CN103936192B - High-concentration ammonia-nitrogen wastewater treatment process - Google Patents
High-concentration ammonia-nitrogen wastewater treatment process Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000001471 micro-filtration Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical group [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 27
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 238000005374 membrane filtration Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- -1 phosphate anion Chemical class 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 4
- 230000008439 repair process Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003337 fertilizer Substances 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 229960002261 magnesium phosphate Drugs 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000009388 chemical precipitation Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000026487 Triploidy Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- QLFFCLRSMTUBEZ-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].[Na].OP(O)(O)=O QLFFCLRSMTUBEZ-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Fertilizers (AREA)
Abstract
The invention relates to a high-concentration ammonia-nitrogen wastewater treatment process which comprises the following steps: (1) adding magnesium salt and phosphate into wastewater to be treated according to the ammonia-nitrogen concentration of the wastewater, wherein the molar ratio of NH<3->N:Mg<2+>: PO4<3-> in the wastewater is controlled at 1:(2-3.5):(1.5-3.0); and adjusting the pH value of the wastewater by a sodium hydroxide solution to 8.5-9, and stirring for 3-5 minutes; (2) after full reaction, filtering the wastewater by a micro-filtration membrane, wherein effluent generated after filtering by the micro-filtration membrane is the wastewater without ammonia-nitrogen; and dehydrating concentrated solution (separated out after filtration of the micro-filtration membrane) by a plate-and-frame filter press; and (3) after dehydration by the plate-and-frame filter press, refluxing the obtained filtrate and mixing with the wastewater to be treated, wherein the main component of the filter residue is struvite which is directly recovered as an agricultural fertilizer or is regenerated to be recycled. The process provided by the invention is low in cost, and not only can treat ammonia-nitrogen in the wastewater to reach the discharge standard, but also can recycle useful components from the wastewater.
Description
Technical field
The present invention relates to environmental technology field, specifically relate to a kind of high-concentration ammonia nitrogenous wastewater treatment process.
Background technology
Develop growth rapidly at present along with the industry such as chemical fertilizer, petrochemical complex, the high ammonia-nitrogen wastewater produced therefrom also becomes one of industry development restraining factors.It is reported, there is red tide up to up to a hundred times in annual China marine site, and ammonia nitrogen is the pollution that one of major reason polluted, particularly high-concentration ammonia nitrogenous wastewater cause.
High-concentration ammonia nitrogenous wastewater treatment technology common at present has blow-off method, vaporizing extract process, distillation method and chemical precipitation method etc.
Blow-off method utilizes the difference existed between the actual concentrations of the volatile matter such as ammonia nitrogen contained in waste water and equilibrium concentration, use air stripping in the basic conditions, make the volatile matter such as the ammonia nitrogen in waste water constantly transfer in gas phase by liquid phase, thus reach the object removing ammonia nitrogen from waste water.Vaporizing extract process is a kind of special stripping method utilizing steam to replace air.Stripping and stripping process high-concentration ammonia nitrogenous wastewater effect are better, but this method must consume the pH value that a large amount of medicaments regulates waste water; According to vaporizing extract process, also need to consume a large amount of energy in the production process of steam.
Distillation method utilizes the boiling point of each component in waste water different, the method making the ammonia nitrogen in waste water be converted into gaseous state to remove from waste water by heated waste water.Although distillation method is simple, this method needs waste water to be heated to comparatively high temps, and energy consumption is high, and it is remaining still to have a certain amount of ammonia nitrogen after distillation in waste water, is difficult to reach emission standard.
Chemical precipitation method in waste water, adds medicament make the ammonia in waste water form the method precipitating and remove from waste water.Chemical precipitation method for treating ammonia nitrogen waste water technical process is simple, and water outlet ammonia nitrogen can accomplish qualified discharge, but the method exists the large shortcoming of settling tank floor space.
Therefore, the treatment process developing a kind of high-concentration ammonia nitrogenous wastewater of economical rationality seems particularly important.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides the high-concentration ammonia nitrogenous wastewater treatment process that a kind of cost is low.
The technical scheme that the present invention solves the employing of its technical problem is that a kind of high-concentration ammonia nitrogenous wastewater treatment process, comprises following concrete steps:
(1) according to the ammonia nitrogen concentration of pending waste water, in waste water, add magnesium salts and phosphoric acid salt, make NH in waste water
3-N ︰ Mg
2+︰ PO
4 3-mol ratio control 1 ︰ (2 ~ 3.5) ︰ (1.5 ~ 3.0), simultaneously with sodium hydroxide solution regulate waste water ph be 8.5 ~ 9, stir 3 ~ 5 minutes;
Described magnesium salts and phosphoric acid salt can adopt commercially available chemical reagent, also can adopt regenerative agent of the present invention (treatment step see continuous under the present invention);
(2) will process through step (1), abundant reacted waste water filtered by microfiltration membrane, after micro-filtration membrane filtration, water outlet is the waste water after removal of ammonia and nitrogen, and the concentrated solution separated after micro-filtration membrane filtration is then by plate-and-frame filter press processed;
(3), after plate-and-frame filter press processed, the backflow of gained filtrate mixes with step (1) pending waste water; Filter residue main component is struvite, can directly reclaim as agricultural fertilizer, also can regenerate Posterior circle and use.
