CN102642919B - Application of hollow glass bead biological membrane carrier in wastewater treatment - Google Patents

Application of hollow glass bead biological membrane carrier in wastewater treatment Download PDF

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CN102642919B
CN102642919B CN2012101340694A CN201210134069A CN102642919B CN 102642919 B CN102642919 B CN 102642919B CN 2012101340694 A CN2012101340694 A CN 2012101340694A CN 201210134069 A CN201210134069 A CN 201210134069A CN 102642919 B CN102642919 B CN 102642919B
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hollow glass
reactor
glass microbead
biofilm
wastewater treatment
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CN102642919A (en
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金仁村
张倩倩
俞津津
邢保山
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Hangzhou Normal University
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Hangzhou Normal University
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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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses application of a hollow glass bead biological membrane carrier in wastewater treatment, which includes that a hollow glass bead is added in a biological membrane reactor for inoculating active sludge, the biological membrane reactor is started to intake water and aerate so as to enable the hollow glass bead to contact with microorganisms in the biological membrane reactor fully, a biological membrane is generated on the surface of the hollow glass bead, and the biological membrane is used for perform wastewater treatment. The weight of a single hollow glass bead is less than 0.001g, grain size of the single hollow glass bead is 0.01-0.075mm, and density of the single hollow glass bead is 180-190Kg.m-3. The hollow glass bead biological membrane carrier is light in weight, small in grain size and density, stable in chemical property and high in mechanical strength, has good sealing performance, wind pressure resistance and corrosion resistance, is not easy to break and good in mobility, can form a turbulence state with the microorganisms, simultaneously can resist strong hydraulic shear action, facilitates the wastewater treatment, and accelerates forming speed of the biological membrane and starting time of the reactor.

Description

The application of a kind of hollow glass microbead biofilm carrier in wastewater treatment
(1) technical field
The present invention relates to a kind of application of hollow glass microbead, the particularly application of a kind of hollow glass microbead biofilm carrier in wastewater treatment.
(2) background technology
Along with the maturation gradually of biological wastewater treatment technology, the treatment processs such as microbial film facture, activated sludge process are widely used in wastewater treatment.Wherein the microbial film waste water treatment process is a kind of sewage aerobic biologic treating technique arranged side by side with activated sludge process.The essence of this facture is that the microfauna of the microorganism, protozoon and metazoan one class that make bacterium and Mycophyta is attached on filler or some carrier growth reproduction and forms membranaceous biological sludge-microbial film thereon.And in the microbial film waste water treatment process most critical be biomembranous formation and renewal.
Along with the development of technology of biological membrane, used carrier from pebbles originally gradually to the light carrier future development.Drawing materials of biofilm carrier is not merely inorganic materials, organic materials simultaneously, and to the matrix material future development.Carrier commonly used or filler material comprise organic and inorganic two large classes.Wherein mineral-type mainly contains: sand, carbonate, glass material, zeolite, pottery, carbon fiber, slag, gac etc., the characteristics of above-mentioned inorganic carrier: physical strength is high, chemical property is relatively stable, specific surface area is large etc.Shortcoming is: carrier proportion is larger, the problem of be unfavorable for application in the fluidized biofilm reactors such as fluidized-bed, turbulent bed, be prone to obstruction, the carrier difficulty being recycled.
The organic carrier is mainly: PVC, PE, PS, PP, various types of resins, plastics, fiber, porous material etc.Though these materials respectively have characteristics, there are many shortcomings when the wastewater treatment carrier, as higher as cost, complete processing is complicated, the solid waste difficult treatment formed after useless for filler, what have also easily produces secondary pollution, harm environment.
(3) summary of the invention
The problem that the present invention is prone in processing according to microbial film, and biomembrane process provides the application of a kind of hollow glass microbead biofilm carrier in wastewater treatment to the requirement of carrier, for wastewater treatment provides a kind of new biofilm carrier.
The technical solution used in the present invention is:
The application of a kind of hollow glass microbead biofilm carrier in wastewater treatment, described being applied as: hollow glass microbead is added in the biofilm reactor of inoculation of activated-sludge, start biofilm reactor water inlet aeration, hollow glass microbead is fully contacted with the microorganism in biofilm reactor, at hollow glass microbead Surface Creation microbial film, utilize microbial film to carry out the processing of waste water; Described hollow glass microbead is spherical shape, Ultralight, the Powdered packing material that a kind of small hollow is airtight.
