CN105271599A - Processing method for nitrate-polluted raw water - Google Patents
Processing method for nitrate-polluted raw water Download PDFInfo
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- CN105271599A CN105271599A CN201410253080.1A CN201410253080A CN105271599A CN 105271599 A CN105271599 A CN 105271599A CN 201410253080 A CN201410253080 A CN 201410253080A CN 105271599 A CN105271599 A CN 105271599A
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Abstract
The invention belongs to the field of environment protection and water processing, and provides a processing method for nitrate-polluted raw water. According to the method, at an ion exchange link, nitrate-polluted raw water is changed into formate-containing ion exchange effluent water by enabling formate functional group to take part in anion exchange resin regeneration, and then formats in the effluent water is removed through aerobic digestion or a denitrification process. Under the premise of properly increasing the ion exchange effluent water processing cost, the processing and cyclic utilization difficulty of high-nitrate high-salt resin regeneration wastewater is reduced, and the method is extremely suitable for large-scale processing of nitrate-polluted underground water and nitrate pollution treatment of circulating-water culture systems.
Description
Technical field
The invention belongs to environment protection and water treatment field, the treatment process of the former water of a kind of azotate pollution is provided.
Background technology
In agriculture production, the poor efficiency of N fertilizer utilizes, and the process of municipal wastewater and solid waste is mishandling, causes in a large amount of N element entered environment, and is finally present in soil and various earth's surface, lowly water body mainly with the form of nitrate.Wherein, mass-producing, intensive industrialized agriculture, livestock industry, fish production and city refuse landfill are particularly evident on the impact of nitrates accumulation in soil and water environment.
Nitrate is that the one of plant can utilize N form, but Soil Nitrate is easy to along with the soil water moves downwards, particularly in half moistening, semiarid area, quite a few Soil Nitrate is not in plant root layer region, and finally along with the motion of the soil water, enters body of groundwater.Therefore, the groundwater azotate pollution of a lot of northern area of China is serious.
Nitrate enters in human body by diet, can change intestinal tract microenvironment, is unfavorable for the activity of beneficial functions flora; Also may be converted into nitrite and be combined with oxyphorase, making it lose oxygen carrying capacity; Or be combined with organic amine material, generate carcinogenic substance.
Water body nitrate pollutes the healthy growth being also unfavorable for aquatic products, livestock and poultry cultivation animal.After have accumulated the nitrate of high density in water body, both bring disadvantageous effect directly to fish production, caused body eutrophication again, cause blue algae bloom.For intensive fish production, because use fish-bait feedstuff in a large number, aquaculture water nitrate concentration rises rapidly, accelerates water quality and degenerates, reduce aquaculture benefit, and frequently changing water increases aquaculture cost, and not processing directly outer row can endanger environment.This disadvantageous effect, the northern area lacked in water resources is particularly remarkable.
To sum up, nature and the azotate pollution of artificial water, create disadvantageous effect to the production of people and life.No matter be that underground drinking water source nitrate exceeds standard, or surface water body (such as aquaculture water) azotate pollution, all need the removal nitrate that pursues the proper method, to eliminate its disadvantageous effect.
In water, the minimizing technology of nitrate mainly contains physico-chemical processes, chemical method and biochemical process.Physico-chemical processes mainly contains distillation, electrodialysis, reverse osmosis, ion-exchange etc.Wherein, former three does not have selectivity, except also been removed other element useful to human body in water while nitre; Ion exchange method is quick, is easy to Automated condtrol, but produces high nitre high-salt wastewater.In fact, all physics chemistry method is transfer and enrichment nitrate just, and the nitrate wastewater of generation needs to carry out suitable subsequent disposal, environment of being allowed for access.But, in the water-deficient area that rainwash is less, regenerate brine, except after nitre or can not outer row easily, because outer salt discharge water is not easy to be taken away by rainwash, but finally enters underground mostly, thus the salinization of promotion soil and groundwater.Therefore, in water-deficient area, recycle ion exchange resin denitration regenerate brine, could reduce its disadvantageous effect to environment to greatest extent.
