CN109607761B - Tourmaline/polyurethane composite filler and preparation method thereof - Google Patents
Tourmaline/polyurethane composite filler and preparation method thereof Download PDFInfo
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- CN109607761B CN109607761B CN201910076818.4A CN201910076818A CN109607761B CN 109607761 B CN109607761 B CN 109607761B CN 201910076818 A CN201910076818 A CN 201910076818A CN 109607761 B CN109607761 B CN 109607761B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 122
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 122
- 229910052613 tourmaline Inorganic materials 0.000 title claims abstract description 112
- 239000011032 tourmaline Substances 0.000 title claims abstract description 112
- 229940070527 tourmaline Drugs 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 239000005056 polyisocyanate Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical group NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000108664 Nitrobacteria Species 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 bis-dimethylamino ethyl Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Biological Treatment Of Waste Water (AREA)
Abstract
The invention discloses a tourmaline/polyurethane composite filler and a preparation method thereof. The invention relates to a water treatment biological filler. The invention aims to provide a bioaffinity filler, a tourmaline/polyurethane composite filler for improving the film forming speed. The tourmaline powder is added in the preparation process of polyurethane to prepare the tourmaline/polyurethane composite filler by combining the biomembrane technology. The microenvironment on the surface of the polyurethane filler is improved through the physicochemical property of the tourmaline, the metabolism mechanism of microorganisms is regulated by combining the tourmaline, and the metabolism activity of the microorganisms in a biological treatment system is increased, so that the starting time of the biological reaction system is shortened, the treatment efficiency and the operation stability of the biological reaction system are improved, and the operation cost of the biological reaction system is reduced. The preparation method has simple process and low cost. Therefore, the invention has certain application value and application prospect in the field of sewage treatment. The invention belongs to the technical field of wastewater treatment processes.
Description
Technical Field
The invention relates to a bio-affinity filler, in particular to a tourmaline/polyurethane composite filler for improving the film forming speed.
Background
The biological filler is used as a carrier on which microorganisms grow and propagate, is one of the cores of a biological membrane water treatment technology, and the material composition and the surface performance of the biological filler directly influence the attachment, growth, propagation and activity of the microorganisms on the surface of the filler, determine the properties of biomass on the surface of the biological filler, the composition structure, compactness and the like of a biological membrane, and further influence the biofilm formation performance and the sewage degradation efficiency of the microorganisms. Compared with other elastic fillers and composite fillers, the polyurethane filler has large specific surface area and can support the attachment growth of a large number of microorganisms. The biomass per unit volume can be basically 25-30 kg/m3In addition, the method is very beneficial to the growth of various microorganisms. The polyurethane filler not only provides the growth space of heterotrophic bacteria, but also creates the growth conditions of autotrophic bacteria, and provides an ideal external ring for biological nitrogen and phosphorus removalAnd (4) environmental conditions. The polyurethane filler ensures the mass transfer efficiency of the system and promotes the activity of microorganisms in the filler. The polyurethane filler can provide three microenvironments of aerobic, anoxic and facultative oxygen simultaneously due to the connectivity of the space structure. The specific gravity of the polyurethane filler is slightly less than that of water, and the carrier in a suspension fluidized state in the water is subjected to mutual collision friction of gas, liquid and solid, so that the activity of the biological membrane is improved, and the mass transfer process can be enhanced. Meanwhile, the aged biological membrane is easy to fall off, the filler has good resilience, and the dissolved oxygen utilization rate and the biological mass transfer rate are improved by combining the corresponding process. The polyurethane filler has stable chemical property and does not participate in biochemical reaction of a biological film, so the polyurethane filler is not biodegradable; it will not dissolve out harmful substance to affect biological activity, and has strong corrosion resistance and durability. Based on the above characteristics of polyurethane fillers, polyurethane fillers have been widely used in organic wastewater treatment.
