vapor inlet; 3. liquidometer mouth; 4. liquidometer mouth; 5. imitate body fluid inlet; 6. not condensing outlet; 7. condensation-water drain; 8. water of condensation import; 9. drain; 10. cross material liquid outlet; 11. negative pressure system interfaces; 12. fluid inlets; 13. liquidometer mouths; 14. liquidometer mouths; 15. slurry inlet; 16. slurries outlets; 17. drains; 18. vertical-type axial-flow pumps; 19. evaporator rooms; 20. heating chambers; 21. circulation tubes; 22. horizontal axial-flow pumps; 23. evaporator rooms; 24. crystallisation chamber; 25. guide shells.
Embodiment
The utility model adopts the method for physics to process, first by ADC whipping agent waste water after sedimentation recycling, insoluble substance is almost nil, for water treatment project provides reliable raw material.Then adopt four-effect countercurrent extraction evaporation technology, the charging of IV effect, I effect high temperature precipitated sodium chloride, after centrifugal sodium-chlor product; Adopt secondary shwoot technique, by an effect clear liquid, after secondary flash device, low temperature is separated out ammonium chloride, after centrifugal ammonium chloride product, recycling condensing water, in production system, is realized wastewater zero discharge.
The first step, by 30～40 ℃, the ADC whipping agent waste water that proportion is 1.23 flows into water collecting basin after being collected by pipeline, then passes through settling tank natural sedimentation, insoluble substance in settling tank is reclaimed with slush pump, the clear liquid above settling tank is promoted to intermediate pool by pump.
Second step, the clear liquid of intermediate pool is extracted out and is input to quadruple effect evaporator by pump, carries out countercurrent evaporation, waste water is concentrated in quadruple effect evaporator, and concentrate to sodium-chlor is separated out, and solid-to-liquid ratio is controlled at 40% left and right, by pump delivery, to slurries bucket, by the whizzer being connected with slurries bucket, sodium-chlor is separated.Filtrate after centrifugal is from flowing to mother liquor pond, and clear liquid arrives flash cooling crystallization kettle by pump delivery.Wherein, the liquid level of quadruple effect evaporator is lower visor below 1/2, and in quadruple effect evaporator, the processing parameter of concentration process is in Table 1.
Table 1:
| Parameter | I effect | II effect | III effect | IV effect |
| Feed temperature (℃) | 100～110 | 85～95 | 70～78 | 50～60 |
| Double evaporation-cooling temperature (℃) | 95～105 | 80～85 | 60～70 | 50～60 |
| Pressure (MPa) | -0.01 | -0.05 | -0.07 | -0.09 |
In quadruple effect evaporator, the processing parameter optimum value of concentration process is in Table 2.
Table 2
| Parameter | I effect | II effect | III effect | IV effect |
| Feed temperature (℃) | 108 | 90 | 72 | 56 |
| Double evaporation-cooling temperature (℃) | 99 | 82 | 66 | 52 |
| Pressure (MPa) | -0.01 | -0.05 | -0.07 | -0.09 |
[0075] as shown in Figure 1, quadruple effect evaporator comprises evaporator room 19 and heating chamber 20, and evaporator room 19 is connected by circulation tube 21 with heating chamber 20, and horizontal axial-flow pump 22 is connected with circulation tube 21, and the liquid in quadruple effect evaporator circulates under the effect of horizontal axial-flow pump 22.Evaporator room 19You Cheng separate chamber, can realize gas-liquid separation.Heating chamber 20 claims again boiling-house, can be to liquid heat.
Evaporator room 19 is provided with secondary vapor outlet 1, liquidometer mouth 3, liquidometer mouth 4, crosses material liquid outlet 10.Heating chamber 20 is provided with heating vapor inlet 2, not condensing outlet 6, condensation-water drain 7, water of condensation import 8.On circulation tube 21, establish effective body fluid inlet 5, drain 9.
The 3rd step, clear liquid is processed through the secondary shwoot of flash cooling crystallization kettle, and process of cooling reduces chloride leach degree, and therefore, ammonium chloride is crystallization in crystallization kettle, and crystal growth reaches certain product granularity.Send into ammonium slurries bucket, through whizzer, isolate chloride solid, chloride solid is outer selling directly.