Chemical reduction can be reductive agent with the active metal such as aluminium, iron simple substance except nitre method, can be also reductive agent with hydrogen, formic acid etc., reduce nitrate under catalyst action.In addition, photochemistry, electrochemical catalysis process also can be adopted for removing nitrate in water.But, all these chemical processes, all easily form nitrite or ammonium class by product, practical application is also subject to the restriction of factors.
Biological denitrification is denitrifying bacterium is the process of nitrogen by nitrate reduction, comprises autotrophy and heterotrophic denitrification two type.Wherein, autotrophic denitrification is using the inorganics such as hydrogen, elemental sulfur as electron donor, and denitrification rate is comparatively slow, but it is better to go out water quality.But, hydrogen solubility is low, explosive, and hydrogen autotrophic denitrification large-scale application is difficult; Sulphur autotrophic denitrification can produce sulfate radical and acidity, is only suitable for treatment of nitric acid salt and exceeds standard not serious and that sulfate concentration is not high former water.Heterotrophic denitrification is using organic carbon source as electron donor, and denitrification rate is very fast, but carbon source interpolation control overflow is high, and excessive meeting is residual and increase subsequent disposal difficulty, adds deficiency and easily causes water outlet nitrite to be accumulated.
The respective advantage playing ion exchange method and chemical method or biochemical process can be combined, with the former water nitrate of ion exchange method transfer enrichment, then thoroughly remove the high concentration nitrate in using ion-exchange resin regenerated waste water with chemistry, biochemical mode.But, high nitre height salt ion exchanges the biochemistry of waste water or chemistry except nitre and all acquires a certain degree of difficulty.Therefore, Selective ion mode exchange process removes nitrate in water, needs if desired to consider the practical problems in ion-exchange and regeneration link.When ion-exchange water outlet quality is not by considerable influence, can considers to change ion exchange mode, comprise and change regenerator etc., to improve the composition of resin regeneration water, reduction biochemistry or chemistry, except the difficulty of nitre, promote the recycle of resin regeneration water.
Summary of the invention
The object of the invention is the treatment process providing the former water of a kind of azotate pollution.
For achieving the above object, the technical solution adopted in the present invention is:
A treatment process for the former water of azotate pollution, by allowing formate participate in anionite-exchange resin regeneration, in ion-exchange link, becomes the former water of azotate pollution into the ion-exchange water outlet containing formate, and the biochemical formate removed wherein.
The above-mentioned ion-exchange water outlet containing formate removes wherein formate by aerobic sigestion; Or ion-exchange water outlet mixes with the former water of azotate pollution, make the mol ratio of nitrate radical and formate in mixing water be 2:7-8, then denitrification synchronously removes formate and nitrate.
Wherein, formate participates in anionite-exchange resin regeneration link, and in regenerate brine, the molar concentration rate of formate and total negatively charged ion is more than 50%.
Control the mol ratio >4:1 of formate and chlorion in resin regeneration brine, thus ion-exchange water outlet is capable of circulation for aquaculture after accepting formate Transformatin.
Control the mol ratio >1:1 of formate and chlorion in resin regeneration brine, thus ion-exchange water outlet can be used for drinking object after accepting formate Transformatin.
The device for the treatment of of nitric acid salt polluted raw comprises, former pond, ion exchange resin column, formate biochemical treatment reactor, aftertreatment pond, resin regeneration pump sump, resin regeneration first stage outlet sump, calcium sulfate precipitation pond, resin regeneration subordinate phase outlet sump, resin cleaning pump sump and resin cleaning outlet sump.
The present invention is advantageously:
1. the present invention is by ion-exchange means, the removal of former water nitrate is converted into the removal of formate, removes former water nitrate relative to biochemistry, and difficulty and the COD load of biochemical removal formate significantly reduce.
