CN107876025A - Hydroxypropyl chitosan microballoon, its preparation method and its application in mineral oil dielectric loss is reduced - Google Patents
Hydroxypropyl chitosan microballoon, its preparation method and its application in mineral oil dielectric loss is reduced Download PDFInfo
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- CN107876025A CN107876025A CN201711146091.XA CN201711146091A CN107876025A CN 107876025 A CN107876025 A CN 107876025A CN 201711146091 A CN201711146091 A CN 201711146091A CN 107876025 A CN107876025 A CN 107876025A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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Abstract
The invention provides a kind of hydroxypropyl chitosan microballoon, its preparation method and its application in mineral oil dielectric loss is reduced, belong to chitin modified field.The preparation method of the hydroxypropyl chitosan microballoon comprises the following steps：Chitosan, isopropanol, the first sodium hydroxide solution are mixed, expoxy propane reaction is instilled after adding TMAH, cool down and filtered using being scattered in after salt acid for adjusting pH to 7 in acetone or water after stirring, washed with absolute ethyl alcohol, be dried in vacuo and obtain hydroxypropyl chitosan, by hydroxypropyl chitosan be made spray solution be washed with water into sodium polyphosphate after cross-linking reaction, filter after be added in sodium hydroxide solution and stir, and add epichlorohydrin reaction and obtain microballoon；The organic solvent that volume fraction is 10~20%, 30~40%, 70~80%, 90~95% is passed sequentially through after microballoon is washed with water to be eluted, be freeze-dried.The modification of chitosan that the preparation method obtains can reduce the dielectric loss of mineral oil.
Description
Technical field
The present invention relates to chitin modified field, in particular to a kind of hydroxypropyl chitosan microballoon, its preparation method
And its application in mineral oil dielectric loss is reduced.
Background technology
Transformer oil refers to the mineral type insulating oil of the natural hydrocarbon mixture obtained from petroleum refining, as oil-filled high pressure
The main insulation of electrical equipment and cooling medium, transformer oil are widely used in transformer's type and breaker kind equipment.Transformer oil
Code simplify check include following items：Oily outward appearance, flash-point, pressure-resistant, water soluble acid (pH value), acid number, Wei Shui, chromatogram, oil
The unqualified reason of middle air content, dielectric dissipation factor etc., wherein transformer oil mainly has：1. oily excessive water content, meeting when serious
Cause oil is pressure-resistant not reach requirement；2. oil chromatography result of laboratory test shows to contain C in oil2H2Or total gas content of oil deviates；3. oil
Dielectric loss it is overproof (>4%).The Crack cause of preceding two defects is more apparent, is also easily processed, and can be heated by vacuum oil-filter
Circulation effectively eliminates safe hidden trouble, and the 3rd oily dielectric loss is exceeded, is difficult to be eliminated with conventional filter oil treatment process.Research
Show, transformer oil dielectric loss factor (hereinafter referred to as dielectric loss) can reflect the quality of transformer oil insulation characterisitic, reflect transformation
Device oil electric field, oxidation and high temperature etc. effect under degree of aging, and in oil the pollution such as polar impurity and charged colloidal particle journey
Degree.In actual use, (cleannes are on the elevated influence of transformer dielectric loss and its processing method by Liu Bohua etc..Transformer
The 6th phase of volume 46) find the reason for transformer oil dielectric loss is exceeded in addition to transformer therein pollutes, it is also possible to including transformation
The pollution from external contaminants suffered by device oil, pollutant such as acidic oxidation products, microorganism, metal oxide, colloid
Generation of the pollutants such as indissoluble thing all to transformer oil dielectric loss value has a significant impact；On the other hand, (transformer oil is situated between Wang Congling etc.
The analysis of the reason for damage increase and regeneration treatment.High-Voltage Technology the 3rd phase in 1997) study the medium for showing transformer oil in operation
Loss value increases, and its main cause is the catalytic action of the oxidation and metallic element of oil to oil oxidation, oil is produced acid oxygen
Change product and greasy filth acidic oxidation products corrosion metal, again increase the tenor in oil, accelerate the oxidation of oil.
Chitosan is in the basic conditions by a kind of derivative formed after deacetylation, its deacetylation by chitin
It is unique a large amount of existing alkaline polysaccharides in nature typically between 65%~90%.Chitosan is a kind of natural high score
Sub- compound, according to raw material and the difference of preparation method, molecular weight is in hundreds of thousands between millions of.Chitosan is by D-
What Glucosamine and 2-acetylamino-2-deoxy-D-glucose were formed by connecting with glycosidic bond, due to chitosan have it is nontoxic, can biology drop
The advantages that solution, extremely strong flocculation, good precipitability, a kind of preferably environmental-protection adsorption agent is become, traditional absorption can be overcome
Agent is difficult to harmless treatment, easily causes the shortcomings that secondary pollution.The adsorption mechanism of chitosan mainly has three, be respectively chelant,
Three kinds of charge neutrality, adsorption bridging effects, but gather for different colloidal particle and suspended particulate, and different systems, shell
The suction-operated of sugar is not single, but based on a kind of mechanism, the coefficient result of other mechanism.Chelant absorption is made
Be chitosan by containing free amine group by hydrogen bond, or borrow the cage molecule that sat linkage forms similar network structure,
Chelant effect occurs with metallic；Charge neutrality suction-operated is that the charge adsorption that chitosan is carried by it is opposite to that electrically
Colloid absorption, so as to remove the charged particle in liquid；Bridge formation suction-operated is backbone of the chitosan by itself
Colloidal solid is adsorbed into the different parts in long-chain, linked up these colloidal solids with long-chain as building bridge, so as to have
Effect removes the colloidal solid in liquid.
