CN109336249A - A kind of modified porous granule of polyvinyl alcohol filler of phase transformation and preparation method thereof and the application in low temperature environment sewage water denitrification - Google Patents
A kind of modified porous granule of polyvinyl alcohol filler of phase transformation and preparation method thereof and the application in low temperature environment sewage water denitrification Download PDFInfo
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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
- 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
- C02F3/108—Immobilising gels, polymers or the like
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/104—Granular carriers
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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Abstract
The present invention provides a kind of modified porous granule of polyvinyl alcohol filler of phase transformation and preparation method thereof and the application in low temperature environment sewage water denitrification, the following steps are included: expanded graphite and phase-change material mixing, it is heated to after melting completely, misting cooling obtains the expanded graphite particles core material of load paraffin；After melamine and formaldehyde heating stirring, core material and sodium chloride is added, for the pH value of regulation system to acidity, heating stirring obtains phase-change microcapsule；Water-soluble poval, phase-change microcapsule, surfactant are added to the water, mechanical mixture, strength ultrasonic disperse, obtain phase transformation modified polyvinylalcohol lotion, then it is added dropwise in freezing liquid and is rapidly frozen, then is freeze-dried, obtain the modified porous granule of polyvinyl alcohol filler of phase transformation.The temperature control of the modified porous granule of polyvinyl alcohol filler of phase transformation prepared by the present invention is good, is conducive to maintaining reaction temperature into 25 DEG C, is more advantageous to the activity for keeping nitrifier, improves the nitric efficiency of biofilm reactor at low ambient temperatures.
Description
Technical field
The invention belongs to low temperature resistant technical field of sewage, and in particular to a kind of modified porous granule of polyvinyl alcohol of phase transformation
Filler and preparation method thereof and the application in low temperature environment sewage water denitrification.
Background technique
With the continuous development of science and technology, a large amount of pollutants are discharged into water body, and wherein nitrate is as main dirty
It is generally existing to contaminate substance, and has the tendency that aggravating year by year, the simple self-cleaning ability for relying on water body pair is far from full
Requirement of the foot society to water quality, if the polluters such as exceeded nitrate can be serious in sewage without sewage treatment process
The nitrate for influencing human health, therefore how going in water removal becomes the emphasis of sewage treatment.And the nitrification of ammonia nitrogen is at sewage
Manage the important prerequisite of denitrogenation.
Technology of biological membrane is a kind of sewage treatment process by membrane technology in conjunction with traditional active sludge processing technique, excellent
Gesture is not only there is preferable organic removal rate, moreover it is possible to be effectively removed ammonia nitrogen and other hard-degraded substances but low in winter
Nitrification ability reduces under the conditions of temperature, and the water quality of processing is made to be difficult to meet the requirement that people use.A variety of reinforcings are had studied at present
Nitrification technology, if running optimizatin is strengthened, biomembrane is strengthened, nitrifier is inoculated with and materialization reinforcement technique, wherein biomembrane strengthens skill
Art can keep original technique and its main body structure structure constant, only need to be modified place to the carrier filler of nitrobacteria growth
Reason can be obtained ideal nitrification efficiency, but traditional nitrifier such as Nitrosomas and Nitromonas are 25 DEG C in temperature
Alkalescent water in activity it is maximum, when temperature is lower than 23 DEG C, their growth will be stagnated gradually, directly affect the nitre of ammonia nitrogen
Change.
