CN103464218B - Method used for direct synthesis of nano particle in waste water, and for water treatment by nano particle - Google Patents

Method used for direct synthesis of nano particle in waste water, and for water treatment by nano particle Download PDF

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Publication number
CN103464218B
CN103464218B CN201310253683.7A CN201310253683A CN103464218B CN 103464218 B CN103464218 B CN 103464218B CN 201310253683 A CN201310253683 A CN 201310253683A CN 103464218 B CN103464218 B CN 103464218B
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waste water
nano particle
water
nano
basic sewage
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CN103464218A (en
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牛春革
宿新泰
阎辉
杨超
李志娟
王吉德
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Xinjiang University
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Xinjiang University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention provides a method used for direct synthesis of a nano particle in waste water, and for water treatment by the nano particle. The nano particle with a certain degree of photocatalytic activity is synthesized by direct precipitation method, wherein the strong basicity and high sulfide content of oil refining alkaline residue waste water are taken advantage of, and a metal salt compound is used as the raw material. In addition, the nano particle is used as a catalyst, and H2O2 is used as an oxidizing agent so as to perform catalytic degradation of oil refining alkaline residue waste water and simulated waste water. It is shown by experiment results that the nano particle possesses high photocatalytic activity. The method is capable of taking advantage of oil refining alkaline residue waste water, and directly synthesizing the nano particle with a relatively small particle size.