2. the high nitre height salt resin regenerative wastewater for the treatment of process of the present invention based on formate, regulates and controls its pH on a large scale and regulates and controls to be very easy to, be applicable to biochemical and chemical process process, to realize recycle.
3. treatment process of the present invention is after microorganism aerobic or denitrification are removed formate, do not increase salinity in ion-exchange water outlet but add bicarbonate alkalinity, both extensive treating groundwater azotate pollution was applicable to, also circulating water cultivation system is suitable for, reduce cultivation water pH and control difficulty, improve the cyclic utilization rate of water.
Accompanying drawing explanation
Fig. 1 is the device of the treatment process of the embodiment of the present invention former water of azotate pollution used.
Wherein, 1. former pond, 2. ion exchange resin column, 3. formate biochemical treatment reactor, 4. aftertreatment pond, 5. resin regeneration pump sump, 6. resin regeneration first stage outlet sump, 7. calcium sulfate precipitation pond, 8. resin regeneration subordinate phase outlet sump, 9. resin cleaning pump sump, 10 resins clean outlet sumies.
Embodiment
Embodiment 1
As shown in Figure 1, former pond 1 water outlet, resin regeneration first stage outlet sump 6 water-in, resin regeneration subordinate phase outlet sump 8 water-in are communicated with one end of ion exchange resin column 2 is parallel respectively by the valvular pipeline of band with resin cleaning outlet sump 10 water-in; Formate biochemical treatment reactor 3 water-in, resin regeneration pump sump 5 water outlet are communicated with the other end of ion exchange resin column 2 is parallel respectively by the valvular pipeline of band with resin cleaning pump sump 9 water outlet.
Ion exchange resin treatment is containing the former water of nitre: the high 100cm of ion exchange column 2, inside fills out the 717 type anionite-exchange resin regenerated.Former water is Simulated Water aquaculture waste, and pH value is 7.4, and nitrate concentration is 6mmol/L, and sulfate concentration is 2mmol/L, and chlorine ion concentration is 6mmol/L, bicarbonate concentration 2mmol/L.Open the valve of former pond 1 water outlet and formate biochemical treatment reactor 3 water-in, under 20-24 DEG C of condition, with the former water of flow velocity process of 13.5BV/h.Move to 6 hours, the nitrate concentration in water outlet, more than 2mmol/L, is closed above-mentioned two valves, is entered the resin regeneration stage.
Ion exchange resin regeneration and cleaning: resin regeneration liquid contains 0.07N sodium-chlor and 0.7N sodium formiate.First opening resin regeneration pump sump 5 and resin regeneration first stage outlet sump 6 Inlet and outlet water valve, is that 4.0BV/h carries out first stage resin regeneration with flow velocity.After 1 hour, during regenerative wastewater sulfate concentration <80mmol/L, close the inlet valve of resin regeneration first stage outlet sump 6, open the inlet valve of resin regeneration subordinate phase outlet sump 8, carry out subordinate phase resin regeneration with the flow velocity of 4.0BV/h.After 2.5 hours, regenerative wastewater nitrate concentration is 18.5mmol/L, closes the Inlet and outlet water valve of resin regeneration pump sump 5 and resin regeneration subordinate phase outlet sump 8.Open the Inlet and outlet water valve of resin cleaning pump sump 9 and resin cleaning outlet sump 10, former water after spent ion exchange resin process, with the flow velocity of 5.5BV/h, cleaning resin 1 hour, then close resin cleaning pump sump 9 and resin cleaning outlet sump 10 Inlet and outlet water valve, complete regeneration of ion-exchange resin and cleaning.
The collection of resin regeneration waste water: the regenerative wastewater that resin regeneration first stage outlet sump 6 is collected enters calcium sulfate precipitation pond 7, add excessive calcium formiate, produce calcium sulfate precipitation, vitriol residual concentration is made to be down to below 60mmol/L, then the supernatant liquor in calcium sulfate precipitation pond 7 is imported resin regeneration subordinate phase outlet sump 8, collect a certain amount of after, in order to biochemical or chemistry except nitre.
