CN105060455B - It is a kind of that the photocatalytic method for removing Heavy Metals in Waters organic pollution can be cooperateed with based on Natural pyrite - Google Patents
It is a kind of that the photocatalytic method for removing Heavy Metals in Waters organic pollution can be cooperateed with based on Natural pyrite Download PDFInfo
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Abstract
The present invention discloses a kind of photocatalytic method that can be cooperateed with based on Natural pyrite and remove Heavy Metals in Waters organic pollution.Catalyst pyrite in the photocatalytic system, pyrite photocatalytic system is constituted after broken, grinding, sieving with ultraviolet light.The pyrite photocatalysis technology being related in the present invention, the collaboration that can be applied to Heavy Metals in Waters Cr (VI) and organic matter malachite green is removed, under ultraviolet light, malachite green and Cr (VI) clearance can reach 97% and more than 52% respectively.Pyrite photochemical catalyst has preferable repeat performance, after being reused through five times, preferable reactivity can also be kept, catalyst is fully used, the catalytic reaction operating condition being related in reaction is simple, catalyst raw material is cheap and easy to get, the pollution control theory based on the treatment of wastes with processes of wastes against one another, with preferable application prospect.
Description
Technical field：
The present invention relates to the method for treating water containing heavy metal-organic contamination, and in particular to one kind is based on natural yellow iron
Ore deposit can cooperate with the photocatalytic method of removal Heavy Metals in Waters-organic pollution.
Background technology：
At present, developing rapidly with industry, the quick raising of economic level, the thing that the mankind ask for and discharged from nature
Matter has also reached unprecedented level, considerably beyond the capacity of environment in itself, so as to cause the serious broken of Environment-Ecosystem
It is bad, occur in that a series of problem of environmental pollution.In face of current severe environmental pollution situation, some are such as chemical precipitation method, thing
Traditional environment restoring methods such as reason absorption method, chemical oxidization method, microorganism treatment are applied to current contaminated environment
In medium, although these environment restoring methods all serve significant role to the current control of environmental pollution, these tradition
Environment remediation technology all exist to some extent efficiency it is low, can not thoroughly by environmental contaminants remove or it is innoxious, easy
Produce new pollution sources；Or using opereating specification it is narrow, be suitable only for specific pollutant；It is uncomfortable or energy consumption is too high, material cost is expensive
Close the limitation in terms of large-scale promotion application.Thus, exploitation is efficiently, low energy consumption, low cost, environment applied widely repair
Multiple Treatment process has turned into current scientific research environmental administration and has been badly in need of one of important topic of solution.
However, a kind of extensive concern for being light-catalysed technology increasingly by environmental worker, it is from 20th century 70
The emerging environment remediation Treatment process that age progressively grows up, it utilizes semiconductor oxide materials surface under light illumination
Can by activation characteristic, the free radical of strong oxidizing property is produced using luminous energy, can efficiently oxidation Decomposition has in a short time
Machine thing, or kill bacterium, eliminate gas with foreign flavor, or the heavy metal ion of electron reduction high price is produced, reduction heavy metal ion
Toxicity.Due to photocatalysis technology have the advantages that simple to operate, reaction thoroughly, energy consumption cost is low, efficiency high and nonhazardous, recognized
To be a kind of environment remediation Treatment process of most application prospect, the reparation for having been widely used for various kinds environmental pollution medium is controlled
Reason field.However, the scavenging effect of photocatalysis technology is directly related to photocatalyst material, and at present, TiO2Conductor photocatalysis
Technology is considered most stable, the most ripe.Except TiO2And its it is material modified outside, other photochemical catalysts such as ZnO,
Al2O3、SnO2、Co3O4Deng and various composite material photocatalysts be also widely used in environmental pollution repairing and treating field, and
Show good environment remediation effect.It is reported that pyrite (FeS2) can also be yellow as a kind of photocatalytic semiconductor material
Iron ore band structure determines that it has good photoelectric properties, the existing phase for pyrite being applied to catalytic degradation organic pollution
Close report.Moreover, pyrite particle also has good absorption property, can adsorb pollutant and remove, in addition, yellow iron
Ore deposit also has stronger reproducibility, and the heavy metal ion of high price such as Cr (VI) can be reduced to Cr (III), reduces heavy metal ion
Toxicity.Therefore, have in terms of having the environment remediation improvement of oxidation and the pyrite of reduction characteristic in pollution medium concurrently good
Application potential.