Description

Direct synthesizing nano-particle and be applied to the method for water treatment in a kind of waste water
Technical field
The present invention relates to the method for direct synthesizing nano-particle in a kind of waste water, and use it in photocatalysis treatment of waste water, belong to field of inorganic nonmetallic material.
Background technology
Along with the development of society, in order to meet the growing material and cultural needs of people, in production, create the increasing waste water containing difficult degradation compound.These waste water mainly contain the cities and towns medical waste water of hypertoxicity, oil refining wastewater, residues of pesticides waste water and waste water from dyestuff etc.The discharge of these waste water causes severe contamination to environment, and the governing problem of this type of waste water has also become the focus that various countries researchers pay close attention to.Photocatalysis treatment technology due to its treatment temperature and pressure lower, higher and obtain the common concern of researcher to the mineralization degree of waste water.
In the application of photocatalysis technology, various green and the semiconductor light-catalyst being easy to reclaim are widely used in such as TiO in photocatalysis 2, CuO, Fe 2o 3, ZnO, WO 3, CuS and ZnS.In addition, along with the develop rapidly of nanosecond science and technology, nano material promote social development and the effect that improves in environment for human survival more and more obvious.In transition metal semiconductor nano material, transition metal nano-sized iron oxide, nano cupric oxide and nano-copper sulfide, because of the physics of its excellence and chemical property, obtain the concern that people are general.Current large quantity research shows, these materials show potential using value in wastewater by photocatalysis.But the preparation process of nano material seems comparatively complicated compared with the preparation process of conventional compounds.It not only needs additionally to add a certain amount of surfactant or template reagent, and needs complicated isolation of purified process.Therefore, explore a kind of simple and convenient, mild condition, the photochemical catalyst synthetic method of environmental protection seems particularly necessary.
In the past few years, heterogeneous mixing nano composite material catalyst because of catalytic activity in the treatment of waste water higher and obtain the common concern of researchers.Transition metal oxide nano-particles, because it is widely in photocatalysis, air-sensitive, the application in solar cell and electrode material and evoked the interest of researcher.In addition, formation of iron based nanoparticles as transistion metal compound is not only a kind of important industrial chemicals, and there is good magnetic, light resistance, to ultraviolet light, there is strong absorption and screen effect, stable chemical performance, catalytic activity is high, can be widely used in novel magnetic recording materials, electronics, dyestuff, plastics, ink, catalyst and bio-science field.But synthesize the cost intensive of these nano materials, building-up process is complicated.So, the method for a kind of simple and effective this type of nano material of synthesis of necessary exploration, and be successfully used in wastewater by photocatalysis.
Refinery basic sewage waste water is a kind of waste water containing high-enriched organics produced in petroleum refining process.Because discharge capacity is large, complicated component and toxicity become more by force and day by day the focus of global concern.Sulfide, volatile phenol, mercaptan, organic acid and benzene class etc. are wherein mainly contained containing a large amount of pollutants in this waste water.Refinery basic sewage waste water color and luster is dark, stench, has severe corrosive, belongs to high concentration, poisonous, the extraordinary organic liquid waste of difficult degradation, be put into " record of National Hazard name " (being numbered HW35).How effective this type of waste water of disposal and utilization has become the problem received much concern in Petrochemical Enterprises.
The invention provides direct synthesizing nano-particle in a kind of waste water and be applied to the method for water treatment, the method is utilized not only effectively to make use of refinery basic sewage waste water, and successfully prepared the multiple nano particle with certain photocatalytic activity, reach the object turned waste into wealth.
Summary of the invention
The present invention's refinery basic sewage waste water does alkali source and sulphur source, and various metal salt compound is raw material, adopts direct precipitation method to synthesize metal-based nano particle.In addition, we make catalyst, H with the sample of synthesis 2o 2make oxidizer catalytic hydrogen peroxide degraded refinery basic sewage waste water and simulated wastewater.Result shows that the nano particle that the present invention synthesizes all shows higher photocatalytic activity.Profit not only effectively make use of refinery basic sewage waste water in this way, but also has directly synthesized the less nano particle of particle diameter, reaches the effect of killing two birds with one stone.
An object of the present invention there are provided a kind of method of direct synthesizing nano-particle in refinery basic sewage waste water, and is successfully used in the experiment of wastewater by photocatalysis.
Another object of the present invention effectively make use of refinery basic sewage waste water, reaches the object turned waste into wealth.
The present invention adopts following technical scheme:
1) under room temperature, take the metallic salt solid of certain mass, make it all be dissolved in water under stirring and obtain metal ion solution;
2) above-mentioned solution is heated to 60-100 oc;
3) a certain amount of refinery basic sewage waste water is poured into, 60-100 under stirring ounder C, constant temperature stirs 30min;
4) cooled and filtered or centrifuge washing, finally obtains powder with absolute ethanol washing; By powder in 80 oc drying obtains iron-based and copper-based nano particle powder;
5) photocatalysis performance evaluation is carried out by the nanocatalyst of following proposal to preparation:
A) photocatalytic degradation refinery basic sewage waste water
The refinery basic sewage waste water after a certain amount of dilution and catalyst mix in quartz ampoule, after stirring certain hour, add a certain amount of H 2o 2solution, reacts the COD (COD) of test solution after certain hour under illumination effect, characterize the catalytic performance of catalyst with COD removal efficiency
COD clearance=(COD 0-COD)/COD 0× 100%
COD in formula 0it is the COD value before waste water reaction; COD is the COD value of waste water water sample after reaction;
B) photocatalytic degradation simulated wastewater rhodamine B (RhB) and methyl orange (MO) solution
Get a certain amount of catalyst to mix with rhodamine B solution or methyl orange solution; After stirring certain hour under the condition of lucifuge, catalyst is disperseed in the solution completely, and make adsorption-desorption reach balance; Add H 2o 2react under rear illumination effect; Often at regular intervals sample liquid sampled and detect with the removal effect of ultraviolet-visible spectrometer to its color.Degraded percentage concentration ratio represents, the RhB solution that wherein concentration ratio is when being different time and the ratio between the concentration of MO solution and the concentration of Initial R hB solution and MO solution.
Beneficial effect of the present invention:
In this method, successfully direct precipitation method is adopted to synthesize nano particle with refinery basic sewage waste water.In addition, we make catalyst, H respectively with the nano particle of synthesis 2o 2make oxidizer catalytic hydrogen peroxide degraded refinery basic sewage waste water and simulated wastewater.Found that, during with copper-based nano ion for catalyst, after illumination 120min, the COD removal efficiency of refinery basic sewage waste water can reach 54%; In simulated wastewater rhodamine B solution 40min, all degraded is complete; During with two kinds of formation of iron based nanoparticles for catalyst, after illumination 120min, the COD clearance of two kinds of catalyst to refinery basic sewage waste water solution can reach 47% and 46% respectively; During photocatalysis degradation simulated wastewater methyl orange solution, found that in 10min and the degradation rate of methyl orange solution can be made to reach 40% and 50% respectively.CuO/CuS nano-complex and the formation of iron based nanoparticles of these the results shows the present invention synthesis all have a very high photocatalytic activity.
Compare with technology with existing additive method, tool of the present invention has the following advantages:
1) the present invention effectively make use of refinery basic sewage waste water solution and has synthesized the nano particle with certain photocatalytic activity;
2) nano-particles size that obtains of the present invention is less, and average grain diameter is at 10-20nm;
3) mild condition of synthesizing nano-particle of the present invention, equipment requirement is simple;
4) nano particle of the present invention's synthesis not only has catalytic action to refinery basic sewage waste water, and also shows very high photocatalytic activity to simulating pollution waste water.
Accompanying drawing explanation
The digital audio-visual picture of Fig. 1 the present invention refinery basic sewage waste water used;
X-ray diffraction (XRD) collection of illustrative plates of CuO/CuS nano-complex prepared by Fig. 2 the present invention;
X-ray diffraction (XRD) collection of illustrative plates: a and b of two kinds of formation of iron based nanoparticles prepared by Fig. 3 the present invention is with FeCl respectively 36H 2o and Fe (NO 3) 39H 2o is the sample that source of iron synthesizes;
The transmission electron microscope collection of illustrative plates (TEM) of CuO/CuS nano-complex prepared by Fig. 4 the present invention;
Fig. 5 the present invention prepare respectively with FeCl 36H 2o (a) and Fe (NO 3) 39H 2the transmission electron microscope collection of illustrative plates (TEM) of two kinds of formation of iron based nanoparticles that O (b) synthesizes for source of iron
CuO/CuS nano-complex photocatalytic degradation refinery basic sewage waste water block diagram prepared by Fig. 6 the present invention;
Fig. 7 the present invention is respectively with FeCl 36H 2o (a) and Fe (NO 3) 39H 2two kinds of formation of iron based nanoparticles photocatalytic degradation refinery basic sewage waste water block diagrams that O (b) is prepared for source of iron (L in figure: illumination, C: catalyst, H:H 2o 2, D: lucifuge);
CuO/CuS nano-complex photocatalytic degradation simulated wastewater rhodamine B solution curve map prepared by Fig. 8 the present invention;
Fig. 9 the present invention is respectively with FeCl 36H 2o (a) and Fe (NO 3) 39H 2photocatalytic degradation simulated wastewater methyl orange (MO) the solution curve map of two kinds of formation of iron based nanoparticles that O (b) prepares for source of iron.
concrete embodiment
Example below further illustrates of the present invention, instead of limit the scope of the invention.
Embodiment 1
2.5 grams of copper sulphate are dissolved in 50ml water, fully stir and solid is all dissolved.The refinery basic sewage waste water of 50ml is added after being warming up to 90oC under mix and blend.90oC constant temperature stops reaction after stirring 30min.Cooled and filtered or centrifuge washing, finally obtain powder with absolute ethanol washing; Powder is obtained the nano combined powder of CuO/CuS in 80oC drying.
Embodiment 2
(initial COD is at 8000mgL for refinery basic sewage waste water add dilution in the quartz ampoule of light-catalyzed reaction instrument after -1), stir 60min after adding catalyst 10mg, then add a certain amount of H 2o 2solution, with 300W mercury lamp for light source light is according to the COD value of test solution after 120min.
Embodiment 3
The CuO/CuS nano-complex getting 10mg adds in the rhodamine B of 50ml; Stirring 60 min under the condition of lucifuge makes catalyst disperse in the solution completely, and makes adsorption-desorption reach balance; Add H 2o 2after react under 350W illumination condition; Often at regular intervals sample liquid sampled and detect with the removal effect of ultraviolet-visible spectrometer to its color.
Embodiment 4
By 2.7 grams of FeCl 36H 2o is dissolved in 50ml water, fully stirs and solid is all dissolved.The refinery basic sewage waste water of 50ml is added after being warming up to 90oC under mix and blend.90oC constant temperature stops reaction after stirring 30min.Cooled and filtered or centrifuge washing, obtain pressed powder after drying.
Embodiment 5
By 4.0 grams of Fe (NO 3) 39H 2o is dissolved in 50ml water, fully stirs and solid is all dissolved.The refinery basic sewage waste water of 50ml is added after being warming up to 90oC under mix and blend.90oC constant temperature stops reaction after stirring 30min.Cooled and filtered or centrifuge washing, obtain pressed powder after drying.
Embodiment 6
Getting concentration is 500mgL -1copper-containing wastewater 50ml, add the refinery basic sewage waste water of 50ml after being warming up to 90oC under stirring.90oC constant temperature stops reaction after stirring 30min.Cooled and filtered or centrifuge washing, obtain pressed powder after washing drying.

