CN104445498A - Device and method for processing mercury-containing wastewater by using photo-catalytic adsorption - Google Patents
Device and method for processing mercury-containing wastewater by using photo-catalytic adsorption Download PDFInfo
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- CN104445498A CN104445498A CN201410643388.7A CN201410643388A CN104445498A CN 104445498 A CN104445498 A CN 104445498A CN 201410643388 A CN201410643388 A CN 201410643388A CN 104445498 A CN104445498 A CN 104445498A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 57
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 52
- 239000002351 wastewater Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 16
- 238000012545 processing Methods 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- 230000008929 regeneration Effects 0.000 claims abstract description 27
- 238000011069 regeneration method Methods 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000010453 quartz Substances 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 49
- 230000003197 catalytic effect Effects 0.000 claims description 36
- 238000010521 absorption reaction Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000013022 venting Methods 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 3
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/322—Lamp arrangement
- C02F2201/3222—Units using UV-light emitting diodes [LED]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a device and a method for efficiently processing mercury-containing wastewater. The device and the method can be used for processing the mercury-containing wastewater up to standard, reusing or discharging the mercury-containing wastewater, and are low in cost. The device for processing mercury-containing wastewater by using photo-catalytic adsorption is integrated with photo-catalytic reduction effect of a photo-catalyst (TiO2, modified TiO2 or other photo-catalyst) and adsorption effect of a carrier; a self-designed LED lamp is used as a light source; a reaction device is made of quartz glass and is externally plated by a mirror, so that the light is used to a greatest extent; the light source is put in an inner quartz sleeve; a photo-catalytic adsorption mixture material is packed between the inner quartz sleeve and an outer quartz sleeve; a water charging and air aerating device is arranged at the lower part of the device; three parts are spliced with each other by virtue of a frosted interface; a regeneration part of the photo-catalytic adsorption mixture material is also attached to the reaction device and is used for recycling collected reaction products.
Description
Technical field
The present invention relates to a kind of devices and methods therefor processing waste water, more specifically to a kind of devices and methods therefor of photochemical catalysis adsorption treatment mercury-containing waste water, belong to heavy metal polluted waste water process field.
Background technology
Mercury is the great heavy metal element of a kind of hazardness, and the burning of volcanic eruption, fossil oil, chlor-alkali industry and the e-life rubbish arbitrarily abandoned all can discharge a large amount of mercury in environment.Mercury can with containing sulfydryl protein binding, the physiologically active affecting organ and tissue is fatal even, and heavy metal element has enrichment effect in vivo, and endanger larger after being converted into organic, so existing standard-required Mercury in Water Body content is low to moderate μ g/L rank.The current treatment process for mercury pollution has absorption, chemical precipitation, flocculation, ion-exchange and Solid-Phase Extraction etc., but due to mercury element characteristic and under state of nature content low, aforesaid method can not process mercury-containing waste water well and be reclaimed.
Since 20 century 70s, photocatalysis technology is sent to great expectations and obtains large quantity research, has been widely used in the fields such as sewage disposal, off gas treatment, photic hydrophilic material, photolysis water hydrogen, antibacterial and self-cleaning surface material.Wherein, as the one of high-level oxidation technology, photocatalysis technology illustrates its superiority relative to other processing modes in the treatment of waste water, as low in consumed energy, and treatment effect is thorough, environmental protection etc.
As typical photocatalyst, TiO
2or doped Ti O
2be most widely used in photocatalysis field, when absorbing the photon of certain energy, TiO
2electrons in valence band transits to conduction band, and correspondingly forms hole in valence band.Light induced electron and photohole have extremely strong reductibility and oxidisability respectively, light induced electron can migrate to surface and the metallic element generation reduction reaction of semi-conductor, for mercury element, catalyzer or adsorbent surface can be adsorbed in after reduzate Elemental Mercury is formed, thus with adsorption, mercury be separated and enrichment from water by reduction.By regenerated liquids such as dust technology, the mercury of enrichment is reclaimed again.
