CN100575277C - A kind ofly utilize Fe °/TiO 2The method of nitrate nitrogen in the photo catalytic reduction water - Google Patents
A kind ofly utilize Fe °/TiO 2The method of nitrate nitrogen in the photo catalytic reduction water Download PDFInfo
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- CN100575277C CN100575277C CN200710011653A CN200710011653A CN100575277C CN 100575277 C CN100575277 C CN 100575277C CN 200710011653 A CN200710011653 A CN 200710011653A CN 200710011653 A CN200710011653 A CN 200710011653A CN 100575277 C CN100575277 C CN 100575277C
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Abstract
The invention belongs to water depth handles and field of photocatalytic material, purpose is to utilize the iron doped catalyst to improve the nitric efficiency of nitrate nitrogen in the photo catalytic reduction water, especially underground water and drinking water source, make denitrogenation more thorough, solve in the past Zero-valent Iron reduction ammonia nitrogen productive rate height, undope that precious metal photocatalyst reduction efficiency is lower, doped precious metal photocatalyst price problem of higher.It is titania-doped to it is characterized in that utilizing chemical reduction to prepare nano zero valence iron, removing dissolved oxygen and additional formic acid is under the situation of electron donor, nitrate nitrogen and reduce total nitrogen content in the water is efficiently reduced in light-catalyzed reaction, avoids forming at high proportion the harmful product of ammonia nitrogen and nitrous acid nitrogen.Effect of the present invention and benefit are: nitrate nitrogen in a kind of novel photocatalysis agent, preparation method and the comparison high efficiency photocatalysis reductive water thereof is provided and has reduced the method for total nitrogen, catalyzer is cheap and efficient.Water purifications such as optic catalytic composite material and underground water tap water be can be widely used in, nitrate nitrogen, hydrochloric ether dechlorination and pollutent removed.
Description
Technical field
The invention belongs to photocatalyst material and water treatment and field of purification.Relate to and utilize Fe
0/ TiO
2Nitrate nitrogen in the photo catalytic reduction water reduces total nitrogen content in the water.Be specifically related to utilize cheap and the titania-doped preparation method of nano zero valence iron efficiently, removing dissolved oxygen and additional formic acid is under the situation of electron donor, nitrate nitrogen is efficiently reduced in light-catalyzed reaction, avoids forming at high proportion the harmful product of ammonia nitrogen and nitrous acid nitrogen.
Background technology
Owing to the excessive use of Agricultural Development, synthetic chemical fertilizer, the concentration of nitrate nitrogen was increase trend in the global water body in recent years.After high density nitric acid salt solution is drunk by the people, nitrate can be reduced to nitrite by microbial transformation in gi tract and saliva, it is ferric iron that nitrite makes the oxidation of divalent in the blood, causes human body to suffer from methemoglobinemia because of anoxic, cause mental retardation, serious causing death died.In order to improve safe drinking water, a lot of in the world countries have all stipulated nitrate and nitrite concentration standard in the tap water with organizing, China existing water quality standard for drinking water regulation NO
3 --N peak concentration is 10mgL
-1(calculating with nitrogen, down together).The peak concentration of the nitrate nitrogen in the tap water of U.S. Environmental Protection Administration (EPA) regulation is 10mgL
-1The peak concentration of the nitrate nitrogen that the European Economic Community allows is 11.3mgL
-1, recommended density is 5.65mgL
-1So the concentration that how to reduce the nitrate nitrogen in the tap water is a very urgent task.
The method that tradition is removed nitrate radical has: ion exchange method, reverse osmosis method, electrolytic process, chemical reduction method and biological denitrification method etc.These methods have all that high energy consumption, investment are big, the difficult operation of technology, need shortcoming such as subsequent disposal.As United States Patent (USP) 6,083, No. 377 is about the nitrogen-containing pollutant electrochemical process for treating, and adding the product that suitable voltage makes formation according to pollutant kind is nitrogen.United States Patent (USP) 20050115905 utilizes selectivity ion-exchange and electrochemical catalysis reductive way to remove nitrate nitrogen in the water.20050252857 of United States Patent (USP)s utilize nanoporous and ion static mould material selectivity to remove nitrate nitrogen from water.And for example: the Chinese patent 200410098590.2 metal modified active carbon fiber electrodes of Ecological Environment Research Center, Chinese Academy of Sciences invention and with the method for this electrode removal nitrate; Granted patent CN1349934 removes the method and the reactor of nitrate nitrogen in the tap water, and the two kinds of processes of heterotroph denitrification and electrochemical autotrophic denitrification that add nutrition source are combined.Benitration reactor for drinking water CN1303819 does not see mandate.With the hard coal is medium, carbon fiber is an electrode, under anoxia condition, pass to lower direct current, can create little electrolytic oxidation reducing environment by media particle, needed hydrogen of online generation denitrifying bacteria and carbon source, the nitrate nitrogen of lower concentration in the tap water is removed, be configured to the filling electrolysis autotrophy Benitration reactor that declines in view of the above.
