CN103464218A - 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
CN103464218A
CN103464218A CN2013102536837A CN201310253683A CN103464218A CN 103464218 A CN103464218 A CN 103464218A CN 2013102536837 A CN2013102536837 A CN 2013102536837A CN 201310253683 A CN201310253683 A CN 201310253683A CN 103464218 A CN103464218 A CN 103464218A
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waste water
particle
nano particle
oil refining
nano
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CN103464218B (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 social development, in order to meet the growing material and cultural needs of people, produced the waste water that more and more contains the difficult degradation compound in production.These waste water mainly contain the cities and towns medical waste water of hypertoxicity, refinery waste water, residues of pesticides waste water and waste water from dyestuff etc.The discharge of these waste water has caused severe contamination to environment, and the governing problem of this type of waste water has also become the focus that the various countries researchers pay close attention to.The photocatalysis treatment technology due to its treatment temperature and pressure lower, higher and obtain researcher's common concern to the mineralization degree of waste water.
In the application of photocatalysis technology, various greens and the semiconductor light-catalyst that is easy to reclaim are widely used in photocatalysis such as TiO 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 is more and more obvious in the effect that promotes social development and improve aspect environment for human survival.In the transition metal semiconductor nano material, the transition metal nano-sized iron oxide, nano cupric oxide and nano-copper sulfide, because of its excellent physics and chemical property, obtain the general concern of people.Current large quantity research shows, these materials show potential using value aspect wastewater by photocatalysis.Yet the preparation process of nano material is compared with the preparation process of conventional compounds and is seemed comparatively complicated.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, it is particularly necessary that the photochemical catalyst synthetic method of environmental protection seems.
In the past few years, heterogeneous mixing nano composite material catalyst is because of the higher common concern that obtains researchers of catalytic activity in wastewater treatment.Transition metal oxide nano-particles, due to it widely in photocatalysis, air-sensitive, the application in solar cell and electrode material and evoked researcher's interest.In addition, be not only a kind of important industrial chemicals as the formation of iron based nanoparticles of transistion metal compound, and there is good magnetic, light resistance, ultraviolet light is had to strong absorption and screen effect, stable chemical performance, catalytic activity is high, can be widely used in novel magnetic recording materials, electronics, dyestuff, plastics, printing ink, catalyst and bio-science field.Yet, the cost costliness of synthetic these nano materials, building-up process complexity.So, the method for a kind of simple and effective synthetic this type of nano material of necessary exploration, and it is successfully used in wastewater by photocatalysis.
The oil refining alkaline sewage is a kind of waste water that contains high-enriched organics produced in the petroleum refinement process.Because discharge capacity is large, complicated component and toxicity become more by force and day by day the focus of global concern.Contain a large amount of pollutants in this waste water and wherein mainly contain sulfide, volatile phenol, mercaptan, organic acid and benzene class etc.Oil refining alkaline sewage color and luster is dark, stench, has severe corrosive, belongs to high concentration, poisonous, the extraordinary organic liquid waste of difficult degradation, is put into " national danger register " (being numbered HW35).How effectively this type of waste water of disposal and utilization has become the problem received much concern in Petrochemical Enterprises.
The invention provides in a kind of waste water direct synthesizing nano-particle and be applied to the method for water treatment, utilize the method not only effectively to utilize the oil refining alkaline sewage, and successfully prepared the multiple nano particle with certain photocatalytic activity, reached the purpose turned waste into wealth.
summary of the invention
The present invention does alkali source and sulphur source with the oil refining alkaline sewage, and various metal salt compound are raw material, adopts direct precipitation method to synthesize the metal-based nano particle.In addition, we make catalyst with synthetic sample, H 2o 2make oxidizer catalytic hydrogen peroxide degraded oil refining alkaline sewage and simulated wastewater.Result shows that the synthetic nano particle of the present invention all shows higher photocatalytic activity.Utilize this method not only effectively to utilize the oil refining alkaline sewage, but also directly synthesized the less nano particle of particle diameter, reach the effect of killing two birds with one stone.
One of purpose of the present invention be to provide a kind of in the oil refining alkaline sewage the direct method of synthesizing nano-particle, and it is successfully used in the experiment of wastewater by photocatalysis.
Another object of the present invention is effectively to have utilized the oil refining alkaline sewage, reaches the purpose turned waste into wealth.
The present invention adopts following technical scheme:
