A kind of minimizing technology of high concentration sulfamate waste water total nitrogenTechnical field
The present invention relates to technical field of waste water processing more particularly to a kind of removals of high concentration sulfamate waste water total nitrogenMethod.
Background technique
Sulfamic acid is important fine chemical product, be widely used in metal and ceramics manufacture a variety of industrial equipments andIn the every field such as civilian cleaning agent, electroplating industry agent, electrochemical polish agent, efficient bleaching agent, standard analysis reagent.ThisA little industries using sulfamic acid are likely to generate the waste water for being rich in sulfamate, especially electrical type, plating class industry,Sulfamate can contribute higher total nitrogen in waste water.
Nitrogen-containing pollutant enters water body, be easy to cause water eutrophication, can cause the natural calamities such as wawter bloom, red tide, meetingLead to water hypoxia, make water quality deterioration, cause aquatic organism mortality, human health can be threatened, will seriously affect social economyIt develops in a healthy way.
Electrical type, plating class industry often only focus on the processing of heavy metal, do not have in technique special in the processing of waste waterFor the processing of sulfamate, cause total nitrogen content in water outlet excessively high.Sulfamic acid is soluble easily in water, but chemical property is stablized.Individual treatment process, the high perhaps treatment effect of processing cost is bad or the processing time is too long.
The processing of electrical type, plating class industry waste water mainly uses chemical precipitation method, chemistry redox method, electrolysis at presentMethod, Coagulation Method, gas floatation process, absorption method, ion-exchange, membrane separation process etc..Chemical process maturation, equipment investment are relativelyProvince, operating cost are lower, and large-scale wastewater treatment plant is more using chemical method, but the sludge containing heavy metal amount that chemical precipitation generatesGreatly, not easy to handle and cause secondary pollution.Although electrolysis method handles electroplating wastewater technical maturity, stable and reliable operation, the methodPower consumption is big, at high cost.Ion-exchange processing cost is high, and technique requires complexity, and resin is easily broken in use to make itPopularization and application are restricted.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of removal side of high concentration sulfamate waste water total nitrogenMethod is effectively reduced the content of sulfamate waste water total nitrogen, reaches discharge standard.
The present invention also technical problems to be solved are, provide a kind of removal side of high concentration sulfamate waste water total nitrogenMethod, step is few, and operating cost is few, at low cost.
In order to solve the above-mentioned technical problems, the present invention provides a kind of removal sides of high concentration sulfamate waste water total nitrogenMethod, for handling the waste water containing sulfamate, comprising the following steps:
(1) sulfamate waste water is collected；
(2) acid solution is added into sulfamate waste water, the pH value of sulfamate waste water is adjusted to less than 5；
(3) the sulfamate waste water in whipping step (2), and nitrite is added, until sulfamate waste water notBubble is generated again, wherein the molal weight of nitrite and the molal weight of sulfamate are equal；
(4) alkaline solution is added to the sulfamate waste water of step (3), the pH value of sulfamate waste water is adjusted to6.5-8 stands, obtains sediment and supernatant；
(5) by step (4) supernatant take out, be placed in another container, to supernatant be added denitrifying bacteria andCarbon source, the dosage of the denitrifying bacteria are 5-500mg/L, and the dosage of the carbon source is 5:1-15:1 meter according to C:N ratioIt calculates.
As an improvement of the above scheme, further comprising the steps of between step (2) and step (3): measuring process (2)The sulfamic acid salinity of middle waste water；
It is further comprising the steps of between step (3) and step (4): the nitrite of waste water in measuring process (3), ifThe concentration of nitrite is 0, then supplements nitrite according to the concentration of 0.05-0.15g/L, until nitrite nitrogen concentration >0。
As an improvement of the above scheme, the denitrifying bacteria is produced by pseudomonas mendocina, Pseudomonas stutzeri and excrementOne or more of alkali bacillus composition.
As an improvement of the above scheme, the carbon source is by glucose, sodium acetate, sodium citrate, sodium succinate and tartaric acidOne or more of potassium sodium composition.
As an improvement of the above scheme, the denitrifying bacteria is more Sa pseudomonads, and the carbon source is glucose.