Due to causing the generation that one of exceeded principal element of transformer oil dielectric loss is acidic materials, these impurity are typically more
In colloid or suspended state, and most of all carry negative electrical charge, inherently a kind of cation high molecular adsorbent of chitosan.
So when the chitosan with positive charge close to when, the negative electrical charge of micelle institute band is partially neutralized, and reduces current potential so that glue
Body occurs to take off surely, is settled with reference to the larger floccule of rear formation volume.Therefore, chitosan is shown in acidic liquid processing
Good absorption property.Yi Huaichang etc. shows that chitosan has strong suction-operated to acid dyes by a series of researchs,
And preferable effect is achieved in the processing of acid dyes waste liquid；
The research that Chitosan-phospholipid complex carries out adsorption treatment to waste oil can be known from prior art.Master studies opinion
Text《The research of chitosan and its modified product to waste lubricating oil deacidification effect》(2016, Industrial and Commercial University Of Chongqing) test shell and gathered
Sugar and its two kinds of modified products are shown, chitosan and its modified product are to useless lubrication waste lubricating oil deacidification effect by research
Oil all has good deacidification effect, is used to handle waste lubricating oil depickling regeneration with feasible by chitosan and its modified product
Property.However, above-cited prior art literature is shown substantially to chitosan absorbent in transformer oil regeneration application aspect
Deficiency, the technical literature causes cotton-shaped chitosan to be scattered in the not low profit of viscosity using chitosan and oil product blended under agitation
Among lubricating oil product, although the purpose that acid number is reduced by flocculation can be reached, the adsorbent of suspended state and point of oil product
It is larger from difficulty, be unfavorable for production application, the Hyarogen-bonding of chitosan itself can reunite strand in addition, reduce with
The real contact area of oil product, reduce its chelant, charge neutrality and adsorption bridging effect.
Therefore, it is necessary to which a kind of structural stability is strong, the modification of chitosan of, epigranular bigger than surface and advantages of good adsorption effect.
The content of the invention
The invention provides a kind of preparation method of hydroxypropyl chitosan microballoon, this method technique is simple and convenient to operate, and is fitted
Conjunction produces and prepared hydroxypropyl chitosan microballoon on a large scale.
Present invention also offers the hydroxypropyl chitosan microballoon being prepared using above-mentioned preparation method, and it has particle diameter equal
The advantages that even, Stability Analysis of Structures, advantages of good adsorption effect, nonhazardous, safety and environmental protection.
Present invention also offers application of the above-mentioned hydroxypropyl chitosan microballoon in mineral oil dielectric loss is reduced, the hydroxypropyl base enclosure
Glycan microballoon can effectively reduce the dielectric loss of mineral oil.
What the present invention was realized in：
A kind of preparation method of hydroxypropyl chitosan microballoon, comprises the following steps：
Chitosan and isopropanol are put into the first sodium hydroxide solution and are mixed evenly to obtain solution, to described molten
Instillation expoxy propane reacts to obtain reaction solution after TMAH is added in liquid, will use hydrochloric acid after reaction solution cooling
It is scattered in after being stirred in acetone or water and filters after regulation pH to 7, is then washed with absolute ethyl alcohol, is dried in vacuo and obtains hydroxypropyl base enclosure
Glycan；
The hydroxypropyl chitosan is dissolved in be sprayed onto in polyphosphoric acids sodium water solution after water and carries out cross-linking reaction, is obtained just
Walk the hydroxypropyl chitosan microballoon of crosslinking；
The hydroxypropyl chitosan microballoon is washed with water, filter drain after be added in the second sodium hydroxide solution and stir
Mix, then add the hydroxypropyl chitosan microballoon that epichlorohydrin reaction obtains secondary cross-linking；
Filter and drain after the hydroxypropyl chitosan microballoon of the secondary cross-linking is washed with water, then pass sequentially through volume integral
Number carries out serial dehydration elution for 10~20%, 30~40%, 70~80%, 90~95% organic solvent, and then freezing is dry
It is dry.
In preferred embodiments of the present invention, the mass concentration of the first sodium hydroxide solution described above is 10~20%,
The mass ratio of the chitosan, the isopropanol and the expoxy propane is 1~2：10~25：10~20.