Summary of the invention
Object of the present invention solves prior art Problems existing with not enough, provides a kind of device and method of efficient process mercury-containing waste water, and these apparatus and method can by reuse up to standard for mercury-containing waste water process or discharge, and cost is lower.
The device of photochemical catalysis adsorption treatment mercury-containing waste water of the present invention, it includes LED light source 1, photochemical catalysis absorption mixing material 2, venting port 3, water outlet 4, catalytic adsorption reactor 5, regeneration module 6, solarization air cell 7, inlet mouth 8, water-in 9 and water distributor 10, described catalytic adsorption reactor 5 silica glass is made, LED light source 1 placed by the internal layer quartz sleeve of catalytic adsorption reactor 5, fill photochemical catalysis between the internal layer quartz sleeve of catalytic adsorption reactor 5 and outer quartz sleeve and adsorb mixing material 2, catalytic adsorption reactor 5 bottom is provided with water distributor 10 and solarization air cell 7 successively, solarization air cell 7 lower end is provided with inlet mouth 8 and water-in 9, catalytic adsorption reactor 5 top is provided with venting port 3 and water outlet 4, wherein venting port is higher than water outlet, regeneration module 6 is connected with catalytic adsorption reactor 5 by pipeline, when photochemical catalysis absorption reaction and catalytic adsorption reactor 5 separate through valve, the valve open that regeneration module 6 can be communicated with catalytic adsorption reactor 5 when the reaction product enriching quantity on photochemical catalysis absorption mixing material 2 surface is higher is incorporated to catalytic adsorption reactor 5, utilize regeneration reagent by the mercury wash-out of absorption, by catalyst regeneration.
The device of photochemical catalysis adsorption treatment mercury-containing waste water of the present invention, its further technical scheme is that described LED light source 1 is made up of LED lamp bead paster, cross section is polyhedron, surrounding laminating adapts to the internal layer quartz sleeve inwall of catalytic adsorption reactor 5, and the length of light source can regulate as required simultaneously.The present invention can select specific lamp pearl according to light wave demand, and the main feature of LED lamp bead be exactly the life-span long, heat production is few.The length of light source can regulate as required, is convenient to the design of catalytic adsorption reactor.
The device of photochemical catalysis adsorption treatment mercury-containing waste water of the present invention, its further technical scheme can also be that described catalytic adsorption reactor 5 outermost layer silica glass plates minute surface outward, is reduced the loss of the inner LED light of device by specular reflection.
The device of photochemical catalysis adsorption treatment mercury-containing waste water of the present invention, its further technical scheme can also be that by carrier and load, the photocatalyst on carrier forms described photochemical catalysis absorption mixing material 2, and photocatalyst uses sol-gel method to be carried on carrier surface.Further technical scheme is described carrier is activated alumina, zeolite, glasscloth, granulated glass sphere or gac; Described photocatalyst is TiO2, modification TiO2 or other photocatalysts.
The device of photochemical catalysis adsorption treatment mercury-containing waste water of the present invention, its further technical scheme can also be that described venting port 3 expellant gas can circulate according to the actual requirements and passes into the reaction unit of series connection, and the processed waste water that water outlet 4 is discharged is according to actual effect circular treatment or discharge.
The device of photochemical catalysis adsorption treatment mercury-containing waste water of the present invention, its further technical scheme can also be described regeneration reagent is dust technology, potassium permanganate solution or thiocarbamide.
The method of the device process mercury-containing waste water using the present invention above-mentioned, it comprises the following steps: will pass through reaction unit containing inorganic mercury and organomercurial waste water, gas and liquid are after solarization air cell 7 fully mixes, evenly rise through water distributor 10 and enter the reaction chamber of catalytic adsorption reactor 5, adsorbed by photochemical catalysis absorption mixing material after photo catalytic reduction reaction; Temperature of reaction is 20-30 DEG C, reaction time pH scope 7-10, aeration is air, and the auxiliary reagent added during reaction is methyl alcohol, ethanol, formic acid or EDTA.
