CN103435236A - Ion exchange-zero-valent iron-denitrifying bacteria coupling denitrification method - Google Patents
Ion exchange-zero-valent iron-denitrifying bacteria coupling denitrification method Download PDFInfo
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- CN103435236A CN103435236A CN2013104207463A CN201310420746A CN103435236A CN 103435236 A CN103435236 A CN 103435236A CN 2013104207463 A CN2013104207463 A CN 2013104207463A CN 201310420746 A CN201310420746 A CN 201310420746A CN 103435236 A CN103435236 A CN 103435236A
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Abstract
The invention provides an ion exchange-zero-valent iron-denitrifying bacteria coupling denitrification method. The ion exchange-zero-valent iron-denitrifying bacteria coupling denitrification method is characterized in that ion exchange resin is used for rapidly removing nitrate, and meanwhile, zero-valent iron and denitrifying bacteria are used for completing the biological denitrification and the harmless reduction of nitrate in water in which the ion exchange resin is regenerated, wherein the ion exchange resin is anion exchange resin with nitrate adsorption capacity, the zero-valent iron is 100-300 meshes of reductive iron powder, and the denitrifying bacteria are facultative anaerobic denitrifying bacteria which grow in an autotrophic manner by using hydrogen under an anaerobic condition. The ion exchange-zero-valent iron-denitrifying bacteria coupling denitrification method has the advantages that the ion exchange and the iron-bacteria coupling denitrification are optimized and combined, so that the reaction time is short in an iron-bacteria coupling process, the generation of toxic byproducts such as ammonium salt is inhibited, and meanwhile, the problems that the ion exchange denitrification is incomplete, lots of alkali liquor is needed for regenerating the ion exchange resin and the like are solved; the reaction and operation process is simple, conditions are easy to control, the removal speed of pollutants is high, and the secondary pollution is avoided.
Description
Technical field
The invention belongs to technical field of water pollution control, be specifically related to a kind of ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method.
Background technology
Autotrophic denitrification, especially hydrogen are supported denitrification, because its product is clean, it is little that water body environment is affected, are considered to a kind of more satisfactory denitrogenation method.Therefore, it is core that the hydrogen of take is supported denitrification, and development group symphysis thing denitride technology has become the focus of the outer scholar's research of Present Domestic, and its core is that the foster denitrifying bacterium of hydrogen searches out suitable hydrogen supply mode.And by itself and the bacterium combined structure denitrogenation of autotrophic denitrification compound system.Yet the solubleness of hydrogen in water is extremely low, the use of additional hydrogen source can reduce anti-nitration reaction speed greatly.
The hydrogen that Anaerobic Corrosion discharges can occur in Zero-valent Iron in water, supplies with the microorganism denitrification, changes nitrate nitrogen into harmless nitrogen.But in actual applications, still exist some problems to need to solve, first reaction usually need a couple of days even the time of several weeks just can complete, nitrate removal speed is too low; It two is to disengage a large amount of OH in the Zero-valent Iron corrosion process simultaneously
-ion, cause system water outlet pH too high.
Based on this, the present invention, by coupling Zero-valent Iron, denitrifying bacteria and anionite-exchange resin, on the one hand, utilizes the ability of ion exchange resin quick adsorption nitrate significantly to improve system response speed; On the other hand, a large amount of OH that utilize the iron bacteria Fourier Series expansion technique to disengage
-ion completes the regeneration of exchange resin, to realize recycling of resin.
Summary of the invention
The object of the invention is to for above-mentioned existing problems, a kind of ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method is provided, the method can improve nitrate removal speed, realizes the innoxious reduction of nitrate.