As an improvement of the above scheme, the pH value of the sulfamate waste water in step (2) is adjusted to 2 or less than 2.
As an improvement of the above scheme, the pH value of the sulfamate waste water in step (4) is adjusted to 7-7.5.
As an improvement of the above scheme, the nitrite in step (3) is sodium nitrite or potassium nitrite.
As an improvement of the above scheme, the acid solution in step (2) is hydrochloric acid, sulfuric acid or phosphoric acid.
As an improvement of the above scheme, the alkaline solution in step (4) is sodium hydroxide solution.
The invention has the following beneficial effects:
The present invention rapidly removes the high concentration sulfamic acid in waste water by the way that nitrite is added, to reduce subsequentThe processing load of denitrifying bacteria；In addition, ensureing nitrite and sulfamate by the dosage of control nitriteSufficiently reaction, avoids remaining nitrite from introducing excessive total nitrogen.
Further, it is remaining total to remove waste water using biochemical denitrification by the way that denitrifying bacteria is added by the present inventionNitrogen, method is simple, and running cost is low, effectively drops total nitrogen to discharge standard hereinafter, avoiding secondary pollution.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention will be made below further detailedDescription.
A kind of minimizing technology of high concentration sulfamate waste water total nitrogen provided by the invention contains amino sulphur for handlingThe waste water of hydrochlorate, comprising the following steps:
(1), sulfamate waste water is collected；
(2), acid solution is added into sulfamate waste water, the pH value of sulfamate waste water is adjusted to less than 5；
In order to accelerate the reaction speed of sulfamate and nitrite, keep reaction more complete, the present invention is adding AsiaBefore nitrate, the pH value of sulfamate waste water is first transferred to 5 or less.When sulfamate waste water pH be greater than 5, amino sulphurHydrochlorate and nitrite cannot react, therefore cannot remove sulfamate.PH value, can chemically reactive between 2-5But reaction is incomplete.Preferably, the pH value of the sulfamate waste water in step (2) is adjusted to 2 or less than 2.PH value 1-2 itBetween, it chemically reacts basic relatively more complete.More preferably, the pH value of the sulfamate waste water in step (2) is adjusted to 1 or less than 1.PH value is transferred to 1 and hereinafter, chemical reaction is completely and fast.Wherein, the acid solution in step (2) is hydrochloric acid, sulfuric acid or phosphoric acid.
(3), the sulfamate waste water in whipping step (2), and nitrite is added, until sulfamate waste water notBubble is generated again；
Sulfamate in waste water is resolved into sulphur by the way that nitrite is added to sulfamate waste water by the present inventionHydrochlorate and nitrogen, to reduce the content of Determination of Total Nitrogen in Waste Water.It should be noted that due to sulfamate can resolve into nitrogen toOuter spilling, therefore when no longer generating bubble in waste water, that is, complete the decomposition of sulfamate.Preferably, it is added in step (3)Nitrite molal weight it is equal with the molal weight of sulfamate.Because excessive nitrite needs denitrification thinBacterium removes, and increases the processing load of denitrifying bacteria.Nitrite of the invention is sodium nitrite or potassium nitrite.It is preferred that, nitrite of the invention is sodium nitrite.
Wherein, in the case where not can determine that sulfamate concentration, the test paper or reagent of test nitrite can be usedTo be determined.
Specifically, the additive amount of nitrite is calculated according to the densimeter of sulfamic acid in waste water, after nitrite is addedIt stirs evenly, measures nitrite nitrogen concentration, nitrite nitrogen concentration is 0, then illustrates that nitrite is not excessive, according to 0.05-The concentration of 0.15g/L supplements nitrite, until nitrite nitrogen concentration > 0, i.e. nitrite are excessive, can stop continuingAdd nitrite.It should be noted that nitrite is supplemented according to the concentration of 0.05-0.15g/L, it will not mistake excessiveAmount is too many, and best situation is exactly sulfamate and nitrite equivalent, but practical somewhat difficult to control, so nitrite canIt is a little excessive suitably to have, but should not be excessively too many.Preferably, nitrite is supplemented according to the concentration of 0.08-0.12g/L.More preferably, nitrite is supplemented according to the concentration of 0.1g/L.