The aerobic treatment of water outlet is exchanged: formate biochemical treatment reactor 3 is made up of the activated charcoal filter (effective volume 350mL) of long 40mL internal diameter 5cm and the aerobic aeration pond of 10L containing formate ions.Before formal process ion-exchange water outlet, activated charcoal filter with the active sludge of municipal sewage plant for bacterial origin, with 6mmol/L sodium formiate for carbon source, activated charcoal filter water inlet and synchronous (the every 6 minutes intervals of aerobic aeration, water inlet and equal 1 minute of aeration, each water inlet 200mL), carry out the enrichment culture of formate aerobic oxidation bacterium, each loop cycle 2 days, continue after 8 days, formic acid processing load reaches more than 80mgCOD/L/h, and the aerobic filtration started for ion-exchange water outlet formate is removed.Formal disposition is as follows: collect ion-exchange water outlet 7L in aerobic aeration pond, wherein formate concentration is 9.4mmol/L, every 6 minutes intervals, water inlet and aeration 1 minute, each water inlet 200mL, runs formate concentration <0.2mmol/L after 48 hours; Water outlet after formate aerobic treatment enters aftertreatment pond 4 and clarifies, for aquaculture object.
Embodiment 2
The structure of ion exchange resin column, the collection of resin regeneration waste water are identical with embodiment 1.
The former water of ion exchange resin treatment: former water is simulation nitrate superstandard drinking water, and pH value is 7.3, and nitrate concentration is 3.0mmol/L, and sulfate concentration is 1.0mmol/L, and chlorine ion concentration is 1.0mmol/L, bicarbonate concentration 1mmol/L.Open the valve being communicated with former pond 1 water outlet and formic acid biochemical treatment reactor 3 water-in, under 20-24 DEG C of condition, with the former water of flow velocity process of 13.5BV/h.Move to 10 hours, the nitrate concentration in water outlet, more than 0.7mmol/L, is closed above-mentioned two valves, is entered the resin regeneration stage.
Ion exchange resin regeneration and cleaning: resin regeneration liquid contains 0.18N sodium-chlor and 0.7N sodium formiate.First opening resin regeneration pump sump 5 and resin regeneration first stage outlet sump 6 Inlet and outlet water valve, is that 4.0BV/h carries out first stage resin regeneration with flow velocity.After 1 hour, during regenerative wastewater sulfate concentration <80mmol/L, close the inlet valve of resin regeneration first stage outlet sump 6, open the inlet valve of resin regeneration subordinate phase outlet sump 8, carry out subordinate phase resin regeneration with the flow velocity of 4.0BV/h.After 2.5 hours, regenerative wastewater nitrate concentration is 15.2mmol/L, closes the Inlet and outlet water valve of resin regeneration pump sump 5 and resin regeneration subordinate phase outlet sump 8.Open the Inlet and outlet water valve of resin cleaning pump sump 9 and resin cleaning outlet sump 10, former water after spent ion exchange resin process, with the flow velocity of 5.5BV/h, cleaning resin 1 hour, then close resin cleaning pump sump 9 and resin cleaning outlet sump 10 Inlet and outlet water valve, complete regeneration of ion-exchange resin and cleaning.
