CN110316894A - Sewage water treatment method and device based on luminous energy - Google Patents
Sewage water treatment method and device based on luminous energy Download PDFInfo
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- CN110316894A CN110316894A CN201910662379.5A CN201910662379A CN110316894A CN 110316894 A CN110316894 A CN 110316894A CN 201910662379 A CN201910662379 A CN 201910662379A CN 110316894 A CN110316894 A CN 110316894A
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- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S20/00—Solar heat collectors specially adapted for particular uses or environments
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/10—Details of absorbing elements characterised by the absorbing material
- F24S70/16—Details of absorbing elements characterised by the absorbing material made of ceramic; made of concrete; made of natural stone
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
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- General Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
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- Sustainable Energy (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
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- Ceramic Engineering (AREA)
- Water Treatment By Sorption (AREA)
- Physical Water Treatments (AREA)
Abstract
The present invention relates to technical field of sewage, in particular to a kind of sewage water treatment method and device based on luminous energy.Sewage treatment steam generator provided by the invention includes: porous material, for adsorbing and transmitting treatment sewage；Photothermal transformation layer, for converting light energy into thermal energy and the hydrone in treatment sewage being made to be converted to gaseous state；Wherein, photothermal transformation layer is located at the surface of the porous material.The high-efficiency cleaning separation of sewage can be effectively realized under the action of luminous energy by the way that carbon nanotube is deposited to manufactured steam generator on porous material, and the steam generator has excellent segregational stability can be with good renewable performance, the solar steam generator blocked because of dye molecule can be re-used by way of calcining, not will cause secondary pollution.
Description
Technical field
The present invention relates to technical field of sewage, in particular to a kind of sewage water treatment method and device based on luminous energy.
Background technique
With the rapid growth of global industry and population, a large amount of pollutants, such as organic dyestuff, surfactant, heavy metal
Ion, oil and other organic solvents are released in river and lake, cause serious health threat water pollution problems.It is this to have
Machine molecular dye, such as methylene blue (MeB), alkaline fusion protein (BF), methyl orange (MO) etc. is widely used in printing, weaving,
Papermaking and leather industry.The dye molecule contained has chemical stability, very because of its complicated aromatic ring structure and heterojunction structure
High toxicity, therefore these industrial wastewaters must be handled carefully before being released to natural water body.In wastewater processing technology,
Photocatalytic degradation, film filtering, absorption process, which is widely used in, removes these organic dyestuff.
Although making some progress in terms of dye wastewater treatment, need to solve there are many problem.For example, light
Catalysis is to handle the common method of waste water, and wherein organic dyestuff can degrade when being exposed to visible light or ultraviolet light.However,
This process leaves organic residue, although the face of waste water from dyestuff there is no the content for really reducing organic carbon in water in water
Color visually changes or disappears.There is also very big limitation, hole is easy to the method that film filters when separating dye molecule
Stopped by dye molecule.The approach of most common cleaning filter membrane is to carry out chemical flush with strong oxidizer, but this will lead to
Erosion destroys the wetability of film and shortens membrane lifetime.In addition to this, the adsorbent of physical absorption depends on adsorbent
Noncovalent interaction power (π-π, interaction of hydrogen bond, electrostatic interaction and soda acid phase interaction between dye molecule
With), this requires there are particular functional groups on dye molecule and adsorbent, therefore significantly limit adsorbent material and separation
The selection of dyestuff.In addition, the quantity of the particular functional group of exposure on the sorbent limits adsorption capacity, cause to adsorb high concentration
Waste water from dyestuff failure.Therefore, exploitation has become world wide for the reproducible high-efficiency purifying method of waste water from dyestuff
Challenge.
Summary of the invention
The present invention provides a kind of sewage water treatment method and device.The research of the invention finds that by the way that carbon nanotube is deposited to
Manufactured steam generator can effectively realize sewage under the action of luminous energy such as solar energy and especially contaminate on porous material
Expect the high-efficiency cleaning separation of sewage, and the steam generator has excellent segregational stability energy and good renewable performance,
The solar steam generator blocked because of dye molecule can be re-used by way of calcining, not will cause secondary dirt
Dye.
Specifically, the present invention provides a kind of sewage treatment steam generator comprising:
Porous material, for adsorbing and transmitting treatment sewage；
Photothermal transformation layer, for converting light energy into thermal energy and the hydrone in treatment sewage being made to be converted to gaseous state；Its
In, the photothermal transformation layer is located at the surface of the porous material.