In fact, pyrite is metal sulfide ore most commonly seen on the earth, and be prevalent in various ores and
In mine tailing, and the oxidation of this mineral discharges substantial amounts of iron ion and sulfuric acid, is the main cause of acid wastewater in mine formation.And
And, the economic use value of pyrite is cheap, is normally thought of as the waste minerals after mining ore dressing.However, in recent years
Come, substantial amounts of domestic and international researcher directly use or transformation waste material come thing of curbing environmental pollution, and pass through experiment acquisition
Good effect.Environmental pollution improvement's theory of this " treatment of wastes with processes of wastes against one another " by refuse reclamation is increasingly by people's
Extensive concern.As the pyrite of mine solid waste, in terms of the improvement that should can be also applied in environmental contaminants.
However, industrial pollution source mainly has heavy metal and organic matter at present, heavy metal mainly has chromium, lead and cadmium etc., and has
Machine thing mainly has phenol, chlorophenol and dyestuff etc..Pollution in actual environment is often that various heavy and organic contamination are deposited jointly
A kind of combined pollution, the pollution of heavy metal-organic composite is the pollution type that biggest threat is produced to environment, in current rigorous
Situation under, the environmental improvement of heavy metal-organic composite contamination characteristics is extremely urgent.Existing most of environment remediation skills
Art is both for simple by heavy metal or Organic Pollution water body, and therefore, striving to find one kind can be while removes in water body
The efficient context restorative procedure of heavy metal-organic contamination has become the most important subject under discussion of Environmental Science.Based on pyrite half
Conductor has photochemical catalytic oxidation and reduction characteristic concurrently, using pyrite as photochemical catalyst, and collaboration removes weight in water body under ultraviolet lighting
Metal-organic pollution, however, up to the present, similar patented technology has not been reported.
The content of the invention：
It is an object of the invention to provide a kind of reaction condition is simple and easy to apply, reaction is thorough, energy consumption cost is low, efficiency high profit
The photocatalysis method of removal Heavy Metals in Waters-organic pollution can be cooperateed with Natural pyrite.This method can be cooperateed with effectively
Heavy metal Cr (VI) and organic matter malachite green are removed, the harm of Cr (VI) and malachite green to environment is reduced；And catalyst
Pyrite, which has, preferably reuses stability, and one is provided for complicated heavy metal-organic composite pollution law
Plant " treatment of wastes with processes of wastes against one another " river harnessing ideas.
The present invention's can cooperate with the photocatalytic method of removal Heavy Metals in Waters-organic pollution based on Natural pyrite, its
It is characterised by, comprises the following steps that：
(1), first catalyst pyrite is crushed, ground, sieved, makes its particle radius in 20~40 μ ms；
(2), water pH value of the regulation containing heavy metal Cr (VI) and organic matter malachite green；
(3), under ultraviolet light conditions, into the water body containing heavy metal Cr (VI) and organic matter malachite green, step is added
Suddenly (1) treated catalyst pyrite, is reacted, and redox collaboration removes Cr (VI) and malachite green in water body.
It is preferred that, the pH value of step (2) is 2~7.
Further preferably, the pH value of step (2) is 3.
The described water body containing heavy metal Cr (VI) and organic matter malachite green, it is preferable that Cr (VI) mass concentration is
2.5~30mg/L.
The described water body containing heavy metal Cr (VI) and organic matter malachite green, it is preferable that the mass concentration of malachite green
For 30mg/L.
Ultraviolet light conditions described in step (3), it is preferable that ultraviolet ray intensity is 10~20W.
Treated catalyst pyrite is added described in step (3), preferably dosage is 0.5~1.5g/L.
Progress described in step (3) is reacted, and the reaction time is preferably 100~120min.
The present invention concerted reaction principle be：Highly toxic Cr (VI) is converted into the low Cr of toxicity by reduction
(Ⅲ)；And then destroy chromophore by oxidation generates small organic molecule to malachite green, and it is eventually converted into water and two
Carbonoxide.Water pollutant concentration after being handled through collaboration is effectively reduced, and alleviates the pressure of subsequent treatment.
It is right after being handled by the method for the present invention the water body containing heavy metal Cr (VI) and organic matter malachite green
Catalyst pyrite carries out centrifugation recovery, and catalyst pyrite is reused number of times and can reach five times.
Compared with prior art, the present invention has advantages below and beneficial effect：
1st, reaction condition is simple to operate：The present invention is that catalyst Huang is added in containing Cr (VI) and the water body of malachite green
Effectively it can be removed simultaneously under iron ore, normal temperature and pressure；
2nd, processing cost is low：Compared to other photochemical catalysts such as TiO2, the pyrite used in the present invention is mine solid waste,
It is cheap and easily-available, and processing procedure is easy, and the environmental improvement theory of the treatment of wastes with processes of wastes against one another has a good application prospect；
3rd, react thorough：In 120min, malachite green realizes more than 97% degraded, and effectively mineralising is dioxy
Change carbon and water；And Cr (VI) then has more than 52% to be converted into Cr (III), toxicity is effectively reduced；
4th, it is applicable object scope wide：The present invention is applicable not only to going for the polluted-water containing Cr (VI) or malachite green
Remove, be also adapted to the removal of the polluted-water simultaneously containing Cr (VI) and malachite green.
