CN107739445A - A kind of modified wood fibre phase-changing energy storage material and preparation method thereof - Google Patents
A kind of modified wood fibre phase-changing energy storage material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of modified wood fibre phase-changing energy storage material and preparation method thereof.The present invention can Effective Regulation wood fibre aperture, while improve the pore passage structure of wood fibre, and improve the compatibility of wood fibre and phase-change material.Supporting matrix using described modified wood fibre as phase-changing energy storage material, more phase-change materials can be retained by effects such as its hydrogen bond, capillary force, intermolecular forces, improve enthalpy of phase change；Combined with aliphatic acid eutectic mixture, the requirement of low temperature energy storage can be met；Meanwhile phase-change material produced by the present invention in transition temperature range without thermal degradation, illustrate that its heat endurance is good；After thermal cycle 100 times, phase-change material illustrates that thermal reliability is good, hot energy storage efficiency is high without leakage.The preparation method technique of the present invention is simple, and raw material wood fiber source is extensive and cheap, and raw material are not required to, by chemical treatment, environmental protection and energy saving, have broad application prospects in the field such as Solar use and building energy conservation.
Description
Technical field
The invention belongs to technical field of phase-change energy storage, more particularly to a kind of modified wood fibre phase-changing energy storage material and
Its preparation method.
Background technology
With developing rapidly for global industry, energy shortage problem increasingly embodies, thus we there is an urgent need to a kind of new
Method is developed and utilized the energy recovery of waste using or by the new energy such as solar energy.Phase-change accumulation energy is higher with it
The advantages that energy storage density, larger thermal capacitance and less volume and quality especially has in terms of using energy source to be attracted
Power.
As fatty acid phase-change material, it has very high enthalpy of phase change, very wide transition temperature range, service life
Long, no supercooling, nontoxic, non-corrosiveness, small volume change is small, good with construction material compatibility, does not occur after cold cycling repeatedly
Many advantages, such as signs of degradation, it has been widely used in building field, packaging field, field of solar energy.Fatty acid phase transformation material
Material, meets the requirement of preferable phase-change material, but it have one it is main the shortcomings that, i.e. leakage problem in phase transition process.It is many to learn
Person is packaged sizing from porous material such as expanded graphite, expanded vermiculite, porous charcoal etc. as matrix can prevent it molten
Leaked during melting, because the capillary force of micropore or hydrogen bond action make it that liquid phase phase-change material is difficult in carrier matrix
To leak.
Chinese patent CN102531550A provides one kind using polyhydric aliphatic acid eutectic mixture as phase-change material, sludge pottery
Grain is support substrate, the method for being prepared into composite phase-change material.This method can largely utilize sludge, promote sludge of sewage treatment plant
Changing waste into resources, but the latent heat of phase change of composite phase-change material and thermal conductivity factor are relatively low, therefore limit its extensive use.
Thank into et al. using porous material timber as skeleton, PEG-6000 0 is transformation unit, passes through the capillary of timber
Pipe sink effect, physical absorption PEG-6000 0, prepare polyethylene glycol wood composite phase-changing energy storage material.Because do not pass through
Cross in the wood powder of processing containing extract with polyethylene glycol poor compatibility, and unseasoned timber porosity causes than relatively low
Polyethylene glycol maximum level is only 50%, and maximum phase transformation enthalpy is 43.22J/g, therefore is unfavorable for utilizing.
Chinese patent CN106590543A discloses a kind of cellulose composite phase-change energy storage material, including cellulose and with institute
Aliphatic acid-fatty alcohol eutectic of cellulose adsorption form combination is stated, wherein, the organic phase change material of melting can be inhaled into
It is filled into cellulose, phase transition temperature is adapted to room temperature to use between 20~25 DEG C, and enthalpy of phase change is high, can reach 130J/g.Phase transformation
When with higher stability, do not produce leakage phenomenon, cladding is good.But cellulose is extracted from biological material mostly
Out, produce that a large amount of waste liquids are not disposable to damage to environment in preparation process.And without treated fiber
Element is micropore size mostly, is mainly distributed on nanometer scale, and porosity is very low, it is difficult to adsorb excessive phase-changing energy storage material.
