CN101613148B - Method for removing nitrate nitrogen, corresponding combination preparation, and preparation method and application thereof - Google Patents
Method for removing nitrate nitrogen, corresponding combination preparation, and preparation method and application thereof Download PDFInfo
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- CN101613148B CN101613148B CN2009100553009A CN200910055300A CN101613148B CN 101613148 B CN101613148 B CN 101613148B CN 2009100553009 A CN2009100553009 A CN 2009100553009A CN 200910055300 A CN200910055300 A CN 200910055300A CN 101613148 B CN101613148 B CN 101613148B
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Abstract
The invention relates to a method for removing nitrate nitrogen which can effectively improve the rate of the reaction that nitrate in water is reduced with nano-iron and the removal rate of nitrate nitrogen by adding nano-iron and aluminum salt or iron salt catalyst in nitrate to react. A combination preparation is prepared by the method that firstly nano-iron and aluminum salt or iron salt catalyst are added in a sealed container containing acetone and then the container is irradiated by ultrasound and stirred. The combination preparation has good chemical stability, can directly remove the nitrate pollutants in water and has simple process and convenient operation.
Description
Technical field
The present invention relates to a kind of composite Nano iron material to nitrate nitrogen, what be useful in surface water, landscape water and nitrate in groundwater removes artificial reparation with other water body fast.
Background technology
Because the using of a large amount of chemical nitrogen fertilizers in Rural areas, the below standard discharging of sanitary sewage and nitrogenous trade effluent and sewage unreasonable recharged to wait and influences the face of land and nitrate nitrogen in underground water (NO jointly
3--N) become one of domestic and international question of common concern now.After drinking the nitrate water body that contains higher concentration, humans and animals can cause anoxic and suffer from methemoglobinemia, in the acid anaerobic environment of this external esophagus and gastrointestinal system, easily be reduced into nitrite, and then form directly acting carcinogens-nitrosamine with secondary amine reaction, so world many countries has all been stipulated the NO in the water body
3--the standard of N mass concentration.For example: the World Health Organization requires to surpass 11.3mg/L, the high-content standard of U.S. EPA is 10mg/L, European Union's tissue is controlled at 5.6mg/L to the permission level of nitrate nitrogen, and the up-to-date water quality standard for drinking water of China is also stipulated the standard less than 10mg/L simultaneously.
Present nitrate removal technology mainly comprises biological denitrificaion method, distillation, electrodialysis, reverse osmosis and ion-exchange and chemical reducing agent method.Biological denitrificaion needs enough carbon sources, and the C/N of water inlet directly influences the biological denitrificaion efficiencies of nitrogen removal; The physics method also can only be confined to small-scale production, and expense is higher; Adopting the reductive agent method to remove in the water nitrate is the focus of research both at home and abroad at present, such as technology such as shortening and Zero-valent Iron reduction.Therefore Zero-valent Iron and the reaction that is reduced between the pollutent are generally carried out on the surface, select specific surface area big and have the active nano grade iron powder of very high surface, can effectively improve the removal effect of its pollutent in water body.At present both at home and abroad existing part bibliographical information the report of applying nano iron technology reduction nitrate, also obtained denitrification effect preferably.But, have a series of practical problemss such as the long poor chemical stability that causes of nanometer iron such as storage period, easily oxidation, easy reunion in actual applications.Therefore how to overcome the problems referred to above, the practicality that develops skill is strengthened removal effect, all is the difficult point and the emphasis of this area all the time.
Summary of the invention
The object of the present invention is to provide a kind of method of removing nitrate nitrogen, corresponding combination preparation and preparation method thereof and use, this method and compound formulation can further improve the clearance of nanometer iron to nitrate nitrogen.
For reaching above purpose, solution of the present invention is:
A kind of method of removing nitrate nitrogen, it adds nanometer iron and catalyst reaction in nitrate.
Described nanometer iron and catalyzer are by weight ratio: nanometer iron is 93-98%, and catalyzer is 2%-7%.
Described catalyzer is one or more in aluminium salt or the molysite.
Described aluminium salt is Tai-Ace S 150, polymerize aluminum chloride; Described molysite is ferrous sulfate, iron(ic) chloride.
