CN103936192B - High-concentration ammonia-nitrogen wastewater treatment process - Google Patents
High-concentration ammonia-nitrogen wastewater treatment process Download PDFInfo
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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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