Prior art selected fatty acid and fatty alcohol there may be the problem of compatibility is low as phase-change material, both materials.In mesh
Before have been reported in the expanding treatment on cellulose, pay glad grade using alkali process cellulose obtain porous cellulose；Li Cuizhen
Porous cellulose is obtained Deng using highly basic dissolving cellulose and regeneration；Luo etc. uses sodium hydroxide/aqueous solution of urea dissolution in low temperature
Cellulose and regenerate obtain porous cellulose microballoon, the condensed state structure of cellulose is substantially changed, and porosity also obtains bright
It is aobvious to improve, contain aqueous slkali in above processing mode, therefore misoperation can cause security incident, while waste liquid needs to handle
It could discharge.
Chinese patent CN104371659A using porous attapulgite as binding matrix, long chain fatty acids, polyalcohol, paraffin,
Hexadecane, n-octadecane, n-eicosane or inorganic hydrated salt etc. are phase-changing energy storage material, and system is stirred by heating in vacuum
Obtain attapulgite base composite phase-change heat accumulating.This method avoids macroscopical container or microcapsules from encapsulating, and preparation technology is simple, material
Cost is cheap.But the mass fraction of phase-change material only 25~50%, relatively low enthalpy of phase change limits the extensive use of the material.
It is phase-change accumulation energy main body by adding that Chinese patent CN101838521A, which is disclosed using bentonite as matrix, binary of fatty acids,
The method of heat fusing blending prepares aliphatic dibasic acid/bentonite composite phase change energy storage.The material is modified to bentonite, expands its layer
Between distance, its is adsorbed more phase-change materials, so as to possess good heat storage capacity, available for used heat, waste heat and the sun
Can the field such as utilize.But by continuous 800 times store thermal cycle after, the attenuation rate of the two enthalpy of phase change is up to respectively
26.0% and 9.9%, i.e., after 800 times circulations, leakage, which occurs, for phase-change material causes enthalpy of phase change to reduce, and reduces its service life.
Therefore, the defects of low latent heat of phase change of phase-changing energy storage material when melting with easily leaking in the prior art, turn at present urgently
Technical problem to be solved.
The content of the invention
The shortcomings that primary and foremost purpose of the present invention is to overcome prior art and deficiency, there is provided a kind of system of modified wood fibre
Preparation Method.The present invention selects similar aliphatic acid phase-change material, therefore is not required to consider consistency problem；Meanwhile utilized wooden
Fiber source is extensive, and raw material are not required to by chemical treatment, is consequently belonging to environmentally friendly material, and the present invention is carried out to raw material
Expanding treatment improves adsorption rate.
A further object of the present invention is to provide by modified wood fibre made from described preparation method.
Another object of the present invention is to provide the phase-changing energy storage material using described modified wood fibre as matrix.
It is still another object of the present invention to provide the preparation method of described phase-changing energy storage material.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of modified wood fibre, comprises the following steps：
After pretreated wood fibre is mixed with complex salt solution, it is ultrasonically treated, then high temperature bakees, and washing filters,
Crushed after being dried, then be dried in vacuo；Produce described modified wood fibre.
The purpose of described pretreatment is the complete moisture removed in wood fibre；Concrete operations are preferably：100~
Dried 12~24 hours at 110 DEG C.
Described wood fibre and the proportioning of complex salt solution preferably in mass ratio 1:(2~5) match；Further preferably press matter
Measure ratio 1:5 proportionings.
Described complex salt solution is preferably that the double salt comprising sodium chloride, sodium nitrate, at least two sodium salts in sodium sulphate is molten
Liquid；More preferably mass ratio is sodium chloride：Sodium nitrate=(1~5):The complex salt solution or sodium sulphate of (9~5)：Sodium nitrate
=(1~5):The complex salt solution or sodium nitrate of (9~5)：Sodium chloride：Sodium sulphate=(5~7):(3~1):2 complex salt solution.
Described complex salt solution is preferably the complex salt solution that mass percent concentration is 10~30%.
The preparation method of described complex salt solution concretely comprises the following steps：It is by matching that described sodium salt is soluble in water, 50
~70 DEG C of stirrings room temperature cooling, produce described complex salt solution to being completely dissolved.
Described water is preferably distilled water, deionized water or ultra-pure water.