A kind of compound formulation, it adopts nanometer iron and catalyzer to make.
Described nanometer iron and catalyzer are by weight ratio: nanometer iron is 93-98%, and catalyzer is 2%-7%.
Described catalyzer is one or more in aluminium salt or the molysite.
Described aluminium salt is Tai-Ace S 150, polymerize aluminum chloride, and its optimum weight proportioning is: nanometer iron 95-98%, Tai-Ace S 150 1-3%, polymerize aluminum chloride 0-2%.
Described molysite is ferrous sulfate, iron(ic) chloride, and its optimum weight proportioning is: nanometer iron 93-95%, ferrous sulfate 2-4%, iron trichloride 3-5%.
The preparation method of described compound formulation, it gets rid of oxygen with the logical nitrogen of low flow in the container of acetone is housed, subsequently nanometer iron and catalyst by proportion are dropped in the container successively and seal, ultrasonic 1 hour of sealed vessel is removed acetone behind the logical high flow capacity nitrogen 1h and is obtained preparation after rocking 6 hours with the rotating speed of 250r/min again.
The application of described compound formulation aspect the removal nitrate nitrogen.
Tai-Ace S 150 of the present invention and polymerize aluminum chloride are better than solid-state dosing method with the dosing method of liquid state.
The test operation process is as follows:
The first step: the preparation of composite Nano iron material: take by weighing a certain amount of commercial grade nanometer iron with electronic balance, have in the wide-necked bottle of 200ml acetone in preparation, with the logical nitrogen 3min of low flow, oxygen in the evacuated vial, again with nanometer iron, three kinds of materials of Tai-Ace S 150 and polymerize aluminum chloride are nanometer iron 95-98% by weight ratio, Tai-Ace S 150 1-3%, the ratio of polymerize aluminum chloride 0-2%, to add nanometer iron earlier, be then the order of Tai-Ace S 150 and polymerize aluminum chloride be added to successively in the acetone dispersion agent will sealing with the unsintered tape sealing reaction flask be to make three kinds of materials be scattered in the acetone fully behind the ultrasonic echography 1h of 60KHz with the frequency, after rocking 6 hours with the rotating speed of 250r/min again, remove acetone behind the logical high flow capacity nitrogen 1h.After leaving standstill 5h after remaining solid washes with ultrapure water, remove supernatant liquor, be placed in the vacuum drier standby after drying up with nitrogen.Also can adopt the array configuration preparation of nanometer iron, ferrous sulfate, iron(ic) chloride during preparation, its by weight ratio the ratio of nanometer iron 93-95%, ferrous sulfate 2-4%, iron trichloride 3-5% put in the acetone dispersion agent and prepare.
Second step: take by weighing commodity nanometer iron and each 1g of compound nano-iron material with electronic balance, be placed on respectively in the 250mL reagent bottle of glass stopper, add the certain density KNO that 200mL has configured rapidly
3Solution compares experiment.The entire operation time is controlled in the 10min, and potassium nitrate solution is formulated by the analytical pure solid.Adopt nanometer iron and catalyzer (aluminium salt, molysite) directly to add and to realize reducing nitrate nitrogen concentration in the nitrate solution;
The 3rd step: place them in the shaking table of room temperature, and the rotating speed that remains on 200r/min reacts.
The 4th step: behind the question response different time, adopt the glass syringe 5mL that takes a sample fast, filter, adopt the nitrate nitrogen concentration in the National Standard Method working sample through millipore filtration (0.22 μ m).
Owing to adopted such scheme, the present invention to have following characteristics:
1, the nanometer iron used of the present invention does not need now to join and keeps its reducing activity, but obtains compound nanometer iron medicament by adding catalyzer, and it has very strong chemical stability, makes can big area promote the use of in the short period of time when azotate pollution.
2, the present invention's experiment need not carried out under airtight oxygen-free environment, can improve the removal efficient of nitrate nitrogen under uncovered room temperature environment by the effect of catalyzer yet.
3, when the nitrate nitrogen initial concentration be 10mg/L, composite Nano iron dosage 5g/L under the condition, reacts that the clearance of nitrate nitrogen is 84% after 6h hour, only is 51% and do not add under the situation.It is remarkable to add compound nano-iron material effect, and the reaction rate constant of nitrate can improve 3-5 doubly in the nanometer iron reductive water.