Further, single quality<0.0001g of preferred described hollow glass microbead, particle diameter 0.01～0.075mm, density are 180～190kgm -3, be preferably Guangzhou million and lead to the hollow glass microbead of 2018 models of glass microballon firm.
Further, total add-on of described hollow glass microbead is less than 10% of reactor effective volume, the addition of common described hollow glass microbead is added according to the effective volume of reactor, and the total addition level of described hollow glass microbead is counted 100～150g/L with the reactor effective volume.
Further, the application of described hollow glass microbead microbial film in wastewater treatment recommended to carry out as follows:
(1) active sludge in the gas stripping type reactor of steady running is inoculated in aerobic biofilm reactor, the active sludge inoculum size accounts for 5～10% of reactor effective volume;
(2) take nitrogenous simulated wastewater as the reaction water inlet, start aerobic biofilm reactor, in water inlet and aeration, add hollow glass microbead, influent ammonium concentration is 70mg/L, and hydraulic detention time is 24h, after hollow glass microbead surface attachment microbial film, stride with 7～28mg/L increases influent ammonium concentration, carries out the processing of waste water, and the method for described biological membrane wastewater treatment is technology well known in the art; Single quality<0.001g of described hollow glass microbead, particle diameter 0.01～0.075mm, density are 180～190Kgm -3, the hollow glass microbead of 2018 models that preferred described hollow glass microbead is Guangzhou million logical glass microballon firm, total add-on of described hollow glass microbead is counted 100～150g/L with the reactor effective volume.
Further, described hollow glass microbead adds in the feed supplement mode, in reactor, add described hollow glass microbead to count 20～24g/L with the reactor effective volume for the first time, operation along with biofilm reactor, the described hollow glass microbead of part can come off because of sluicing and biomembranous aging, make the described hollow glass microbead amount in system reduce gradually, for guaranteeing the treatment effect of reactor, need constantly in reactor, to add described hollow glass microbead, addition adds according to actual waste water treatment capacity and reactor effective volume size, when the reactor effluent quality obviously worsens, be that the water outlet ammonia-nitrogen content is during apparently higher than 5mg/L, add described hollow glass microbead in reactor, the maximum addition first of described hollow glass microbead and process between the waste water water yield that to close be 15～20g/L, the each maximum additional amount of described hollow glass microbead is counted 8～10g/L with the reactor effective volume, the total addition level of described hollow glass microbead is counted 100～150g/L with the effective volume of reactor, if the biofilm system collapse phenomenons such as film comes off entirely appear in reactor, be that the microbial film water treatment effect significantly reduces, the effluent quality index can't meet GB (GB1891-2002) requirement, and (wherein total nitrogen content should be lower than 15mg/L, ammonia-nitrogen content is lower than 5mg/L) time, need to again add hollow glass microbead, addition identical with add-on 20～24g/L for the first time or factually the border situation take the circumstances into consideration to add, add again new hollow glass microbead after also part hollow glass microbead in reactor can being taken out, make its maximum addition count 100～150g/L with the effective volume of reactor.
Further, hollow glass microbead of the present invention can be processed all kinds of waste water that is applicable to biofilm reactor, and it is simulated wastewater that the present invention adopts nitrogenous effluent, the consisting of of described nitrogenous simulated wastewater: (NH 4) 2sO 4for (2.5～3.8) mgL -1and NaHCO 3for (4.1～6.1) mgL -1, KH 2pO 4for (25～30) mgL -1, CaCl 22H 2o is (135～140) mg/L, MgSO 47H 2o is that (298～303) mg/L and the micro-I that maintains microorganism growth are that 1.25mL/L, micro-II are 1.25mL/L; Described micro-I is EDTA (4990～5010) mg/L, FeSO 47H 2o (9135～9145) mg/L, micro-II is EDTA (14980～15010) mg/L, H 3bO 4(13～18) mg/L, MnCl 24H 2o (980～1000) mg/L, CuSO 45H 2o (245～255) mg/L, ZnSO 47H 2o (420～435) mg/L, NiCl 26H 2o (200～220) mg/L, NaMoO 42H 2o (210～225) mg/L, NaSeO 410H 2o (200～215) mg/L.