In preferred embodiments of the present invention, chitosan described above and the isopropanol put into first hydroxide
0.5~1.5h is mixed in sodium solution at 25~35 DEG C.
It is above-mentioned that the expoxy propane is instilled into the solution after at 55~65 DEG C in preferred embodiments of the present invention
4~6h of stirring reaction obtains the reaction solution.
In preferred embodiments of the present invention, hydroxypropyl chitosan described above is dissolved in water and is configured to mass concentration as 0.5
It is sprayed onto after~3% aqueous solution in the polyphosphoric acids sodium water solution of mass fraction 1~5% and carries out cross-linking reaction.
In preferred embodiments of the present invention, it is above-mentioned by the hydroxypropyl chitosan microballoon be added to mass fraction for 2~
Stirred in 8% the second sodium hydroxide solution, then add epichlorohydrin reaction and obtain the secondary cross-linking in 2~5 hours
Hydroxypropyl chitosan microballoon, wherein the amount ratio of the chitosan and the epoxychloropropane is 1~2g：5~20ml.
In preferred embodiments of the present invention, organic solvent described above includes one kind in methanol, ethanol, acetone.
In preferred embodiments of the present invention, the viscosity of chitosan described above is 0.25~0.65Pas.
Present invention also offers a kind of hydroxypropyl chitosan microballoon, and it is the system using above-mentioned hydroxypropyl chitosan microballoon
Preparation Method is prepared.
Present invention also offers application of the above-mentioned hydroxypropyl chitosan microballoon in mineral oil dielectric loss is reduced.
The beneficial effects of the invention are as follows：The preparation method of hydroxypropyl chitosan microballoon provided by the invention includes following step
Suddenly：Chitosan, isopropanol, the first sodium hydroxide solution are mixed, expoxy propane reaction is instilled after adding TMAH,
Cool down and filtered using being scattered in after salt acid for adjusting pH to 7 in acetone or water after stirring, washed, be dried in vacuo with absolute ethyl alcohol
Obtain hydroxypropyl chitosan, by hydroxypropyl chitosan be made spray solution be washed with water into sodium polyphosphate after cross-linking reaction,
It is added in sodium hydroxide solution and stirs after filtering, and adds epichlorohydrin reaction and obtain microballoon；After microballoon is washed with water
The organic solvent that volume fraction is 10~20%, 30~40%, 70~80%, 90~95% is passed sequentially through to be eluted, freezed
Dry.The preparation method technique is simple and convenient to operate, and can prepare hydroxypropyl chitosan microballoon on a large scale.Use above-mentioned system
The hydroxypropyl chitosan microballoon that Preparation Method obtains has Stability Analysis of Structures reliable, and specific surface area is big, pollution-free harm, safety and environmental protection
Advantage.Present invention also offers application of the above-mentioned hydroxypropyl chitosan microballoon in mineral oil dielectric loss is reduced.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the schematic flow sheet that adsorbent carries out adsorption treatment to mineral oil；
Fig. 2 is the electromicroscopic photograph for the hydroxypropyl chitosan microballoon that the embodiment of the present invention 3 is prepared；
Fig. 3 is the electromicroscopic photograph for the hydroxypropyl chitosan microballoon that control group 1 of the present invention is prepared；
Fig. 4 is the electromicroscopic photograph for the hydroxypropyl chitosan microballoon that control group 2 of the present invention is prepared.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase
Product.
The embodiment of the present invention is specifically described below.
Present embodiments provide a kind of hydroxypropyl chitosan microballoon, its preparation method and its in mineral oil dielectric loss is reduced
Using.
A kind of preparation method of hydroxypropyl chitosan microballoon is present embodiments provided, is comprised the following steps：
S1, chitosan and isopropanol are put into the first sodium hydroxide solution are mixed evenly to obtain solution, Xiang Rong
Instillation expoxy propane reacts to obtain reaction solution after TMAH is added in liquid, is adjusted after reaction solution is cooled down using hydrochloric acid
It is scattered in after being stirred in acetone or water and filters after pH to 7, is then washed with absolute ethyl alcohol, is dried in vacuo and obtains hydroxypropyl
Sugar；Wherein, the viscosity of chitosan is preferably 0.25~0.65Pas；Preferably, the mass concentration of the first sodium hydroxide solution is
10~20%, the mass ratio of chitosan, isopropanol and expoxy propane is 1~2：10~25：10~20, chitosan and isopropanol
Put into and mix 0.5~1.5h in the first sodium hydroxide solution at 25~35 DEG C；It is preferred that epoxy third is instilled into solution
Alkane obtains reaction solution after 4~6h of stirring reaction at 55~65 DEG C.
S2, hydroxypropyl chitosan is dissolved in after water being sprayed onto in polyphosphoric acids sodium water solution and carries out cross-linking reaction, obtained just
Walk the hydroxypropyl chitosan microballoon of crosslinking；Preferably, it is 0.5~3% that hydroxypropyl chitosan, which is dissolved in water to be configured to mass concentration,
It is sprayed onto after the aqueous solution in the polyphosphoric acids sodium water solution of mass fraction 1~5% and carries out cross-linking reaction；Further preferably make
Hydroxypropyl sugar aqueous solution is sprayed onto in polyphosphoric acids sodium water solution with the nozzle of electrostatic spinning machine.
