CN104671357A - Method for degrading dimethyl phthalate by virtue of cooperation of low-temperature plasma and bismuth tungstate catalyst - Google Patents
Method for degrading dimethyl phthalate by virtue of cooperation of low-temperature plasma and bismuth tungstate catalyst Download PDFInfo
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- CN104671357A CN104671357A CN201510039542.4A CN201510039542A CN104671357A CN 104671357 A CN104671357 A CN 104671357A CN 201510039542 A CN201510039542 A CN 201510039542A CN 104671357 A CN104671357 A CN 104671357A
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- bismuth tungstate
- dimethyl phthalate
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- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 57
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229960001826 dimethylphthalate Drugs 0.000 title claims abstract description 53
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 40
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 40
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 230000000593 degrading effect Effects 0.000 title abstract 3
- 230000015556 catabolic process Effects 0.000 claims abstract description 32
- 238000006731 degradation reaction Methods 0.000 claims abstract description 32
- 239000002351 wastewater Substances 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
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- 230000002195 synergetic effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
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- 230000003197 catalytic effect Effects 0.000 abstract description 6
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- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
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- 229920003023 plastic Polymers 0.000 description 3
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- 230000004913 activation Effects 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
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Abstract
The invention discloses a method for degrading dimethyl phthalate by virtue of cooperation of low-temperature plasma and a bismuth tungstate catalyst. The method comprises the steps of adding wastewater containing dimethyl phthalate between a needle type hollow high voltage electrode and a grounding electrode to submerge the grounding electrode, firstly supplying air into the needle type hollow high voltage electrode in the presence of the bismuth tungstate catalyst to suspend the bismuth tungstate catalyst in a wastewater, turning on a high voltage power supply, connecting the high voltage power supply with the needle type hollow high voltage electrode to carry out corona discharge, inducing the activity of the bismuth tungstate catalyst by virtue of ultraviolet light and visible light produced in the corona discharge process, and carrying out catalytic oxidation on bismuth tungstate catalyst which is difficultly degraded in the wastewater by virtue of cooperation between generated oxidized groups and plasma produced in the corona discharge process,. According to the method, the low-temperature plasma is utilized by virtue of photocatalysis, lots of chemical reagents do not need to be fed, the synergistic effect among plasma oxidization, catalyst adsorption and catalyst catalytic degradation can be realized, and the degrading rate of dimethyl phthalate is increased.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of method of low-temperature plasma synergistic bismuth tungstate catalyst degradation dimethyl phthalate.
Background technology
Phthalic ester (PAEs) is mainly used as the property-modifying additive of plastics, to increase plasticity-and the intensity of plastics; Also can be used for the process for processing of agricultural chemicals, coating, printing and dyeing, makeup and spices etc., meanwhile, PAEs has estrogen effect, can disturb internal secretion and the reproductive system of animal and the mankind, infringement reproduction and development.
Dimethyl phthalate (DMP) is as the maximum softening agent of usage quantity, the macromolecular material auxiliary agent be industrially widely used.Along with widely using of plastics, dimethyl phthalate is transferred in various surrounding medium gradually, has been the maximum class organic pollutant in the whole world at present, has been listed in by China in the Black List of preferential detection of contamination.Its waste strength is high, should not be degraded, and a large amount of discharge can cause very large harm to water body.
Present stage, the treatment process of dimethyl phthalate waste water comprised: physico-chemical processes, biological oxidation process, various advanced oxidation processes, but each method all exists certain limitation.
Physico-chemical processes mainly contains: the technology such as absorption, coagulation-precipitation, air supporting, membrane sepn, all have certain removal effect, but need add a large amount of chemical reagent, processing cost is high, complicated operation, and can generate a large amount of by product, easily causes secondary pollution.
Biological treatment mainly comprises: Aerobic biological process, anaerobic biological treatment and aerobic-anaerobism coupling technique.Because dimethyl phthalate waste strength is higher, need during water inlet to carry out dilution several times and hundreds of times, clear water, power consumption are larger, and processing cost is high, and actual treatment efficiency is also lower.Under current anaerobic condition, the research of dimethyl terephthalate is fewer, lacks the research to its wastewater biological toxicity.And the construction production of aerobic-anaerobism coupling technique and treatment facility require higher, lack the research of the intermediate product toxicity to its fermentating metabolism simultaneously, therefore also quite disputed on always.
Photocatalyst technology is considered to a kind of promising technology at present, but its quantum yield low, need the restrictions such as ultraviolet light conditions, range of application is narrower.