The detection method of reactor biofilm of the present invention success comprises: (1) monitoring effluent quality index sign whether successful as biofilm, after the Biofilm Colonization success, respectively characterize the comparatively obvious desired value lower than pollutent in water inlet of desired value of pollutent in the reactor water outlet; (2) also can have or not mud to come off and intuitively obtain whether biofilm is successful by range estimation reactor water outlet; (3) also can by the film thickness on carrier in the assaying reaction device (being hollow glass microbead) (before biofilm carrier surface without thickness, after biofilm, the carrier surface thickness than biofilm before thickness increase; (4) can pass through the formed microbe species of sediments microscope inspection biofilm surface and biomembranous structure, if there is a large amount of wheel animalcules to occur, stable effluent quality, illustrate the biofilm maturation; (5) observe biomembranous color by biofilm surface and excessively the time, illustrate that biofilm successfully to golden yellow to creamy white by initial white.
Hollow glass microbead of the present invention is that a kind of naked eyes look very small, inner be full of the gas such as carbonic acid gas, hollow closure, the rough-shape spherical shape powder in surface, particle diameter is between 1～500 μ m, density is at 0.1～0.3g/m 3between, have that the light specific surface area of quality is large, thermal conductivity is low, ultimate compression strength is high, the advantage of dispersiveness, mobility, good stability.In addition, also there is self-lubricating, corrosion-resistant, anti-blast, the excellent properties such as nontoxic, can replace the packing material of part bronze powder, molybdenumdisulphide and white carbon black etc.Described hollow glass microbead consists of inorganic materials, and its chemical constitution is silicon-dioxide, aluminum oxide, zirconium white, magnesium oxide, water glass etc.The preparation method of described hollow glass microbead is known technology.
The hollow glass microbead of employing preferred for this invention is the hollow glass microbead of taking from 2018 models of Guangzhou million logical glass microballon firm.In the present invention, the concrete physical properties of hollow glass microbead used is as follows: light weight (single carrier quality approximately<0.0001g), particle diameter 0.01～0.075mm, density are 180～190kgm -3, surface property (Hollow Glass Sphere is shaggy spherical shape), physical strength higher (good stopping property, anti-blast, corrosion-resistant, be difficult for breaking), chemical stability (for glass carrier, chemical stability that the simple glass strengthening forms good).
Hollow glass microbead of the present invention is as follows as the characteristic of biofilm carrier:
1) in general, biofilm reactor is from starting to the time that steady running need to be longer.For the pollutent energy in waste water is completed and biomembranous Contact-sorption within a short period of time, usually need to carry out stirring in various degree, this stirring will produce very strong hydraulic shear effect.The experimental results shows: biomembranous solid support material must have enough physical strengths, to resist this strong hydraulic shear effect, prevents that carrier is broken in motion, collision process.And hollow glass microbead is suitable for biofilm carrier because itself having good physical strength (good stopping property, anti-blast, corrosion-resistant, be difficult for breaking).
2) surfaceness is considered to affect the important factor that microorganism adheres at carrier surface, fixes to a great extent.This be because: one, with smooth surface, compare, coarse carrier surface has increased the effective contact area between microorganism and carrier; Two, for avoiding washing away of hydraulic shear effect, microbial total, be the coarse part that preferentially is attached to carrier surface, as recess, gap etc.Therefore, the carrier surface roughness is larger, and the microorganism adhered to is just more.Hollow glass microbead, because its material is glass, is the tiny spherical shape powder of cutting after processing, and its appearance is coarse but not smooth as simple glass, therefore is conducive to microorganic adhesion, is easy to biofilm and film difficult drop-off.
During 3) as biofilm carrier, the quality of used carrier also affects the treatment effect of membrane bioreactor to a certain extent.Hollow glass microbead in the present invention is because the more general carrier of its quality light (single quality approximately<0.0001g), density are 180～190kgm -3, be easy in the biofilm reactor of the fluidized such as fluidized-bed, turbulent bed, easily with microorganism formation turbulence state.And also be easy to recycling in the processing such as coming off of microbial film later stage.Because of its light weight, even if the situation that exists carrier to run off with water outlet in microbial film is processed, also easily solve (settling tank that can be follow-up through membrane bioreactor is back in membrane bioreactor), come off after not existing microbial film aging and cause the problem of secondary pollution.And carrier can reuse, economic benefit is also higher.