S3, hydroxypropyl chitosan microballoon is washed with water, filter drain after be added in the second sodium hydroxide solution and stir,
Then addition epichlorohydrin reaction obtains the hydroxypropyl chitosan microballoon of secondary cross-linking；It is preferred that hydroxypropyl chitosan microballoon is added
Enter into the second sodium hydroxide solution that mass fraction is 2~8% and stir, then add epichlorohydrin reaction and obtain for 2~5 hours
The hydroxypropyl chitosan microballoon of secondary cross-linking is obtained, the wherein amount ratio of chitosan and epoxychloropropane is 1~2g：5~20ml.
S4, filter and drain after the hydroxypropyl chitosan microballoon of secondary cross-linking is washed with water, then pass sequentially through volume integral
Number carries out serial dehydration elution for 10~20%, 30~40%, 70~80%, 90~95% organic solvent, and then freezing is dry
It is dry.Organic solvent preferably includes one kind in methanol, ethanol, acetone.
The preparation method of hydroxypropyl chitosan microballoon provided in an embodiment of the present invention, it is by 1 by chitosan and isopropanol
~2：10~25 mass ratio is mixed and put into the first sodium hydroxide solution that mass fraction is 10~20% 25~35
0.5~1.5h is mixed at DEG C to be reacted, and expoxy propane is instilled in 55 after then adding catalyst TMAH
4~6h of stirring reaction obtains reaction solution at~65 DEG C, and the wherein mass ratio of chitosan and expoxy propane is 1~2：10~20, will
Reaction solution cooling after using be scattered in after salt acid for adjusting pH to 7 in acetone or water stir after filter, washed with absolute ethyl alcohol, vacuum
It is dried to obtain hydroxypropyl chitosan.Wherein, shape can be made as raw material from the chitosan that viscosity is 0.25~0.65Pas
Into hydroxypropyl chitosan microballoon there is appropriate particle diameter with rock-steady structure, according to chitosan molecule amount it is too big, be readily able to
Plug nozzle, it is difficult to complete crosslinking operation；According to chitosan molecule amount it is too small, then the microballoon machinery that can cause to ultimately form
Insufficient strength.
Hydroxypropyl chitosan then is configured to use after the aqueous solution of mass concentration 0.5~3% to the spray of electrostatic spinning machine
Mouth is sprayed onto in the polyphosphoric acids sodium water solution of mass fraction 1~5% and carries out preliminary cross-linking reaction, using the spray of electrostatic spinning machine
Mouth system carries out spraying operation, and the microballoon quantity not only prepared in the unit interval is much larger than common manual syringe needle drop method, and
And the size for the microballoon being prepared can be controlled by changing the pinhole size of nozzle；By preliminary cross-linking reaction hydroxypropyl
Chitosan microball is washed with water, filters to be added to after draining in the second sodium hydroxide solution that mass fraction is 2~8% and stir,
Then 5~20ml of addition epichlorohydrin reactions, 2~5 hours hydroxypropyl chitosan microballoons for obtaining secondary cross-linking, using substep
Cross-linking method, be advantageous to shaping, the solidification of hydroxypropyl chitosan microballoon, successively using 10~20%, 30~40%, 70~80%,
90~95% organic solvent carries out serial dehydration elution to hydroxypropyl chitosan microballoon, makes hydroxypropyl chitosan microballoon dehydrated
Journey is progressively carried out in proportion, avoids swelling fracture phenomena of the microballoon in dehydration and occurs, finally using freeze-drying
Dry, situations such as microballoon caused by avoiding heated drying inside contracts, void collapse, so as to obtain uniform particle sizes, structural integrity, compare table
Area is big, the hydroxypropyl chitosan microballoon of advantages of good adsorption effect.
Present invention also offers a kind of hydroxypropyl chitosan microballoon, and it is the system using above-mentioned hydroxypropyl chitosan microballoon
Preparation Method is prepared, and a diameter of 5~15 μm of the hydroxypropyl chitosan microballoon, the particle diameter of the hydroxypropyl chitosan microballoon is equal
It is even, controllable and there is Stability Analysis of Structures, advantages of good adsorption effect, nonhazardous, safety and environmental protection.
Present invention also offers application of the above-mentioned hydroxypropyl chitosan microballoon in mineral oil dielectric loss is reduced.The hydroxypropyl base enclosure
Glycan microballoon can effectively reduce the dielectric loss in oil product, and the waste oil dielectric loss after adsorption treatment is up to state standards, its adsorption effect
It is substantially better than the industrial adsorption material such as activated carbon, atlapulgite.
The feature and performance of the inventive method are described in further detail with reference to embodiments.