The denitrification biochemical treatment of ion-exchange water outlet: formate biochemical treatment reactor 3 is made up of the activated charcoal filter (effective volume 700mL) of long 80mL internal diameter 5cm.Before formal process ion-exchange water outlet, activated charcoal filter with the active sludge of municipal sewage plant for bacterial origin, with 4.0mmol/L sodium formiate for carbon source, with 1.0mmol/L SODIUMNITRATE for electron acceptor(EA), carry out the denitrifying bacteria enrichment culture that water stopping time is 40 minutes, 10 days by a definite date, when pending formic acid load reaches more than 70mgCOD/L/h, the synchronous removal of start to exceed standard for ion-exchange water outlet and the nitrate mixed formate of former water and nitrate.Formal disposition is as follows: with reference to the formate mean concns (2.7mmol/L) of ion-exchange water outlet, ion-exchange water outlet and nitrate exceed standard after former water mixes in the ratio of 6:1, enter formate biochemical treatment reactor 3, water stopping time is 30 minutes, water outlet NO3-N and NO2-N concentration is all lower than 0.05mmol/L, and concentration of formate greater is lower than 0.1mmol/L; The water outlet of denitrification process enters in aftertreatment pond 4, after sand filtration, activated carbon filtration and ozonization, for tap water object.
Claims (5)
1. a treatment process for the former water of azotate pollution, is characterized in that: by allowing formate participate in anionite-exchange resin regeneration, in ion-exchange link, becomes the former water of azotate pollution into the ion-exchange water outlet containing formate, and the biochemical formate removed wherein.
2., by the treatment process of the former water of azotate pollution according to claim 1, it is characterized in that:
Ion-exchange water outlet containing formate removes wherein formate by aerobic sigestion; Or ion-exchange water outlet mixes with the former water of azotate pollution, make the mol ratio of nitrate radical and formate in mixing water be 2:7-8, then denitrification synchronously removes formate and nitrate.
3., by the treatment process of the former water of azotate pollution according to claim 1, it is characterized in that:
Formate participates in anionite-exchange resin regeneration link, and in regenerate brine, the molar concentration rate of formate and total negatively charged ion is more than 50%.
4., by the treatment process of the former water of azotate pollution described in Claims 2 or 3, it is characterized in that:
Control the mol ratio >4:1 of formate and chlorion in resin regeneration brine, thus ion-exchange water outlet is capable of circulation for aquaculture after accepting formate Transformatin.
5., by the treatment process of the former water of azotate pollution described in Claims 2 or 3, it is characterized in that:
Control the mol ratio >1:1 of formate and chlorion in resin regeneration brine, thus ion-exchange water outlet can be used for drinking after accepting formate Transformatin.
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| CN201410253080.1A CN105271599B (en) | 2014-06-06 | 2014-06-06 | A kind of processing method of azotate pollution raw water |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4479877A (en) * | 1983-07-28 | 1984-10-30 | The United States Of America As Represented By The Administrator Environmental Protection Agency | Removal of nitrate from water supplies using a tributyl amine strong base anion exchange resin |
| US4944878A (en) * | 1989-11-16 | 1990-07-31 | Iowa State University Research Foundation, Inc. | Decontamination of water using nitrate selective ion exchange resin |
| CN101746926A (en) * | 2009-12-11 | 2010-06-23 | 中国海洋大学 | Method for removing nitrate in drinking water and process thereof |
| CN103435236A (en) * | 2013-09-16 | 2013-12-11 | 农业部环境保护科研监测所 | Ion exchange-zero-valent iron-denitrifying bacteria coupling denitrification method |
-
2014
- 2014-06-06 CN CN201410253080.1A patent/CN105271599B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4479877A (en) * | 1983-07-28 | 1984-10-30 | The United States Of America As Represented By The Administrator Environmental Protection Agency | Removal of nitrate from water supplies using a tributyl amine strong base anion exchange resin |
| US4944878A (en) * | 1989-11-16 | 1990-07-31 | Iowa State University Research Foundation, Inc. | Decontamination of water using nitrate selective ion exchange resin |
| CN101746926A (en) * | 2009-12-11 | 2010-06-23 | 中国海洋大学 | Method for removing nitrate in drinking water and process thereof |
| CN103435236A (en) * | 2013-09-16 | 2013-12-11 | 农业部环境保护科研监测所 | Ion exchange-zero-valent iron-denitrifying bacteria coupling denitrification method |
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