4, the present invention is simple to operate, and it is not high to produce in the process purity requirement to catalyzer, and it is simple to have technology, easy to operate and characteristics that the nitrate nitrogen clearance is high.
Description of drawings
Fig. 1 is that different Tai-Ace S 150 content composite Nano iron materials are to the nitrate removal design sketch.
Fig. 2 is that different composite nanometer iron dosage is to the nitrate removal design sketch.
Fig. 3 handles the removal effect figure of different nitrate nitrogen starting point concentrations for compound.
Fig. 4 is that the compound of different ingredients is to the nitrate removal design sketch.
Fig. 5 is that independent nanometer iron and compound are to nitrate nitrogen removal effect comparison diagram in the former water of little pollution Huangpu River.
Fig. 6 is the removal effect comparison diagram of composite Nano iron powder to nitrate nitrogen in the contaminated landscape water.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.
Embodiment 1:
Nitrate concentration is 10mg/L in the configuration deionized water, and pH is 5.5, and the composite Nano iron material that adds different ingredients respectively carries out nitrate degraded test, and the plant and instrument that uses in the process of the test is as shown in table 1.
The plant and instrument that table 1 test is used
Press material concentration calculating in the water, nanometer iron dosage is 5g/L, and the Tai-Ace S 150 dosage is respectively under the condition of 0mg/L, 30mg/L, 50mg/L, 65mg/L, 80mg/L, 100mg/L, and the time dependent curve of concentration of nitric acid as shown in Figure 1.
Can clearly find out from Fig. 1: along with the increase of Tai-Ace S 150 content the composite Nano iron material, significantly increasing appears in the removal speed of nitrate and clearance.Corresponding different composite Nano iron material is formed content, reacts that the clearance of nitrate reaches 51%, 57%, 61%, 70%, 76% and 83% respectively after 6 hours.Hence one can see that, and the Tai-Ace S 150 catalyzer that adds certain content in simple nanometer iron can effectively improve the removal effect of nitrate in the water, and this conclusion is also further confirmed in the test of applying nano iron reduction halogenated acetic acids simultaneously.
Embodiment 2:The plant and instrument that uses in the process of the test is as shown in table 1.When the nitrate initial concentration is 5mg/L, pH is 5.5 o'clock and under normal temperature condition, (the material proportion relation is composite Nano iron behind the reaction 6h in the composite Nano iron: nanometer iron 98%, the nitrate removal rate was respectively 22%, 29%, 38%, 54%, 61%, 83%, 88% when Tai-Ace S 150 2%) dosage was respectively 0.5g/L, 1g/L, 2.5g/L, 3g/L, 4g/L, 5g/L, saw Fig. 2 for details.The increase of composite Nano iron dosage has improved the concentration of substrate reaction thing on the one hand, has increased the impellent of reaction; Effectively increase the total surface area of composite Nano iron and the chance that unsalted surface contacts with nitrate nitrogen on the other hand, under both actings in conjunction, effectively improved the speed of reduction reaction and the clearance of nitrate.
Embodiment 3:The plant and instrument that uses in the process of the test is as shown in table 1.Composite Nano iron dosage is a 5g/L (nanometer iron 98%, Tai-Ace S 150 2%), pH is that the starting point concentration of 5.5 o'clock nitrate nitrogens is respectively 1,3,5,10,20,30, during 50mg/L, under the normal temperature behind the 6h clearance to nitrate be respectively 92%, 89%, 85%, 83%, 68%, 53%, 44%, its result sees Fig. 3 for details.As seen this technological method all has good removal effect for different initial concentration nitrate.
Embodiment 4:The plant and instrument that uses in the process of the test is as shown in table 1.When the nitrate initial concentration is 1mg/L, pH is 5.5 o'clock, and under normal temperature condition, composite Nano iron dosage 5g/L (nanometer iron 98%, catalyzer 2%), react after 6 hours separately that nanometer iron, nanometer iron+polymerize aluminum chloride, nanometer iron+iron trichloride, nanometer iron+ferrous sulfate and nanometer iron+Tai-Ace S 150 are respectively 22%, 48%, 71%, 81%, 85% to the nitrate removal rate, see Fig. 4 for details.By this result as seen, catalyzer adopts polymerize aluminum chloride, iron trichloride, ferrous sulfate and Tai-Ace S 150 all to have to improve the speed of reaction effect preferably.