1) under room temperature, take the metallic salt solid of certain mass, under stirring, make it all be dissolved in water and make metal ion solution;
2) above-mentioned solution is heated to 60-100 oc;
3) pour a certain amount of oil refining alkaline sewage into, 60-100 under the stirring ounder C, constant temperature stirs 30min;
4) cooled and filtered or centrifuge washing, finally obtain powder with absolute ethanol washing; By powder in 80 othe C drying obtains iron-based and copper-based nano particle powder;
5) by following scheme, the nanocatalyst prepared is carried out to the photocatalysis performance evaluation:
A) photocatalytic degradation oil refining alkaline sewage
Oil refining alkaline sewage and catalyst mix after a certain amount of dilution, after the stirring certain hour, add a certain amount of H in quartz ampoule 2o 2solution, under the illumination effect, the COD (COD) of test solution after the reaction certain hour, remove with COD the catalytic performance that efficiency characterizes catalyst
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
Getting a certain amount of catalyst mixes with rhodamine B solution or methyl orange solution; After stirring certain hour under the condition of lucifuge, catalyst is dispersed in solution fully, and makes adsorption-desorption reach balance; Add H 2o 2under rear illumination effect, react; Every at regular intervals to the sample liquid sampling and the removal effect to its color is detected with ultraviolet-visible spectrometer.The degraded percentage means with concentration ratio, the ratio between the concentration that wherein concentration ratio is RhB solution while being different time and MO solution and the concentration of Initial R hB solution and MO solution.
Beneficial effect of the present invention:
In this method, successful use oil refining alkaline sewage adopts direct precipitation method to synthesize nano particle.In addition, we make respectively catalyst, H with synthetic nano particle 2o 2make oxidizer catalytic hydrogen peroxide degraded oil refining alkaline sewage and simulated wastewater.Found that, take the copper-based nano ion during as catalyst, after illumination 120min, the COD of oil refining alkaline sewage removes efficiency and can reach 54%; In simulated wastewater rhodamine B solution 40min, all degraded is complete; Take two kinds of formation of iron based nanoparticles during as catalyst, and after illumination 120min, two kinds of catalyst can reach respectively 47% and 46% to the COD clearance of oil refining alkaline sewage solution; During photocatalysis degradation simulated wastewater methyl orange solution, found that the degradation rate that can make methyl orange solution in 10min reaches respectively 40% and 50%.These the results shows synthetic CuO/CuS nano-complex and the formation of iron based nanoparticles of the present invention all there is very high photocatalytic activity.
With existing additive method and technology, compare, the present invention has following advantage:
1) the present invention has effectively utilized oil refining alkaline sewage solution to synthesize the nano particle with certain photocatalytic activity;
2) nano-particles size that the present invention obtains 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) the synthetic nano particle of the present invention not only has catalytic action to the oil refining alkaline sewage, and simulating pollution waste water is also shown to very high photocatalytic activity.
The accompanying drawing explanation
The digital audio-visual picture of Fig. 1 the present invention oil refining alkaline sewage 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 the b of two kinds of formation of iron based nanoparticles prepared by Fig. 3 the present invention are respectively with FeCl 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 oil refining alkaline sewage 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 oil refining alkaline sewage block diagram (L in figure: illumination, C: catalyst, H:H prepared for source of iron by O (b) 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
Following example is to further illustrate of the present invention, rather than limits the scope of the invention.
Embodiment 1
2.5 gram copper sulphate are dissolved in 50ml water, fully stir solid is all dissolved.Be warming up to after 90oC the oil refining alkaline sewage that adds 50ml 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 to the nano combined powder of CuO/CuS in the 80oC drying.
Embodiment 2
(initial COD is at 8000mgL for oil refining alkaline sewage 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, take the 300W mercury lamp as the COD value of light source light according to test solution after 120min.
Embodiment 3
The CuO/CuS nano-complex of getting 10mg adds in the rhodamine B of 50ml; Stir 60 min under the condition of lucifuge catalyst is dispersed in solution fully, and make adsorption-desorption reach balance; Add H 2o 2after under the 350W illumination condition, react; Every at regular intervals to the sample liquid sampling and the removal effect to its color is detected with ultraviolet-visible spectrometer.
Embodiment 4
By 2.7 gram FeCl 36H 2o is dissolved in 50ml water, fully stirs solid is all dissolved.Be warming up to after 90oC the oil refining alkaline sewage that adds 50ml 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 gram Fe (NO 3) 39H 2o is dissolved in 50ml water, fully stirs solid is all dissolved.Be warming up to after 90oC the oil refining alkaline sewage that adds 50ml 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, be warming up to after 90oC the oil refining alkaline sewage that adds 50ml under stirring.90oC constant temperature stops reaction after stirring 30min.Cooled and filtered or centrifuge washing, obtain pressed powder after the washing drying.