Ozonation has good removal effect to its waste water, but using ozone also can cause certain pollution to environment.
Plasma technique is a kind of high-level oxidation technology, has the feature of non-selectivity, non-secondary pollution, but still comes with some shortcomings, as higher in processing cost, processing efficiency is not high.
As can be seen here, all there is certain deficiency in the treatment process of current dimethyl terephthalate, therefore find a kind of efficient, simple, avoid the method for secondary pollution extremely urgent.
Summary of the invention
The object of the invention is the technical problem proposed for background technology, a kind for the treatment of process of dimethyl phthalate waste water is provided, the method utilizes the process of plasma body cooperative photocatalysis technology containing dimethyl phthalate waste water, has the advantages such as processing efficiency is high, non-secondary pollution, reaction conditions are gentle.
Object of the present invention can be achieved through the following technical solutions:
A kind of method adopting low-temperature plasma synergistic bismuth tungstate catalyst degradation dimethyl phthalate, to join containing the waste water of dimethyl phthalate between pin type hollow high-pressure electrode and ground-electrode and ground-electrode described in not have, first air to be passed under bismuth tungstate catalyzer existent condition in described pin type hollow high-pressure electrode and to make bismuth tungstate catalyzer be in suspended state in waste water, then open high-voltage power supply to connect described pin type hollow high-pressure electrode and carry out corona discharge, the UV-light utilizing discharge process to produce and visible light-inducing bismuth tungstate catalyst activity, produce reactive species and work in coordination with the plasma body produced in discharge process, the dimethyl phthalate of difficult degradation in catalyzed oxidation waste water, wherein air flux 1.2 ~ 6L/h, the voltage of high-voltage power supply is 60 ~ 120V, electric current 0.35 ~ 0.5A, and discharge frequency is 50Hz.
Described bismuth tungstate catalyzer adopts following steps preparation: (1) uses deionized water dissolving Na
2wO
42H
2o and Bi (NO
3)
35H
2o, makes Na respectively
2wO
42H
2o solution and Bi (NO
3)
35H
2o solution; (2) by Na
2wO
42H
2o dropwise joins Bi (NO
3)
35H
2mixing solutions is made, Na in mixing solutions in O solution
2wO
42H
2o and Bi (NO
3)
35H
2the mol ratio of O is 1:2; (3) add in above-mentioned mixing solutions after sodium lauryl sulphate stirs and load standing 2 ~ 4h in polytetrafluoroethylliner liner, heat 20h ~ 24h at 160 DEG C ~ 180 DEG C after, cold filtration obtains light yellow precipitate, is dried by precipitate washed with water and obtains bismuth tungstate catalyzer.
Na described in step (1)
2wO
42H
2the concentration of O solution is 0.05 ~ 0.08mol/L, described Bi (NO
3)
35H
2the concentration of O solution is 0.1 ~ 0.15mol/L.
Described in step (3), the mass volume ratio of sodium lauryl sulphate and described mixing solutions is 5 ~ 7g/L.
Above-mentioned air flux 1.5 ~ 4L/h.
The treatment time of described waste water is 15min ~ 60min, is preferably 20min ~ 40min.
The concentration of the described waste water containing dimethyl phthalate is 50 ~ 200mg/L, is preferably 80mg/L ~ 100mg/L.
The pH of the described waste water containing dimethyl phthalate is 2 ~ 10, and optimum condition is 3 ~ 8.
The output rating of described high-voltage power supply is preferably 30W ~ 70W.
The mass volume ratio of described bismuth tungstate catalyzer and waste water is 0.5 ~ 0.9g/L.
The present invention's catalyzer used can be standby by hydro-thermal legal system, and concrete steps are:
Get Na
2wO
42H
2o, Bi (NO
3)
35H
2o joins in deionized water and makes the Na that concentration is 0.0625mol/L respectively
2wO
42H
2o solution and concentration are the Bi (NO of 0.125mol/L
3)
35H
2o solution.By Na
2wO
42H
2o dropwise adds Bi (NO
3)
35H
2mixing solutions is made, Na in mixing solutions in O solution
2wO
42H
2o and Bi (NO
3)
35H
2the mol ratio of O is 1:2; In mixing solutions, add sodium lauryl sulphate according to the ratio of 6.25g/L to stir, load in polytetrafluoroethylliner liner, after leaving standstill 3h, put into thermostatic drying chamber, heat 20h ~ 24h at 160 DEG C ~ 180 DEG C after, cool under normal temperature.Obtained light yellow precipitate is filtered, with distilled water flushing to neutral and be placed in the oven dry of 80 DEG C, baking oven, obtains catalyst sample.