Further, the photothermal transformation layer is located at least one face or multiple faces of the porous material.When the steam
When generator is irradiated by light source, the part at least irradiated by institute's light source is equipped with photothermal transformation layer.
In some embodiment of the invention, the photothermal transformation layer is located at all surfaces of the porous material.
Under normal conditions, can be bigger by the range (such as area) for the photothermal transformation layer that light source is irradiated to, it also has more
More luminous energy are converted to thermal energy, are conducive to lifting sewage separating rate.
Further, the porous material is porous super hydrophilic ceramics, commercially available to buy.Porous super hydrophilic ceramics are internal to be contained
Have and enrich a large amount of through-hole, these through-holes have given the path of Water Transport, realize that moisture transmits from the bottom to top.In addition the ceramics
Super hydrophilicity enables to ceramics that can effectively absorb (dyestuff) waste water, and is the light at ceramic surface (such as top)
Heat conversion continuously provides the important foundation of moisture.
In some embodiments of the present invention, the size of the porous material is 2.5cm × 2.5cm × 4cm.
Further, photothermal transformation layer of the present invention is carbon nanotube；It is commercially available to buy.
Carbon nanotube is a kind of excellent optical-thermal conversion material, has good photo-thermal absorbent properties, can effectively inhale
Sunlight or other light sources are received, higher absorptivity can be realized in wider wavelength.Therefore this photothermal transformation layer is used
Sunlight or other light sources can be more absorbed, realize higher photothermal conversion efficiency.
In some embodiments of the present invention, graphitization carboxyl multi-walled carbon nanotube is used.
In some embodiments of the present invention, used carbon nanotube diameter is 30-50nm, 10 μm or so long.
Further, the photothermal transformation layer with a thickness of 20-200mm, preferably 40-60mm.Both may be used under this condition
Porous material is comprehensively covered with realizing, guarantees photothermal conversion effect, and the saving of cost may be implemented.
Particularly, the present invention is by, for porous material, (being especially graphitized carboxylic with carbon nanotube with porous super hydrophilic ceramics
Quito wall carbon nano tube) it is used as optical-thermal conversion material, it fully ensure that the fast transportation of the efficient conversion and moisture of photo-thermal, most
With the realizing vapour transpiration and Water Transportation dynamic equilibrium of big degree ground.
Sewage treatment steam generator provided by the invention can be used following method and be prepared:
Photothermal transformation layer solution (example is made in water by photothermal conversion layer material (such as carbon nanotube powder) is evenly dispersed
Such as carbon nano-tube solution)；Preferably it to be made to be uniformly dispersed, ultrasonic treatment can be used, such as ultrasound 30 minutes act on.
The photothermal transformation layer solution (such as carbon nano-tube solution) is coated on porous material surface, or by porous material
It is soaked in the photothermal transformation layer solution (such as carbon nano-tube solution), it is dry, make the photothermal transformation layer (such as carbon nanometer
Pipe) it is deposited on the porous material surface, the sewage treatment steam generator with double-layer structure can be obtained.
In general, when providing the concentration for controlling the photothermal transformation layer solution (such as carbon nano-tube solution), coating or impregnating
Between can prepare the photothermal transformation layer of different-thickness.
Sewage treatment steam generator provided by the invention, application method and cleaning principle are summarized as follows:
The sewage treatment is placed in sewage to be processed (such as dye wastewater) with steam generator, in the steam generation
The top of device is irradiated with light source；Sewage can be along the micropore of the opening of porous material in the steam generator from the steam generation
The bottom of device is transported to top.Due to the suction-operated of porous material, smaller part of impurity or pollutant (such as dyestuff point
Son) be intercepted at the porous material (such as porous super hydrophilic ceramics) inside transmission path in, and most of do not blocked
The impurity or pollutant (such as dye molecule) cut can reach the top of the steam generator along flow path；The steam generator
Photothermal transformation layer convert light energy into thermal energy, thus be up to top sewage heating be evaporated to it in ambient enviroment.By
It is very big in the evaporating temperature difference of water and impurity therein or pollutant (such as dye molecule), when liquid water is heated into gas
When state water, impurity or pollutant (such as dye molecule) therein will not be evaporated and are deposited on the surface of the steam generator,
To realize the separation of water and impurity therein or pollutant (such as dye molecule)；It may then pass through the side of condensed steam
Formula obtains pure water.The structure of the steam generator is as shown in Figure 1.
