CN107601737A - A kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage - Google Patents
A kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage Download PDFInfo
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- CN107601737A CN107601737A CN201711130545.4A CN201711130545A CN107601737A CN 107601737 A CN107601737 A CN 107601737A CN 201711130545 A CN201711130545 A CN 201711130545A CN 107601737 A CN107601737 A CN 107601737A
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Abstract
The invention discloses a kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage, comprise the following steps：Nitrogen or inert gas are passed through into organic sewage first and with ultraviolet light irradiation organic sewage, while the gas mercury evaporated is absorbed with iodine solution absorption plant；Finally, after ultraviolet light irradiation terminates, to adding coagulant in sewage, stir, remove the mercury simple substance remained in sewage.The present invention is not required to add other chemical agents, it is green, also avoid using advanced oxidation agent and catalyst, cost greatly reduces, simple equipments, simple to operate, processing speed is fast, improves operating efficiency, do not produce sludge, there is no secondary pollution generation, it is preferable for mercury removal effect in sewage, have a good application prospect.
Description
Technical field
The present invention relates to photocatalytic pollutant degradation field, and in particular to a kind of matrix auxiliary UV photocatalysis removes organic
The method of mercury in sewage.
Background technology
The heavy metal contaminants being primarily present in China's water body are：Mercury, arsenic, chromium, nickel, copper, lead, cadmium etc..The pollution of mercury is outstanding
It is serious, according to requirement of the surface water environment quality Group III water quality to mercury（It must not exceed 0.1 μ g/L）, the river mercury in China 35%
It is exceeded.Again because mercury has heavy metal pollution own characteristic, excrete as continuation is not easy metabolism long, in vivo, may be used also
So that by the formation biological concentration of food chain, the threat to human health can not be ignored, and mercury can also give birth to through microbial action
The alkyl mercury bigger into toxicity, this is a kind of hypertoxic organo-metallic compound with strong carcinogenesis.Mercury is to human health
Threat can not be ignored.
At present, both at home and abroad processing the method containing mercury metal sewage mainly have chemical precipitation method, absorption method, electrolysis, from
Sub- exchange process, hyperfiltration and ultraviolet cooperating oxidation etc..Chemical deposition method is by the heavy metal ion in dissolved state
The stable heavy metal compound not readily dissolved is converted to by chemical reaction, forms precipitation in aqueous, then sink by gravity
It is separated general who has surrendered from the aqueous solution, and conventional means have alkaline sedimentation, by adding alkalization in heavy metal containing sewage
Learning thing or sulphide salt is precipitated out heavy metal ion, and the subject matter of alkaline sedimentation is heavy metal ion and alkaline chemical combination
The particle diameter of caused heavy metal oxyhydroxide is very tiny after thing reaction, it is difficult to carries out precipitation separation, easily causes secondary dirt
Dye, heavy metal complex is easily formed additionally, due to heavy metal ion in the solution, in the case where there is complex compound interference through alkali
Property sedimentation processing sewage water outlet heavy metal ion content it is still exceeded, it is difficult to reach the discharge standard of national regulation.Absorption
It by absorption method is to utilize porosu solid adsorbent that method, which is, and make in sewage heavy metal ion adsorbed removes in adsorbent surface
A kind of method, the method is wide to applicability containing heavy metal containing sewage, non-secondary pollution, but because adsorbent is to various heavy metal ion
Adsorptive selectivity it is not high, in sewage other non-heavy metal ions can heavy metal ion form competitive Adsorption, influence a huge sum of money
Belong to the exchange adsorption of ion, so as to cause the removal effect of heavy metal ion bad.Electrolysis be using platinum group oxide or
PbO2 makees anode, regulation sewage pH to appropriate value, then by flocculating, precipitating, filter progress heavy metals removal, but the method energy consumption
Larger, cost is higher and correlation technique is also immature.Ion-exchange is the same sewage of active group by ion exchange resin
In heavy metal ion swap, so as to reach the purpose of heavy-metal ion removal, this method is simple to operate, is easy to regenerate, but
Easily by resin adsorption capacity limit, and resin is easy to be poisoned, and processing cost is higher.Hyperfiltration is the weight in sewage is not changed
Concentrated and separated using biotechnology heavy metal sewage under conditions of the chemical form of metal ion, particularly as be by
The effect of ambient pressure makes the water of sewage retain heavy metal ion through pellicle, and the method is by one in economic and technical
A little limitations, the problems such as investment is larger, and operating cost is high be present, be also unsuitable for the industrial wastewater for handling big flow at present.Common
Ultraviolet cooperating oxidation technology has ultraviolet light-hydrogen peroxide synergistic oxidation（UV/H2O2）Technology, ultraviolet light-ozone cooperative oxidation technology
（UV/O3）, ultraviolet light-Fenton synergistic oxidation technology（UV-Fenton）And ultraviolet light-electrochemical process oxidation technology.With it is other
Oxidation technology is compared, and ultraviolet oxidation technology possesses the advantages of no secondary reagent introduces pollution, therefore is a kind of more green
Sewage oxidation processing method.It is but general using addition catalyst in order to improve the photocatalysis efficiency of ultraviolet light in synergistic oxidation
Advanced oxidation agent with high concentration is such as：The higher oxidant of the prices such as hydrogen peroxide, chlorine dioxide, ozone, so, just greatly
Add cost, equally cause ultraviolet oxidation catalysis technique advantage to lose to the greatest extent.