Actual water body embodiment one:
Investigated and taken from the former water of little pollution Huangpu River, its detailed condition of water quality variation range is as shown in table 2.The plant and instrument that uses in the process of the test is as shown in table 1.
The little pollution Huangpu River of table 2 raw water quality index
Composite Nano iron that independent nanometer iron and this test the make removal effect to nitrate nitrogen in the water has been compared in this test.The dosage of nanometer iron and composite Nano iron material all is 5g/L separately, and the dosage of catalyzer is 100mg/L in the composite Nano iron, and the nitrate removal effect as shown in Figure 5 under the different time condition.
The compound nano-iron material promptly has 75% clearance to former water in the time of 3h, 100% clearance is promptly arranged in 6h; And independently nano-iron material clearance to former water in 3h only has about 15%, and the clearance in 6h only has 40%.Data show the degrade nitrate nitrogen that the composite Nano iron material can be rapidly and efficiently in the short period of time in actual water body.
Actual water body embodiment two:
The test water sample is Tongji University campus three good depressed place landscape water, and this water body has eutrophication largely, and nitrate and ammonia nitrogen concentration are all higher, and its water quality specific targets are as shown in table 3:
Table 3 Tongji University campus three good depressed place landscape water quality indexs
As shown in Figure 6, the compound nano-iron material promptly has 80% clearance to landscape water in the time of 3h, 100% clearance is promptly arranged in 6h; And independently nano-iron material clearance to landscape water in 3h only has about 5%, and the clearance in 6h only has 36%.Illustrate that this composite Nano iron material equally also adapts to the control of nitrate in the landscape water body of removing the condition of water quality complexity.
To the composite Nano iron material reasonable removal nitrate nitrogen effect Analysis can be arranged: under the condition that adds composite Nano iron nitrate nitrogen concentration in time prolongation and reduce, ammonia nitrogen concentration prolongs in time and raises, and the change in concentration of nitrite nitrogen is little, reduces again after just increase being arranged slightly again.This phenomenon explanation NO
2 -Be NO
3 -The intermediate product of reaction, final product or NH
4 +, kept the reaction inorganic nitrogen budgets in front and back between the three substantially.When oxygen in water concentration is higher, can quicken the formation of the fine and close shell of iron surface, reduce the outer field permeability of iron, form the passivation protection layer, stop the contact reacts of nanometer iron and nitrate nitrogen.And the dissolved oxygen in the solution also makes the oxidized generation ferriferous oxide of nanometer iron surface and nanometer iron reactive behavior is reduced.The composite Nano iron material adds active aluminum and the iron ion in the catalyzer, can effectively promote the dissolving of the fine and close thing of nanometer iron surface; The higher specific conductivity of solution is accelerated speed of reaction and is improved electronics, ion migration speed simultaneously, sulfate ion also can be broken through the passivation film structure that the ferriferous oxide surface generates in addition, make in iron and the water nitrate react and be released, thereby strengthened the characteristic of its reduction and part absorption with the ionic form.Test finds that this tunic structure on ferriferous oxide surface can wrap a part of nitrate and make total nitrogen content reduce, but along with the carrying out that reacts, the quilt of the membrane structure of passivation is broken makes this part nitrate come back in the solution, makes total nitrogen content go up.
By plasma emission spectrum ICP-AES the ferro element total content analysis in the reaction soln is found, increasing the back at the content of observing solvability iron under the 238.204 wavelength characteristic peaks in initial very short time reduces gradually along with the increase of time, the reaction initial stage, add a large amount of nano simple substance iron and make the activated iron of part react with nitrate at once, and be converted into solvability iron rapidly.Along with the carrying out of reaction, nano iron particles can play absorption to deliquescent iron, makes solvability iron amount reduce greatly.On the other hand, the ironing surface ferriferous oxide of nanometer is broken the generation iron ion by catalyzer, and iron ion is also adsorbed by nanometer iron simultaneously.Therefore, degraded is the periodicity reaction process of a complexity to nitrate nitrogen to add the composite Nano iron that catalyzer produces.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (6)
1. method of removing nitrate nitrogen, it is characterized in that: it adds nanometer iron and catalyst reaction in nitrate; Described catalyzer is more than one in aluminium salt or the molysite; Described aluminium salt is Tai-Ace S 150, polymerize aluminum chloride; Described molysite is ferrous sulfate, iron(ic) chloride; Described nanometer iron and catalyzer are by weight ratio: nanometer iron is 93-98%, and catalyzer is 2%-7%.