The polyurethane filler is easy to be mixed with other materials in the production process, thereby improving certain performance of the filler and enabling the filler to be more suitable for a certain wastewater treatment process. Leson et al, in 1991, published by An Innovative Air Pollution Control Technology for VOC emulsions, used agar-filled polyurethane fillers for fluidized bed treatment of volatile organic compounds with good results. Sharefdeen et al, in 1993, published in Biofiltration of methane Vapor, applied polyurethane filler mixed perlite and vermiculite to biofilter treatment of Methanol wastewater with good results. Joeng et al published 2003 in the paper "Practical applications of Nitrogen and phosphorus Removal with flowing Media SBBR" applied polyurethane sponge filler as a bio-carrier to SBBR reactors achieved good denitrification efficiency. Liyanfeng et al' invention patent in 2005 modified nano SiO2In the composite polyurethane foam and its index method and application (patent No. CN1631976A), nano SiO is added in polyurethane filler2Improves the affinity, mass transfer performance and physical and chemical stability of the filler to microorganisms. Invention patent "tourmaline/chitosan composite material preparation method" published in 2018 by Chengzeli et al (publication No. 1081876)30) In the method, tourmaline and chitosan are mixed and then subjected to heat treatment and the like to obtain the tourmaline and chitosan composite material which is used for adsorbing garbage percolate and has better effect. However, the modified biological filler made of the nano material is expensive and not easy to obtain, and has certain limitation in popularization. Therefore, the research and development of the functional biological carrier filler with low cost and high quality have important significance for improving the biofilm formation speed of the filler and the unit volume biological load in the reactor.
Tourmaline is a cyclic silicate crystal mineral containing boron, aluminum, sodium, iron, calcium and magnesium, and has unique physical and chemical properties such as pyroelectricity, piezoelectricity and adsorption effect, wherein the most remarkable property is spontaneous electric polarity. The pH value of the wastewater can be spontaneously adjusted due to the permanent electrode action of the tourmaline. Under the acidic condition, a large number of hydroxyl groups on the surface of the tourmaline are easily absorbed by H in an acidic solution+Attract and neutralize, cause the rapid rise of pH; under alkaline conditions, OH-The release of hydroxyl on the surface of the tourmaline is inhibited, and the fracture of Si-O bonds and triangular B-O bonds in silicon-oxygen tetrahedron causes the combination of Si and B on the surface and the hydroxyl in water, thereby causing the reduction of pH. In addition, the tourmaline has dangling bond on its surface, and can be used for treating H+Resulting in ion exchange adsorption or sorption. Researches show that the activity of microorganisms can be improved under the action of the tourmaline self-generating field, and the removal of pollutants is promoted. Other scholars find that the tourmaline has the performance of spontaneously adjusting the pH value of the water environment in tests, thereby causing the change of liquid water clusters and generating various biological effects.
In a paper published by Yankee elder et al in 2013, namely preparation and performance research of a supported biological carrier, polyurethane filler is used as a matrix, aqueous polyurethane is used as a medium, tourmaline is coated on the surface of the polyurethane filler, and the tourmaline-loaded biological filler is prepared to treat high-ammonia-nitrogen wastewater, so that the removal rates of ammonia nitrogen and nitrite nitrogen are respectively improved by 8.12% and 9.08%. However, the coating method has the defects of uneven distribution of tourmaline, easy falling and the like, and a reaction system is difficult to maintain efficient and stable operation for a long time. Therefore, the tourmaline is doped in the production process of the polyurethane filler, so that the problems can be solved, and the tourmaline has important significance in the modification application of the polyurethane filler.
Disclosure of Invention
The invention provides a tourmaline/polyurethane composite filler and a preparation method thereof, aiming at solving the problems that the existing biomembrane filler has slow film forming speed, does not have the capability of automatically regulating the pH value of the microecology of a biomembrane and has unstable operation of a biological system; the tourmaline/polyurethane composite filler provided by the invention has the advantages of wide raw material source, low price, simple process and easy large-scale production.
The preparation method of the tourmaline/polyurethane composite filler comprises the following steps:
1) at least one polyol, a chain extender, a foaming agent, a stabilizer, a gel catalyst and tourmaline are mixed according to a certain proportion and a certain sequence, and are stirred vigorously and uniformly at a certain temperature to form a mixed solution A.