Claims (1)

1. in waste water, the nano particle of directly synthesis is applied to a method for water treatment, the steps include:
(1), under room temperature, the copper of preparation 0.001-1 mol/L or the metal salt solution of iron, make it all be dissolved in water and obtain solion under stirring;
(2) above-mentioned solution is heated to 60-100 DEG C;
(3) target process waste water is refinery basic sewage waste water, oil extraction waste water or waste water from dyestuff, to alkaline waste water sulfuric acid, its pH value is adjusted to 8-11, and acid waste water adopts ammoniacal liquor or NaOH adjusted to ph to 8-11;
(4) under stirring, mixed by the waste water of above-mentioned (3) with the metal salt solution of (1), mixed proportion is that at volume ratio 1:1,60-100 DEG C, constant temperature stirs 30min;
(5) cooled and filtered, finally wash drying and obtain solid, namely synthesize copper base or formation of iron based nanoparticles, particle diameter is 10-20nm;
(6) with dried sample for catalyst photocatalytic degradation refinery basic sewage waste water, oil extraction waste water or waste water from dyestuff.
CN201310253683.7A 2013-06-25 2013-06-25 Method used for direct synthesis of nano particle in waste water, and for water treatment by nano particle Expired - Fee Related CN103464218B (en)

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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN1792866A (en) * 2005-11-29 2006-06-28 合肥工业大学 Process for treating waste water of methylene blue dye and process for preparing catalyst
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CN1792866A (en) * 2005-11-29 2006-06-28 合肥工业大学 Process for treating waste water of methylene blue dye and process for preparing catalyst
CN101792172A (en) * 2010-03-03 2010-08-04 天津理工大学 Method for preparing copper hydroxide and copper oxide nano material and application
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