The cultural method of a kind of low temperature resistant nitrifier disclosed in Chinese patent CN 106554930A and its in the treatment of waste water
Application, which is to be adopted as 18~40 DEG C of room temperature and the training of 8~18 DEG C of low temperature using industrial ammonia-containing water as culture solution
Mode alternately is supported, and to addition calcium salt, mantoquita, magnesium salts and/or ferrous salt metal in the activated sludge rich in nitrifier
The nitrobacteria growth that salt and spermine, spermidine, hydroxylamine hydrochloride, hydroxyl sulfate or phosphatic hydroxylamine polyamines form promotes
Agent carries out enrichment culture, and in Enrichment culture method, each batch replacement culture solution while adds nitrobacteria growth promoter,
Obtain low temperature resistant nitrifier.The low temperature-resistant strains body of this method preparation can realize high-efficient deamination nitrogen under cryogenic, can solve
Certainly winter low temperature fluctuation of service, the problems such as sewage treatment is not up to standard.Chinese patent CN103342417B discloses a kind of resistance to low
The enrichment and its sewage anoxic denitrogenation application of warm heterotrophism synchronous nitration and denitrification microbial inoculum, using ammonia nitrogen and nitrate nitrogen containing organic carbon source
Combined sewage is used as raw material, and composition includes sodium acetate, NH4Cl, KNO3, KH2PO4, MgSO47H2O, CaCl2
2H2O, FeSO4.7H2O and NaHCO3, surplus are water, in 10 DEG C of temperature control low temperature rooms, first under aerobic condition, to contain organic carbon
Ammonia nitrogen and nitrate nitrogen combined sewage culture enrichment, then under anoxic conditions in SBR with containing organic carbon ammonia nitrogen and nitrate nitrogen it is mixed
The further acclimating of sewage is closed, heterotrophic nitrification aerobic/anoxic denitrification microbial inoculum of low temperature tolerance characteristics is obtained.The microbial inoculum is at 10 DEG C
Cryogenic conditions under, with sodium acetate be unique organic carbon source, in the environment that ammonia nitrogen and nitrate nitrogen coexist, can be in aerobic or anoxic
Environment realize synchronous nitration and denitrification, stablize model, under anoxic conditions also have very high TN removel rate.By above-mentioned
The prior art it is found that currently in order to improve low temperature under nitration reaction efficiency, be mostly to be modified to the lower temperature resistance of nitrifier,
It is actually rare to the surface side filler heat insulating ability aspect of its nitrifier attachment.Phase-change material is introduced into biofilm reactor by the present invention
Filler in, to improve the nitration reaction efficiency of biofilm reactor under low temperature environment.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of modified porous granule of polyvinyl alcohol filler of phase transformation and its preparations
Method and the application in low temperature environment sewage water denitrification, the present invention will coat melamine resin and be prepared into after expanded graphite Adsorption Paraffin
To phase-change microcapsule be added in the preparation process of porous polyethylene alcohol particle, make porous polyethylene alcohol filler have temperature control
Can, be conducive to maintaining reaction temperature into 25 DEG C, be more advantageous to the activity for keeping nitrifier, improves biofilm reactor in low temperature
Nitric efficiency under environment.
In order to solve the above technical problems, the technical scheme is that
A kind of modified porous granule of polyvinyl alcohol filler of phase transformation, which is characterized in that the modified porous polyvinyl alcohol of phase transformation
Granular filler includes phase-change microcapsule, and the phase-change microcapsule includes resin wall material, phase-change material core material and adsorbent support material.
As a preferred embodiment of the above technical solution, the resin wall material melamine resin, the adsorbent support material are expansion stone
Ink.
The present invention also provides a kind of preparation methods of the modified porous granule of polyvinyl alcohol filler of phase transformation described above, special
Sign is: the following steps are included:
(1) expanded graphite and phase-change material mixing, are heated to after melting completely, misting cooling, obtain the swollen of load paraffin
Swollen graphite particle core material；
(2) expanded graphite particles of the load paraffin of step (1) preparation after melamine and formaldehyde heating stirring, will be added
Core material and sodium chloride, for the pH value of regulation system to acidity, heating stirring is uniform, obtains phase-change microcapsule；
(3) phase-change microcapsule, surfactant prepared by water-soluble poval, step (2) are added to the water, machinery is mixed
After conjunction, strength ultrasonic disperse obtains phase transformation modified polyvinylalcohol lotion；
(4) phase transformation modified polyvinylalcohol lotion is added dropwise in freezing liquid and is rapidly frozen, then is freeze-dried, obtain phase transformation
Modified porous granule of polyvinyl alcohol filler.