The method of process mercury-containing waste water of the present invention, its further technical scheme is when the photochemical catalysis absorption photocatalysis treatment ability of mixing material and the nearly state of saturation of loading capacity, by regeneration branch, regeneration reagent is passed into reaction unit, by the reaction product enrichment on photochemical catalysis absorption mixing material surface after reaction, photochemical catalysis absorption mixing material is regenerated.Further technical scheme is described regeneration reagent is dust technology, potassium permanganate solution or thiocarbamide.
In the present invention, light source placed by internal layer quartz sleeve, fills photochemical catalysis and adsorb mixing material between internal layer quartz sleeve and outer quartz sleeve, and bottom is water inlet and aerating apparatus, and three parts are spliced by frosted interface.
Compared with prior art the present invention has following beneficial effect:
(1) light source designed in the present invention uses LED lamp bead paster to make, and cross section is polyhedron, and surrounding laminating adapts to sleeve lining, and light intensity is high, and evenly luminous, the life-span is long, and heating is few.Photocatalytic reaction device is made up of silica glass, reduces the absorption to UV-light, and outermost layer silica glass plates minute surface outward, is reduced the loss of the inner LED UV-light of device, utilize LED UV-light to greatest extent by specular reflection.
(2) photochemical catalysis absorption mixing material its support chemistry stable in properties, is combined well with catalyzer, has higher specific surface area and photopermeability is good.Not only can realize the photo catalytic reduction of mercury, and to photo catalytic reduction product, there is good adsorption effect.
(3) designed reactor is flow reactor, and the series connection of many group reactions device can be used, and treatment capacity is large.
(4) inorganic mercury and organomercurial waste water, through aeration mixing, through TiO
2adsorbed by photochemical catalysis absorption mixing material after photo catalytic reduction reaction; By controlling the condition optimizing treatment effect such as interpolation, reaction times of temperature of reaction, reaction pH, aeration rate and aeration kind, auxiliary reagent.
(5) when the photochemical catalysis absorption photocatalysis treatment ability of mixing material and the nearly state of saturation of loading capacity, by regeneration branch, regeneration reagent is passed into reaction unit, to be adsorbed in the reaction product enrichment on photochemical catalysis absorption mixing material surface after reaction, photochemical catalysis absorption mixing material is regenerated.
Accompanying drawing explanation
Fig. 1 is the structural representation of apparatus of the present invention.
Fig. 2 is LED light source 1 structural representation.
Fig. 3 is water distributor 10 structural representation
Embodiment
Device in the embodiment of the present invention, it includes LED light source 1, photochemical catalysis absorption mixing material 2, venting port 3, water outlet 4, catalytic adsorption reactor 5, regeneration module 6, solarization air cell 7, inlet mouth 8, water-in 9 and water distributor 10, described catalytic adsorption reactor 5 silica glass is made, LED light source 1 placed by the internal layer quartz sleeve of catalytic adsorption reactor 5, fill photochemical catalysis between the internal layer quartz sleeve of catalytic adsorption reactor 5 and outer quartz sleeve and adsorb mixing material 2, catalytic adsorption reactor 5 bottom is provided with water distributor 10 and solarization air cell 7 successively, solarization air cell 7 lower end is provided with inlet mouth 8 and water-in 9, catalytic adsorption reactor 5 top is provided with venting port 3 and water outlet 4, wherein venting port is higher than water outlet, regeneration module 6 is connected with catalytic adsorption reactor 5 by pipeline, when photochemical catalysis absorption reaction and catalytic adsorption reactor 5 separate through valve, the valve open that regeneration module 6 can be communicated with catalytic adsorption reactor 5 when the reaction product enriching quantity on photochemical catalysis absorption mixing material 2 surface is higher is incorporated to catalytic adsorption reactor 5, utilize regeneration reagent by the mercury wash-out of absorption, by catalyst regeneration.Described LED light source 1 is made up of LED lamp bead paster, and cross section is polyhedron, and surrounding laminating adapts to the internal layer quartz sleeve inwall of catalytic adsorption reactor 5, and the length of light source can regulate as required simultaneously.Light source sleeve outer diameter is 5.5cm, and long is 55cm, and inside and outside sleeve interlayer spacing is 0.8cm, and outer layer sleeve plates minute surface outward.Light source is regular hexahedron cross section paster LED lamp, and spectral range is UV-light, reaches more than 50000 hours work-ing life.