Plasma body-absorption-catalysis coupling technique process difficult degradation dimethyl phthalate waste water, is enriched with organic pollutants by sorbent material, catalyzer and plasma body cooperative effect, has that process range is wide, processing efficiency is high, the feature of non-secondary pollution.While making full use of the physics of plasma exciatiaon, chemical effect, add the activation energy that catalyzer reduces reaction, and the UV-light utilizing discharge process to produce and visible ray, induction light catalyzer bismuth tungstate is active, produce reactive species and work in coordination with the plasma body produced in discharge process, the dimethyl phthalate of difficult degradation in catalyzed oxidation waste water.So will likely become the developing direction of following treatment of Organic Wastewater.
Be photocatalyst with semiconductor material, utilizing sun power removal of pollutants, is research topic more important in recent years.It for protection of the environment, maintain the eubiosis, realize Sustainable development and be significant.At present, the photocatalyst generally adopted is as TiO
2, SrTiO
3, NaTaO
3etc. mostly being wide bandgap semiconductor, only there is response at ultraviolet region.And plasma body is in discharge process, not only can produces a large amount of free radical materials, also can produce UV-light and visible ray, therefore developing the catalyzer all responded UV-light and visible ray is improve plasma processing efficiency, the final key point realizing application.
Bismuth tungstate is the important catalyst model material of a class.In addition, this compounds also can be used as ionophore, acousto-material, optical conductor, gas sensor and photocatalyst due to the physicals of its uniqueness.Research shows, bismuth tungstate can have stronger photoabsorption and higher photocatalytic activity at ultraviolet region and visible region simultaneously, may be used for radiation of visible light condition to go down degradation of organic substances, as tropeolin-D, rhodamine etc., it is a kind of novel visible light-responded bismuth-system compound oxide catalytic material.Plasma body is by the molecular complex system of multiple grain, and when catalyzer and Plasma contact, catalyst surface physicochemical property change, and make catalyzer more stable, activity is higher.Simultaneously due to the change of catalyzer, promote the chemical reaction of plasma body, make the two concerted reaction efficiency higher.
In present method, low-temperature plasma and bismuth tungstate catalyzer are combined and have synergistic function, its result of use is significantly better than the effect that low-temperature plasma and bismuth tungstate catalyzer are used alone, the method can utilize the activity of UV-light and visible light-inducing catalyzer, reduce activation energy, and produce dimethyl phthalate in oxidisability active group coordinated with plasma catalyzed oxidation waste water, the bismuth tungstate catalyzer prepared by the inventive method and low-temperature plasma is adopted to be combined treatment effect better, and this catalyst sedimentation is effective, be convenient to recycle.
Present method compared with prior art, has the following advantages:
1, by plasma technique and photocatalysis technology coupling, the synergy of plasma oxidation-Catalyst Adsorption-catalyst degraded can be realized, significantly improve degradation effect.
2, produce a large amount of oxidative free radical during electric discharge, be swift in response and non-selectivity, wide adaptability, clearance are high.
3, the UV-light utilizing discharge process to produce and visible ray, induction light catalyzer bismuth tungstate is active, produces reactive species and works in coordination with the plasma body produced in discharge process, the dimethyl phthalate of difficult degradation in catalyzed oxidation waste water.
4, without the need to adding a large amount of chemical reagent, processing cost is low, simple to operate.
5, this reaction can be carried out at normal temperatures and pressures, and reaction conditions is gentle, and reaction parameter is easy to regulate.
Accompanying drawing explanation
Fig. 1 is the one simple corona discharge reaction unit structural representation that the present invention adopts.
1-electromagnetic air pump, 2-air flowmeter, 3-pin type hollow high-pressure electrode, 4-dividing plate, 5-ground-electrode, 6-venting hole, 7-reactor, 8-thief hole, 9-magnetic stirring apparatus, 10-high-voltage power supply
Fig. 2 is the bismuth tungstate catalyzer stereoscan photograph that the present invention adopts hydrothermal method to prepare.