As a preferred embodiment of the above technical solution, in the step (1), phase-change material is paraffin wax, expanded graphite and phase
Become the mass ratio of material as 1:0.3-0.6.
As a preferred embodiment of the above technical solution, in the step (1), the partial size of the expanded graphite particles core material of paraffin is loaded
For micron order.
As a preferred embodiment of the above technical solution, in the step (2), the expanded graphite of paraffin is loaded in phase-change microcapsule
The content of grain core material is 15-25%.
As a preferred embodiment of the above technical solution, in the step (3), water-soluble poval includes that mass ratio is 1:1.5-
The polyvinyl alcohol that the polyvinyl alcohol and molecular weight that 2.3 molecular weight is 2.5-3.5W are 17-22W.
As a preferred embodiment of the above technical solution, in the step (3), the technique of strength ultrasonic disperse are as follows: with 1000-
The power of 1500W is ultrasonically treated 3-5min under the frequency of 15-20kHz, then with the power of 1600-2000W, in 20-
30-90min is ultrasonically treated under the frequency of 25kHz.
As a preferred embodiment of the above technical solution, in the step (4), freezing liquid is liquid nitrogen or frozen ethanol, when freezing
Between be 5-10s, rate of addition 0.5-1mL/min.
The present invention also provides the modified porous granule of polyvinyl alcohol fillers of any phase transformation in low temperature environment sewage
Application in denitrogenation.
Compared with prior art, the invention has the following advantages:
(1) the modified porous granule of polyvinyl alcohol filler of phase transformation prepared by the present invention includes phase-change microcapsule, is that phase transformation is micro-
Capsule is mixed with water-soluble poval, and porous polyethylene alcohol, the water that the present invention selects is prepared by freeze drying process
Soluble polyvinyl alcohol contains the polyvinyl alcohol of low molecular weight and the polyvinyl alcohol of high molecular weight, mechanical stirring technique in the early stage
In, the polyvinyl alcohol of low molecular weight preferentially coats phase-change microcapsule, the group with the wall material melamine resin surface of phase-change microcapsule
It is cross-linked with each other, recycles the processing of strength ultrasonic disperse, the polyvinyl alcohol of a small amount of high molecular weight is coated and phase-change microcapsule again
Surface forms stable lotion, and the rate being then added dropwise by control controls the partial size of granule of polyvinyl alcohol, last chilled
The modified porous granule of polyvinyl alcohol filler of phase transformation is prepared in drying process.
(2) phase-change microcapsule is secured by polyvinyl alcohol in the modified porous granule of polyvinyl alcohol filler of phase transformation prepared by the present invention
Cladding, avoids the infiltration problem of phase-change material in use, and the partial size of phase-change material is small, is dispersed in porous poly-
In vinyl alcohol particle, therefore the modified porous granule of polyvinyl alcohol filler of phase transformation prepared has excellent temperature control performance, makes biology
Membrane reactor still has good heat storing and heat preserving performance in low temperature environment, because of the phase transition temperature for the phase-change material that the present invention selects
It is 25 DEG C or so, therefore biofilm reactor is also beneficial to maintaining reaction temperature into 25 DEG C, is more advantageous to and keeps nitrifier
Activity improves the nitric efficiency of biofilm reactor at low ambient temperatures.
(3) in addition, the present invention selects expanded graphite conduct to further increase the heat storing and heat preserving performance of phase-change microcapsule
Backing material, the large specific surface area and hole configurations of expanded graphite are complete, are conducive to securely adsorb paraffin phase change material wherein,
It is coated again through wall material, the leakage for reducing phase-change microcapsule is possible, and the wall material of selection is melamine resin, and melamine resin is melamine
Formaldehyde resin belongs to amino resins, heat resistance and excellent in mechanical performance, and water resistance is excellent, and phase-change microcapsule can be improved in dirt
Stability in water process improves the service life of the filler of biofilm reactor.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) expanded graphite and paraffin wax that mass ratio is 1:0.3 are mixed, are heated to after melting completely, misting cooling,
Obtain the expanded graphite particles core material of micron-sized load paraffin.