Zero-valent Iron can be removed the nitrate radical in the water, and mainly be translated into ammonia nitrogen (Li Tielong, bang water, golden morning sunlight etc., Jilin University's journal (engineering version), 2006,36:0264-0268).Such denitrogenation method is not thorough.The water that contains ammonia nitrogen still needs to handle.The nano zero valence iron preparation method has 2 of Chinese patents: one is 200610088383.8 1 kinds improves nanometer nulvalent iron particle and preparation method thereof (Nanjing University).Two is 200510062301.8 emulsified nanometer grade zero valent irons and the bimetallic preparation method and its usage of nano level (CN1806974 of Zhejiang University), can remove multiple pollutents such as chlorine organic in the water, nitrate radical and heavy metal simultaneously.
In recent years, the photochemical catalysis denitride technology became the emphasis of research.Wherein study more catalyzer TiO is arranged
2Have advantages such as chemical stability, toxicological harmless and low cost because of it, become the research focus of photochemical catalysis denitride technology.
Pure TiO
2Almost do not reduce the activity of nitrate radical, therefore to TiO
2Metal-doped and adding hole trapping agents is necessary.In early days about TiO
2The research of reduction nitrate radical mainly concentrates on the precious metal doping, as Pd, and Pt, Ru etc. (Fuxiang Zhang, Ruicai Jin, Jixin Chen et al., Journal ofCatalysis, 2005,232:424-431).The effect of utilizing silver-colored adulterated catalyzer photochemical catalysis to remove nitrate nitrogen is relatively good.But only do not find as yet in order to reduce the photocatalysis technology and the patent of nitrate nitrogen.China's photochemical catalysis remove inorganic nitrogen patent in the water at be the water body that contains oxidation state and go back the different shape inorganic nitrogen of ortho states.And catalyzer needs the carried noble metal composition.(Dalian University of Technology 200610046172.8, publication number CN1830830): go under the dissolved oxygen conditions, utilize and to mix silver, platinum titanium deoxide catalyst can be coupled oxidizing reaction and reduction reaction, remove ammonia nitrogen and nitrous acid nitrogen or nitrate nitrogen in the water simultaneously.The selectivity that forms gaseous product such as nitrogen is higher.These precious metal prices are higher, and there is potential harm in environment.
Summary of the invention
The objective of the invention is to utilize the iron doped catalyst to improve the nitric efficiency of nitrate nitrogen in the photo catalytic reduction water, especially remove the nitrate nitrogen in underground water and the drinking water source, make denitrogenation more thorough, when solving the nitrate nitrogen of Zero-valent Iron reduction in the past, ammonia nitrogen productive rate height; Base metal photocatalyst reduction efficiency is lower, doped precious metal catalyzer price problem of higher.A kind of Fe is provided
0/ TiO
2The preparation method of photocatalyst and utilize the method for nitrate nitrogen and more efficient denitrogenation in this catalyzer photo catalytic reduction water.
Technical scheme of the present invention is to adopt chemical reduction method to synthesize the adulterated titanium deoxide catalyst of nano zero valence iron (mass content of Zero-valent Iron is between 0.01%～15% in the catalyzer), the water body photo catalytic reduction nitrate nitrogen that carries out of high reactivity, highly selective reacts, and mainly form more gaseous product but not ammonia nitrogen, and the formation ratio of nitrous acid nitrogen is extremely low.The efficiency ratio of removing total nitrogen in the water is higher.
Implementation step of the present invention is as follows
1. the salt dissolving formation solution that the raw material of Zero-valent Iron is contained ferrous ion, as sulfurous acid iron, iron protochloride, add mass content that the amount of salt makes the final Zero-valent Iron that forms in the catalyzer between 0.01%～15%, the titanium dioxide hybrid infusion 10min～5h of this solution and titania powder or load.Solution is water or the organic solvent that contains certain water.Organic solvent comprises common solvent such as ethanol etc.Feed nitrogen and remove liquid phase dissolved oxygen.