Photochemical catalysis absorption mixing material carrier is activated alumina, by sol-gel method load TiO
2, concrete grammar is:
(1) activated alumina particle diameter is about 3mm, uses methyl alcohol and washed with de-ionized water respectively, then in 100 DEG C of dryings;
(2) nonionic surface active agent is dissolved in Virahol as pore-creating agent, then adds appropriate second acid for adjusting pH and be about 6.4, then dropwise adds in colloidal sol quadrol as doping nitrogen source.Under vigorous stirring state, dropwise add isopropyl titanate subsequently, then add remaining acetic acid.Room temperature for overnight obtains transparent, even, stable colloidal sol.Commodity TiO is added in colloidal sol
2, addition is 6g/L, and sonic oscillation makes it dispersed.
(3) activated alumina after clean dry is immersed in colloidal sol, take out nature after sonic oscillation 10min and place 10min, then dry 20min at 100 DEG C, repeat 3 times, finally in temperature programming retort furnace, rise to 500 DEG C with the heat-up rate of 2 DEG C/min, naturally cooling after insulation 120min.
Embodiment 1: by Hg
2+concentration is 10.0mg/L waste water, and adjust ph is 8, and holding temperature 25 DEG C adds methyl alcohol and is about 1% to its concentration.Open light source, open top venting port and water outlet.Entered below device with the flow velocity of 50mL/min by waste water, control aeration flow velocity is 50mL/min simultaneously.Hg in water sample after use atomic fluorescence spectroscopy (AFS) detection reaction
2+concentration.Experimental result shows, after treatment, and Hg in water outlet
2+removal amount reaches 99.9%.
After light-catalyzed reaction, regeneration module is incorporated to reactor, uses 0.02%KMnO
4solution is (containing 3%H
2sO
4) as regenerated liquid, mixing material is adsorbed in photochemical catalysis and regenerates, reacted mercury is reclaimed simultaneously.Through content detection and calculating, the mercury rate of recovery can reach more than 99%.
Embodiment 2: methyl mercury concentration is the waste water of 1.0mg/L, adjust ph is 10, holding temperature 25 DEG C, adds methyl alcohol and is about 1% to its concentration.Open light source, open top venting port and water outlet.Entered below device with the flow velocity of 50mL/min by waste water, control aeration flow velocity is 50mL/min simultaneously.To use after atomic fluorescence spectroscopy (AFS) detection reaction methyl mercury and mercury concentration in water sample.Experimental result shows, in waste water, methyl mercury removal amount reaches more than 99.9%.
After light-catalyzed reaction, regeneration module is incorporated to reactor, uses 0.02%KMnO
4solution is (containing 3%H
2sO
4) as regenerated liquid, mixing material is adsorbed in photochemical catalysis and regenerates, reacted mercury is reclaimed simultaneously.Through content detection and calculating, the mercury rate of recovery can reach more than 99%.
Embodiment 3: by Hg
2+concentration is 10.0mg/L waste water, and adjust ph is 7, and holding temperature 30 DEG C adds methyl alcohol and is about 1% to its concentration.Open light source, open top venting port and water outlet.Entered below device with the flow velocity of 50mL/min by waste water, control aeration flow velocity is 50mL/min simultaneously.Hg in water sample after use atomic fluorescence spectroscopy (AFS) detection reaction
2+concentration.Experimental result shows, after treatment, and Hg in water outlet
2+removal amount reaches 99.9%.