2) And adding polyisocyanate into the mixed solution A, mechanically stirring to uniformly mix the polyisocyanate and the mixed solution A, and quickly pouring the mixed solution A into a foaming box for foaming.
3) Opening the mold after 30min, taking out the soft polyurethane foam block, and curing.
In the first step, the polyol is selected from polyether polyol and polyester polyol. The molecular weight of the polyether polyol is 2000-5000, and the functionality is 2-3; the polyether polyol has a molecular weight of 2000-4000 and a functionality of 2-3.
In the first step, the chain extender is selected from ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanediol or triethanolamine.
In the first step, the foaming agent is selected from carbamide, water, liquid carbon dioxide, dichloromethane or bis-dimethylamino ethyl ether.
The stabilizer in the step one is silicone oil.
In the first step, the gel catalyst is organic bismuth, namely dibutyltin dilaurate or stannous octoate or triethylene diamine.
The tourmaline in the step one is commercialized tourmaline. 1) The content of tourmaline is 100-300 kg/m3(ii) a 2) The density is 0.58 to 0.77g/cm3(ii) a 3) The filler is a cube with the side length of 2-5 cm and the porosity of 50 &70 percent, and the aperture is 2-4 mm.
In the first step, the particle size of the tourmaline is 2-50 μm.
The polyisocyanate in the second step is toluene diisocyanate or xylene methane diisocyanate.
In the first step, the tourmaline/polyurethane composite filler is prepared by taking 100 parts by weight of polyol as a reference, 1-1.3 parts by weight of chain extender and 3-6 parts by weight of foaming agent. The foam stabilizer is 0.8-1.0 part by weight, the gel catalyst is 11-14 parts by weight, the tourmaline is 1.6-16 parts by weight, and the isocyanate is 37-40 parts by weight.
The tourmaline/polyurethane composite filler is prepared by the steps I and II, wherein the temperature is 20-25 ℃, the stirring time is 1-3 min, and the stirring speed is 300-1000 rpm.
The tourmaline/polyurethane composite filler is cured at normal temperature for 24-72 hours in the third step.
The invention has the following beneficial effects:
the tourmaline powder is added in the preparation process of the polyurethane to prepare the tourmaline/polyurethane composite filler by combining with the biomembrane technology, the microenvironment on the surface of the polyurethane filler is improved by the physicochemical property of the tourmaline, the metabolic mechanism of microorganisms is regulated by combining with the tourmaline, the metabolic activity of the microorganisms in a biological treatment system is increased, the starting time of the biological reaction system is further shortened, the treatment efficiency of the biological reaction system is improved, the operation cost of the biological reaction system is reduced, and the tourmaline/polyurethane composite filler prepared by the coating method is stable in operation compared with the tourmaline/polyurethane composite filler prepared by the coating method, so that the tourmaline/polyurethane composite filler has certain application value and application prospect in the field of sewage treatment.
Drawings
Figure 1, picture of polyurethane filler without tourmaline
FIG. 2 is a picture of tourmaline/polyurethane composite filler of the invention
FIG. 3 is SEM photograph of tourmaline/polyurethane composite filler of the present invention
FIG. 4 shows the ammonia nitrogen concentration change of inlet and outlet water in the tourmaline/polyurethane composite filler reaction system
FIG. 5 shows the ammonia nitrogen concentration change of inlet and outlet water in a common polyurethane composite filler reaction system
FIG. 6 shows the film-forming effect (x 10000 times) of a conventional polyurethane composite filler
FIG. 7 shows the effect of tourmaline/polyurethane composite filler coating (x 10000 times)
FIG. 8 shows COD removal variation under different gas-water ratios
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The tourmaline powder with a certain proportion is added in the preparation process of the polyurethane to form the tourmaline/polyurethane composite filler.
Example 1
100 parts of polyether polyol, 1.1 parts of triethanolamine, 1.2 parts of an organic silicon foam stabilizer, 4.0 parts of distilled water, 13 parts of dibutyltin dilaurate and 13.6 parts of tourmaline (the mass fraction of the tourmaline is 8%). The above drugs are sequentially added into 500ml beaker to form component A, and stirred vigorously for 3min at constant temperature of 20 deg.C and 800rpm to mix well.