2. according to the amount that adds ferrous ion, the reductive agent that adds corresponding chemical metering ratio is in above-mentioned solution, and reductive agent comprises POTASSIUM BOROHYDRIDE or sodium borohydride.Logical nitrogen reaction 10～180min.
3. will react the titanium deoxide catalyst and the liquid phase separation of the doping iron that forms.Water and washing with alcohol 2～6 times.
4. 40～80 ℃ of vacuum-dryings in vacuum drying oven promptly get the exsiccant catalyzer.
5. the water that will contain nitrate nitrogen is introduced in the photo catalysis reactor, feeds nitrogen or titanium dioxide gas and removes dissolved oxygen, adds a certain amount of formic acid, and making its concentration is 0.001～0.5mM.
6. open light source, the light intensity irradiation reactor with certain carries out the reaction of photo catalytic reduction nitrate nitrogen, can reduce nitrate nitrogen content and total nitrogen content in the water after for some time.
Effect of the present invention and benefit are to utilize cheap and the chemical reduction nano zero valence iron is titania-doped efficiently, removing dissolved oxygen and additional formic acid is under the situation of carbon source electron donor, nitrate nitrogen is efficiently reduced in light-catalyzed reaction, avoid forming a large amount of a high proportion of ammonia nitrogen products or nitrous acid nitrogen simultaneously, it is higher to remove total nitrogen efficient.
Description of drawings
Accompanying drawing is to utilize in the titania-doped ultraviolet germicidal photo catalytic reduction of the 0.5% nanometer iron water each form content of inorganic nitrogen in and changing trend diagram thereof in the nitrate nitrogen process.
Embodiment
Introduce implementation method of the present invention and step in detail with specific embodiment below.
Embodiment 1
Fe
0/ TiO
2Preparation: take by weighing 1.00g 300 ℃ of activation P-25 titanium dioxide behind the 1h in retort furnace.Add a certain amount of iron vitriol, add the deionized water constant volume to 50mL, logical nitrogen 30min adds stoichiometric sodium borohydride behind the ultra-sonic dispersion 20min, continues to lead to behind the nitrogen 30min with precipitation and centrifugal separation.Water and absolute ethanol washing are three times respectively.60 ℃ of vacuum-dryings in vacuum drying oven promptly get required composite catalyst powder particle.
Fe
0/ TiO
2The test of photo catalytic reduction nitrate nitrogen: quartzy tubular reactor is adopted in the photochemical catalysis experiment, and employing 20W predominant wavelength is that the ultraviolet germicidal of 254nm is a light source.Catalyst concn is 1gL
-1, nitrate concentration is 100mgL
-1(calculating) with the nitrogen element.In reactor with 100mLmin
-1Speed is led to CO
2Add a certain amount of formic acid behind the gas 30min, making its concentration is 0.030mM, opens light source.Every 30min sampling.Adopt the concentration of ultraviolet spectrophotometry, N-(how basic 1-is)-quadrol light-intensity method, nessler reagent spectrphotometric method for measuring nitrate nitrogen, nitrous acid nitrogen and ammonia nitrogen respectively.
The doping of iron is 0.5wt%TiO
2, the concentration of formic acid is 0.030mM, photo catalytic reduction concentration is 100mgL
-1The changing conditions of total nitrogen, nitrate nitrogen, nitrous acid nitrogen, ammonia nitrogen concentration is in the nitrate nitrogen process: nitrate nitrogen transformation efficiency 52.06% behind the illumination 2h, total conversion rate of nitrogen 36.77%.The 52.06mgL that is reduced
-1Has only 29.36% (12.5mgL in the nitrate nitrogen
-1) be converted into ammonia nitrogen, there is not nitrous acid nitrogen to generate remaining 39.5mgL in the reaction process
-1Form with gas is discharged in the atmosphere.
Fe
0/ TiO
2With Fe
0The reduction nitrate radical is compared, and the latter is a primary product with the ammonia nitrogen, the nitrous acid nitrogen that the generation ratio is very big in the reaction process, the amount of total nitrogen is almost constant, the former ammonia nitrogen productive rate is very low, and the nitrate nitrogen that is reduced has only 29.36% to be converted into ammonia nitrogen, and does not have nitrite anions to generate in the reaction process.Fe
0/ TiO
2With with quadrat method synthetic Ag/TiO
2The reduction nitrate radical is compared, and the transformation efficiency of latter 0.5h nitrate nitrogen is 100%, and the concentration of nitrite anions increases afterwards earlier and reduces in the reaction process, and it is lower slightly that the former nitrate nitrogen is removed efficient, endangers more serious nitrite anions but generate in the reduction process.In addition because iron is more much lower than the price of silver, thus utilize nano zero valence iron doped titanium dioxide photocatalytic reduction to handle nitrate radical in the water body, safer, more economical.