Embodiment 1
A kind of hydroxypropyl chitosan microballoon is present embodiments provided, its specific preparation method is as follows：
S101, prepare the hydroxypropyl sugar juice that mass fraction is 0.5%；Chitosan and isopropanol are pressed 1：15 matter
Amount obtains solution than putting into mass concentration to mix 1h at 30 DEG C in 10% the first sodium hydroxide solution, to solution
Expoxy propane stirring reaction 5h at 60 DEG C is instilled after middle addition TMAH and obtains reaction solution, chitosan and epoxy third
The mass ratio of alkane is 1：10, after reaction solution is cooled down using be scattered in after salt acid for adjusting pH to 7 in acetone or water stir after filter,
Then washed with absolute ethyl alcohol, be dried in vacuo and obtain hydroxypropyl chitosan；Hydroxypropyl chitosan is dissolved in water and is configured to quality point
Number is 0.5% hydroxypropyl sugar juice；Wherein the viscosity of chitosan is 0.48Pas；
S102, the hydroxypropyl sugar juice that mass fraction is 0.5% disperseed using the nozzle system of electrostatic spinning machine
In the polyphosphoric acids sodium water solution that mass fraction is 1%, the preliminary cross-linking reaction of 2h progress is reacted at 25 DEG C, will be tentatively crosslinked
Filter and drain after hydroxypropyl chitosan microballoon distillation water washing afterwards, be added to the sodium hydroxide solution that mass concentration is 5%
Middle stirring, and 15ml epoxychloropropane is added as crosslinking agent, 2h secondary cross-linking reaction is carried out at 25 DEG C, obtains secondary friendship
The hydroxypropyl chitosan microballoon of connection；
S103, the hydroxypropyl chitosan microballoon distilled water washing and filtering by secondary cross-linking, then use volumetric concentration successively
10%th, 30%, 70%, 95% ethanol water carries out serial dehydration elution, is freezed after draining, then handled with freeze drier
24h, that is, obtain dry hydroxypropyl chitosan microballoon.
The hydroxypropyl chitosan microballoon of preparation is loaded into cloth bag, after sealing, cloth bag is fixed on into number of patent application is
201420078137.4 transformer insulated oil regeneration multilayer adsorption tanks adsorption filter board among, as shown in figure 1, start heating
The devices such as device, vacuum oil-filter, mineral insulating oil is set continuously to be filtered by adsorption filter board at 55 DEG C, wherein hydroxypropyl chitosan
The mass ratio of microballoon and mineral insulating oil is 5：1000, different time sections sample detection medium consumption factor, testing standard according to
According to GB/T5654-2007.
Embodiment 2
A kind of hydroxypropyl chitosan microballoon is present embodiments provided, its specific preparation method is as follows：
S201, prepare the hydroxypropyl sugar juice that mass fraction is 2%；Chitosan and isopropanol are pressed 1：20 quality
Solution is obtained to mix 1h at 25 DEG C in 15% the first sodium hydroxide solution than putting into mass concentration, into solution
Instillation expoxy propane stirring reaction 5h at 55 DEG C obtains reaction solution, chitosan and expoxy propane after adding TMAH
Mass ratio be 1：15, after reaction solution is cooled down using be scattered in after salt acid for adjusting pH to 7 in acetone or water stir after filter, with
Washed afterwards with absolute ethyl alcohol, be dried in vacuo and obtain hydroxypropyl chitosan；Hydroxypropyl chitosan is dissolved in water and is configured to mass fraction
For 2% hydroxypropyl sugar juice；Wherein the viscosity of chitosan is 0.54Pas；
S202, the hydroxypropyl sugar aqueous solution that mass fraction is 2% disperseed using the nozzle system of electrostatic spinning machine
In the polyphosphoric acids sodium water solution that mass fraction is 3%, the preliminary cross-linking reaction of 3h progress is reacted at 25 DEG C, will be tentatively crosslinked
Filter and drain after hydroxypropyl chitosan microballoon distillation water washing afterwards, be added to the sodium hydroxide solution that mass concentration is 7%
Middle stirring, and 10ml epoxychloropropane is added as crosslinking agent, 4h secondary cross-linking reaction is carried out at 25 DEG C, obtains secondary friendship
The hydroxypropyl chitosan microballoon of connection；
S203, the hydroxypropyl chitosan microballoon distilled water washing and filtering by secondary cross-linking, then use volumetric concentration successively
15%th, 35%, 75%, 90% methanol aqueous solution carries out serial dehydration elution, is freezed after draining, then handled with freeze drier
24h, that is, obtain dry hydroxypropyl chitosan microballoon.
The hydroxypropyl chitosan microballoon of preparation is loaded into cloth bag, after sealing, cloth bag is fixed on into number of patent application is
201420078137.4 transformer insulated oil regeneration multilayer adsorption tanks adsorption filter board among, as shown in figure 1, start heating
The devices such as device, vacuum oil-filter, mineral insulating oil is set continuously to be filtered by adsorption filter board at 60 DEG C, wherein hydroxypropyl chitosan
The mass ratio of microballoon and mineral insulating oil is 5：1000, different time sections sample detection medium consumption factor, testing standard according to
According to GB/T5654-2007.