Brief description of the drawings：
Fig. 1 is influences of the different pH to Cr (VI) and malachite green removal effect；
Fig. 2 is influence of the different catalysts amount to Cr (VI) and malachite green removal effect；
Fig. 3 is the influence that different pollutant concentrations compare Cr (VI) and malachite green removal effect；
Fig. 4 is that pyrite photocatalysis cooperates with the reuse effect for removing Cr (VI) and malachite green；
Embodiment：
Following examples are that the present invention is further illustrated, rather than limitation of the present invention.
The concentration of Cr (VI) ion in the examples below, in water sample is determined using diphenyl carbazide spectrophotometry
(GB7467-87)：In Cr (VI) sample solution after 10mL dilutions, 0.5mL 1 is separately added into:1 sulfuric acid solution and 0.5mL
1:1 phosphoric acid solution, shakes up；2mL 200mg/L diphenylcarbazide solution is added, is shaken up, develop the color 5~10min,
At 540nm wavelength, reference is done with water, absorbance is determined.The clearance of Cr (VI) is calculated by absorbance.And malachite green
Concentration use UV-VIS spectrophotometry, wavelength be 618nm locate measure absorbance change calculate its clearance.
Embodiment 1：
First catalyst pyrite is crushed, ground, sieved, makes its particle radius in 20~40 μ ms；Regulation
Water pH value 2~7 containing heavy metal Cr (VI) and organic matter malachite green；It is heavy to 10mg/L is contained under ultraviolet light conditions
In the water body of metal Cr (VI) and 30mg/L organic matter malachite greens, treated catalyst pyrite 1.0g/L is added, 10
Under~20W ultraviolet lights, average rate stirring is kept, is reacted, react 100~120min, redox collaboration removes water body
In Cr (VI) and malachite green.Determine the change of Cr (VI) and malachite green concentration in the front and rear water body of reaction.
In the result of embodiment 1 as shown in figure 1, as seen from Figure 1, after reaction 120min, Cr (VI) and malachite green
Downward trend is presented with pH rise for clearance, wherein, malachite green and Cr (VI) the clearance highest in pH=3,
97.3% and 53.1% are respectively reached.
Comparative example 1：
In this comparative example, the water body containing malachite green is individually handled using pyrite as different from Example 1, it is past
Reactor adds the malachite green solution that concentration is 30mg/L, and pH value of solution regulation to 3, other conditions are same as Example 1.It is right
The result of ratio 1 is as shown in table 1, as can be seen from Table 1, when pyrite individually handles malachite green solution, the removal of malachite green
Rate is 76.9%, and when removing Cr (VI) and malachite green at the same time, its clearance has reached that 97.3%, Cr (VI) presence has
Effect promotes the efficiency of pyrite photocatalysis malachite green, and Cr (VI) can also realize synchronous removal.
Comparative example 2：
In this comparative example, the water body containing Cr (VI) is individually handled using pyrite as different from Example 1, it is past anti-
Device is answered to add Cr (VI) solution that concentration is 10mg/L, pH value of solution regulation to 3, other conditions are same as Example 1.Comparative example
As shown in table 1, as can be seen from Table 1, when pyrite individually handles Cr (VI) solution, Cr (VI) clearance is 2 results
28.5%, and Cr (VI) and malachite green compound tense are being removed, its clearance has reached 53.1%, and the presence of malachite green is effective
Pyrite photocatalysis Cr (VI) efficiency is promoted, and malachite green can also realize that synchronous high-efficiency is removed.
Table 1. compares for the Cr (VI) and malachite green removal effect under different technology conditions
Embodiment 2：
Difference from Example 1 is that the initial pH value of regulation polluted-water is 3, the dosage of catalyst pyrite
For 0.5~1.5g/L, the change of Cr (VI) and malachite green concentration in the front and rear water body of reaction is determined.In the result of embodiment 2 such as Fig. 2
Shown, as seen from Figure 2, after reaction 120min, malachite green and Cr (VI) clearance are with pyrite photochemical catalyst
The increase of dosage and elevated trend is presented, when dosage be 1.0g/L when, malachite green and Cr (VI) clearance are several
Maximum is reached, when dosage is more than 1.0g/L, malachite green and Cr (VI) clearance no longer change.