Sewage treatment provided by the invention preferably uses the sun for light source with steam generator, can use other light sources.
Sewage treatment provided by the invention is that it is reproduced in which can be convenient with another significant advantage of steam generator.Example
Can such as be made by the method for calcining after using porous material by water impurity or pollutant (such as dye molecule) block
Steam generator restore process performance substantially as before.The advantages of regeneration method is not will cause secondary dirt
Dye.
For convenience of sewage treatment and collection is used for, the present invention also provides a kind of sewage-treatment plants comprising: above-mentioned sewage
Steam generator is used in processing；Further include steam condenser, or further comprises water purification collector.
Further, sewage-treatment plant of the present invention further includes the equipment for containing treatment sewage.
Wherein, this field can be selected in the steam condenser, water purification collector and the equipment for containing treatment sewage
Conventional equipment.
Further, the present invention also provides above-mentioned sewage treatment steam generators or sewage-treatment plant in sewage treatment
In application.
Specifically, the present invention also provides a kind of sewage water treatment methods, comprising:
By above-mentioned sewage treatment steam generator and waste water to be processed, make the photothermal conversion of the steam generator
Layer can be by light source direct irradiation；
Make the sewage treatment steam generator photothermal transformation layer obtain luminous energy, and convert light energy into thermal energy to
Hydrone in treatment sewage is converted into gaseous state.
Specifically, above-mentioned sewage water treatment method, steam generator is wanted and waste water, but should at least have a photo-thermal
Not with waste water, this photothermal conversion layer surface, which is used to apply photothermal transformation layer and receives light source, irradiates on conversion layer surface,
And the steam generated is also escaped from this surface.
Further, above-mentioned sewage water treatment method further includes being converted into gaseous hydrone to be condensed so that its turn
The step of being changed to liquid water molecules；Or further comprises and be converted into what the hydrone (i.e. purified water) of liquid was collected
Step.
It is demonstrated experimentally that sewage treatment of the present invention with steam generator be suitable for processing organic pollutant, heavy metal contaminants,
The sewage of the sewage of the types such as industrial wastewater pollution object, dyestuff contaminant, especially dye type.These dyestuffs include rhodamine
B, methyl orange, methyl blue are Congo red etc..
When concentration typically for dirty water pollutant (such as dyestuff) is 0.002-2mg/mL, sewage treatment of the present invention
80% or more sewage separation rate is still able to maintain with steam generator.As it can be seen that its concentration tolerance level for dirty water pollutant
It is higher.
In the present invention, the sewage separation rate refers to the concentration variation of dye molecule in the dye wastewater of separation front and back, meter
It is as follows to calculate formula:
Sewage separative efficiency=(dyestuff molecular concentration after dye molecule concentration-separation before separating)/dye wastewater before separating
Concentration) × 100
It is demonstrated experimentally that sewage treatment of the present invention can count to 5 sun numbers in 1 sun of intensity of illumination with steam generator
Under the conditions of obtain preferable sewage separation rate；Usually up to 98% or more.
It is demonstrated experimentally that sewage treatment of the present invention has good ph stability with steam generator.When dirt to be processed
Water pH from 0 become 14 when, the high separating efficiency (> 98%) of dye molecule is barely affected.This shows that bronsted lowry acids and bases bronsted lowry will not destroy
The form of steam generation facility, and will not influence the efficiency of separation dyestuff.
It is demonstrated experimentally that sewage treatment steam generator of the present invention also has good durability, up to 200 hours
Its separative efficiency can almost keep constant over time in the processing time.
The present invention is by quickly and easily deposited one layer of carbon nanometer with good photo absorption performance in porous material surface
Pipe has been made solar steam generator and has been used to sewage purification, and equipment needed for preparation method is few, easy to operate.Utilize this hair
Bright steam generator carries out dye wastewater purification, and efficient isolation of purified, efficiency can be realized under different purification conditions
Stablize.In addition, clarifier of the present invention can be reused by calcining.The present invention is that sewage treatment especially contains soluble contaminant
The sewage treatment purification of object provides new thinking, may advantageously facilitate the further development for promoting wastewater purification technology.