The content of the invention
For deficiencies of the prior art, it is an object of the invention to provide a kind of matrix auxiliary UV photocatalysis
The method for removing mercury in organic sewage, solve existing mercury metal sewage water treatment method and have that removal effect is bad, easily causes two
Secondary pollution, cost are high and the problem of energy consumption is big.
To achieve the above object, the present invention adopts the following technical scheme that：A kind of matrix auxiliary UV photocatalysis removes organic
The method of mercury, comprises the following steps in sewage：
1）Nitrogen or inert gas are passed through into organic sewage；
2）Under conditions of nitrogen or inert gas is passed through, the organic sewage described in ultraviolet light irradiation, light-catalyzed reaction is carried out；Together
When with iodine solution absorb the gas mercury that evaporates；Preferably, the concentration of iodine solution is 0.05 ~ 0.2mol/L.
3）After ultraviolet light irradiation terminates, to adding coagulant in sewage, stir, remove the mercury list remained in sewage
Matter.
Found through experiment：If the selection of ultraviolet EWL is too short, propagation distance of the ultraviolet light in reactor is too
Short, the pollutant process amount under unit power substantially reduces, and can not meet basic processing requirement, if but ultraviolet wavelength choosing
That selects is oversize, and the energy of ultraviolet photon will be reduced substantially, and the ultraviolet photon of low energy can not destroy the molecular link of organic matter, so as to
The free radical of sufficient concentrations of reproducibility can not be produced.And energy consumption increases substantially, the economy of system is reduced, by comprehensive
Found after detection and analysis, ultraviolet EWL is 160nm-380nm.Wherein optimal wavelength is 253.7 nm.Its catalytic efficiency
It is higher.The low pressure mercury lamp of in the market purchase can launch 253.7nm ultraviolet light, and be not in that heating is serious in the course of work
Phenomenon, it is not required that water cooling plant, convenient operation.It is preferred that the ultraviolet light irradiation time is 10 ~ 30min.
Because the dissolved oxygen in usual water body is generally existing, oxygen can consume reducing substances, reduce in sewage
The concentration of reducing substances.Hydrone and dissolved oxygen in water can produce the stronger ozone of oxidisability, mistake under ultraviolet light
Hydrogen oxide, hydroxyl radical free radical isoreactivity material, so as to which oxidation operation is resolved into carbon dioxide and water.Therefore in ultraviolet light spoke
According to while, nitrogen or inert gas are passed through into sewage solution, the oxygen in sewage can be taken out of, to avoid organic matter quilt
Oxidation.And nitrogen or inert gas do not react with material in sewage, so the composition of sewage will not be changed, it is especially low
The content of molecular weight organic material.When the gas flow rate being passed through reaches 200ml/min, the flow velocity for continuing to increase nitrogen is gone to mercury
Except efficiency influences less, so currently preferred, the flow velocity of nitrogen or inert gas is 50 ~ 200ml/min.
Found through experiment：The dosing coagulant before ultraviolet light, the clearance of mercury is with coagulant such as aluminium polychloride
（PAC）Dosage increase and reduce on the contrary, this is due to that after coagulant in sewage forms coagulating sedimentation, have impact on ultraviolet light
Penetrability, photocatalysis efficiency is caused to reduce.In addition, coagulant eliminates the organic substance in sewage so that photocatalysis occurred
Indispensable reducing substances concentration reduces in journey, therefore photocatalysis efficiency significantly reduces.So the present invention is in ultraviolet lighting
Coagulant is added after penetrating, contributes to precipitation and the removal of metal.It is preferred that the addition of coagulant is 2 ~ 10mg/l, preferably coagulation
Agent is aluminium polychloride, ferric trichloride, ferrous sulfate or magnesium sulfate.