(2) after heating stirring, load paraffin is added at 70 DEG C in melamine and formaldehyde that amount ratio is 3g:6mL
Expanded graphite particles core material and sodium chloride, for the pH value of regulation system to 2, heating stirring is uniform at 80 DEG C, obtains the micro- glue of phase transformation
Capsule, the content that the expanded graphite particles core material of paraffin is wherein loaded in phase-change microcapsule is 15%.
(3) by the molecular weight that mass ratio is 1:1.5 be 2.5-3.5W polyvinyl alcohol and molecular weight be 17-22W poly- second
Enol, phase-change microcapsule, neopelex surfactant are added to the water, after mechanical mixture, with the power of 1000W,
It is ultrasonically treated 3min under the frequency of 15kHz, then with the power of 1600W, is ultrasonically treated 30min under the frequency of 20kHz and dissipates,
Obtain phase transformation modified polyvinylalcohol lotion.
(4) phase transformation modified polyvinylalcohol lotion is added dropwise in liquid nitrogen frozen liquid with the rate of 0.5mL/min and is rapidly frozen
5s is handled, then freeze-dried, obtains the modified porous granule of polyvinyl alcohol filler of phase transformation.
Embodiment 2:
(1) expanded graphite and paraffin wax that mass ratio is 1:0.6 are mixed, are heated to after melting completely, misting cooling,
Obtain the expanded graphite particles core material of micron-sized load paraffin.
(2) after heating stirring, load paraffin is added at 75 DEG C in melamine and formaldehyde that amount ratio is 3g:6mL
Expanded graphite particles core material and sodium chloride, for the pH value of regulation system to 3, heating stirring is uniform at 90 DEG C, obtains the micro- glue of phase transformation
Capsule, the content that the expanded graphite particles core material of paraffin is wherein loaded in phase-change microcapsule is 25%.
(3) by the molecular weight that mass ratio is 1:2.3 be 2.5-3.5W polyvinyl alcohol and molecular weight be 17-22W poly- second
Enol, phase-change microcapsule, lauryl sodium sulfate surfactant are added to the water, after mechanical mixture, with the power of 1500W,
It is ultrasonically treated 5min under the frequency of 20kHz, then with the power of 2000W, is ultrasonically treated 90min under the frequency of 25kHz and dissipates, obtain
To phase transformation modified polyvinylalcohol lotion.
(4) phase transformation modified polyvinylalcohol lotion is added dropwise to fast quickly cooling in frozen ethanol freezing liquid with the rate of 1mL/min
Freeze processing 10s, then freeze-dried, obtains the modified porous granule of polyvinyl alcohol filler of phase transformation.
Embodiment 3:
(1) expanded graphite and paraffin wax that mass ratio is 1:0.5 are mixed, are heated to after melting completely, misting cooling,
Obtain the expanded graphite particles core material of micron-sized load paraffin.
(2) after heating stirring, load paraffin is added at 73 DEG C in melamine and formaldehyde that amount ratio is 3g:6mL
Expanded graphite particles core material and sodium chloride, for the pH value of regulation system to 2.5, heating stirring is uniform at 83 DEG C, and it is micro- to obtain phase transformation
Capsule, the content that the expanded graphite particles core material of paraffin is wherein loaded in phase-change microcapsule is 18%.
(3) by the molecular weight that mass ratio is 1:1.9 be 2.5-3.5W polyvinyl alcohol and molecular weight be 17-22W poly- second
Enol, phase-change microcapsule, cetyl trimethylammonium bromide surfactant are added to the water, after mechanical mixture, with the function of 1300W
Rate is ultrasonically treated 4min under the frequency of 18kHz, then with the power of 1800W, is ultrasonically treated 60min under the frequency of 23kHz
It dissipates, obtains phase transformation modified polyvinylalcohol lotion.