38 parts of toluene diisocyanate was added to component A, mechanically stirred for 1min to mix well, and poured into a foaming box rapidly for foaming.
Opening the die after foaming for 30min, taking out the soft polyurethane foam, and curing for 48h to form the tourmaline/polyurethane composite filler.
The tourmaline/polyurethane composite filler prepared by the method is applied to high ammonia nitrogen wastewater treatment as follows:
the supernatant of the sludge digestion tank is used as inlet water in the experiment, and the water quality condition is shown in table 1.
TABLE 1 Water quality index of influent
In order to accelerate the start time of biofilm formation, the two SBR reactors are firstly added with the residual sludge of the aerobic tank of the municipal sewage plant, mixed with high ammonia nitrogen wastewater, kept stand for 8 hours, aerated for 22 hours, kept stand for 55 minutes, and filled with water by 50 percent, the biofilm is cultured by water inflow for 5 days according to the method, aerated for 10 hours in each period, kept stand for 55 minutes and then drained. The SBR reactor added with the tourmaline/polyurethane composite filler forms a tourmaline/polyurethane composite filler reaction system, the SBR reactor added with the common polyurethane composite filler forms a common polyurethane composite filler reaction system, except different types of carriers, the rest operating conditions are completely the same, the aeration quantity is 100L/h, the initial pH value of wastewater is 6.9-7.5, the HRT is 11h, the influence of the carriers on the start of the microbial biofilm is inspected by comparing the degradation rate of ammonia nitrogen in the tourmaline/polyurethane composite filler reaction system and the common polyurethane composite filler reaction system, the used fillers are shown in attached figure 1 and attached figure 2, and the SEM image of the tourmaline/polyurethane composite filler is shown in attached figure 3.
As can be seen from the attached figure 4, the ammonia nitrogen degradation rate is low 6 days before the tourmaline/polyurethane composite filler reaction system operates, a thin biological film can be seen through observation, the distribution is not uniform, and individual yellow or brown spots can be seen. The reason is that the biological membrane is not cured, the microorganisms carry out metabolic activity in order to adapt to the environment, the quantity of the microorganisms is small, and the uncured biological membrane has no stable capability of degrading ammonia nitrogen. The ammonia nitrogen degradation rate of the tourmaline/polyurethane composite filler reaction system is gradually increased after the tourmaline/polyurethane composite filler reaction system operates for 6 days, when the tourmaline/polyurethane composite filler reaction system operates to 13 th days, the ammonia nitrogen degradation rate is 83.4%, the ammonia nitrogen degradation rate tends to a stable state, and a uniform white villous biomembrane is distributed on the filler when the tourmaline/polyurethane composite filler reaction system is examined under a microscope. The reason is that the microorganisms convert ammonia nitrogen to generate energy, synthesize DNA and protein, and are used for increasing the number of microorganisms, so that the biological membrane is cured, the cured biological membrane has the capability of stably degrading ammonia nitrogen, and the degradation rate of ammonia nitrogen is maintained in a stable state.
Comparing fig. 4 and fig. 5, it can be seen that, at the 6 th day, the ammonia nitrogen degradation rate of the tourmaline/polyurethane composite filler reaction system is 22.8%, the ammonia nitrogen degradation rate of the common polyurethane composite filler reaction system is 15.1%, and the ammonia nitrogen degradation rate of the tourmaline/polyurethane composite filler reaction system is higher. The ammonia nitrogen degradation rate of the tourmaline/polyurethane composite filler reaction system between the 6 th and 13 th days is greatly improved, and the ammonia nitrogen degradation rate after the 13 th day is 83.4 percent and tends to be stable; the ammonia nitrogen degradation rate of the common polyurethane composite filler reaction system is greatly improved to 6-15 days, and the ammonia nitrogen degradation rate after 15 days is 66.0 percent and is kept stable. The degradation rate of ammonia nitrogen in the tourmaline/polyurethane composite filler reaction system is stabilized at about 80%, the degradation rate of a common polyurethane composite filler reaction system is stabilized at about 60%, after the tourmaline/polyurethane composite filler reaction system enters a stabilization stage, the degradation rate of the tourmaline/polyurethane composite filler reaction system is about 20% higher than that of the common polyurethane composite filler reaction system, the time for stabilizing the tourmaline/polyurethane composite filler reaction system is shortened by 2d compared with that of the common polyurethane composite filler reaction system, the concentration of the ammonia nitrogen in effluent of the tourmaline/polyurethane composite filler reaction system is 41mg/L, the concentration of the ammonia nitrogen in effluent of the common polyurethane composite filler reaction system is 69mg/L, and the quality of the effluent of the tourmaline/polyurethane composite filler reaction system is better than that of the common polyurethane composite filler reaction system.