4) hollow glass microbead is to be processed from strand by simple glass, and its composition is the same with simple glass, is mainly silicate (Na 2siO 3, CaSiO 3, SiO 2or Na 2oCaO6SiO 2deng), and the elements such as sodium, calcium are the necessary nutritive element of microorganism growth, therefore using hollow glass microbead, as biofilm carrier, for biological wastewater treatment, microorganism are had no side effect.
5) because hollow glass microbead is small ball, there is mobility preferably than sheet, needle-like or erose packing material in liquid, be easy to the microorganism contact, thereby accelerate biomembranous formation and replace speed, be beneficial to the biological treatment of waste water.
To sum up: hollow glass microbead has the function as biofilm carrier, and its range of application is expanded to the biological wastewater treatment field from general construction timber.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: hollow glass microbead biofilm carrier light weight of the present invention, particle diameter and density is less, stable chemical performance, physical strength are high, have good stopping property, anti-blast, corrosion-resistant, be difficult for breaking, good fluidity, can form the turbulence state with microorganism, resist strong hydraulic shear effect simultaneously; Hollow glass microbead biofilm carrier surface irregularity, be convenient to microorganic adhesion, makes the microbial film difficult drop-off, is conducive to the processing of waste water; Because microbial film easily adheres on hollow glass microbead, and, due to hollow glass microbead light weight and easy and descending current and ascending gas formation turbulence fluidized state, accelerated the start time of biomembranous formation speed and reactor.
(4) accompanying drawing explanation
Fig. 1 tests SBR aerobic biofilm reactor structural representation used for this, wherein 1 be water-in simultaneously also as the material-feeding port of follow-up hollow glass microbead, 2 is water outlet, 3 is aerating apparatus.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
The present invention adopts SBR aerobic biofilm reactor (as shown in Figure 1), and described reactor is made by synthetic glass, cumulative volume 5L, and effective volume 2.5L, whole reactor is fluidized state; Described reactor bottom has water outlet 2 and aerating apparatus 3, and water-in 1 is arranged at top, and described aerating apparatus 3 is placed in reactor body by outside aerating system.Wherein the operating time of sbr reactor device is as follows: a circulation is 8 hours, comprising: intake 360 minutes; Aeration 440 minutes; Precipitate 15 minutes; Draining 25 minutes.
Embodiment 1
1) biofilm of biofilm reactor
Respectively the active sludge in the gas stripping type reactor of laboratory steady running is inoculated in to all identical aerobic biofilm reactor R of two configurations and reactor size 1, R 2in (shown in Fig. 1), R wherein 1, R 2the active mud content of middle inoculation is identical, and the seed sludge volume is 1.5L, wherein R 1(its profile is fibrous, is a kind of film with supporting role, and its physical parameter is: internal diameter 0.4mm, external diameter 0.8mm, membrane pore size 0.2 * 10 as biofilm carrier to add polyether sulphone hollow fibre film in aerobic biofilm reactor -3mm, porosity 80%, film total area 0.36m 2, manufacturer: Shanghai Bing Qi Chemical Industry Science Co., Ltd provides); R 2adding carrier in reactor is that (its Parameter Conditions is: single the about 0.001g of quality, particle diameter 0.01～0.075mm, density are 180～190Kgm to described hollow glass microbead -3, manufacturer: 2018 type products of Guangzhou million logical glass microballon firm).
Consisting of of nitrogenous simulated wastewater: (NH 4) 2sO 4for 3mgL -1and NaHCO 3for 3.8mgL -1, KH 2pO 4for 27mgL -1, CaCl 22H 2o is 136mg/L, MgSO 47H 2o is that 300mg/L and the micro-I that maintains microorganism growth are that 1.25mL/L, micro-II are 1.25mL/L; Described micro-I is that EDTA is 5000mg/L, FeSO 47H 2o is 9140mg/L, and micro-II is that EDTA is 15000mg/L, H 3bO 4for 14mg/L, MnCl 24H 2o is 990mg/L, CuSO 45H 2o is 250mg/L, ZnSO 47H 2o is 430mg/L, NiCl 26H 2o is 210mg/L, NaMoO 42H 2o is 220mg/L, NaSeO 410H 2o is 210mg/L.