Embodiment 3：
Difference from Example 1 is that the concentration ratio that adjust malachite green and Cr (VI) is 12:1~1:1, determine
The change of Cr (VI) and malachite green concentration in the front and rear water body of reaction.In the result of embodiment 3 as shown in figure 3, can be seen by Fig. 3
Go out, reaction 120min after, Cr (VI) clearance declines with the reduction of concentration ratio, and the removal of malachite green take the lead in
The reduction of concentration ratio and rise, when concentration ratio is more than 3:When 1, the clearance of malachite green but with the reduction of concentration ratio under
Drop.Therefore, when malachite green/Cr (VI) is 3:When 1, malachite green and Cr (VI) clearance have respectively reached maximum.
Embodiment 4：
Difference from Example 1 is that the initial pH value of regulation polluted-water is 3, and reacted pyrite is carried out
Reclaim five times and reused, the change of Cr (VI) and malachite green concentration in the front and rear water body of reaction is determined every time.Implementing
The result of example 4 is as shown in figure 4, as seen from Figure 4, when photocatalysis reuses first three time, catalyst also maintains very in itself
High activity, malachite green and Cr (VI) clearance are respectively maintained at 95% and 51% level above.After the 4th time, two
The clearance of person occurs in that downward trend, but after reusing the 5th time, malachite green and Cr (VI) clearance
76.5% and 39.4% can also be reached, pyrite keeps preferable catalytic activity.
Claims (1)
1. the photocatalytic method of removal Heavy Metals in Waters-organic pollution can be cooperateed with based on Natural pyrite, it is characterised in that tool
Body step is as follows：
(1), first catalyst pyrite is crushed, ground, sieved, makes its particle radius in 20~40 μ ms；
(2) water pH value containing heavy metal Cr (VI) and organic matter malachite green, is adjusted to 3；
(3), under ultraviolet light conditions, into the water body containing heavy metal Cr (VI) and organic matter malachite green, step (1) is added
Treated catalyst pyrite, is reacted, and redox collaboration removes Cr (VI) and malachite green in water body；
The described water body containing heavy metal Cr (VI) and organic matter malachite green, Cr (VI) mass concentration is 30mg/L；
Ultraviolet light conditions described in step (3), ultraviolet ray intensity is 10~20W；
The treated catalyst pyrite of step (1) is added described in step (3), dosage is 0.5~1.5g/L；
Progress described in step (3) is reacted, and the reaction time is 100~120min.
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| CN105458294B (en) * | 2016-01-18 | 2018-11-23 | 中国科学院南海海洋研究所 | A kind of iron standby nano zero valence iron and the preparation method and application thereof using in acidic mine waste water |
| CN106957078B (en) * | 2017-02-17 | 2020-06-12 | 湖南有色金属研究院 | Method for degrading residual agent in beneficiation wastewater by photocatalytic semiconductor sulfide ore based on iron-oxidizing bacteria |
| CN107611009B (en) * | 2017-08-30 | 2020-10-13 | 尚妙根 | Preparation method of zinc oxide composite semiconductor material |
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| CN110918102A (en) * | 2019-12-10 | 2020-03-27 | 桂林理工大学 | Preparation method of graphene oxide modified metal sulfide composite photocatalyst |
| CN112642576B (en) * | 2020-09-17 | 2022-02-01 | 中南大学 | Selective oxidation and flotation separation method for pyrite gangue in sulfide ore |
| CN112206790B (en) * | 2020-11-12 | 2022-04-22 | 厦门理工学院 | Preparation method and application of modified pyrite with photocatalytic performance |
| CN113060817B (en) * | 2021-03-18 | 2022-08-16 | 中南大学 | Method for treating chromium-containing electroplating wastewater by using mineral modified material |
| CN113880218B (en) * | 2021-10-12 | 2022-11-29 | 中南大学 | Utilize organic dyestuff effluent disposal system of pyrite tailing |
| NL2031328B1 (en) | 2022-03-18 | 2023-09-29 | Univ Wageningen | Process for the generation of hydrogen sulfide in the presence of pyrite as catalyst |
| CN114702117B (en) * | 2022-05-20 | 2023-08-29 | 中国地质大学（北京） | Method for simultaneously removing mine heavy metals and organic pollutants by utilizing iron-containing solid wastes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1040968A (en) * | 1988-09-06 | 1990-04-04 | 厦门大学 | A kind of method of photocatalysis treatment of waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1040968A (en) * | 1988-09-06 | 1990-04-04 | 厦门大学 | A kind of method of photocatalysis treatment of waste water |
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