The analysis shows that compared with the common polyurethane composite filler reaction system, the tourmaline/polyurethane composite filler reaction system has the advantages that the biofilm formation is started quickly, the degradation of microorganisms to ammonia nitrogen is facilitated, namely, the microorganisms are easy to form a biofilm on the tourmaline/polyurethane composite filler, and the activity of a living film is good. The reason is that the tourmaline on the tourmaline/polyurethane composite filler can reduce the association degree of water molecules, improve the utilization rate of microorganisms to water and promote the synthesis of DNA and protein in cells, thereby accelerating the cell proliferation speed, increasing the number of microorganisms, quickly starting a system and having good treatment effect. In addition, the tourmaline/polyurethane composite filler has the capability of automatically adjusting the pH value of a microenvironment, and promotes the increase of the quantity of nitrobacteria and denitrifying bacteria and the enhancement of biological activity.
In order to compare the growth conditions of microorganisms on the tourmaline/polyurethane composite filler and the common polyurethane composite filler, the biomembrane during the start-up process of biofilm formation is observed by a Scanning Electron Microscope (SEM), and the SEM images are shown in an attached figure 6 and an attached figure 7. As can be seen from the attached figures 6 and 7, the microorganisms can form a biological film on the common polyurethane composite filler and the tourmaline/polyurethane composite filler, but the microorganisms are different in amount, the microorganisms on the tourmaline/polyurethane composite filler are more in amount and are connected with each other, and the bacteria are plump compared with the bacteria on the common polyurethane composite filler.
Example 2
100 parts of polyether polyol, 1.28 parts of triethanolamine, 0.9 part of an organic silicon foam stabilizer, 3.5 parts of distilled water, 11 parts of dibutyltin dilaurate and 6.48 parts of tourmaline (the mass fraction of the tourmaline is 4%). The above drugs are sequentially added into 500ml beaker to form component A, and stirred vigorously for 3min at constant temperature of 20 deg.C and 800rpm to mix well.
And (3) adding 39 parts of toluene diisocyanate into the component A, mechanically stirring for 1min to uniformly mix the toluene diisocyanate and the component A, and quickly pouring the mixture into a foaming box for foaming.
Opening the die after foaming for 30min, taking out the soft polyurethane foam block, curing for 48h and preparing the tourmaline/polyurethane composite filler.
The tourmaline/polyurethane composite filler prepared by the method is applied to the treatment of printing and dyeing wastewater as follows:
the wastewater used in the test is discharged from a secondary sedimentation tank of a wastewater treatment station of a textile enterprise in Heilongjiang province, and the current treatment process of the enterprise adopts A2The water quality characteristics of the/O process are shown in Table 2.
Table 2 Experimental study on the quality of printing and dyeing wastewater
Because most of the water after the secondary biochemical treatment of the original sewage plant is macromolecular dye and auxiliary agent which are difficult to degrade, the domestic sewage mixed printing and dyeing wastewater is adopted to help culture and domesticate the microorganisms in the biofilm formation stage, and the water inlet load in the biofilm formation stage is 0.18m3/(m2H). After the operation for one week, a biological film begins to grow, and after 3 weeks, the ammonia nitrogen removal rate of the effluent is obvious and tends to be stable. The water inflow rate in the experimental stage is 8-16 mL/min, and the water inflow velocity is 0.25 &0.5m/h, keeping COD between 80 and 95mg/L and gas-water ratio between 4:1 and 15: 1.