Embodiment 3
A kind of hydroxypropyl chitosan microballoon is present embodiments provided, its specific preparation method is as follows：
S301, prepare the hydroxypropyl sugar juice that mass fraction is 3%；Chitosan and isopropanol are pressed 1：25 quality
Solution is obtained to mix 1h at 30 DEG C in 20% the first sodium hydroxide solution than putting into mass concentration, into solution
Instillation expoxy propane stirring reaction 4h at 65 DEG C obtains reaction solution, chitosan and expoxy propane after adding TMAH
Mass ratio be 1：20, after reaction solution is cooled down using be scattered in after salt acid for adjusting pH to 7 in acetone or water stir after filter, with
Washed afterwards with absolute ethyl alcohol, be dried in vacuo and obtain hydroxypropyl chitosan；Hydroxypropyl chitosan is dissolved in water and is configured to mass fraction
For 3% hydroxypropyl sugar juice；Wherein the viscosity of chitosan is 0.65Pas；
S302, the hydroxypropyl sugar aqueous solution that mass fraction is 3% disperseed using the nozzle system of electrostatic spinning machine
In the polyphosphoric acids sodium water solution that mass fraction is 5%, the preliminary cross-linking reaction of 5h progress is reacted at 25 DEG C, will be tentatively crosslinked
Filter and drain after hydroxypropyl chitosan microballoon distillation water washing afterwards, be added to the sodium hydroxide solution that mass concentration is 3%
Middle stirring, and 6ml epoxychloropropane is added as crosslinking agent, 5h secondary cross-linking reaction is carried out at 25 DEG C, obtains secondary friendship
The hydroxypropyl chitosan microballoon of connection；
S303, the hydroxypropyl chitosan microballoon distilled water washing and filtering by secondary cross-linking, then use volumetric concentration successively
20%th, 40%, 80%, 95% aqueous acetone solution carries out serial dehydration elution, is freezed after draining, then handled with freeze drier
24h, that is, obtain dry hydroxypropyl chitosan microballoon.
The hydroxypropyl chitosan microballoon of preparation is loaded into cloth bag, after sealing, cloth bag is fixed on into number of patent application is
201420078137.4 transformer insulated oil regeneration multilayer adsorption tanks adsorption filter board among, as shown in figure 1, start heating
The devices such as device, vacuum oil-filter, mineral insulating oil is set continuously to be filtered by adsorption filter board at 65 DEG C, wherein hydroxypropyl chitosan
The mass ratio of microballoon and mineral insulating oil is 5：1000, different time sections sample detection medium consumption factor, testing standard according to
According to GB/T5654-2007.
Control group 1
The hydroxypropyl chitosan method for preparing microsphere that control group 1 uses is similar with method in embodiment 3, but control group 1 is not
Using serial dehydration lessivation, freezed after the hydroxypropyl chitosan microballoon of secondary cross-linking is directly drained, then with freeze-drying
Machine processing 24h obtains dry hydroxypropyl chitosan microballoon.
Control group 2
The hydroxypropyl chitosan method for preparing microsphere that control group 2 uses is similar with method in embodiment 3, but control group 2 will
The hydroxypropyl chitosan microballoon of secondary cross-linking processing uses heated drying method to replace freeze-drying after being eluted, drained using serial dehydration
Method handles to obtain dry hydroxypropyl chitosan microballoon.
Control group 3
With activated carbon as a control group 3.
Control group 4
With atlapulgite as a control group 4.
The hydroxypropyl chitosan microballoon being prepared using above-described embodiment 1 is entered at 55 DEG C to transformer mineral insulating oil
Row processing, the hydroxypropyl chitosan microballoon being prepared using above-described embodiment 2 are entered at 60 DEG C to transformer mineral insulating oil
Row processing, the hydroxypropyl chitosan microballoon being prepared using above-described embodiment 3 are entered at 65 DEG C to transformer mineral insulating oil
The medium consumption factor of row processing, respectively front and rear and under the different disposal time the transformer mineral insulating oil of detection process, as a result
As shown in table 1.
The dielectric loss change of the present embodiment hydroxypropyl chitosan of table 1 processing mineral insulating oil
As can be seen from Table 1, the hydroxypropyl chitosan microballoon provided using the embodiment of the present invention 1, embodiment 2, embodiment 3
The dielectric loss of treated transformer mineral insulating oil is remarkably decreased, and processing time is longer, and dielectric loss declines more, table
The hydroxypropyl chitosan microballoon that bright the present embodiment provides can effectively reduce the dielectric loss of transformer mineral oil.