Embodiment:
As shown in Figure 1, high-voltage power supply 10 is connected with pin type hollow high-pressure electrode 3 with ground-electrode 5 the simple corona discharge reaction unit that following each embodiment adopts respectively, and pin type hollow high-pressure electrode 3 is under ground-electrode 5.Pin type hollow high-pressure electrode 3 is connected by air flowmeter 2, and air flowmeter 2 is connected with electromagnetic air pump 1 again, and gas is then entered in reactor 7 by pin type hollow high-pressure electrode 3.Catalyzer is placed in the bottom of reactor 7, during reaction, by the stirring action of air-blowing and magnetic stirring apparatus 9, makes the catalyzer of bottom be in suspended state, better utilised UV-light and visible ray, produces higher activity.When leaving standstill, be sunken to bottom of device, can high efficiente callback and utilization be carried out.Dividing plate 4 is semicircle dividing plate, it is evenly covered with the circular hole that radius is 2mm, the acting as of dividing plate 4 makes the gas distance that walks in reactor 7 longer, and extend the duration of contact of gas and reaction soln, being covered with even circular hole is the catalyzer suspension activity avoiding stopping bottom.
The catalyzer employing following methods preparation that the present invention is used:
Get 0.0025mol Na
2wO
42H
2o, 0.005mol Bi (NO
3)
35H
2o, adds in the deionized water of 40mL respectively.Bi (NO
3)
35H
2after O solution magnetic agitation 5min, by Na
2wO
42H
2o dropwise adds Bi (NO
3)
35H
2in O solution, add 0.5g sodium lauryl sulphate in above-mentioned solution, after magnetic agitation 30min, load in polytetrafluoroethylliner liner, after leaving standstill 3h, put into thermostatic drying chamber, heat 24h at 180 DEG C after, cool under normal temperature.Obtained light yellow precipitate is filtered, with distilled water flushing to neutral and be placed in the oven dry of 80 DEG C, baking oven, obtains Bi
2wO
6sample.
The high-voltage power supply adopted in the embodiment of the present invention is CTP-2000K discharge power supply that Nanjing Su Man Electronics Co., Ltd. produces, and regulates voltage and the power of power supply, thus control outward current by voltate regulator.The voltage of high-voltage power supply is 60 ~ 120V, electric current 0.35 ~ 0.5A, and discharge frequency is 50Hz.
The silica glass adopted in the embodiment of the present invention makes cylindrical reactor vessel 7, and basal diameter is 6cm, high 12cm, and pin type hollow high-pressure electrode 3 adopts No. 12 hollow draw points, and connect power supply high-pressure stage, air is entered in reactor 7 by hollow draw point.Ground-electrode 5 is located at above high voltage electrode.The lower-left end of reactor 7 is directly passed by pin type hollow high-pressure electrode 3, and gas enters in reactor 7 by pin type hollow high-pressure electrode 3, can adjusting gas flow by air flowmeter 2.The bottom right section of reactor 7 is the thief hole 8 of internal diameter 3mm, for sampling and measuring.The venting hole 6 of the upper right side of reactor 7 to be internal diameter be 5mm, for exhaust.In discharge process, air is ionized at high voltage electrode place, produces UV-light and visible light-inducing bismuth tungstate catalyzer generation photocatalytic activity simultaneously, produces reactive species and enter in the aqueous solution, react.The active substance be not consumed such as ozone is discharged with the venting hole 6 of air from reactor 7.
Water sample containing dimethyl phthalate is passed in reactor, water sample need not have ground-electrode, first air to be passed under bismuth tungstate catalyzer existent condition in described pin type hollow high-pressure electrode and to make bismuth tungstate catalyzer be in suspended state in waste water, then open high-voltage power supply to connect described pin type hollow high-pressure electrode and carry out corona discharge, the UV-light utilizing discharge process to produce and visible light-inducing bismuth tungstate catalyst activity, produce reactive species and work in coordination with the plasma body produced in discharge process, the dimethyl phthalate of difficult degradation in catalyzed oxidation waste water, the high performance liquid chromatography that the measuring method of dimethyl phthalate adopts hewlette-packard to produce detects.
Embodiment one
Be make the water surface not have described ground-electrode during the dimethyl phthalate water sample 100mL of 50mg/L, 100mg/L, 150mg/L (pH is respectively 6.51,6.82,6.72) joins as shown in Figure 1 reaction unit by concentration, pass into air, open magnetic stirring apparatus, and switch on power, output power of power supply is 50W, air flow quantity 2L/h, when discharging 30min, after testing, when adding 0.07g catalyzer, the degradation rate of dimethyl phthalate is respectively 96%, 92.3%, 90.6%.Do not add other treatment process of catalyzer identical time, the degradation rate of dimethyl phthalate is respectively 78.9%, 65.2%, 60.5%.When adding bismuth tungstate catalyzer, the starting point concentration containing dimethyl phthalate water sample is that the treatment effect of 50mg/L ~ 150mg/L all can reach more than 90%, has good place to go effect.