As shown in the attached figure 8, after the gas-water ratio is increased from 4:1 to 10:1, the removal efficiency of COD of the two fillers is obviously increased, which shows that under the condition of certain organic load, the increased gas-water ratio can provide a better environment for aerobic bacteria and enhance the effect of biochemical reaction, besides the increased supply of oxygen, the disturbance to water flow is also an important aspect of promoting the transfer capacity of media in a biological membrane, so that a certain positive effect on the reduction of COD is generated. When the gas-water ratio is continuously increased to 15:1, the COD of the effluent of the two reactors is slightly increased, because the biofilm falls off due to the overlarge gas-water ratio, and the volume load of the reactors is increased. After 2-3 days of operation, the effluent of the two reactors is stable again, and the COD of the effluent of the tourmaline/polyurethane composite filler reactor is observed to be always obviously lower than that of the effluent of the common polyurethane composite filler reactor. The tourmaline/polyurethane composite filler biomembrane is more stable than the common polyurethane composite filler biomembrane under the condition of high gas-water ratio, namely the affinity and the adhesive force of the tourmaline/polyurethane composite filler to the biomembrane are stronger than those of the common polyurethane composite filler. In the aspect of the form of the biomembrane, the biomembrane on the tourmaline/polyurethane composite filler is compact, and the compact biomembrane of the tourmaline/polyurethane composite filler and the rich microbial biomass can be seen under a microscope. And the biological film on the surface of the common polyurethane composite filler is fluffy.
The advanced treatment of the printing and dyeing wastewater by using the reaction system of the tourmaline/polyurethane composite filler and the common polyurethane composite filler has difference in effluent COD and chromaticity, wherein the effluent COD is 36-48 mg/L, the effluent chromaticity range is 35-55 degrees, the effluent COD is 60-70 mg/L, the effluent chromaticity range is 55-72 degrees, and the effluent turbidity and ammonia nitrogen have no significant difference. The turbidity of the effluent of the two reactors is between 1.2 and 3.5NTU, and the ammonia nitrogen of the effluent is about 0.5 to 2.5 mg/L.
Example 3
100 parts of polyether polyol, 1.3 parts of triethanolamine, 1.0 part of an organic silicon foam stabilizer, 3.5 parts of distilled water, 11.5 parts of dibutyltin dilaurate and 3.1 parts of tourmaline (the mass fraction of the tourmaline is 2%). The above drugs are sequentially added into 500ml beaker to form component A, and stirred vigorously for 3min at constant temperature of 20 deg.C and 800rpm to mix well.
36 parts of toluene diisocyanate are added into the component A, mechanically stirred for 1min to be uniformly mixed, and quickly poured into a foaming box for foaming.
Opening the die after foaming for 30min, taking out the soft polyurethane foam block, curing for 48h and preparing the tourmaline/polyurethane composite filler.
The tourmaline/polyurethane composite filler prepared by the method is applied to black and odorous water body treatment as follows:
the common polyurethane composite filler reaction system and the tourmaline/polyurethane composite filler reaction system take excess sludge of a municipal sewage treatment plant as inoculated sludge, and start the reaction systems by adopting a 4-hour aeration-2-hour intermittent operation mode. Firstly, controlling HRT at 15h, finishing the starting of a reaction system, namely successfully hanging and touching the filler, and keeping the quality of the effluent water stable. And then gradually increasing the water inlet load of the polluted river water, namely reducing the HRT from 15h to 11h, 9h and 7h in turn, wherein each HRT lasts for 10d, and the temperature of the reactor is controlled to be 25 +/-1 ℃. Table 3 shows the water quality of the inlet and outlet water for the two fillers at different hydraulic retention times.