Claims (6)

1. direct synthesizing nano-particle and be applied to the method for water treatment in a waste water, the steps include:
(1), under room temperature, the metal salt compound such as the copper of configuration 0.001-1 mol/L, iron, aluminium, manganese, zinc, cobalt, molybdenum, tungsten, make it all be dissolved in water and make solion under stirring;
(2) above-mentioned solution is heated to 60-100 oc;
(3) target processing waste water can be that oil refining alkaline sewage, oil extraction waste water, waste water from dyestuff etc. are various containing organic waste water, and alkaline waste water is adjusted to 8-11 with sulfuric acid by its pH value, and acid waste water adopts ammoniacal liquor or NaOH to adjust the pH value to 8-11;
(4) under stirring, the waste water of above-mentioned (3) is mixed with the metal salt solution of (1), mixed proportion is 1:1 (volume ratio), 60-100 ounder C, constant temperature stirs 30min;
(5) cooled and filtered or centrifuge washing, finally wash drying and obtain solid;
(6) take dried sample as catalyst photocatalytic degradation oil refining alkaline sewage, oil extraction waste water, waste water from dyestuff etc. various containing organic waste water.
2. direct synthesizing nano-particle and directly apply to the method for water treatment in a kind of waste water according to claim 1, its characteristic feature is to effectively utilize waste water, direct synthesizing nano-particle in waste water.
3. direct synthesizing nano-particle and directly apply to the method for water treatment in a kind of waste water according to claim 1, is characterized in that gentle (the temperature 60-100 of synthesis condition oc), equipment requirement is simple.
4. direct synthesizing nano-particle and directly apply to the method for water treatment in a kind of waste water according to claim 1, it is characterized in that: metallic salt used is a kind of of the metallic salts such as copper, iron, aluminium, manganese, zinc, cobalt, molybdenum, tungsten or more than one any combination.
5. direct synthesizing nano-particle and directly apply to the method for water treatment in a kind of waste water according to claim 1, its characteristic feature is the copper base or the formation of iron based nanoparticles that synthesize, and particle is less, and particle diameter is 10-20nm.
6. the copper base synthesized or formation of iron based nanoparticles not only can be refined oil alkaline sewage, oily waste water and the solution such as dye wastewater methylene blue, methyl orange and rhodamine B of can degrading for photocatalytic degradation.
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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106006690A (en) * 2016-05-24 2016-10-12 新疆大学 Aluminum oxide/carbon nano composite material prepared from alkali slag wastewater and aluminum-containing waste acid

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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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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
CN101798104A (en) * 2010-04-08 2010-08-11 洛阳师范学院 Preparation method for copper sulphide nano particles

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106006690A (en) * 2016-05-24 2016-10-12 新疆大学 Aluminum oxide/carbon nano composite material prepared from alkali slag wastewater and aluminum-containing waste acid

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