(4) phase transformation modified polyvinylalcohol lotion is added dropwise in frozen ethanol freezing liquid quickly with the rate of 0.6mL/min
Freezing processing 8s, then it is freeze-dried, obtain the modified porous granule of polyvinyl alcohol filler of phase transformation.
Embodiment 4:
(1) expanded graphite and paraffin wax that mass ratio is 1:0.4 are mixed, are heated to after melting completely, misting cooling,
Obtain the expanded graphite particles core material of micron-sized load paraffin.
(2) after heating stirring, load paraffin is added at 74 DEG C in melamine and formaldehyde that amount ratio is 3g:6mL
Expanded graphite particles core material and sodium chloride, for the pH value of regulation system to 2.8, heating stirring is uniform at 88 DEG C, and it is micro- to obtain phase transformation
Capsule, the content that the expanded graphite particles core material of paraffin is wherein loaded in phase-change microcapsule is 23%.
(3) by the molecular weight that mass ratio is 1:2 be 2.5-3.5W polyvinyl alcohol and molecular weight be 17-22W polyethylene
Alcohol, phase-change microcapsule, nonylphenol polyoxyethylene ether surfactant are added to the water, after mechanical mixture, with the power of 1400W,
It is ultrasonically treated 3.5min under the frequency of 18kHz, then with the power of 1900W, is ultrasonically treated 45min under the frequency of 24kHz and dissipates,
Obtain phase transformation modified polyvinylalcohol lotion.
(4) phase transformation modified polyvinylalcohol lotion is added dropwise in liquid nitrogen frozen liquid with the rate of 0.6mL/min and is rapidly frozen
8s is handled, then freeze-dried, obtains the modified porous granule of polyvinyl alcohol filler of phase transformation.
Embodiment 5:
(1) expanded graphite and paraffin wax that mass ratio is 1:0.4 are mixed, are heated to after melting completely, misting cooling,
Obtain the expanded graphite particles core material of micron-sized load paraffin.
(2) after heating stirring, load paraffin is added at 75 DEG C in melamine and formaldehyde that amount ratio is 3g:6mL
Expanded graphite particles core material and sodium chloride, for the pH value of regulation system to 2.1, heating stirring is uniform at 83 DEG C, and it is micro- to obtain phase transformation
Capsule, the content that the expanded graphite particles core material of paraffin is wherein loaded in phase-change microcapsule is 19%.
(3) by the molecular weight that mass ratio is 1:2.1 be 2.5-3.5W polyvinyl alcohol and molecular weight be 17-22W poly- second
Enol, phase-change microcapsule, lauryl sodium sulfate surfactant are added to the water, after mechanical mixture, with the power of 1450W,
It is ultrasonically treated 4.5min under the frequency of 16kHz, then with the power of 1900W, is ultrasonically treated 60min under the frequency of 23kHz and dissipates,
Obtain phase transformation modified polyvinylalcohol lotion.
(4) phase transformation modified polyvinylalcohol lotion is added dropwise in frozen ethanol freezing liquid quickly with the rate of 0.7mL/min
Freezing processing 9s, then it is freeze-dried, obtain the modified porous granule of polyvinyl alcohol filler of phase transformation.
Embodiment 6:
(1) expanded graphite and paraffin wax that mass ratio is 1:0.3 are mixed, are heated to after melting completely, misting cooling,
Obtain the expanded graphite particles core material of micron-sized load paraffin.
(2) after heating stirring, load paraffin is added at 75 DEG C in melamine and formaldehyde that amount ratio is 3g:6mL
Expanded graphite particles core material and sodium chloride, for the pH value of regulation system to 2, heating stirring is uniform at 90 DEG C, obtains the micro- glue of phase transformation
Capsule, the content that the expanded graphite particles core material of paraffin is wherein loaded in phase-change microcapsule is 15%.