Technical scheme of the present invention:
A kind of ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method, with ion exchange resin fast eliminating nitrate, the water body nitrate that simultaneously utilizes Zero-valent Iron and denitrifying bacterium to complete biological denitrification and ion exchange resin regeneration carries out harmless reduction, described ion exchange resin is the anionite-exchange resin with nitrate adsorptive power, Zero-valent Iron is 100-300 order reductibility iron powder, denitrifying bacterium is under anaerobic condition, to utilize hydrogen to carry out the amphimicrobian denitrifying bacterium of autophyting growth, and step is as follows:
1) take the NaOH solution that hydrochloric acid that concentration is 1mol/L or concentration is 1mol/L regulates the question response water pH value to 6.5-7.5;
2) measure nitrate content in the question response water body;
3) according to nitrate content in water body and ion exchange resin exchange capacity, select suitable ion exchange resin type number also to determine the ion exchange resin actual amount, determine the Zero-valent Iron dosage;
4) determine the volume of required interpolation denitrifying bacterium bacterium liquid according to the pending water yield;
5) sealed reactor, react under 20-35 ℃ and get final product in 4-7 days.
Described ion exchange resin actual amount is 1.5-2.0 with the ratio of theoretical consumption, the ratio that wherein theoretical consumption is nitrate content and exchange capacity of resin in staying water.
The mass ratio of described Zero-valent Iron and nitrate is 20-40.
The mass ratio of described denitrifying bacterium bacterium liquid and the pending water yield is 0.02-0.05, and in denitrifying bacteria liquid, total plate count is 1.2-1.5 * 10
5cFU/mL.
The present invention is with nitrate in ion exchange resin quick adsorption water body, then by the coupling between Zero-valent Iron and denitrifying bacteria, by nitrate reduction, be gaseous nitrogen, utilize the hydroxide ion produced in Zero-valent Iron Anaerobic Corrosion process simultaneously, realize the regeneration of anionite-exchange resin.
The present invention has the following advantages:
1. support hydrogen autotrophic denitrification process with the zeroth order iron powder of surface passivation, the unfavorable factor in this conventional Zero-valent Iron reaction of ferroelectric oxide layer is converted into to the favourable condition of denitration reaction, at utmost suppress the generation that ammonium salt etc. has toxic byproduct;
2. ion-exchange and iron bacteria coupling denitrogenation is optimized to combination, on the one hand, solves long reaction time, water outlet pH in the iron bacteria coupling process and cross the problems such as high, on the other hand, also solved the ion-exchange denitration not thoroughly, need the problem such as a large amount of alkali liquid regenerations;
3. operation technique is simple, and condition is easily controlled, and pollutant removal speed is fast, non-secondary pollution.
The accompanying drawing explanation
The denitrogenation schematic flow sheet that Fig. 1 is ion-exchange-Zero-valent Iron-denitrifying bacteria Fourier Series expansion technique.
Fig. 2 is ion-exchange-Zero-valent Iron-denitrifying bacteria Fourier Series expansion technique scanning electron microscopy.
Fig. 3 is ion-exchange-Zero-valent Iron-denitrifying bacteria coupling nitrogen removal performance curve.
Embodiment
The present invention further illustrates by reference to the accompanying drawings by following examples, but the described technology contents of the present embodiment is only illustrative, indefiniteness, should not limit to according to this use range of the present invention.
Embodiment 1:
A kind of ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method, with ion exchange resin fast eliminating nitrate, the water body nitrate that simultaneously utilizes Zero-valent Iron and denitrifying bacterium to complete biological denitrification and ion exchange resin regeneration carries out harmless reduction, described ion exchange resin is the anionite-exchange resin with nitrate adsorptive power, Zero-valent Iron is 300 order reductibility iron powders, denitrifying bacterium is under anaerobic condition, to utilize hydrogen to carry out the amphimicrobian denitrifying bacterium of autophyting growth, and step is as follows:
1) pending former volume of water is 1L, with 1 mol/L hydrochloric acid soln, regulates question response water pH value to 7.0;
2) take in this water body of determined by ultraviolet spectrophotometry nitrate content as 50 mg/L(with N);
3) selecting 717 anionite-exchange resin, exchange capacity is that 54.5 mg/mL are reacted, and calculating resin demand is 1.5mL, and 300 order reductibility iron powder consumptions are 1.5g;
4) determine that Ralstonia eutropha bacterium liquid consumption is 25mL, total plate count 1.2 * 10
5cFU/mL;
5) sequentially add the bacterium liquid of ion exchange resin, Zero-valent Iron and denitrifying bacterium according to the above-mentioned dosage calculated in the 1.2L glass reactor, and sealed reactor, set temperature is 25 ℃, and successive reaction 7 days is monitored nitrate in water, nitrite, amounts of ammonium salt every day and got final product.