The processing parameter of secondary shwoot is in Table 3.
Table 3:
| Parameter | A shwoot | Secondary shwoot |
| Feed temperature (℃) | 55～65 | 35～45 |
| Double evaporation-cooling temperature (℃) | 45～55 | 30～36 |
| Pressure (Mpa) | -0.09 | -0.097 |
The processing parameter optimum value of secondary shwoot is in Table 4.
Table 4:
| Parameter | A shwoot | Secondary shwoot |
| Feed temperature (℃) | 60 | 40 |
| Double evaporation-cooling temperature (℃) | 50 | 32 |
| Pressure (Mpa) | -0.09 | -0.097 |
As shown in Figure 2, flash cooling crystallization kettle comprises evaporator room 23 and crystallisation chamber 24, and liquid enters evaporator room 23 by guide shell 25 under the effect of vertical-type axial-flow pump 18.
Evaporator room 23 is provided with negative pressure system interface 11, liquidometer mouth 13, and crystallisation chamber 24 is provided with fluid inlet 12, liquidometer mouth 14, slurry inlet 15, slurries outlet 16, drain 17.
The condensation water recycling that production process produces is in production system, and waste water reaches emission standard.
The above only, to preferred embodiment of the present utility model, is not limited to the utility model, and for a person skilled in the art, the utility model can have various modifications and variations.Every in claim limited range of the present utility model, any modification of making, be equal to replacement, improvement etc., all should be within protection domain of the present utility model.
Claims (1)
1. a device for treating high-concentration ammonia, it is characterized in that, comprise water collecting basin, settling tank, intermediate pool, quadruple effect evaporator, slurries bucket, whizzer and flash cooling crystallization kettle, between described water collecting basin and described settling tank, by pipeline, connect, between described settling tank and described intermediate pool, by pump, be connected, between described intermediate pool and described quadruple effect evaporator, by pump, be connected, described quadruple effect evaporator is connected with described slurries bucket, described slurries bucket is connected with described whizzer, between described whizzer and described flash cooling crystallization kettle, by pump, is connected;
Described quadruple effect evaporator comprises evaporator room and heating chamber, and described evaporator room is connected by circulation tube with described heating chamber; Described circulation tube is connected with horizontal axial-flow pump; Described evaporator room is provided with secondary vapor outlet, liquidometer mouth, liquidometer mouth and crosses material liquid outlet; Described heating chamber is provided with heating vapor inlet, not condensing outlet, condensation-water drain, water of condensation import; Described circulation tube is established effective body fluid inlet, drain;
Described flash cooling crystallization kettle comprises evaporator room and crystallisation chamber, and the evaporator room of described flash cooling crystallization kettle is provided with negative pressure system interface and liquidometer mouth, and described crystallisation chamber is provided with fluid inlet, liquidometer mouth, slurry inlet, slurries outlet and drain.
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Cited By (4)
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| CN104556587A (en) * | 2015-01-13 | 2015-04-29 | 湖南大学 | Refuse leachate treatment method |
| CN105000740A (en) * | 2015-07-16 | 2015-10-28 | 广州市心德实业有限公司 | Garbage leachate treatment process and system |
| CN105645602A (en) * | 2016-03-30 | 2016-06-08 | 浙江大学 | Automatic fed-batch type efficient iron salt denitrification reaction device and automatic fed-batch type efficient iron salt denitrification reaction method for bacteria |
| CN107512808A (en) * | 2017-09-30 | 2017-12-26 | 李兴龙 | A kind of equipment for handling painting workshop biological wastewater |
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2014
- 2014-03-28 CN CN201420144633.5U patent/CN203820583U/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556587A (en) * | 2015-01-13 | 2015-04-29 | 湖南大学 | Refuse leachate treatment method |
| CN105000740A (en) * | 2015-07-16 | 2015-10-28 | 广州市心德实业有限公司 | Garbage leachate treatment process and system |
| CN105645602A (en) * | 2016-03-30 | 2016-06-08 | 浙江大学 | Automatic fed-batch type efficient iron salt denitrification reaction device and automatic fed-batch type efficient iron salt denitrification reaction method for bacteria |
| CN107512808A (en) * | 2017-09-30 | 2017-12-26 | 李兴龙 | A kind of equipment for handling painting workshop biological wastewater |
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