(4), alkaline solution is added to the sulfamate waste water of step (3), the pH value of sulfamate waste water is adjustedFor 6.5-8, stands, obtain sediment and supernatant；
After sulfamate in waste water has been decomposed, the pH value of waste water is adjusted to 6.5-8 by the present invention, to obtainSediment and supernatant.The sediment is generally hydroxide sediment.Since pH value of the waste water before step (4) is less than5, be not suitable for the growth of denitrifying bacteria, influence the denitrification of denitrifying bacteria.Therefore, the present invention is to add denitrification thinBefore bacterium, it is necessary to which the pH value for adjusting waste water is 6.5-8, could fully remove total nitrogen.In addition, the present invention is by the pH value tune of waste waterSection is 6.5-8, the metal ion in waste water can also be formed to sediment, and then remove the metal ion in waste water.Preferably,The pH value of sulfamate waste water in step (4) is adjusted to 7-7.5.
In order to not influence the denitrification of denitrifying bacteria, the present invention is by sediment and supernatant separation in step (4).Specifically, can by directly topple over or siphon mode by step (4) supernatant take out, be placed in another container.Wherein,The sediment is pressed dry, is disposed according to waste sludge.
(5), by step (4) supernatant take out, be placed in another container, to supernatant be added denitrifying bacteria andCarbon source, the dosage of the nitrobacteria are 5-500mg/L, and the dosage of the carbon source is 5:1-15:1 calculating according to C:N ratio.
In order to further remove the nitrite and remaining total nitrogen in waste water, the total nitrogen of the waste water is made to reach discharge markDenitrifying bacteria and carbon source is added to supernatant in standard, the present invention, and the dosage of the denitrifying bacteria is 5-500mg/L.If anti-The dosage of nitrobacteria is lower than 5mg/L, and the time that bacterium starting needs is longer, works slow, if denitrifying bacterium dosage is greater than500mg/L, then dosage is improved, it is unobvious to onset time shortening, increase cost instead.Within the scope of 5-500mg/L, increaseDenitrifying bacterium dosage can significantly shorten the processing time, and be greater than 500mg/L and increasing the dosage processing time without being obviously shortened.
Wherein, the dosage of the carbon source is 5:1-15:1 calculating according to C:N ratio.If carbon-nitrogen ratio is lower than 5, denitrificationNot exclusively, still there is more total nitrogen in system；In 5:1-15:1, total nitrogen degradation effect increases carbon-nitrogen ratio with the raising of carbon-nitrogen ratioBy force；If carbon-nitrogen ratio is greater than 15, then improves carbon-nitrogen ratio, better total nitrogen degradation effect will not be obtained, increases cost instead.
Preferably, the dosage of the denitrifying bacteria is 50-200mg/L, and the dosage of the carbon source is according to C:N ratio8:1-12:1 is calculated.
It should be noted that denitrifying bacteria is by pseudomonas mendocina, Pseudomonas stutzeri and Bacillus foecalis alkaligenesOne or more composition；Carbon source is by one of glucose, sodium acetate, sodium citrate, sodium succinate and sodium potassium tartrate tetrahydrate or severalKind composition.Preferably, carbon source is made of one or more of glucose, sodium acetate and sodium citrate.More preferably, carbon source is lemonLemon acid sodium.
Wherein, for the removal of total nitrogen, denitrifying bacteria and carbon source are indispensable, more Sa pseudomonads collocation glucose,It is not only at low cost, it is easy to get, and efficiencies of nitrogen removal is good.
The present invention rapidly removes the high concentration sulfamic acid in waste water by the way that nitrite is added, to reduce subsequentThe processing load of denitrifying bacteria；In addition, ensureing nitrite and sulfamate by the dosage of control nitriteSufficiently reaction, avoids remaining nitrite from introducing excessive total nitrogen.
Further, it is remaining total to remove waste water using biochemical denitrification by the way that denitrifying bacteria is added by the present inventionNitrogen, method is simple, and running cost is low, effectively drops total nitrogen to discharge standard hereinafter, avoiding secondary pollution.
