CN103172194A - Process for realizing manganese-containing wastewater recycling - Google Patents
Process for realizing manganese-containing wastewater recycling Download PDFInfo
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- CN103172194A CN103172194A CN2011104447330A CN201110444733A CN103172194A CN 103172194 A CN103172194 A CN 103172194A CN 2011104447330 A CN2011104447330 A CN 2011104447330A CN 201110444733 A CN201110444733 A CN 201110444733A CN 103172194 A CN103172194 A CN 103172194A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 67
- 239000011572 manganese Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 41
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 27
- 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
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 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
- 238000006243 chemical reaction Methods 0.000 description 4
- 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
- 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
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 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
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, the Mn-bearing waste water mn ion is processed up to standard, by follow-up except the ammonia unit further removing ammonium radical ion in water, make its resource utilization generate the struvite slow-release fertilizer, and reclaim and to contain the qualified slurries of manganese, realize the technique of Mn-bearing waste water recycle.
Background technology
Manganese has very important strategic position in China's economy, mainly as reductor and the sweetening agent in ironmaking and steelmaking process, and be used for alloying.China is a manganese ore big country, accounts for the 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.Existing treatment technology to Mn-bearing waste water is mainly and adopts iron reduction method and lime neutralisation that it is processed, but above-mentioned technology is not carried out the 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) that it is processed, the 2nd, utilize biological method that it is processed.
One kind of Chinese patent ZL200910040863 prepares the method for manganous carbonate take slag containing Mn and waste water as raw material, adopt oxalic acid reduction Manganse Dioxide wherein, be that ferric iron forms precipitation of hydroxide with hydrogen peroxide oxidation ferrous iron wherein, and with ammonia neutralization sulfuric acid wherein, remove heavy metal ion with the ammonium sulfide precipitation again, concentrate and obtain the ammonium manganous sulfate crystallization; Ammonium manganous sulfate and bicarbonate of ammonia reaction prepare manganous carbonate, can obtain ammonium sulfate simultaneously.
Chinese patent ZL200810143859 treatment method for manganese-containing wastewater biological agent according to Manganese in Waste Water concentration, is that 0.2～1.2: 1 ratio adds biotechnological formulation according to biotechnological formulation/manganese mass ratio under whipped state; 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 the Mn-bearing waste water technical matters, carries out the reaction of materialization or bioid on the basis of adding medicament, obtains supernatant liquor and discharges or return the technique use, and manganese element and medicament reaction generate manganese salt, are back to production technique.But the manganese salt concn in the uncontrollable recovery slurries of above patent, and must obtain manganese salt under the condition of adding medicament, being difficult to accomplish need not add medicament, the qualified slurries that can generate different concns are back to production.
Summary of the invention
The objective of the invention is, design a kind of technique that realizes the Mn-bearing waste water recycle, with Mn-bearing waste water by ultra filtration unit, nano-filtration unit, reverse osmosis units, except the ammonia unit it being carried out Treatment and recovery, make that in Mn-bearing waste water, mn ion 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 the Mn-bearing waste water recycle; And further remove the ammonium radical ion by follow-up except the ammonia unit, reach the synchronous purpose that realizes of wastewater treatment and resource utilization.
For achieving the above object, technical scheme of the present invention is a kind of technique that realizes the Mn-bearing waste water recycle, comprises ultra filtration unit, nano-filtration unit, reverse osmosis units, except the 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, use safety with protection subsequent ultrafiltration membrane module, enter ultra filtration unit, after ultrafiltration, fresh water enters nano-filtration unit (being the manganous sulfate recovery process), and dense water returns to further processing except the ammonia unit;
(2) nano-filtration unit: adopt secondary nanofiltration series connection, after ultrafiltration, fresh water enters nano-filtration unit, circulate by pipeline and hold back the manganous sulfate of waste water, improve in the dense water of nanofiltration and contain manganese ion concentration, make the qualified slurries of 10000-36000mg/L different concns, return and use in production system, the secondary nano-filtration unit can be useed security system as, with the auxiliary 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 ammonium radical ion in nano-filtration unit fresh water, make the mn ion qualified discharge, and hold back a part of ammonium radical ion;
(4) except the 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 the struvite dilution is fertile, water outlet continues to take the chlorination oxidation removal, removes from waste water thereby ammonia nitrogen is oxidized to nitrogen; And establish the diatomite adsorption device in the rear end, residual ammonium root in Adsorption waste water is guaranteed the recovery up to standard of water outlet ammonium radical ion or discharging.
A kind of technique that realizes the Mn-bearing waste water recycle as above, its ultra filtration unit adopt some the ultra-filtration membranes of filling the 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 the Mn-bearing waste water recycle as above, its nano-filtration unit adopt 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 the 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 the Mn-bearing waste water recycle as above, its except the ammonia unit adopts add medicament and generate the struvite precipitation after, 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 the manganese process for reclaiming synchronizeing with ammonium radical ion Transformatin and carrying out, reduced the difficulty of subsequent disposal ammonium radical ion, make the ammonium radical ion realize resource utilization, generate the struvite slow-release fertilizer, technique is produced water and is far smaller than primary standard in " integrated wastewater discharge standard ", generation contain manganese concentration at the qualified slurries direct reuse of 10000mg/L-36000mg/L in production technique, realize the recycle of Mn-bearing waste water, opened up Treatment of Wastewater With Manganese and resource technology frontier.The present invention is applicable to the Mn-bearing waste water utilization process.