Embodiment two
Be make the water surface not have described ground-electrode during the dimethyl phthalate water sample 100mL of 100mg/L (pH is 6.82) adds as shown in Figure 1 reaction unit by concentration, pass into air, open magnetic stirring apparatus, and switch on power, output power of power supply is 52W, air flow quantity 2L/h, 20min is respectively in electric discharge, 30min, during 40min, after testing, when adding catalyzer 0.07g, the degradation rate of dimethyl phthalate is respectively 89.6%, 92.3%, 94.1%, do not add other treatment process of catalyzer identical time, the degradation rate of dimethyl phthalate is respectively 60.5%, 65.2%, 68.9%.When adding bismuth tungstate catalyzer, the reaction times is that 20min ~ 40min all can reach high treatment effect.
Embodiment three
Be make the water surface not have described ground-electrode during the dimethyl phthalate water sample 100mL of 100mg/L (pH is 6.82) adds as shown in Figure 1 reaction unit by concentration, pass into air, open magnetic stirring apparatus, and switch on power, output power of power supply is respectively 40W, 50W, 64W, air flow quantity 2L/h, when discharging 30min, after testing, when adding 0.07g catalyzer, the degradation rate of dimethyl phthalate is respectively 85%, 92.3%, 96%, do not add other treatment process of catalyzer identical time, the degradation rate of dimethyl phthalate is respectively 56%, 65.3%, 72.5%.Plasma body has good removal effect in conjunction with bismuth tungstate catalyzer.
Embodiment four
First group of experiment: be make the water surface not have described ground-electrode during the dimethyl phthalate water sample 100mL of 100mg/L (pH is 6.82) adds as shown in Figure 1 reaction unit by concentration, pass into air, open magnetic stirring apparatus, and switch on power, output power of power supply is 50W, air flow quantity is 2L/h, add catalytic amount and be respectively 0.05g, 0.07g, 0.09g, electric discharge 30min, after testing, after adding corresponding catalyst, the degradation rate of dimethyl phthalate is respectively 88.9%, 92.3%, 89.1%.Second group of experiment: the catalyzer of 0.05g, 0.07g, 0.09g is placed in reaction vessel respectively, disconnect high-voltage power supply, plasma body does not discharge, the adsorption of Study of Catalyst, after testing, the degradation rate of dimethyl phthalate is respectively 3%, 5%, 8%.The degradation rate of plasma body cooperative catalyst treatment is about 90%, and the degradation rate of Cement Composite Treated by Plasma is 65.3% separately, the adsorption of independent catalyzer also only has about 5%, as can be seen here, the adsorption of catalyzer is very weak, in plasma body cooperative catalyzer electric discharge system, the katalysis of catalyzer plays a major role, and the UV-light that plasma discharge produces and visible ray have good inducing effect to this catalyzer, and adding a small amount of catalyzer just can have good treatment effect.Plasma body and catalyzer are combined has significant synergistic function.
Embodiment five
Be make the water surface not have described ground-electrode during the dimethyl phthalate water sample 100mL of 100mg/L (pH is 6.82) adds as shown in Figure 1 reaction unit by concentration, pass into air capacity and be respectively 1.6L/h, 2L/h, 4L/h, open magnetic stirring apparatus, and switch on power, output power of power supply is 50W, when discharging 30min, after testing, when adding 0.07g catalyzer, the degradation rate of dimethyl phthalate is respectively 88%, 92.3%, 94.5%, do not add other treatment process of catalyzer identical time, the degradation rate of dimethyl phthalate is respectively 61%, 65.3%, 68%.Plasma body has good treatment effect in conjunction with bismuth tungstate catalyzer.
Embodiment six
Adjustment concentration is the pH of the dimethyl phthalate water sample 100mL of 100mg/L, the pH of solution is made to be 3.03,7.01,9.18, add respectively in reaction unit as shown in Figure 1 and make the water surface not have described ground-electrode, pass into air, open magnetic stirring apparatus, and switch on power, output power of power supply is 50W, air flow quantity is 2L/h, adding catalytic amount is 0.07g, and discharge time is 30min, after testing, when adding catalyzer, the degradation rate of dimethyl phthalate is respectively 96.9%, 92.3%, 86.4%.Do not add other treatment process of catalyzer identical time, the degradation rate of dimethyl phthalate is respectively 70.1%, 65.3%, 60.1%.Acidic solution is conducive to the degradation rate improving dimethyl phthalate, and alkaline condition can reduce the degradation rate of dimethyl phthalate.