Take above-mentioned nitrogenous simulated wastewater as the reactor water inlet, by reactor outside aerating system, carry out aeration, open water inlet, with 0.8～1.0m 3the speed aeration of/h, simultaneously from the water-in 1 of reactor to aerobic biofilm reactor R 1in add polyether sulphone hollow fibre film 20g, to aerobic biofilm reactor R 2water-in 1 in add described hollow glass microbead 20g, influent ammonium concentration is respectively 70mg/L, hydraulic detention time is respectively 24h, carries out the biofilm of biofilm reactor, aerobic biofilm reactor R 1, R 2after moving respectively 15 days, 10 days, the faint yellow microbial film of one deck is all adhered on polyether sulphone hollow fibre film and hollow glass microbead surface, shows aerobic biofilm reactor R 1, R 2the biofilm success.
2) startup of biofilm reactor
After the success of aerobic biofilm reactor biofilm, with 0.8～1.0m 3the speed of/h is to two reactor aerations, keep influent ammonium concentration to be 70mg/L simultaneously, hydraulic detention time (HRT) is 24h, measure effluent quality every day, when water outlet ammonia nitrogen amount, during lower than 5mg/L, keep HRT constant, increase influent ammonium concentration and make ammonia nitrogen loading in reactor increase, influent ammonium concentration increases with the 28mg/L stride, measures effluent quality every day.As aerobic biofilm reactor R 1or aerobic biofilm reactor R 2the denitrification percent of water outlet is lower than 50% the time, respectively from water-in 1 to reactor system R 1middle interpolation Polyethersulfone Hollow Fiber Plasma; R 2middle interpolation hollow glass microbead, add the maximum of carrier (polyether sulphone hollow fibre film or hollow glass microbead) at every turn and count 8～10g/L with the reactor effective volume, and the total add-on of described carrier is counted 80g/L with the reactor effective volume.After carrier (polyether sulphone hollow fibre film or hollow glass microbead) has been added, reactor continues operation, measures effluent quality simultaneously.When the influent ammonium concentration of two reactors all reaches 350mg/L, the reactor nitric efficiency of mensuration, result is: reactor R 1denitrification percent from initial 10% be increased to end of run 70% and remain constant; Reactor R 2denitrification percent reaches 88.4% and remain constant from initial 10%, shows that larger difference appears in the denitrification percent when adding the Polyethersulfone Hollow Fiber Plasma carrier and adding described hollow glass microbead, and the nitric efficiency of hollow glass microbead is better.
Embodiment 2
Take real life sewage as the biofilm reactor water inlet, each parameter of intaking is: (COD600mg/L, SS 150mg/L, pH 6～8), add described hollow glass microbead in biofilm reactor, biofilm reactor configuration and biofilm process operation are with embodiment 1, after the biofilm success, aeration speed is 0.8～1.0m 3/ h, (also can carry out according to actual needs size adjustment, adjusting range is 1 to close between flooding velocity: (7.7～8.5) m 3/ h, hydraulic detention time is 5h, the operation biofilm reactor, because microbial film easily adheres on hollow glass microbead, and due to hollow glass microbead light weight and easy and descending current and ascending gas formation turbulence fluidized state, accelerate the start time of biomembranous formation speed and reactor, made the biomass be detained in reactor many.In the reactor operational process, the Real-Time Monitoring effluent quality, when effluent quality lower than GB, require (wherein total nitrogen content should be lower than 15mg/L, ammonia-nitrogen content is lower than 5mg/L, GB GB1891-2002) time or large number of biological film while coming off, should add hollow glass microbead from water-in 1 immediately, the maximum addition of each hollow glass microbead is counted (8～10g/L) with the reactor effective volume, and the total addition level of described hollow glass microbead is counted 100g/L with the reactor effective volume simultaneously.After adding carrier, reactor continues to keep operation, and when reactor steady running, after 30 days, effluent COD concentration is 42mg/L, and water outlet SS amount is 5mg/L, and the COD clearance reaches 93%, and SS removes rate 96%.