Found through experiment：With the increase of mercury concentration in sewage sample, the removal efficiency of mercury gradually reduces.Its reason is dirty
Organic matter content in water has run out of, and can not produce more reducing substanceses and mercury ion is reduced into mercury simple substance.Cause
This is in the sewage of quantity of organic, and after the irradiation of ultraviolet light, the maximum of caused reducing substances depends on dirt
The concentration of Organic substance in water matter, even if providing the ultraviolet light irradiation of longer time and higher intensity, without the reproducibility of abundance
Material participates in light-catalyzed reaction, and photocatalysis efficiency is will not be increased.Therefore the concentration of mercury is higher in sewage sample, and it removes effect
Rate is lower.So the present invention preferably adds organic matter before ultraviolet light irradiation in sewage, it is organic to be preferably added to low molecule amount
Thing, the organic matter of low molecule amount is formic acid, methanol or acetic acid, and the addition of organic matter is needed according to specific dirty Organic substance in water
Concentration and the concentration of mercury determine that the waste or mercury for avoiding organic matter can not be removed effectively.
Compared with prior art, the present invention has the advantages that：
The method that the present invention removes mercury in organic sewage using the photocatalysis of matrix auxiliary UV, mainly make use of in sewage simultaneously
Contain substantial amounts of organic substance（The especially organic matter of low molecule amount）And the characteristics of mercury, organic substance is under the irradiation of ultraviolet light
It can decompose and produce the reducing substances containing reductive free radical, these reducing substanceses can be by heavy metal（Mercury）Ion reduction Cheng Chong
Metal（Mercury）Simple substance, heavy metal（Mercury）Simple substance is removed it with the precipitation method or gas purging again, can also be to the huge sum of money in sewage
Category（Mercury）Recycled, turned waste into wealth.The organic matter in sewage is also been removed simultaneously.Therefore the present invention is not required to add other
Chemical agent, it is green, also avoid using advanced oxidation agent and catalyst, greatly reduce cost, simple equipments, behaviour
Make simply, processing speed is fast, improves operating efficiency, does not produce sludge, is produced without secondary pollution, and effect is removed for mercury in sewage
Fruit is up to 98%.Have a good application prospect.
Brief description of the drawings
Fig. 1 is the photocatalytic chemical reactor figure of the present invention；
Fig. 2 is influence of the nitrogen to mercury removal efficiency；
Fig. 3 is influence of the organic matter to mercury removal efficiency.
Embodiment
The present invention is described in further detail with reference to specific embodiments and the drawings.The original used in following embodiments
Material is commercially available prod.Atomic fluorescence spectrophotometer：AFS-2100, Beijing Haiguang Instrument Co., Ltd.；Ultraviolet tube：Type
Number it is UVC220-2H, power 15W, brand Cnight, made in China；Aluminium polychloride（PAC）Purchased from the blue clean running water in Chongqing
Materials Co., Ltd；The chemical reagent such as nitric acid, formic acid are bought from the western Gansu Province chemical reagent factory in Chongqing.
Because ultraviolet light runs into the particles such as the dust in air in air borne and can cause purple through glassware
Outer luminous intensity is significantly lost, and in order to ensure that light-catalyzed reaction is fully carried out, lifts ultraviolet light photocatalysis efficiency, and ultraviolet lamp tube is straight
In the sewage for patching beaker.Ultraviolet light can make the oxygen in air be ionized into ozone, and excessive ozone concentration is harmful to health strong
Health, whole experiment should be carried out under sound ventilation environment.Experiment reaction unit is placed in fume hood by the work of this experimental study
Carry out, effectively avoid caused ozone in experimentation from being detrimental to health.In addition ultraviolet light is harmful to skin, can trigger skin
Disease, experimentation should take measures the irradiation for avoiding human body from receiving ultraviolet light.The work of this experimental study will test reaction unit
It is placed in inside a closed flight data recorder, effectively avoids the leakage of ultraviolet light.Photocatalytic chemical reactor as shown in Figure 1,
By ultraviolet tube 3 vertically from container of the center of beaker 2 insertion equipped with organic sewage, whole device be placed on one it is closed black
The inside of box 1, and keep divulging information.Then closed flight data recorder is connected with the iodine solution absorption plant of routine with gas conduit,
The gas mercury for enabling to evaporate enters in iodine solution along gas conduit, and is fully reacted with iodine.Described iodine solution preserves
In Brown Glass Brown glass bottles and jars only.