Embodiment seven
Be make the water surface not have described ground-electrode during the dimethyl phthalate water sample 100mL of 100mg/L (pH is 6.82) adds as shown in Figure 1 reaction unit by concentration, pass into air, open magnetic stirring apparatus, and switch on power, output power of power supply is 50W, air flow quantity is 2L/h, add catalytic amount and be respectively 0.07g, after exoelectrical reaction 30min, suction filtration is carried out to reacted solution, the catalyzer of gained is utilized again and reacts, reuse three times, recording degradation rate is respectively 92.3%, 90.1%, 89%, 87.6%, the repeating utilization factor that can obtain this catalyzer is thus very high, and too large reduction can not be there is in degradation rate.
Visible plasma is worked in coordination with bismuth tungstate catalyzer dimethyl terephthalate waste water and is had good removal effect, and adding of bismuth tungstate can improve degradation rate greatly, reduces expected cost.Dimethyl phthalate can be degraded into carbonic acid gas and water and some small organic molecules by the method, and environmentally safe, is with a wide range of applications, and also may substitute current conventional processes, becomes the future trend in following field of Environment Protection.
Claims (10)
1. one kind adopts the method for low-temperature plasma synergistic bismuth tungstate catalyst degradation dimethyl phthalate, it is characterized in that joining containing the waste water of dimethyl phthalate between pin type hollow high-pressure electrode and ground-electrode and ground-electrode described in not have, first air to be passed under bismuth tungstate catalyzer existent condition in described pin type hollow high-pressure electrode and to make bismuth tungstate catalyzer be in suspended state in waste water, then open high-voltage power supply to connect described pin type hollow high-pressure electrode and carry out corona discharge, the UV-light utilizing discharge process to produce and visible light-inducing bismuth tungstate catalyst activity, produce reactive species and work in coordination with the plasma body produced in discharge process, the dimethyl phthalate of difficult degradation in catalyzed oxidation waste water, wherein air flux 1.2 ~ 6L/h, the voltage of high-voltage power supply is 60 ~ 120V, electric current 0.35 ~ 0.5A, and discharge frequency is 50Hz.
2. method according to claim 1, is characterized in that described bismuth tungstate catalyzer adopts following steps preparation: (1) uses deionized water dissolving Na
2wO
42H
2o and Bi (NO
3)
35H
2o, makes Na respectively
2wO
42H
2o solution and Bi (NO
3)
35H
2o solution; (2) by Na
2wO
42H
2o dropwise joins Bi (NO
3)
35H
2mixing solutions is made, Na in mixing solutions in O solution
2wO
42H
2o and Bi (NO
3)
35H
2the mol ratio of O is 1:2; (3) add in above-mentioned mixing solutions after sodium lauryl sulphate stirs and load standing 2 ~ 4h in polytetrafluoroethylliner liner, heat 20h ~ 24h at 160 DEG C ~ 180 DEG C after, cold filtration obtains light yellow precipitate, is dried by precipitate washed with water and obtains bismuth tungstate catalyzer.
3. method according to claim 2, is characterized in that Na described in step (1)
2wO
42H
2the concentration of O solution is 0.05 ~ 0.08mol/L, described Bi (NO
3)
35H
2the concentration of O solution is 0.1 ~ 0.15mol/L.
4. method according to claim 2, is characterized in that the mass volume ratio of described sodium lauryl sulphate and described mixing solutions is 5 ~ 7g/L.
5. method according to claim 1, is characterized in that described air flux 1.5 ~ 4L/h.
6. method according to claim 1, is characterized in that the treatment time of described waste water is 15min ~ 60min, is preferably 20min ~ 40min.
7. method according to claim 1, is characterized in that the concentration of the described waste water containing dimethyl phthalate is 50 ~ 200mg/L, is preferably 80mg/L ~ 100mg/L.
8. method according to claim 1, it is characterized in that the pH of the described waste water containing dimethyl phthalate is 2 ~ 10, optimum condition is 3 ~ 8.
9. method according to claim 1, is characterized in that the output rating of described high-voltage power supply is preferably 30W ~ 70W.
10. method according to claim 1, is characterized in that the mass volume ratio of described bismuth tungstate catalyzer and waste water is 0.5 ~ 0.9g/L.
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Application publication date: 20150603 |