CN103172194B - Process for realizing manganese-containing wastewater recycling - Google Patents
Process for realizing manganese-containing wastewater recycling Download PDFInfo
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- CN103172194B CN103172194B CN201110444733.0A CN201110444733A CN103172194B CN 103172194 B CN103172194 B CN 103172194B CN 201110444733 A CN201110444733 A CN 201110444733A CN 103172194 B CN103172194 B CN 103172194B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 67
- 239000011572 manganese Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 44
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title abstract 6
- 238000001728 nano-filtration Methods 0.000 claims abstract description 53
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013505 freshwater Substances 0.000 claims abstract description 25
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 ammonium ions Chemical class 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 12
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000003337 fertilizer Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 238000013016 damping Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 229940099596 manganese sulfate Drugs 0.000 abstract 1
- 235000007079 manganese sulphate Nutrition 0.000 abstract 1
- 239000011702 manganese sulphate Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000036470 plasma concentration Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a process for realizing manganese-containing wastewater recycling. The process comprises an ultra-filtration unit, a nano-filtration unit, a reverse osmosis unit and an ammonia removal unit and comprises the following steps of: taking the manganese-containing wastewater to the ultra-filtration unit through a lift pump and a filter, taking the ultra-filtration concentration water to the ammonia removal unit for further treatment, taking the fresh water into a primary nano-filtration unit to circulate to generate qualified manganese-containing slurry for realizing the recycling, taking the fresh water into a reverse osmosis system after the primary nano-filtration fresh water is taken into a secondary nano-filtration unit for further separation so as to further remove the manganese and ammonium ions contained in the wastewater certainly, returning the secondary nano-filtration concentration water to the primary nano-filtration circular process, discharging water through the reverse osmosis unit to further remove the ammonium ions by the ammonia removal unit, thus ensuring that the drainage is superior to the primary standard in the fourth table of Comprehensive Sewage Discharge Standard (GB8978-1996). The process for realizing manganese-containing wastewater recycling provided by the invention has the advantages of realizing the manganese-containing wastewater recycling and generating qualified manganese sulfate slurry and struvite slow-release fertilizer in high concentration and is suitable for the recycling process of manganese-containing wastewater. Furthermore, the produced water can meet the standard discharged requirements.
Description
Technical field
The invention belongs to Treatment of Wastewater With Manganese and resource utilization recovery technology field, be particularly related to and utilize ultrafiltration, nanofiltration, reverse osmosis membrane combination, Mn-bearing waste water mn ion is processed up to standard, by the follow-up ammonia unit that removes, further remove ammonium radical ion in water, make its resource utilization generate struvite slow-release fertilizer, and reclaim containing the qualified slurries of manganese, realize the technique of Mn-bearing waste water recycle.
Background technology
In Meng China economy, there is very important strategic position, mainly as reductor and the sweetening agent in ironmaking and steelmaking process, and be used for alloying.China Shi Yige manganese ore big country, accounts for second place of the world.Manganese in Mn-bearing waste water, ammonium root plasma concentration is high, process difficulty up to standard, not only causes the pollution of surrounding environment, and affects the environmental image of enterprise.The existing treatment technology to Mn-bearing waste water is mainly and adopts iron reduction method and lime neutralisation to process it, but above-mentioned technology is not carried out resource utilization recovery to manganese element, ammonia nitrogen element.
Treatment of Wastewater With Manganese and resource utilization have following two kinds of techniques at present: the one, and adopt physical chemistry method (extraction, coagulating sedimentation) to process it, the 2nd, utilize biological method to process it.
Mono-kind of Chinese patent ZL200910040863 be take slag containing Mn and waste water and is prepared the method for manganous carbonate as raw material, adopt oxalic acid reduction Manganse Dioxide wherein, with hydrogen peroxide oxidation ferrous iron wherein, be that ferric iron forms precipitation of hydroxide, and with ammonia neutralization sulfuric acid wherein, by ammonium sulfide precipitation, remove heavy metal ion again, concentrate and obtain ammonium manganous sulfate crystallization; Ammonium manganous sulfate reacts and prepares manganous carbonate with bicarbonate of ammonia, can obtain ammonium sulfate simultaneously.