The hydroxypropyl chitosan provided using above-described embodiment 1, embodiment 2, embodiment 3, control group 1, control group 2 is micro-
The atlapulgite that ball and the activated carbon of the offer of control group 3, control group 4 provide carries out the place of 48 hours to transformer mineral insulating oil
After reason, the acid number of transformer mineral insulating oil before and after the processing is determined according to GB/T5530-2005；Surveyed according to GB/T5654-2007
The medium consumption factor of transformer mineral insulating oil before and after the quasi- test processes of test-object；Using inductive coupling plasma emission spectroscopy
Method enters the measure of metal element content in line transformer mineral insulating oil, with three kinds of metal element contents of iron copper aluminium as a comparison
Value；Granularity quantity and the distribution in transformer mineral insulating oil are determined using granularity counter measures, as a result such as the institute of table 2
Show.
The hydroxypropyl chitosan microballoon of table 2, activated carbon, the result of atlapulgite processing mineral oil
As can be seen from Table 2, the hydroxypropyl chitosan microballoon provided using the embodiment of the present invention 1, embodiment 2, embodiment 3
Acid number, metal element content, granularity quantity and the equal dielectric loss of treated transformer mineral insulating oil are remarkably decreased, and
The adsorption effect for the hydroxypropyl chitosan microballoon that embodiment 1, embodiment 2, embodiment 3 provide is significantly better than control group 1, control group
The atlapulgite that the 2 hydroxypropyl chitosan microballoons provided and the activated carbon of the offer of control group 3, control group 4 provide.
Electron-microscope scanning is carried out to the hydroxypropyl chitosan microballoon that embodiment 3, control group 1 and control group 2 provide, as a result as schemed
2nd, shown in Fig. 3 and Fig. 4.As shown in Fig. 2 the hydroxypropyl chitosan microballoon microstructure prepared using the inventive method is complete, grain
Degree is uniform；As shown in figure 3, using the preparation method of control group 1, the hydroxypropyl obtained without serial dehydration elution technique
Sugared microballoon spheroid ruptures, and spheroid shows irregular shape more, and this is due to the hydrogen bond work of hydrone and chitosan
With in the freezing dry process of microballoon, the integrality of microballoon being destroyed when hydrone in micropore by escaping, causes spheroid to occur
Rupture, reduce the structural strength and adsorption effect of chitosan；As shown in figure 4, using the preparation method of control group 2, without
Freeze drying process but the hydroxypropyl chitosan microballoon spheroid that uses heated drying method to obtain occur collapsing and reduced, and cause oil
Diffusion of the son in microballoon becomes difficult, reduces the real contact area of chitosan and oil product, reduces adsorption effect.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of hydroxypropyl chitosan microballoon, it is characterised in that comprise the following steps：
Chitosan and isopropanol are put into the first sodium hydroxide solution and are mixed evenly to obtain solution, into the solution
Instillation expoxy propane reacts to obtain reaction solution after adding TMAH, will be adjusted after reaction solution cooling using hydrochloric acid
It is scattered in after being stirred in acetone or water and filters after pH to 7, is then washed with absolute ethyl alcohol, is dried in vacuo and obtains hydroxypropyl
Sugar；
The hydroxypropyl chitosan is dissolved in be sprayed onto in polyphosphoric acids sodium water solution after water and carries out cross-linking reaction, is tentatively handed over
The hydroxypropyl chitosan microballoon of connection；
The hydroxypropyl chitosan microballoon is washed with water, filter drain after be added in the second sodium hydroxide solution and stir, with
The hydroxypropyl chitosan microballoon that epichlorohydrin reaction obtains secondary cross-linking is added afterwards；
Filter and drain after the hydroxypropyl chitosan microballoon of the secondary cross-linking is washed with water, then passing sequentially through volume fraction is
10~20%, 30~40%, 70~80%, 90~95% organic solvent carries out serial dehydration elution, then freeze-drying.
2. the preparation method of hydroxypropyl chitosan microballoon according to claim 1, it is characterised in that first hydroxide
The mass concentration of sodium solution is 10~20%, and the mass ratio of the chitosan, the isopropanol and the expoxy propane is 1~2：
10~25：10~20.
3. the preparation method of hydroxypropyl chitosan microballoon according to claim 1, it is characterised in that the chitosan and institute
State isopropanol and put into first sodium hydroxide solution and 0.5~1.5h is mixed at 25~35 DEG C.
4. the preparation method of hydroxypropyl chitosan microballoon according to claim 1, it is characterised in that dripped into the solution
Enter the expoxy propane and obtain the reaction solution after 4~6h of stirring reaction at 55~65 DEG C.
5. the preparation method of hydroxypropyl chitosan microballoon according to claim 1, it is characterised in that the hydroxypropyl
Sugar is dissolved in water and is configured to mass concentration to be sprayed onto the sodium polyphosphate water of mass fraction 1~5% after 0.5~3% aqueous solution
Cross-linking reaction is carried out in solution.
6. the preparation method of hydroxypropyl chitosan microballoon according to claim 1, it is characterised in that by the hydroxypropyl base enclosure
Glycan microballoon is added in the second sodium hydroxide solution that mass fraction is 2~8% and stirred, and then adds epichlorohydrin reaction
The hydroxypropyl chitosan microballoon for obtaining the secondary cross-linking in 2~5 hours, wherein the use of the chitosan and the epoxychloropropane
It is 1~2g to measure ratio：5~20ml.