Description of drawings
Fig. 1 is a kind of process flow sheet of realizing the 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 the ammonia unit, 10-struvite slow-release fertilizer, 11-diatomite adsorption device, 12-Mn-bearing waste water, the 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 the Mn-bearing waste water recycle, by ultra filtration unit, two-stage nano-filtration unit, reverse osmosis units, except the 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) uses safety; operate in less than carrying out under 0.3MPa pressure; 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 that produces 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 through topping-up pump by nanofiltration fresh-water tank (7) and the salt clearance is reached 99% reverse osmosis units (8), continue to remove mn ion and the ammonium radical ion that contains in fresh water after secondary nano-filtration unit (5) is processed, dense water returns to nanofiltration fresh-water tank (7).
4. except the ammonia unit: the fresh water that reverse osmosis units (8) produces continues to enter except ammonia unit (9).Hold back on the basis of removing a part of ammonium radical ion at reverse osmosis units (8), 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 the struvite damping fluid, water outlet continues to take the chlorination oxidation removal, removes from waste water thereby ammonia nitrogen is oxidized to nitrogen; And establish diatomite adsorption device (11) in the rear end, 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, namely by ultra filtration unit, nano-filtration unit, reverse osmosis units, except the ammonia unit, containing the manganese concentrated solution after processing is that in qualified slurries, the manganous sulfate ionic concn is 10000-36000mg/L, draining is better than " integrated wastewater discharge standard " (GB8978-1996) primary standard in 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, namely by ultra filtration unit, nano-filtration unit, reverse osmosis units, except the ammonia unit, contain after processing more than in the manganese concentrated solution, the manganous sulfate ionic concn reaches 10000mg/L, draining reaches " integrated wastewater discharge standard " (GB8978-1996) primary standard in table 4, be total manganese≤2mg/L, SS≤70mg/L, COD＜100mg/l.
Claims (5)
1. technique that realizes the Mn-bearing waste water recycle by ultra filtration unit, nano-filtration unit, reverse osmosis units, except the ammonia unit forms, 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) uses safety, operate in less than carrying out under 0.3MPa pressure, 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 that produces 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 through topping-up pump by nanofiltration fresh-water tank (7) and the salt clearance is reached 99% reverse osmosis units (8), continue to remove mn ion and the ammonium radical ion that contains 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 ammonia unit employing 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 the struvite damping fluid, water outlet continues to take the chlorination oxidation removal, removes from waste water thereby ammonia nitrogen is oxidized to nitrogen; And establish diatomite adsorption device (11) in the rear end, 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 the 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 the hollow fiber ultrafiltration membrane material and forms.
3. a kind of technique that realizes the 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, two-stage nano-filtration unit (5) core filled high polymer nanofiltration membrane material forms.
4. a kind of technique that realizes the 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 the Mn-bearing waste water recycle as claimed in claim 1, is characterized in that, after ammonia unit (9) employing interpolation medicament generation struvite slow-release fertilizer precipitation, supernatant liquor flows into rear end diatomite adsorption device (11) and processes.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104176857A (en) * | 2014-09-12 | 2014-12-03 | 上海三夫工程技术有限公司 | Treatment technique of manganese-containing wastewater in wet electrolytic manganese production process |
| 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 |
| CN107324516A (en) * | 2017-06-29 | 2017-11-07 | 广州市金强工贸发展有限公司 | A kind of sewage treatment process |
| CN107381847A (en) * | 2017-06-29 | 2017-11-24 | 广州市金强工贸发展有限公司 | A kind of effluent cycle handling process capable of washing |
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| CN109851084A (en) * | 2018-12-19 | 2019-06-07 | 国家海洋局天津海水淡化与综合利用研究所 | Reduce the recycling processing method of ammonia nitrogen in Mn-bearing waste water, calcium and magnesium ion content |
| CN109851084B (en) * | 2018-12-19 | 2022-01-25 | 自然资源部天津海水淡化与综合利用研究所 | Resourceful treatment method for reducing content of ammonia nitrogen, calcium and magnesium ions in manganese-containing wastewater |
| CN111362471A (en) * | 2020-04-17 | 2020-07-03 | 莱特莱德（北京）环境技术股份有限公司 | Device for removing sodium sulfate in coal chemical industry byproduct sodium chloride saturated solution |
| CN112553481A (en) * | 2020-12-11 | 2021-03-26 | 中南大学 | Production method of electrolytic manganese |
| CN112742345A (en) * | 2020-12-29 | 2021-05-04 | 广西风向标环保科技有限公司 | Wastewater dephosphorization and denitrification treatment method of modified diatomite |
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