Below the present invention will be illustrated with specific embodiment
Embodiment 1
(1) the sulfamic acid nickel waste water of certain electronic material industrial group output is collected；
(2) hydrochloric acid is added in sulfamic acid nickel waste water, the pH value of waste water is adjusted to 2；
(3) whipping step (2) waste water, and sodium nitrite is added, until no longer generating bubble, the nitrous acid of addition in waste waterThe molal weight of sodium and the molal weight of sulfamate are equal；
(4) sodium hydroxide solution is added to step (3) waste water, the pH value of waste water is adjusted to 7.5, stands, obtains hydroxideNickel sediment and supernatant；
(5) supernatant in step (4) is taken out, is placed in another container, it is false that 500mg/L Amur is added to supernatantMonad and 400mg/L sodium acetate.
It wherein, will be useless behind biochemical reaction 6 days in the supernatant and step (5) in waste water in step (1), step (4)Water is tested, as a result as shown in the table:
"-" expression does not detect this project.
Embodiment 2
(1) the sulfamic acid nickel waste water of certain electronic material industrial group output is collected；
(2) hydrochloric acid is added in sulfamic acid nickel waste water, the pH value of waste water is adjusted to 1；
(3) whipping step (2) waste water, and sodium nitrite is added, until no longer generating bubble, the nitrous acid of addition in waste waterThe molal weight of sodium and the molal weight of sulfamate are equal；
(4) sodium hydroxide solution is added to step (3) waste water, the pH value of waste water is adjusted to 8, stands, obtains nickel hydroxideSediment and supernatant；
(5) supernatant in step (4) is taken out, is placed in another container, 100mg/L excrement is added to supernatant and produces alkaliBacillus and 4000mg/L sodium acetate.
It wherein, will be useless behind biochemical reaction 6 days in the supernatant and step (5) in waste water in step (1), step (4)Water is tested, as a result as shown in the table:
| Project | Total nitrogen (mg/L) | Total phosphorus (mg/L) | Nitrate nitrogen (mg/L) | Nitrite nitrogen (mg/L) |
| Raw water | 1126 | 10.3 | 8.28 | 1.02 |
| Supernatant | 83.4 | 24.1 | 4.27 | 49.8 |
| After processing | 14.3 | 5.80 | 2.83 | 0.02 |
Embodiment 3
(1) the sulfamic acid nickel waste water of certain electronic material industrial group output is collected；
(2) hydrochloric acid is added in sulfamic acid nickel waste water, the pH value of waste water is adjusted to 1；
(3) whipping step (2) waste water, and sodium nitrite is added, until no longer generating bubble, the nitrous acid of addition in waste waterThe molal weight of sodium and the molal weight of sulfamate are equal；
(4) sodium hydroxide solution is added to step (3) waste water, the pH value of waste water is adjusted to 7.5, stands, obtains hydroxideNickel sediment and supernatant；
(5) supernatant in step (4) is taken out, is placed in another container, it is false single that the more Sas of 5mg/L are added to supernatantBorn of the same parents bacterium and 500mg/L glucose.
It wherein, will be useless behind biochemical reaction 6 days in the supernatant and step (5) in waste water in step (1), step (4)Water is tested, as a result as shown in the table:
| Project | Total nitrogen (mg/L) | Total phosphorus (mg/L) | Nitrate nitrogen (mg/L) | Nitrite nitrogen (mg/L) |
| Raw water | 220 | 2.31 | 3.21 | 0.12 |
| Supernatant | 21.0 | 2.12 | 1.23 | 16.2 |
| After processing | 10.2 | 3.91 | 2.19 | 0.17 |
In the experiment of embodiment 1-3, using the sulfamic acid root water accounting of various concentration as variable, as a result showPreferable total nitrogen removal effect, total nitrogen are discharged in 15mg/L hereinafter, meeting " discharge standard for electroplating pollutants " (GB21900-2008) quality standard as defined in table 3 in.
Above disclosed is only a preferred embodiment of the present invention, cannot limit the power of the present invention with this certainlySharp range, therefore equivalent changes made in accordance with the claims of the present invention, are still within the scope of the present invention.