7. the preparation method of hydroxypropyl chitosan microballoon according to claim 1, it is characterised in that the organic solvent bag
Include one kind in methanol, ethanol, acetone.
8. the preparation method of hydroxypropyl chitosan microballoon according to claim 1, it is characterised in that the chitosan sticks
Spend for 0.25~0.65Pas.
9. a kind of hydroxypropyl chitosan microballoon, it is characterised in that it is the hydroxypropyl any one of usage right requirement 1-8
The preparation method of chitosan microball is prepared.
10. application of the hydroxypropyl chitosan microballoon as claimed in claim 9 in mineral oil dielectric loss is reduced.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410497A (en) * | 2018-05-03 | 2018-08-17 | 湖北工程学院 | A kind of application of alkaline chitosan microballoon in mineral oil |
| CN109092267A (en) * | 2018-09-30 | 2018-12-28 | 湖北工程学院 | Hydroxypropyl chitosan phytic acid porous composite film and the method for removing metal impurities |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008126971A1 (en) * | 2007-04-13 | 2008-10-23 | Korea Research Institute Of Bioscience And Biotechnology | Polymer nano particle containing uv blocking material and method for preparing the same |
| CN101844059A (en) * | 2010-04-22 | 2010-09-29 | 上海理工大学 | Preparation method of chitosan/sodium polyphosphate porous microcarrier |
| CN102050887A (en) * | 2010-12-10 | 2011-05-11 | 北京联合大学生物化学工程学院 | Preparation method of O-hydroxypropyl-N-alkylated chitosan surfactant |
| CN102641727A (en) * | 2012-04-25 | 2012-08-22 | 大连中汇达科学仪器有限公司 | Chitosan collagen biological adsorbent prepared based on ionic liquid serving as solvent |
| CN104289199A (en) * | 2014-10-25 | 2015-01-21 | 济南大学 | Preparation method of magnetic HPCS/GO adsorbing agent for removing heavy metals and application |
| CN104338185A (en) * | 2014-11-06 | 2015-02-11 | 石家庄亿生堂医用品有限公司 | Carboxymethyl chitosan microsphere embolization agent and preparation method thereof |
-
2017
- 2017-11-17 CN CN201711146091.XA patent/CN107876025A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008126971A1 (en) * | 2007-04-13 | 2008-10-23 | Korea Research Institute Of Bioscience And Biotechnology | Polymer nano particle containing uv blocking material and method for preparing the same |
| CN101844059A (en) * | 2010-04-22 | 2010-09-29 | 上海理工大学 | Preparation method of chitosan/sodium polyphosphate porous microcarrier |
| CN102050887A (en) * | 2010-12-10 | 2011-05-11 | 北京联合大学生物化学工程学院 | Preparation method of O-hydroxypropyl-N-alkylated chitosan surfactant |
| CN102641727A (en) * | 2012-04-25 | 2012-08-22 | 大连中汇达科学仪器有限公司 | Chitosan collagen biological adsorbent prepared based on ionic liquid serving as solvent |
| CN104289199A (en) * | 2014-10-25 | 2015-01-21 | 济南大学 | Preparation method of magnetic HPCS/GO adsorbing agent for removing heavy metals and application |
| CN104338185A (en) * | 2014-11-06 | 2015-02-11 | 石家庄亿生堂医用品有限公司 | Carboxymethyl chitosan microsphere embolization agent and preparation method thereof |
Non-Patent Citations (8)
| Title |
|---|
| 冯炜玮: ""去甲斑蝥素—羟丙基壳聚糖纳米粒的制备及其体外抗肿瘤性能研究"", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
| 孟范平等: ""壳聚糖微球的制备及其对酸性染料的吸附性能"", 《化工进展》 * |
| 方亮主编: "《药用高分子材料学》", 31 August 2015 * |
| 杨鸣波等: "《塑料成型工艺学（第3版）》", 30 June 2014 * |
| 甘孟瑜等: "《大学化学》", 31 October 2014 * |
| 莫秀红等译: "《静电纺丝与纳米纤维导论》", 30 September 2012 * |
| 钱旭耀: "《变压器油及相关故障诊断处理技术》", 31 October 2006 * |
| 陈诗琪: ""壳聚糖及其改性产物对废润滑油脱酸效果的研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410497A (en) * | 2018-05-03 | 2018-08-17 | 湖北工程学院 | A kind of application of alkaline chitosan microballoon in mineral oil |
| CN108410497B (en) * | 2018-05-03 | 2020-03-27 | 湖北工程学院 | Application of alkaline chitosan microspheres in mineral oil |
| CN109092267A (en) * | 2018-09-30 | 2018-12-28 | 湖北工程学院 | Hydroxypropyl chitosan phytic acid porous composite film and the method for removing metal impurities |
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