Claims (5)

1. the application of hollow glass microbead biofilm carrier in wastewater treatment, it is characterized in that described being applied as: hollow glass microbead is added in the biofilm reactor of inoculation of activated-sludge, start biofilm reactor water inlet aeration, hollow glass microbead is fully contacted with the microorganism in biofilm reactor, at hollow glass microbead Surface Creation microbial film, utilize microbial film to carry out the processing of waste water; Single quality<0.0001g of described hollow glass microbead, particle diameter 0.01～0.075mm, density are 180～190kgm -3, be shaggy spherical shape.
2. the application of hollow glass microbead biofilm carrier in wastewater treatment as claimed in claim 1 is characterized in that: total dosage of described hollow glass microbead is counted 100～150g/L with the reactor effective volume.
3. the application of hollow glass microbead biofilm carrier in wastewater treatment as claimed in claim 1, it is characterized in that: described application is carried out as follows:
(1) active sludge in the gas stripping type reactor of steady running is inoculated in aerobic biofilm reactor, active mud content accounts for 5～10% of reactor effective volume;
(2) take nitrogenous simulated wastewater as the reaction water inlet, start aerobic biofilm reactor, in water inlet and aeration, add hollow glass microbead, influent ammonium concentration is 70mg/L, and hydraulic detention time is 24h, after hollow glass microbead surface attachment microbial film, stride with 7～28mg/L increases influent ammonium concentration, carries out the processing of waste water; Single quality<0.0001g of described hollow glass microbead, particle diameter 0.01～0.075mm, density are 180～190Kgm -3, total dosage of described hollow glass microbead is counted 100～150g/L with the reactor effective volume.
4. as the application of hollow glass microbead biofilm carrier in wastewater treatment as described in claim 2 or 3, it is characterized in that: described hollow glass microbead adds in the feed supplement mode, in biofilm reactor, add described hollow glass microbead to count 20～24g/L with the effective volume of reactor for the first time, when total nitric efficiency of reactor water outlet lower than 50% the time, add described hollow glass microbead in reactor, the single additional amount of described hollow glass microbead is counted 8～10g/L with the effective volume of reactor, the interpolation total amount of described hollow glass microbead is counted 100～150g/L with the effective volume of reactor.
5. the application of hollow glass microbead biofilm carrier in wastewater treatment as claimed in claim 3 is characterized in that: the consisting of of described nitrogenous simulated wastewater: (NH 4) 2sO 4be 2.5～3.8mgL -1and NaHCO 3be 4.1～6.1mgL -1, KH 2pO 4be 25～30mgL -1, CaCl 22H 2o is 135～140mg/L, MgSO 47H 2o is that 298～303mg/L and the micro-I that maintains microorganism growth are that 1.25mL/L, micro-II are 1.25mL/L; Described micro-I is EDTA4990～5010mg/L, FeSO 47H 2o9135～9145mg/L, micro-II is EDTA14980～15010mg/L, H 3bO 413～18mg/L, MnCl 24H 2o980～1000mg/L, CuSO 45H 2o245～255mg/L, ZnSO 47H 2o420～435mg/L, NiCl 26H 2o200～220mg/L, NaMoO 42H 2o210～225mg/L, NaSeO 410H 2o200～215mg/L.
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CN103196781B (en) * 2013-04-15 2015-05-20 杭州师范大学 Measuring method and device for mechanical strength of granular sludge
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CN101186380A (en) * 2007-11-29 2008-05-28 同济大学 Photocatalysis aeration filter pool for water treatment
CN101423686A (en) * 2008-12-12 2009-05-06 中国建筑材料科学研究总院 Solvent type heat insulation fluorocarbon exterior wall coating
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CN101186380A (en) * 2007-11-29 2008-05-28 同济大学 Photocatalysis aeration filter pool for water treatment
CN101712835A (en) * 2008-10-08 2010-05-26 上海汇丽涂料有限公司 Heat reflection paint with hollow glass microballoon
CN101423686A (en) * 2008-12-12 2009-05-06 中国建筑材料科学研究总院 Solvent type heat insulation fluorocarbon exterior wall coating

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