The denitrogenation schematic flow sheet that Fig. 1 is ion-exchange-Zero-valent Iron-denitrifying bacteria Fourier Series expansion technique.
Fig. 3 is ion-exchange-Zero-valent Iron-denitrifying bacteria coupling nitrogen removal performance curve.In figure, show: after 7 days, the nitrate removal rate reaches more than 85%, and without nitrite and ammonium salt, produces in system.With simple use Zero-valent Iron-denitrifying bacterium, compare, nitrate removal speed is able to remarkable lifting, only needs can realize in 2 hours the removal of nitrate.
Fig. 2 is ion-exchange-Zero-valent Iron-denitrifying bacteria Fourier Series expansion technique scanning electron microscopy, in figure, show: due to microorganism growth in resin surface, having hindered Zero-valent Iron directly contacts and reduction reaction occurs with the nitrate on being adsorbed in resin, thereby in the denitrogenation product, the ratio of ammonium salt is able to remarkable reduction.
Embodiment 2:
A kind of ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method, with ion exchange resin fast eliminating nitrate, the water body nitrate that simultaneously utilizes Zero-valent Iron and denitrifying bacterium to complete biological denitrification and ion exchange resin regeneration carries out harmless reduction, described ion exchange resin is the anionite-exchange resin with nitrate adsorptive power, Zero-valent Iron is 100 order reductibility iron powders, denitrifying bacterium is under anaerobic condition, to utilize hydrogen to carry out the amphimicrobian denitrifying bacterium of autophyting growth, and step is as follows:
1) pending former volume of water is 1.5L, with 1 mol/L hydrochloric acid soln, regulates question response water pH value to 7.0;
2) take in this water body of determined by ultraviolet spectrophotometry nitrate content as 65 mg/L(with N);
3) selecting 717 anionite-exchange resin, exchange capacity is that 54.5 mg/mL are reacted, and calculating resin demand is 2.0mL, and 100 order reductibility iron powder consumptions are 2.0g;
4) determine that Ralstonia eutropha bacterium liquid consumption is 45mL, total plate count 1.2 * 10
5cFU/mL;
5) sequentially add the bacterium liquid of ion exchange resin, Zero-valent Iron and denitrifying bacterium according to the above-mentioned dosage calculated in the 1.2L glass reactor, and sealed reactor, set temperature is 25 ℃, and successive reaction 5 days is monitored nitrate in water, nitrite, amounts of ammonium salt every day and got final product.
This embodiment ion-exchange-Zero-valent Iron-denitrifying bacteria coupling nitrogen removal performance curve and scanning electron microscopy are substantially the same manner as Example 1.
Claims (4)
1. an ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method, it is characterized in that: with ion exchange resin fast eliminating nitrate, the water body nitrate that simultaneously utilizes Zero-valent Iron and denitrifying bacterium to complete biological denitrification and ion exchange resin regeneration carries out harmless reduction, described ion exchange resin is the anionite-exchange resin with nitrate adsorptive power, Zero-valent Iron is 100-300 order reductibility iron powder, denitrifying bacterium is under anaerobic condition, to utilize hydrogen to carry out the amphimicrobian denitrifying bacterium of autophyting growth, and step is as follows:
1) take the NaOH solution that hydrochloric acid that concentration is 1mol/L or concentration is 1mol/L regulates the question response water pH value to 6.5-7.5;
2) measure nitrate content in the question response water body;
3) according to nitrate content in water body and ion exchange resin exchange capacity, select suitable ion exchange resin type number also to determine the ion exchange resin actual amount, determine the Zero-valent Iron dosage;
4) determine the volume of required interpolation denitrifying bacterium bacterium liquid according to the pending water yield;
5) sealed reactor, react under 20-35 ℃ and get final product in 4-7 days.
2. ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method according to claim 1, it is characterized in that: described ion exchange resin actual amount is 1.5-2.0 with the ratio of theoretical consumption, the ratio that wherein theoretical consumption is nitrate content and exchange capacity of resin in staying water.
3. ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method according to claim 1, it is characterized in that: the mass ratio of described Zero-valent Iron and nitrate is 20-40.
4. ion-exchange-Zero-valent Iron-denitrifying bacteria coupling denitrogenation method according to claim 1, it is characterized in that: the mass ratio of described denitrifying bacterium bacterium liquid and the pending water yield is 0.02-0.05, and in denitrifying bacteria liquid, total plate count is 1.2-1.5 * 10
5cFU/mL.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271599A (en) * | 2014-06-06 | 2016-01-27 | 中国科学院沈阳应用生态研究所 | Processing method for nitrate-polluted raw water |
| CN105906072A (en) * | 2016-06-22 | 2016-08-31 | 同济大学 | Method for removing perchlorate in water |
| CN106746178A (en) * | 2016-11-23 | 2017-05-31 | 南京华淳环保股份有限公司 | A kind of sewage deep denitrification process based on the transfer of nitrate nitrogen Chemical Decomposition physics |
| CN107445294A (en) * | 2017-08-25 | 2017-12-08 | 安徽优科生态农业有限公司 | A kind of breeding water body denitrification processing particle and preparation method thereof |
| CN110156107A (en) * | 2019-06-11 | 2019-08-23 | 泉州南京大学环保产业研究院 | The processing method of low concentration nitrate nitrogen waste water |
| CN112143505A (en) * | 2020-08-31 | 2020-12-29 | 华南理工大学 | Cadmium-polluted soil and underground water repairing agent and method for repairing cadmium-polluted soil and underground water by using same |
| CN113044976A (en) * | 2021-03-22 | 2021-06-29 | 北京工业大学 | Water treatment device and method for strengthening anaerobic ammonia oxidation |
-
2013
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| 童桂华等: "离子交换树脂去除水中硝酸盐的研究", 《工业用水与废水》, vol. 39, no. 4, 31 August 2008 (2008-08-31), pages 73 - 76 * |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271599A (en) * | 2014-06-06 | 2016-01-27 | 中国科学院沈阳应用生态研究所 | Processing method for nitrate-polluted raw water |
| CN105271599B (en) * | 2014-06-06 | 2017-12-26 | 中国科学院沈阳应用生态研究所 | A kind of processing method of azotate pollution raw water |
| CN105906072A (en) * | 2016-06-22 | 2016-08-31 | 同济大学 | Method for removing perchlorate in water |
| CN106746178A (en) * | 2016-11-23 | 2017-05-31 | 南京华淳环保股份有限公司 | A kind of sewage deep denitrification process based on the transfer of nitrate nitrogen Chemical Decomposition physics |
| CN106746178B (en) * | 2016-11-23 | 2020-03-20 | 南京华淳环保股份有限公司 | Advanced sewage denitrification process based on chemical separation-physical transfer of nitrate and nitrogen |
| CN107445294A (en) * | 2017-08-25 | 2017-12-08 | 安徽优科生态农业有限公司 | A kind of breeding water body denitrification processing particle and preparation method thereof |
| CN110156107A (en) * | 2019-06-11 | 2019-08-23 | 泉州南京大学环保产业研究院 | The processing method of low concentration nitrate nitrogen waste water |
| CN112143505A (en) * | 2020-08-31 | 2020-12-29 | 华南理工大学 | Cadmium-polluted soil and underground water repairing agent and method for repairing cadmium-polluted soil and underground water by using same |
| CN113044976A (en) * | 2021-03-22 | 2021-06-29 | 北京工业大学 | Water treatment device and method for strengthening anaerobic ammonia oxidation |
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