Claims (9)
1. the device of a photochemical catalysis adsorption treatment mercury-containing waste water and recovery mercury, it is characterized in that including LED light source (1), photochemical catalysis absorption mixing material (2), venting port (3), water outlet (4), photochemical catalysis adsorptive reactor (5), regeneration module (6, solarization air cell (7), inlet mouth (8), water-in (9) and water distributor (10), described photochemical catalysis adsorptive reactor (5) is made up of silica glass, LED light source (1) placed by the internal layer quartz sleeve of catalytic adsorption reactor (5), fill photochemical catalysis between the internal layer quartz sleeve of catalytic adsorption reactor (5) and outer quartz sleeve and adsorb mixing material (2), catalytic adsorption reactor (5) bottom is provided with water distributor (10) and solarization air cell (7) successively, solarization air cell (7) lower end is provided with inlet mouth (8) and water-in (9), catalytic adsorption reactor (5) top is provided with venting port (3) and water outlet (4), wherein venting port is higher than water outlet, regeneration module (6) is connected with catalytic adsorption reactor (5) by pipeline, when photochemical catalysis absorption reaction and catalytic adsorption reactor (5) separate through valve, the valve open that regeneration module (6) can be communicated with catalytic adsorption reactor (5) when the reaction product enriching quantity on photochemical catalysis absorption mixing material (2) surface is higher is incorporated to catalytic adsorption reactor (5), regeneration reagent is utilized to reclaim, the mercury of absorption by catalyst regeneration.
2. the device of photochemical catalysis adsorption treatment mercury-containing waste water according to claim 1 and recovery mercury, it is characterized in that described LED light source (1) is made up of LED lamp bead paster, cross section is polyhedron, surrounding laminating adapts to the internal layer quartz sleeve inwall of catalytic adsorption reactor (5), and the length of light source can regulate as required simultaneously.
3. the device of photochemical catalysis adsorption treatment mercury-containing waste water according to claim 1 and recovery mercury, it is characterized in that described catalytic adsorption reactor (5) outermost layer silica glass plates minute surface outward, reduced the loss of the inner LED light of device by specular reflection.
4. the device of photochemical catalysis adsorption treatment mercury-containing waste water according to claim 1 and recovery mercury, it is characterized in that the photocatalyst on carrier forms by carrier and load in described photochemical catalysis absorption mixing material (2), photocatalyst uses sol-gel method to be carried on carrier surface.
5. the device of photochemical catalysis adsorption treatment mercury-containing waste water according to claim 4 and recovery mercury, is characterized in that described carrier is activated alumina, zeolite, glasscloth, granulated glass sphere or gac; Described photocatalyst is TiO
2, modification TiO
2or other photocatalysts.
6. the device of photochemical catalysis adsorption treatment mercury-containing waste water according to claim 1 and recovery mercury, it is characterized in that described venting port (3) expellant gas can circulate according to the actual requirements and pass into the reaction unit of series connection, the processed waste water that water outlet (4) is discharged is according to actual effect circular treatment or discharge.
7. one kind use as arbitrary in claim 1-6 as described in the method for device process mercury-containing waste water, it is characterized in that comprising the following steps: reaction unit will be passed through containing inorganic mercury and organomercurial waste water, gas and liquid are after solarization air cell (7) fully mixes, evenly rise through water distributor (10) and enter the reaction chamber of catalytic adsorption reactor (5), adsorbed by photochemical catalysis absorption mixing material after photo catalytic reduction reaction; Temperature of reaction is 20-30 DEG C, reaction time pH scope 7-10, aeration is air, and the auxiliary reagent added during reaction is methyl alcohol, ethanol, formic acid or EDTA.
8. the method for process mercury-containing waste water according to claim 7, it is characterized in that when the photochemical catalysis absorption photocatalysis treatment ability of mixing material and the nearly state of saturation of loading capacity, by regeneration branch, regeneration reagent is passed into reaction unit, the reaction product on photochemical catalysis absorption mixing material surface after reaction reclaimed, photochemical catalysis absorption mixing material is regenerated.
9. the method for process mercury-containing waste water according to claim 8, is characterized in that described regeneration reagent is dust technology, potassium permanganate solution or thiocarbamide.
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| CN110203998A (en) * | 2019-06-13 | 2019-09-06 | 常州大学 | The vaporising device and its method of high slat-containing wastewater |
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| CN114853199B (en) * | 2021-02-03 | 2023-10-13 | 中国石油化工股份有限公司 | Treatment system and method for benzopyrene-containing wastewater |
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