TABLE 3 quality of Water in and out of the reaction System
As can be seen from Table 3, with the hydraulic retention time shortened from 15 hours to 7 hours, the concentrations of pollutants in the effluent of the two reaction systems are increased to different degrees, wherein the mass concentrations of COD, ammonia nitrogen and nitrite in the effluent of the common polyurethane composite filler reaction system are respectively increased from 2.1mg/L, 0.1mg/L and 0.4mg/L to 4.6mg/L, 1.6mg/L and 0.6mg/L, and the mass concentrations of tourmaline/polyurethane composite filler reaction system are respectively increased from 1.5mg/L, 0.1mg/L and 0.3mg/L to 2.9mg/L, 0.5mg/L and 0.5 mg/L. Therefore, under different operating conditions, the quality of the effluent water of the tourmaline/polyurethane composite filler reaction system is superior to that of the effluent water of the common polyurethane composite filler reaction system. The water inlet load of the reaction system is increased, the contact chance and the reaction time of microorganisms and pollutants are reduced, and meanwhile, the shearing force effect on the biological membrane is increased due to the increase of the water inlet load, so that the mass concentration of the pollutants in the effluent of the two reaction systems is increased along with the shortening of the HRT. Compared with the common polyurethane composite filler, the tourmaline/polyurethane composite filler has stronger affinity and adhesive force to the biological membrane, compact structure of the biological membrane, reduced influence of destruction of shearing force and relatively stable microbial community structure, so that the water quality of the effluent of the tourmaline/polyurethane composite filler reaction system is better than that of the common polyurethane composite filler reaction system under the same HRT condition.
Claims (1)
1. The tourmaline/polyurethane composite filler comprises polyol, a chain extender, a foaming agent, a stabilizer, a gel catalyst and tourmaline, wherein the tourmaline is uniformly distributed in a polyurethane reticular structure, and the preparation method of the tourmaline/polyurethane composite filler is carried out according to the following steps:
1) based on 100 parts by weight of polyol, 1-1.3 parts by weight of chain extender, 3-6 parts by weight of foaming agent, 0.8-1.0 part by weight of stabilizer, 11-14 parts by weight of gel catalyst and 1.6-16 parts by weight of tourmaline are used; mixing the reagents in sequence, and uniformly stirring at 20-25 ℃, wherein the stirring speed is 300-1000 rpm, and the stirring time is 1-3 min to form a mixed solution A; the polyol is polyether polyol, the chain extender is triethanolamine, the foaming agent is water, the stabilizer is an organic silicon foam stabilizer, the gel catalyst is dibutyltin dilaurate, and the isocyanate is toluene diisocyanate;
2) adding 37-40 parts by weight of isocyanate into the mixed liquid A, mechanically stirring at the stirring speed of 300-1000 rpm for 1-3 min, uniformly mixing, quickly pouring into a foaming box, foaming, opening the mould after 30min, taking out the soft polyurethane foam, curing at normal temperature for 24-72 h to finally obtain the tourmaline/polyurethane composite filler, wherein the density of the tourmaline/polyurethane composite filler is 0.58-0.77 g/c, the porosity of the tourmaline/polyurethane composite filler is 50-70%, the pore diameter of the tourmaline/polyurethane composite filler is 2-4 mm, and finally cutting the tourmaline/polyurethane composite filler into cubes with the side length of 2-5 cm; the tourmaline is commercial tourmaline, the particle diameter is 2-50 μm, and the tourmaline content is 100-300 kg/m3；
The molecular weight of the polyether polyol is 2000-5000, and the functionality is 2-3; the molecular weight of the polyester polyol is 2000-4000, and the functionality is 2-3.
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| CN102786646A (en) * | 2012-08-17 | 2012-11-21 | 江苏大学 | Acid modified palygorskite-polyurethane porous material as well as preparation method and application thereof |
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| CN102786646A (en) * | 2012-08-17 | 2012-11-21 | 江苏大学 | Acid modified palygorskite-polyurethane porous material as well as preparation method and application thereof |
| CN105348448A (en) * | 2015-12-14 | 2016-02-24 | 青岛水务集团有限公司科技中心 | Preparation method of netty polyurethane microbial carrier with interpenetrating polymer network structure |
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