Further, in step (1), the preferred magnesium chloride of described magnesium salts, described phosphoric acid salt preferably phosphoric acid disodium hydrogen.
Further, in step (2), the preferred cross flow filter of mode of described micro-filtrate membrane filtration.
The reclaiming of filter residue can be adopted with the following method: joining in the water being equivalent to filter residue 3 ~ 4 times of volumes by the solid filter residue obtained in step (3), is 8 ~ 8.5 by sodium hydroxide solution adjust ph, be heated to >=120 DEG C, keep regenerating for 1 ~ 2 hour.The gas produced in regenerative process can reclaim acquisition ammoniacal liquor, solution after regeneration can use (contain the magnesium ion reacted with ammonia nitrogen in waste water and phosphate anion in the solution after regeneration, can directly join in waste water as a solution) as the compound of magnesium ion and phosphate anion that provides in step (1).
Beneficial effect of the present invention is as follows:
1) this technique can process the ammonia nitrogen in waste water, makes it meet emission standard, also can reclaim composition useful in waste water;
2) compared with the chemical precipitation method of routine, utilize microfiltration membrane to replace settling tank, the floor space of project can be reduced, the incomplete problem of the sludge settling that may run in precipitation process can also be solved;
3) part retained in micro-filtrate membrane filtration process directly can enter pressure filter and carry out press filtration process, saves the step of sludge condensation, reduces the expense of building sludge thickener;
4) microporous filtration adopts the mode of cross flow filter, filter required pressure less, the work-ing life of film can be extended, and the shearing force that wastewater streams produces when face can take away the pollutent that face retains, reduce the probability of face blocking, reduce the frequency of back flushing;
5) this technique carries out manipulation of regeneration recycle to the filter residue produced, and decreases the consumption of medicament.
The equal Absorbable organic halogens ground of the rate of recovery of magnesium of the present invention and phosphorus reaches more than 85%, and in waste water, the rate of recovery of ammonia nitrogen can reach more than 90%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.Without departing from the idea case in the present invention described above, the various replacement made according to ordinary skill knowledge and customary means or change, all should comprise within the scope of the invention.
Embodiment 1
Certain electrolytic manganese factory, water outlet ammonia nitrogen concentration 800 ~ 1000mg/L, pH value is 4 ~ 6.
The high-concentration ammonia nitrogenous wastewater treatment process of the present embodiment, comprises following concrete steps:
(1) pending waste water is sent into reaction tank, in reaction tank, add magnesium chloride, Sodium phosphate dibasic, make NH in waste water
3-N ︰ Mg
2+︰ PO
4 3-mol ratio is 1:2.5:1.5, and hydro-oxidation sodium regulates waste water ph to 8.5 simultaneously, reacts 5 minutes;
(2) will process through step (1), abundant reacted waste water sent into microporous filtration and filtered by microfiltration membrane, after micro-filtration membrane filtration, water outlet is the waste water after removal of ammonia and nitrogen, and the concentrated solution separated after micro-filtration membrane filtration is then by plate-and-frame filter press processed;
The mode of described micro-filtrate membrane filtration is cross flow filter;
Ammonia nitrogen in waste water concentration stabilize after the present embodiment removal of ammonia and nitrogen, at 8 ~ 10mg/L, reaches " integrated wastewater discharge standard " (GB8978-1996) primary standard;
(3), after plate-and-frame filter press processed, the backflow of gained filtrate mixes with step (1) pending waste water; Filter residue main component is struvite, can directly reclaim as agricultural fertilizer, also can regenerate Posterior circle and use.
The reclaiming of filter residue is adopted with the following method: the solid filter residue obtained in step (3) joined and be equivalent to, in the long-pending water of filter residue triploid, by sodium hydroxide solution adjust ph to 8, be heated to 120 DEG C, keep regenerating for 2 hours.The gas recovery produced in regenerative process obtains ammoniacal liquor, and the solution after regeneration can use as the compound of magnesium ion and phosphate anion that provides in step (1).
The rate of recovery of the present embodiment magnesium and phosphorus all can reach 85%, and in waste water, the rate of recovery of ammonia nitrogen reaches 90%.