2. the method for removal nitrate nitrogen as claimed in claim 1 is characterized in that: described catalyzer adopts Tai-Ace S 150 and polymerize aluminum chloride, and its weight proportion is: nanometer iron 95-98%, Tai-Ace S 150 1-3%, polymerize aluminum chloride 0-2%; Described catalyzer adopts ferrous sulfate and iron(ic) chloride, and its weight proportion is: nanometer iron 93-95%, ferrous sulfate 2-4%, iron trichloride 3-5%.
3. compound formulation, it is characterized in that: it adopts nanometer iron and catalyzer to make; Described catalyzer is more than one in aluminium salt or the molysite; Described aluminium salt is Tai-Ace S 150, polymerize aluminum chloride; Described molysite is ferrous sulfate, iron(ic) chloride; Described nanometer iron and catalyzer are by weight ratio: nanometer iron is 93-98%, and catalyzer is 2%-7%.
4. compound formulation as claimed in claim 3 is characterized in that: described catalyzer adopts Tai-Ace S 150 and polymerize aluminum chloride, and its weight proportion is: nanometer iron 95-98%, Tai-Ace S 150 1-3%, polymerize aluminum chloride 0-2%; Described catalyzer adopts ferrous sulfate and iron(ic) chloride, and its weight proportion is: nanometer iron 93-95%, ferrous sulfate 2-4%, iron trichloride 3-5%.
5. the preparation method of compound formulation as claimed in claim 3, it is characterized in that: it gets rid of oxygen with the logical nitrogen of low flow in the container of acetone is housed, subsequently nanometer iron and catalyst by proportion are dropped in the container successively and seal, ultrasonic 1 hour of sealed vessel is removed acetone behind the logical high flow capacity nitrogen 1h and is obtained preparation after rocking 6 hours with the rotating speed of 250r/min again.
6. the application of compound formulation as claimed in claim 3 aspect the removal nitrate nitrogen.
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| CN103755042B (en) * | 2014-02-13 | 2015-04-29 | 长江水利委员会长江科学院 | Preparation method and application of attapulgite/nano-iron composite material-microorganism coupled body |
| CN109607734A (en) * | 2018-12-31 | 2019-04-12 | 南京格洛特环境工程股份有限公司 | A kind of low-temperature denitration medicament and preparation method thereof |
| CN112624270A (en) * | 2020-12-04 | 2021-04-09 | 上海电力大学 | Medicament for removing nitrate nitrogen in water, preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| CN101066795A (en) * | 2007-06-08 | 2007-11-07 | 大连理工大学 | Process of catalytically reducing nitrate nitrogen in water with Fe0/TiO2 |
| CN101306863A (en) * | 2008-07-04 | 2008-11-19 | 绍兴文理学院 | Finishing agent for modified bentonite and zero-valent molten iron |
| CN101428868A (en) * | 2007-11-05 | 2009-05-13 | 北京师范大学 | Restoration agent for groundwater pollution of refuse landfill and restoration method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101066795A (en) * | 2007-06-08 | 2007-11-07 | 大连理工大学 | Process of catalytically reducing nitrate nitrogen in water with Fe0/TiO2 |
| CN101428868A (en) * | 2007-11-05 | 2009-05-13 | 北京师范大学 | Restoration agent for groundwater pollution of refuse landfill and restoration method |
| CN101306863A (en) * | 2008-07-04 | 2008-11-19 | 绍兴文理学院 | Finishing agent for modified bentonite and zero-valent molten iron |
Non-Patent Citations (1)
| Title |
|---|
| F.Cheng et al..Reduction of nitrate to ammonia by zero-valent iron.《chemosphere》.1997,第35卷(第11期),2689-2695. * |
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