With the concentration of mercury ion in atomic fluorescence light splitting photometry detection organic sewage, instrument parameter is shown in Table 1.
The atomic fluorescence spectrophotometer running parameter of table 1
| Instrument parameter | Parameter value |
| Lamp current (mA) | 80 |
| Photomultiplier negative high voltage (V) | -280 |
| Atomizer height (mm) | 10 |
| Flow rate of carrier gas (ml/min) | 500 |
| Shield gas flow speed (ml/min) | 1200 |
Embodiment 1
A kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage, comprises the following steps：
1）To 1L organic sewage（Containing 50 μ g/L mercury）In be passed through nitrogen, the flow velocity of wherein nitrogen is respectively 0,50,100,200,
400th, 600,800 and 1000ml/min.
2）It is inserted directly into simultaneously with a length of 253.7nm low pressure mercury lamps of ultraviolet light wave in the sewage of beaker and irradiates 15min, is carried out
Light-catalyzed reaction, the gas mercury evaporated is absorbed with iodine solution absorption plant；Wherein the concentration of iodine solution is 0.1mol/L.
3）After ultraviolet light irradiation terminates, 2.5mg aluminium polychloride is added into organic sewage, with 200r/min speed
Sewage is stirred, removes the mercury simple substance remained in sewage.As shown in Figure 2.
Figure it is seen that in obstructed nitrogen, the clearance of Mercury sewage is only 75% in organic sewage；With different in flow rate
Nitrogen is passed through, improves ultraviolet light to varying degrees to mercury removal efficiency.When the flow velocity of nitrogen is 100ml/min, mercury
Clearance rises to 90%.When the flow velocity of nitrogen is more than 200ml/min, the removal on mercury influences little.
Embodiment 2
A kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage, comprises the following steps：
1）Organic sewage is divided into 2 groups, each group of organic sewage has 7 kinds of different mercury concentration, it is respectively 10,20,50,
100th, 500,1000,2000 μ g/L, one of which add the 10% of 10ml（V/V）Formic acid, be well mixed, another set addition
The deionized water of same volume.
2）Then nitrogen is passed through, the flow velocity of wherein nitrogen is respectively 100ml/min.It is simultaneously a length of with ultraviolet light wave
253.7nm low pressure mercury lamps, which are inserted directly into the sewage of beaker, irradiates 15min, light-catalyzed reaction is carried out, with iodine solution absorption plant
Absorb the gas mercury evaporated；Wherein the concentration of iodine solution is 0.2mol/L.
3）After ultraviolet light irradiation terminates, 2.5mg aluminium polychloride is added into organic sewage, with 200r/min speed
Sewage is stirred, removes the mercury simple substance remained in sewage.As shown in Figure 3.
From figure 3, it can be seen that when adding formic acid not into sewage, with the increase of mercury concentration in sewage sample, mercury
Removal efficiency gradually reduces, and when ion concentration of mercury is 1000 μ g/L, the clearance of mercury is only 50%.When adding first into sewage
When sour, with the increase of mercury concentration in sewage sample, the removal efficiency reduction degree of mercury is little, when ion concentration of mercury is 1000 μ
During g/L, the clearance of mercury is 90%.When ion concentration of mercury is 100 μ g/L, the clearance of mercury is up to 95%.
Embodiment 3
A kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage, comprises the following steps：
1）To the organic sewage equipped with 1L（Containing 50 μ g/L mercury）The 10% of middle addition 5ml（V/V）Acetic acid, be well mixed, Ran Houtong
Enter nitrogen, the flow velocity of nitrogen is 150ml/min respectively.
2）Under conditions of nitrogen is passed through, a length of 360nm of ultraviolet light wave ultraviolet lamp tube is inserted directly into the sewage of beaker
Middle irradiation 10min, carry out light-catalyzed reaction；The gas mercury evaporated is absorbed with iodine solution absorption plant simultaneously；Wherein iodine is molten
The concentration of liquid is 0.1mol/L.