Embodiment 2
Certain electrolytic manganese factory, water outlet ammonia nitrogen concentration 800 ~ 1000mg/L, pH value is 4 ~ 6.
The high-concentration ammonia nitrogenous wastewater treatment process of the present embodiment, comprises following concrete steps:
(1) pending waste water is sent into reaction tank, in reaction tank, add magnesium chloride, SODIUM PHOSPHATE, MONOBASIC, make NH in waste water
3-N ︰ Mg
2+︰ PO
4 3-mol ratio is 1:3.5:3.0, and hydro-oxidation sodium regulates waste water ph to 9 simultaneously, reacts 3 minutes;
(2) will process through step (1), abundant reacted waste water sent into microporous filtration and filtered by microfiltration membrane, after micro-filtration membrane filtration, water outlet is the waste water after removal of ammonia and nitrogen, and the concentrated solution separated after micro-filtration membrane filtration is then by plate-and-frame filter press processed;
The mode of described micro-filtrate membrane filtration is cross flow filter;
Ammonia nitrogen in waste water concentration stabilize after the present embodiment removal of ammonia and nitrogen, at 8 ~ 11mg/L, reaches " integrated wastewater discharge standard " (GB8978-1996) primary standard;
(3), after plate-and-frame filter press processed, the backflow of gained filtrate mixes with step (1) pending waste water; Filter residue main component is struvite, can directly reclaim as agricultural fertilizer, also can regenerate Posterior circle and use.
The reclaiming of filter residue is adopted with the following method: join in the water being equivalent to filter residue 4 times of volumes by the solid filter residue obtained in step (3), by sodium hydroxide solution adjust ph to 8.5, is heated to 130 DEG C, keeps regenerating for 2 hours.The gas recovery produced in regenerative process obtains ammoniacal liquor, and the solution after regeneration can use as the compound of magnesium ion and phosphate anion that provides in step (1).
The rate of recovery of the present embodiment magnesium and phosphorus all can reach 88%, and in waste water, the rate of recovery of ammonia nitrogen reaches 92%.
Claims (3)
1. a high-concentration ammonia nitrogenous wastewater treatment process, is characterized in that, comprises following concrete steps:
(1) according to the ammonia nitrogen concentration of pending waste water, in waste water, add magnesium salts and phosphoric acid salt, make NH in waste water
3-N ︰ Mg
2+︰ PO
4 3-mol ratio control 1 ︰ (2 ~ 3.5) ︰ (1.5 ~ 3.0), simultaneously with sodium hydroxide solution regulate waste water ph be 8.5 ~ 9, stir 3 ~ 5 minutes;
Described magnesium salts and phosphoric acid salt adopt commercially available chemical reagent or regenerative agent of the present invention;
(2) will process through step (1), abundant reacted waste water filtered by microfiltration membrane, after micro-filtration membrane filtration, water outlet is the waste water after removal of ammonia and nitrogen, and the concentrated solution separated after micro-filtration membrane filtration is then by plate-and-frame filter press processed;
The mode of described micro-filtrate membrane filtration is cross flow filter;
(3), after plate-and-frame filter press processed, the backflow of gained filtrate mixes with step (1) pending waste water; Filter residue main component is struvite, and regeneration Posterior circle uses;
The reclaiming of filter residue is adopted with the following method: joining in the water being equivalent to filter residue 3 ~ 4 times of volumes by the solid filter residue obtained in step (3), is 8 ~ 8.5 by sodium hydroxide solution adjust ph, be heated to >=120 DEG C, keep regenerating for 1 ~ 2 hour; The gas recovery produced in regenerative process obtains ammoniacal liquor, and the solution after regeneration uses as the compound of magnesium ion and phosphate anion that provides in step (1).
2. according to the treatment process of the high-concentration ammonia nitrogenous wastewater described in claim 1, it is characterized in that, in step (1), described magnesium salts is magnesium chloride.
3. according to the treatment process of the high-concentration ammonia nitrogenous wastewater described in claim 1, it is characterized in that, in step (1), described phosphoric acid salt is Sodium phosphate dibasic.
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CN107686192A (en) * | 2017-09-28 | 2018-02-13 | 辽宁工程技术大学 | A kind of phosphorous and Ammonia-nitrogen wastewater treatment technology |
CN108117190B (en) * | 2017-12-14 | 2021-04-02 | 瓮福(集团)有限责任公司 | Process for treating low-concentration ammonia nitrogen wastewater of phosphate fertilizer plant |
CN114195314A (en) * | 2021-12-23 | 2022-03-18 | 秦皇岛华恒生物工程有限公司 | Wastewater treatment method and application thereof |
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