Claims (3)
1. one kind is utilized Fe
0/ TiO
2The method of nitrate nitrogen in the photo catalytic reduction water, utilize chemical reduction to prepare zeroth order nanometer iron doping titanium dioxide catalyst, under removing dissolved oxygen conditions and add formic acid and carry out nitrate nitrogen in the light-catalyzed reaction reductive water under as the situation of carbon source and electron donor, form gaseous product and reduce total nitrogen content in the water; It is characterized in that the iron in the catalyzer is Zero-valent Iron, is the chemical reduction method preparation, and its mass content is between 0.01%～15%.
2. a kind of Fe that utilizes according to claim 1
0/ TiO
2The method of nitrate nitrogen in the photo catalytic reduction water is characterized in that: the reaction of photo catalytic reduction nitrate nitrogen is to carry out under the condition of adding formic acid and removal dissolved oxygen, and formic acid concn is 0.001～0.5mM; Light-catalysed light source comprises ultraviolet lamp, halogen lamp, fluorescent lamp, sunlight or mesolow mercury lamp.
3. a kind of Fe that utilizes according to claim 1
0/ TiO
2The method of nitrate nitrogen in the photo catalytic reduction water is characterized in that: described zeroth order nanometer iron doping titanium dioxide catalyst comprises powder or supported catalyst.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362092B (en) * | 2008-09-11 | 2010-06-09 | 浙江理工大学 | Preparation method of magnetic iron supported titanium dioxide nano-rod photo-catalyst |
| KR20120103539A (en) * | 2009-06-24 | 2012-09-19 | 바스프 에스이 | Method for photocatalytic water purification |
| CN101613148B (en) * | 2009-07-24 | 2011-07-27 | 同济大学 | Method for removing nitrate nitrogen, corresponding combination preparation, and preparation method and application thereof |
| CN102784647A (en) * | 2012-08-14 | 2012-11-21 | 浙江大学 | Preparation method for (101)-surface nanoFe-TiO2 high-efficiency nitrogen-fixing photocatalyst |
| CN102989461B (en) * | 2012-11-15 | 2015-04-15 | 苏州科技学院 | Preparation method and application of magnetic nickel ferrite photocatalysis material |
| CN104045129B (en) * | 2014-04-29 | 2016-04-27 | 成都理工大学 | A kind of preparation method removing the Nanoscale Iron charcoal micro-electrolysis material of nitrate nitrogen |
| CN104828900A (en) * | 2015-06-05 | 2015-08-12 | 广西大学 | Method for using photocatalytic reduction to treat waste water containing nitroimidazole antibiotics |
| CN105060389B (en) * | 2015-07-16 | 2017-10-13 | 广西大学 | A kind of method of perfluoro caprylic acid in precious metal doping gallium oxide photocatalytic degradation water |
| CN105140550B (en) * | 2015-07-29 | 2019-05-10 | 大连理工大学 | A kind of photoelectrocatalysis for handling Recalcitrant chemicals and microbiological fuel cell coupled system |
| CN107952464B (en) * | 2017-12-13 | 2020-09-11 | 大连理工大学 | Novel photocatalytic material and double-photocatalytic-electrode self-bias pollution control system |
| CN108940309A (en) * | 2018-07-19 | 2018-12-07 | 王晶 | A kind of preparation method of the catalysis reduction bed of rapid sewage treating |
| CN108975507B (en) * | 2018-07-31 | 2021-08-13 | 苏州科技大学 | Method for simultaneously removing nitrite and ammonia nitrogen by using zinc ferrite-fullerene photocatalyst |
| CN109173977A (en) * | 2018-09-17 | 2019-01-11 | 河南师范大学 | A kind of preparation method and applications of calcium carbonate load nano zero-valence iron composite material |
| CN111672469B (en) * | 2020-06-17 | 2022-09-13 | 西南科技大学 | Fe-Ti bimetallic nanoparticle-loaded honey carbon material and preparation method and application thereof |
| CN115770573A (en) * | 2022-11-14 | 2023-03-10 | 中国药科大学 | Fe 0 /TiO 2 @ D201 type composite material and preparation method and application thereof |
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