Detailed description of the invention
Fig. 1 shows sewage treatment of the present invention steam generator structural schematic diagrams.
Fig. 2-Fig. 5 respectively indicates dirty for various concentration dye wastewater, different Intensity of the sunlight, different pH value dyestuffs
The clean-up effect of water and different operating times.
Fig. 6 indicates calcining contaminated steam generator after-purification dye wastewater effect.
Fig. 7 is the optical picture of calcining front and back evaporator and the optical picture of clear water washing front and back evaporator.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..It is not specified in embodiment specific
Technology or conditions person, described technology or conditions according to the literature in the art, or carried out according to product description.It is used
Production firm person is not specified in reagent or instrument, is the conventional products that can be commercially available by regular distributor.
Porous material used below is porous super hydrophilic ceramics, is purchased from new chemical materials Co., Ltd, Pingxiang City Hengchang.Make
The fritter having a size of 2.5cm × 2.5cm × 4cm or so is cut into preceding, then will be put into tap water after boiling 30 minutes
It pulls out, with distilled water flow wash 10 minutes, it is ensured that the soil dust adhered on removal ceramics.
Hydrophilic porous ceramics after cleaning are placed on observed under electron microscope discovery, the ceramic surface and section are all shown
The irregular porous structure that aperture is 10~25 μm, can provide path for the transport of moisture.
The photothermal transformation layer is graphitization carboxyl multi-walled carbon nanotube, and diameter 30-50nm is 10 μm or so long, purchased from south
The first rich nanometer Co., Ltd in capital.
1 sewage treatment steam generator of embodiment and its preparation
It is soluble in water that carboxyl multi-wall carbon nano-tube pipe powder will be graphitized, ultrasound 30 minutes, it is the equal of 2mg/ml that concentration, which is made,
The carbon nano-tube solution of even dispersion；It is then coated in porous material surface, it is dry, so that carbon nanotube is deposited on the porous material
Photothermal transformation layer is formed on surface, and the sewage treatment steam generator with double-layer structure can be obtained.Its structural schematic diagram
As shown in Figure 1.
Through detecting, sewage treatment steam generator made from the present embodiment, photothermal transformation layer with a thickness of 50um a left side
It is right.
Experimental example
Sewage treatment steam generator prepared by Example 1, sewage cup；It is placed in the sewage cup equipped with dye wastewater
In, the hole of the steam generator and sewage rim of a cup is filled up with foam and is sealed with sealed membrane.Steam generator will be housed
Sewage cup is placed under light source, and the light vertical irradiation for emitting light source forms sewage steam generation in the top of steam generator
Device is set.Using solar simulator as light source, tested as follows.
Dye wastewater used below is rhdamine B sewage.
1) dye wastewater of different concentration is purified
The dye wastewater solution for purifying various concentration in the case where three sun numbers irradiate using the steam generator, even if sewage
Middle water-soluble dye concentration is respectively 0.002,0.02,0.2,2mg/ml, and the dye wastewater separation rate of the steam generator is still protected
The adverse effect for showing that the steam generation facility is not changed by concentration 80% or more is held, and for the ultrahigh concentration of 2mg/ml
Waste water from dyestuff still has very high isolation of purified efficiency.As a result see Fig. 2.
2) the purifying dyestuff sewage under different Intensity of the sunlight
The steam generator is placed under the sunlight of varying strength, purified concentrations are the waste water from dyestuff of 0.2mg/ml, knot
Fruit discovery, separative efficiency is all 98% or more under conditions of intensity of illumination is 1,2,3,4,5 sun numbers.As a result see Fig. 3.
3) dye wastewater under different pH value is purified
The steam generator is immersed in the solution of different pH 48 hours, then takes out and carries out dye separation test.It immerses
Measurement separative efficiency afterwards is as shown in the picture.When the pH of solution becomes 14 from 0, the high separating efficiency (> 98%) of dye molecule
It is barely affected.This shows that bronsted lowry acids and bases bronsted lowry will not destroy the form of steam generator, and will not influence the efficiency of separation dyestuff.
As a result see Fig. 4, show that the steam generator also shows good ph stability.