3）After ultraviolet light irradiation terminates, 8mg ferric trichloride is added into sewage, sewage is entered with 200r/min speed
Row stirring, removes the mercury simple substance remained in sewage.
The clearance of Mercury sewage is 98% in organic sewage.
Embodiment 4
A kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage, comprises the following steps：
1）To the organic sewage equipped with 1L（Containing 50 μ g/L mercury）The 5% of middle addition 20ml（V/V）Methanol, it is well mixed to be passed through helium
Gas, the flow velocity of helium is 200ml/min respectively.
2）Under conditions of nitrogen is passed through, a length of 160nm of ultraviolet light wave ultraviolet lamp tube is inserted directly into the sewage of beaker
Middle irradiation 30min, carry out light-catalyzed reaction；The gas mercury evaporated is absorbed with iodine solution absorption plant simultaneously；Wherein iodine is molten
The concentration of liquid is 0.05mol/L.
3）After ultraviolet light irradiation terminates, 10mg ferrous sulfate is added into sewage, with 200r/min speed to sewage
It is stirred, removes the mercury simple substance remained in sewage.
The clearance of Mercury sewage is 96% in organic sewage.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (9)
1. a kind of method that matrix auxiliary UV photocatalysis removes mercury in organic sewage, it is characterised in that comprise the following steps：
1）Nitrogen or inert gas are passed through into organic sewage；
2）Under conditions of nitrogen or inert gas is passed through, the organic sewage described in ultraviolet light irradiation, light-catalyzed reaction is carried out, together
When with iodine solution absorb the gas mercury that evaporates；
3）After ultraviolet light irradiation terminates, to adding coagulant in sewage, stir, remove the mercury simple substance remained in sewage.
2. the method that the photocatalysis of matrix auxiliary UV removes mercury in organic sewage according to claim 1, it is characterised in that institute
The flow velocity for stating nitrogen or inert gas is 50 ~ 200 ml/min.
3. the method that matrix auxiliary UV photocatalysis according to claim 1 removes mercury in organic sewage, it is characterised in that
The wavelength of the ultraviolet light is 160nm ~ 380nm.
4. the method that the photocatalysis of matrix auxiliary UV removes mercury in organic sewage according to claim 1, it is characterised in that institute
It is 10 ~ 30min to state the ultraviolet light irradiation time.
5. the method that the photocatalysis of matrix auxiliary UV removes mercury in organic sewage according to claim 1, it is characterised in that institute
The concentration for stating iodine solution is 0.05 ~ 0.2mol/L.
6. the method that the photocatalysis of matrix auxiliary UV removes mercury in organic sewage according to claim 1, it is characterised in that institute
It is aluminium polychloride, ferric trichloride, ferrous sulfate or magnesium sulfate to state coagulant.
7. the method that the photocatalysis of matrix auxiliary UV removes mercury in organic sewage according to claim 1, it is characterised in that institute
The addition for stating coagulant is 2 ~ 10mg/L.
8. the method that the photocatalysis of matrix auxiliary UV removes mercury in organic sewage according to claim 1, it is characterised in that
Step 2）Before, in addition to：Organic matter is added in the organic sewage.
9. the method that matrix auxiliary UV photocatalysis according to claim 8 removes mercury in organic sewage, it is characterised in that
The organic matter is low-molecular-weight organic matter, and described low-molecular-weight organic matter is formic acid, methanol or acetic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112777850A (en) * | 2020-12-15 | 2021-05-11 | 上海傲江生态环境科技有限公司 | Treatment method and treatment system for mercury-containing high-concentration organic pesticide wastewater |
| CN112794491A (en) * | 2020-12-10 | 2021-05-14 | 西南兵工重庆环境保护研究所有限公司 | Combined water treatment process for removing hexavalent chromium in wastewater |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112794491A (en) * | 2020-12-10 | 2021-05-14 | 西南兵工重庆环境保护研究所有限公司 | Combined water treatment process for removing hexavalent chromium in wastewater |
| CN112777850A (en) * | 2020-12-15 | 2021-05-11 | 上海傲江生态环境科技有限公司 | Treatment method and treatment system for mercury-containing high-concentration organic pesticide wastewater |
| CN112777850B (en) * | 2020-12-15 | 2023-10-10 | 上海傲江生态环境科技有限公司 | Treatment method and treatment system for high-concentration organic pesticide wastewater containing mercury |
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