(3) by the molecular weight that mass ratio is 1:2.3 be 2.5-3.5W polyvinyl alcohol and molecular weight be 17-22W poly- second
Enol, phase-change microcapsule, nonylphenol polyoxyethylene ether surfactant are added to the water, after mechanical mixture, with the power of 1000W,
It is ultrasonically treated 3min under the frequency of 20kHz, then with the power of 2000W, is ultrasonically treated 90min under the frequency of 20kHz and dissipates,
Obtain phase transformation modified polyvinylalcohol lotion.
(4) phase transformation modified polyvinylalcohol lotion is added dropwise in frozen ethanol freezing liquid quickly with the rate of 0.5mL/min
Freezing processing 10s, then it is freeze-dried, obtain the modified porous granule of polyvinyl alcohol filler of phase transformation.
Embodiment 7:
(1) expanded graphite and paraffin wax that mass ratio is 1:0.6 are mixed, are heated to after melting completely, misting cooling,
Obtain the expanded graphite particles core material of micron-sized load paraffin.
(2) after heating stirring, load paraffin is added at 70 DEG C in melamine and formaldehyde that amount ratio is 3g:6mL
Expanded graphite particles core material and sodium chloride, for the pH value of regulation system to 3, heating stirring is uniform at 80 DEG C, obtains the micro- glue of phase transformation
Capsule, the content that the expanded graphite particles core material of paraffin is wherein loaded in phase-change microcapsule is 25%.
(3) by the molecular weight that mass ratio is 1:1.5 be 2.5-3.5W polyvinyl alcohol and molecular weight be 17-22W poly- second
Enol, phase-change microcapsule, cetyl trimethylammonium bromide surfactant are added to the water, after mechanical mixture, with the function of 1500W
Rate is ultrasonically treated 5min under the frequency of 15kHz, then with the power of 1600W, is ultrasonically treated 30min under the frequency of 25kHz
It dissipates, obtains phase transformation modified polyvinylalcohol lotion.
(4) phase transformation modified polyvinylalcohol lotion is added dropwise to liquid nitrogen or frozen ethanol freezing liquid with the rate of 1mL/min
Middle fast freezing handles 5s, then freeze-dried, obtains the modified porous granule of polyvinyl alcohol filler of phase transformation.
Through detecting, embodiment 1-7 preparation the modified porous granule of polyvinyl alcohol filler of phase transformation and the prior art it is porous
The diameter of granule of polyvinyl alcohol filler, specific surface area, the result of pore volume are as follows:
As seen from the above table, the modified porous granule of polyvinyl alcohol filler of phase transformation prepared by the present invention and traditional porous polyethylene
Diameter, specific surface area, the pore volume of alcohol granular filler are similar, are applicable to the requirement of biofilm reactor completely.
The modified porous granule of polyvinyl alcohol filler of phase transformation prepared by embodiment 1-7 is placed in biofilm reactor, through with
The porous polyethylene alcohol granular filler of the prior art is transported in the same moving bed biofilm reactor at 10 DEG C as filler
Row, the result for measuring biofilm biomass, biofilm time and COD, ammonia nitrogen removal effect are as shown in the table:
As seen from the above table, the modified porous granule of polyvinyl alcohol filler of phase transformation prepared by the present invention is for the life under low temperature environment
In object membrane reactor, the efficiency of biofilm is significantly improved, improves the total amount and activity of biomembrane, ensure that denitrification ammonia effect, is solved
Sewage treatment problem not up to standard at low ambient temperatures, reduces production energy consumption and cost.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of modified porous granule of polyvinyl alcohol filler of phase transformation, which is characterized in that the modified porous polyvinyl alcohol of phase transformation
Particulate filler includes phase-change microcapsule, and the phase-change microcapsule includes resin wall material, phase-change material core material and adsorbent support material.