4) the purifying dyestuff sewage under different operating times
Prolonged dye separation test is carried out using the steam generator, makes steam generation facility in three sun intensity
Irradiation under continuous evaporation concentration be 0.2mg/ml waste water from dyestuff up to 200 hours.As a result as shown in figure 5, collecting evaporation time
Respectively 0, the product of purifying in 40,80,120,160,200 hours, by the quantitative analysis of purified product, six separative efficiencies
Respectively 99.4%, 99.5%, 99.7%, 99.3%, 99.6% and 99.6%, show the separation effect of dye vapour generating device
Rate can almost keep constant over time.
5) contaminated solar steam generator after-purification dye wastewater is being calcined
The steam generator shows excellent regenerability, and the invention is also discussed for the first time and steamed by calcination and regeneration
The method of vapour generator.When steam generator continuously separates the dyestuff that concentration is 0.2mg/ml in the case where three sun are according to intensity illumination
At waste water 200 hours, evaporation rate will be gradually lowered to about 1.8 from 3.0 as can be seen from Figure 6.At this point, we are by evaporation rate
The steam generation facility of reduction by 30% is put into Muffle furnace, and is calcined 6 hours under 800 °.Calcined optical photograph display dye
The porous hydrophilic ceramics of material accumulation can be cleaned effectively, this is because carbon nanotube and dye molecule on steam generator
It is combusted into carbon dioxide and moisture, and ceramics are saved due to its high temperature resistant.Meanwhile we also compare traditional regeneration
Method: cleaning the ceramics of dye discoloration with water, and the picture in Fig. 7 is shown to be rinsed once with a up-flow water, twice, three times, five times,
Ten times and 15 times ceramic photos.As can be seen that the color of pollution ceramics can effectively be diluted by cleaning, but washing
Effect substantially reduces after washing five times.And it is bad, the water for cleaning contaminated ceramics becomes red, leads to serious two
Secondary pollution, as a result as shown in Figure 7.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of sewage treatment steam generator characterized by comprising
Porous material, for adsorbing and transmitting treatment sewage；
Photothermal transformation layer, for converting light energy into thermal energy and the hydrone in treatment sewage being made to be converted to gaseous state；Wherein, institute
State the surface that photothermal transformation layer is located at the porous material.
2. sewage treatment steam generator according to claim 1, which is characterized in that the porous material is porous super
Hydophilic ceramics；And/or the photothermal transformation layer is carbon nanotube, is preferably graphitized carboxyl multi-walled carbon nanotube.
3. sewage treatment steam generator according to claim 1 or 2, which is characterized in that the photothermal transformation layer position
In at least one face or multiple faces of the porous material.
4. sewage treatment steam generator according to claim 1-3, which is characterized in that the photothermal conversion
Layer with a thickness of 20-200um, preferably 40-60um.
5. a kind of sewage-treatment plant, which is characterized in that including any one of the claim 1-4 sewage treatment steam generation
Device；It further include steam condenser；Or further comprise water purification collector.
6. sewage-treatment plant described in any one of the claim 1-4 sewage treatment steam generator or claim 5 exists
Application in sewage treatment.
7. a kind of sewage water treatment method characterized by comprising
By any one of the claim 1-4 sewage treatment steam generator and waste water to be processed, send out the steam
The photothermal transformation layer of raw device can be by light source direct irradiation；
So that the photothermal transformation layer of the sewage treatment steam generator is obtained luminous energy, and converts light energy into thermal energy to will be to
Hydrone in processing sewage is converted to gaseous state.
8. sewage water treatment method according to claim 7, which is characterized in that further include be converted into gaseous hydrone into
Row condensation is so that the step of it is converted to liquid water molecules；Or further comprises and be converted into the hydrone of liquid and received
The step of collection.
9. sewage water treatment method according to claim 7 or 8, which is characterized in that the sewage includes organic pollutant dirt
Water, heavy metal contaminants sewage, industrial wastewater pollution object sewage, dyestuff contaminant sewage；
It is preferred that the dyestuff in the dyestuff contaminant sewage includes rhodamine B, methyl orange, methyl blue, it is one of Congo red or
It is several；The concentration of dyestuff is 0.002-2mg/mL in the more preferable dyestuff contaminant sewage.
10. according to the described in any item sewage water treatment methods of claim 7-9, which is characterized in that the light source is the sun, preferably
The intensity of illumination of the light source is that 1 sun counts to 5 sun numbers.
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