Chinese patent ZL200810143859 treatment method for manganese-containing wastewater biological agent, according to Manganese in Waste Water concentration, the ratio that is 0.2～1.2: 1 according to biotechnological formulation/manganese mass ratio under whipped state adds biotechnological formulation; Complex reaction 20～40 minutes, adds alkali regulation system pH value to 9～11, and stir hydrolysis reaction 20～60 minutes, then add flocculation agent according to the ratio of 2～6mg/L, precipitate and separate, supernatant liquor returns to use.
Above patent relates to processes Mn-bearing waste water technical matters, carries out materialization or bioid reaction on the basis of adding medicament, obtains supernatant liquor and discharges or return technique use, and manganese element reacts with medicament and generates manganese salt, is back to production technique.But the manganese salt concn in the uncontrollable recovery slurries of above patent, and must under the condition of adding medicament, obtain manganese salt, being difficult to accomplish not need to add medicament, the qualified slurries that can generate different concns are back to production.
Summary of the invention
The object of the invention is, design a kind of technique that realizes Mn-bearing waste water recycle, by Mn-bearing waste water by ultra filtration unit, nano-filtration unit, reverse osmosis units, except ammonia unit it being carried out to Treatment and recovery, mn ion in Mn-bearing waste water is concentrated by film unit, make qualified slurries, be back to production, and produce the product water be strict in primary standard in sewage drainage standard and can be back to production technique as process water, realize Mn-bearing waste water recycle; And except ammonia unit, further remove ammonium radical ion by follow-up, reach the synchronous object realizing of wastewater treatment and resource utilization.
For achieving the above object, technical scheme of the present invention is a kind of technique that realizes Mn-bearing waste water recycle, comprises ultra filtration unit, nano-filtration unit, reverse osmosis units, removes ammonia unit, and its concrete operation is:
(1) ultra filtration unit: Mn-bearing waste water is delivered to deep bed filter or sand filtration strainer by lift pump, remove the suspended substance (SS) in waste water, with protection subsequent ultrafiltration membrane module, use safety, enter ultra filtration unit, after ultrafiltration, fresh water enters nano-filtration unit (being manganous sulfate recovery process), and dense water returns to further processing except ammonia unit;
(2) nano-filtration unit: adopt secondary nanofiltration series connection, after ultrafiltration, fresh water enters nano-filtration unit, by pipeline, circulate and hold back the manganous sulfate of waste water, improve in the dense water of nanofiltration containing manganese ion concentration, make the qualified slurries of 10000-36000mg/L different concns, return and use in production system, secondary nano-filtration unit can be useed security system as, to assist the requirement that guarantees to realize the qualified slurries of different concns;
(3) reverse osmosis units: in the fresh water that nano-filtration unit produces, manganese ion concentration does not reach emission request, enter follow-up reverse osmosis units and further remove mn ion and the ammonium radical ion in nano-filtration unit fresh water, make mn ion qualified discharge, and hold back a part of ammonium radical ion;
(4) except ammonia unit: hold back on the basis of removing most ammonium radical ions at reverse osmosis units, add SODIUM PHOSPHATE, MONOBASIC, make the magnesium ion in ammonium radical ion and waste water form magnesium ammonium phosphate sediment, be that struvite dilution is fertile, water outlet continues to take chlorination oxidation removal, thereby ammonia nitrogen is oxidized to nitrogen, from waste water, removes; And in rear end, establish diatomite adsorption device, residual ammonium root in Adsorption waste water, guarantees the recovery up to standard of water outlet ammonium radical ion or discharge.
A kind of technique that realizes Mn-bearing waste water recycle as above, its ultra filtration unit adopts some the ultra-filtration membranes of filling hollow fiber ultrafiltration membrane material to form, and the quantity of ultra-filtration membrane and model can arrange according to the different treatment water yield.
A kind of technique that realizes Mn-bearing waste water recycle as above, its nano-filtration unit adopts the nanofiltration membrane of some same model of the two poles of the earth filled high polymer nanofiltration membrane material to form, and quantity and the model of nanofiltration membrane can arrange according to the different treatment water yield in every grade.
A kind of technique that realizes Mn-bearing waste water recycle as above, its reverse osmosis units adopts some reverse osmosis membranes of filled high polymer material (as acetic acid acid cellulose and aromatic polyamides class) to form, and the quantity of reverse osmosis membrane and model can arrange according to the different treatment water yield.