2. the modified porous granule of polyvinyl alcohol filler of a kind of phase transformation according to claim 1, which is characterized in that the resin
Wall material melamine resin, the adsorbent support material are expanded graphite.
3. a kind of preparation method of the modified porous granule of polyvinyl alcohol filler of phase transformation as claimed in claim 2, it is characterised in that: packet
Include following steps:
(1) expanded graphite and phase-change material mixing, are heated to after melting completely, and misting cooling obtains the expansion stone of load paraffin
Black particle core material；
(2) the expanded graphite particles core material of the load paraffin of step (1) preparation after melamine and formaldehyde heating stirring, will be added
And sodium chloride, for the pH value of regulation system to acidity, heating stirring is uniform, obtains phase-change microcapsule；
(3) phase-change microcapsule, surfactant prepared by water-soluble poval, step (2) are added to the water, mechanical mixture
Afterwards, strength ultrasonic disperse obtains phase transformation modified polyvinylalcohol lotion；
(4) phase transformation modified polyvinylalcohol lotion is added dropwise in freezing liquid and is rapidly frozen, then is freeze-dried, it is modified to obtain phase transformation
Porous polyethylene alcohol granular filler.
4. a kind of preparation method of the modified porous granule of polyvinyl alcohol filler of phase transformation according to claim 3, feature exist
In: in the step (1), phase-change material is paraffin wax, and the mass ratio of expanded graphite and phase-change material is 1:0.3-0.6.
5. a kind of preparation method of the modified porous granule of polyvinyl alcohol filler of phase transformation according to claim 3, feature exist
In: in the step (1), the partial size for loading the expanded graphite particles core material of paraffin is micron order.
6. a kind of preparation method of the modified porous granule of polyvinyl alcohol filler of phase transformation according to claim 3, feature exist
In: in the step (2), the content that the expanded graphite particles core material of paraffin is loaded in phase-change microcapsule is 15-25%.
7. a kind of preparation method of the modified porous granule of polyvinyl alcohol filler of phase transformation according to claim 3, feature exist
In: in the step (3), water-soluble poval include mass ratio be 1:1.5-2.3 molecular weight be 2.5-3.5W poly- second
The polyvinyl alcohol that enol and molecular weight are 17-22W.
8. a kind of preparation method of the modified porous granule of polyvinyl alcohol filler of phase transformation according to claim 3, feature exist
In: in the step (3), the technique of strength ultrasonic disperse are as follows: with the power of 1000-1500W, surpass under the frequency of 15-20kHz
Sonication 3-5min is ultrasonically treated 30-90min under the frequency of 20-25kHz then with the power of 1600-2000W.
9. a kind of preparation method of the modified porous granule of polyvinyl alcohol filler of phase transformation according to claim 3, feature exist
In: in the step (4), freezing liquid is liquid nitrogen or frozen ethanol, cooling time 5-10s, rate of addition 0.5-1mL/
min。
10. the modified porous granule of polyvinyl alcohol filler of any phase transformation according to claim 1 to 2 is in low temperature environment dirt
Application in denitrogenation of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811282296.5A CN109336249B (en) | 2018-10-31 | 2018-10-31 | Phase-change modified porous polyvinyl alcohol particle filler, preparation method thereof and application thereof in low-temperature environment sewage denitrification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811282296.5A CN109336249B (en) | 2018-10-31 | 2018-10-31 | Phase-change modified porous polyvinyl alcohol particle filler, preparation method thereof and application thereof in low-temperature environment sewage denitrification |
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| JP2021045699A (en) * | 2019-09-17 | 2021-03-25 | 国立大学法人 鹿児島大学 | Microcapsule and method for producing microcapsule |
| CN115093832A (en) * | 2022-06-09 | 2022-09-23 | 武汉中科先进材料科技有限公司 | Preparation method of environment-friendly heat-insulation temperature-control flame-retardant material |
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