A kind of technique that realizes Mn-bearing waste water recycle as above, it adds after medicament generation struvite precipitation except ammonia unit adopts, and supernatant liquor flows into rear end diatomite adsorption device and processes.
Positively effect of the present invention is, realize the processing of Mn-bearing waste water and reclaim manganese process for reclaiming and synchronize and carry out with ammonium radical ion Transformatin, reduced the difficulty of subsequent disposal ammonium radical ion, make ammonium radical ion realize resource utilization, generate struvite slow-release fertilizer, technique is produced water and is far smaller than primary standard in < < integrated wastewater discharge standard > >, produce containing manganese concentration at the qualified slurries direct reuse of 10000mg/L-36000mg/L in production technique, realized the recycle of Mn-bearing waste water, Treatment of Wastewater With Manganese and resource technology frontier have been opened up.The present invention is applicable to Mn-bearing waste water utilization process.
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet of realizing Mn-bearing waste water recycle of the present invention
In figure, 1-strainer, 2-ultra filtration unit, 3-ultrafiltration fresh-water tank, 4-one-level nano-filtration unit, 5-secondary nano-filtration unit, the qualified slurry tank of 6-, 7-nanofiltration fresh-water tank, 8-reverse osmosis units, 9-is except ammonia unit, 10-struvite slow-release fertilizer, 11-diatomite adsorption device, 12-Mn-bearing waste water, 13-draining, the qualified slurries of 14-
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
As shown in Figure 1, a kind of technique that realizes Mn-bearing waste water recycle, by ultra filtration unit, two-stage nano-filtration unit, reverse osmosis units, except ammonia unit forms, its concrete operation is:
1. ultra filtration unit: Mn-bearing waste water (12) is squeezed into strainer (1) through lift pump; with the suspended substance (SS) in waste water in removing; protection subsequent ultrafiltration unit (2) is used safety; operate in to be less than under 0.3MPa pressure and carry out; after ultrafiltration, freshet is to ultrafiltration fresh-water tank (3), and dense water is to further processing except ammonia unit (9).
2. nano-filtration unit: waste water is promoted to one-level nano-filtration unit (4) by ultrafiltration fresh-water tank (3) through topping-up pump, the dense water producing through one-level nano-filtration unit (4) enters qualified slurry tank (6), working pressure is at 1.0-3.0MPa, final qualified slurries (14) are back to electrolytic manganese production technique, the rear fresh water of one-level nano-filtration unit (4) enters secondary nano-filtration unit (5) and continues to hold back mn ion and ammonium radical ion, produce freshet to nanofiltration fresh-water tank (7), concentrate recirculation is concentrated again to one-level nano-filtration unit (4).
3. reverse osmosis units: waste water is flow to the reverse osmosis units (8) that salt clearance is reached to 99% through topping-up pump by nanofiltration fresh-water tank (7), continue to remove mn ion and the ammonium radical ion containing in fresh water after secondary nano-filtration unit (5) is processed, dense water returns to nanofiltration fresh-water tank (7).
4. except ammonia unit: the fresh water that reverse osmosis units (8) produces continues to enter except ammonia unit (9).At reverse osmosis units (8), hold back on the basis of removing a part of ammonium radical ion, except adopting, ammonia unit (9) adds SODIUM PHOSPHATE, MONOBASIC, make the magnesium ion in ammonium radical ion and waste water form magnesium ammonium phosphate sediment under pH8-9.5, reaction times 30-90min, sedimentation time 30-90min condition, it is struvite damping fluid, water outlet continues to take chlorination oxidation removal, thereby ammonia nitrogen is oxidized to nitrogen, from waste water, removes; And in rear end, establish diatomite adsorption device (11), residual ammonium root in Adsorption waste water, guarantees that draining/reuse water (13) ammonium radical ion is up to standard.
Case study on implementation one is Treatment of Wastewater With Manganese amount 500m
3/ d, in Mn-bearing waste water, mn ion content is 1500-2000mg/L, ammonia nitrogen is 2000mg/L, adopt as above-mentioned treatment process, pass through ultra filtration unit, nano-filtration unit, reverse osmosis units, remove ammonia unit, after processing, containing manganese concentrated solution, be that in qualified slurries, manganous sulfate ionic concn is 10000-36000mg/L, draining is better than the primary standard in < < integrated wastewater discharge standard > > (GB8978-1996) table 4, be total manganese≤0.5mg/L, ammonia nitrogen≤10mg/L, SS≤60mg/L.
Case study on implementation two is Treatment of Wastewater With Manganese amount 1200m
3/ d, in Mn-bearing waste water, mn ion content is 300-400mg/L, ammonia nitrogen is 2000mg/L, adopt as above-mentioned treatment process, pass through ultra filtration unit, nano-filtration unit, reverse osmosis units, remove ammonia unit, more than reaching 10000mg/L containing manganous sulfate ionic concn in manganese concentrated solution after processing, draining reaches the primary standard in < < integrated wastewater discharge standard > > (GB8978-1996) table 4, be total manganese≤2mg/L, SS≤70mg/L, COD < 100mg/l.
Claims (5)
1. realize a technique for Mn-bearing waste water recycle, by ultra filtration unit, nano-filtration unit, reverse osmosis units, except ammonia unit forms, it is characterized in that:
Mn-bearing waste water in ultra filtration unit (12) is squeezed into strainer (1) through lift pump, with the suspended substance in waste water in removing, protection subsequent ultrafiltration unit (2) is used safety, operate in to be less than under 0.3MPa pressure and carry out, after ultrafiltration, freshet is to ultrafiltration fresh-water tank (3), and dense water together enters follow-up nano-filtration unit with Mn-bearing waste water (12) before returning to lift pump;
In nano-filtration unit, waste water is promoted to one-level nano-filtration unit (4) by ultrafiltration fresh-water tank (3) through topping-up pump, the dense water producing through one-level nano-filtration unit (4) enters qualified slurry tank (6), working pressure is at 1.0-3.0MPa, final qualified slurries (14) are back to electrolytic manganese production technique, the rear fresh water of one-level nano-filtration unit (4) enters secondary nano-filtration unit (5) and continues to hold back mn ion and ammonium radical ion, produce freshet to nanofiltration fresh-water tank (7), concentrate recirculation is concentrated again to one-level nano-filtration unit (4);
Waste water is flow to the reverse osmosis units (8) that salt clearance is reached to 99% through topping-up pump by nanofiltration fresh-water tank (7), continue to remove mn ion and the ammonium radical ion containing in fresh water after secondary nano-filtration unit (5) is processed, dense water returns to nanofiltration fresh-water tank (7);
The fresh water that reverse osmosis units (8) produces continues to enter except ammonia unit (9), except adopting, ammonia unit adds SODIUM PHOSPHATE, MONOBASIC, make the magnesium ion in ammonium radical ion and waste water form magnesium ammonium phosphate sediment under pH8-9.5, reaction times 30-90min, sedimentation time 30-90min condition, it is struvite damping fluid, water outlet continues to take chlorination oxidation removal, thereby ammonia nitrogen is oxidized to nitrogen, from waste water, removes; And in rear end, establish diatomite adsorption device (11), residual ammonium root in Adsorption waste water, guarantees that draining (13) ammonium radical ion is up to standard.
2. a kind of technique that realizes Mn-bearing waste water recycle as claimed in claim 1, is characterized in that, ultra filtration unit (2) core department adopts by the ultra-filtration membrane of filling hollow fiber ultrafiltration membrane material and forms.
3. a kind of technique that realizes Mn-bearing waste water recycle as claimed in claim 1, is characterized in that, the nanofiltration membrane of one-level nano-filtration unit (4) and employing the two poles of the earth, secondary nano-filtration unit (5) core filled high polymer nanofiltration membrane material forms.
4. a kind of technique that realizes Mn-bearing waste water recycle as claimed in claim 1, is characterized in that, reverse osmosis units (8) adopts the reverse osmosis membrane of filled high polymer material to form.
5. a kind of technique that realizes Mn-bearing waste water recycle as claimed in claim 1, is characterized in that, except ammonia unit (9) adopts, adds after medicament generation struvite slow-release fertilizer precipitation, and supernatant liquor flows into rear end diatomite adsorption device (11) and processes.
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| CN104710032A (en) * | 2013-12-16 | 2015-06-17 | 中节能六合天融环保科技有限公司 | Resource process suitable for manganese-containing wastewater in electrolytic manganese production process |
| CN104176857B (en) * | 2014-09-12 | 2016-06-01 | 上海三夫工程技术有限公司 | The treatment process of Mn-bearing waste water in wet method electrolysis manganese production process |
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