Described ultrasonic power parameter is preferably 100~450W, more preferably 200~350W, more preferably 280
~330W；Described ultrasonic set of frequency is 30~70KHz, more preferably 35~60KHz, more preferably 47~
51KHz；The described ultrasonic time is 0.5~2h, preferably 1~1.5h, is further 1.2h.
The temperature that described high temperature bakees is preferably 150~200 DEG C, more preferably 160~190 DEG C, more preferably
170~180 DEG C；The time that described high temperature bakees is preferably 0.5~3 hour, more preferably 1~2.5 hour, more preferably
For 1.5~2 hours.
Described high temperature is bakeed and preferably carried out under vacuum.
Described drying is dried 12~24 hours preferably at 100~110 DEG C.
Described vacuum drying is preferably carried out at 80 DEG C, it is therefore an objective to modified wood fibre is reached over dry.
The modified wood fibre being prepared by described preparation method.
A kind of phase-changing energy storage material, including described modified wood fibre and binary or the minimum congruent melting mixing of polyhydric aliphatic acid
Thing, wherein described binary or the percetage by weight of the minimum eutectic mixture of polyhydric aliphatic acid are 60~80%.
The phase transition temperature of described phase-changing energy storage material is 15~55 DEG C, and enthalpy of phase change is 26~170J/g.
Described binary or the minimum eutectic mixture of polyhydric aliphatic acid be preferably capric acid, octanoic acid, laurate, myristic acid,
Any polyhydric aliphatic acid such as the eutectic mixture of two or more, ternary, quaternary can also realize this hair in palmitic acid or stearic acid
It is bright.
Described binary or the constituent mass proportioning of the minimum eutectic mixture of polyhydric aliphatic acid and minimum eutectic temperature can roots
According to the phase transition temperature and enthalpy of phase change of single fat acid, it is calculated by Schroeder's formula.
Binary or the phase transition temperature of the minimum eutectic mixture of polyhydric aliphatic acid are more beneficial for applying in low temperature field (10~60
DEG C), and it is good as same class phase-change material compatibility, therefore, consider the phase transition temperature and system of minimum azeotrope
The applicability of the simplicity of standby technique, described binary or the minimum eutectic mixture of polyhydric aliphatic acid more preferably octanoic acid-
The minimum eutectic mixture of myristic acid binary, the octanoic acid-minimum eutectic mixture of palmitic acid binary, octanoic acid-stearic acid binary are minimum
Eutectic mixture, the laurate-minimum eutectic mixture of myristic acid binary, the laurate-minimum eutectic mixture of palmitic acid binary,
Laurate-minimum the eutectic mixture of stearic acid binary, the myristic acid-minimum eutectic mixture of palmitic acid binary, capric acid-stearic acid
The minimum eutectic mixture of the binary of fatty acids such as minimum eutectic mixture of binary；The minimum eutectic mixture of polyhydric aliphatic acid is further excellent
Elect octanoic acid-myristic acid-palmitic acid ternary eutectic as, octanoic acid-laurate-stearic acid ternary eutectic,
The polyhydric aliphatic acid eutectic mixture such as laurate-myristic acid-palmitic acid ternary eutectic.
Described binary or the minimum eutectic mixture of polyhydric aliphatic acid are preferably prepared by the following procedure method and are made：According to applying sieve
The mass ratio for the corresponding aliphatic acid that moral formula is calculated, mixed by proportioning, then higher than any single fat acid transformation temperature 15
It is heated to melting completely at a temperature of~35 DEG C, then stirs 5~7 hours, cool down at room temperature, produces described binary or more
First minimum eutectic mixture of aliphatic acid.
Described temperature is preferably more than the temperature of any 20 DEG C of single fat acid transformation temperature.
The preparation method of described phase-changing energy storage material, comprises the following steps：
(1) heating makes described binary or the minimum eutectic mixture of polyhydric aliphatic acid melt completely, adds described modification
Wood fibre, enter vacuum adsorbed dipping in the case where holding binary or the minimum eutectic mixture of polyhydric aliphatic acid are in molten condition,
Until the binary or the minimum eutectic mixture of polyhydric aliphatic acid of described wood fibre absorption melting reach saturation state, answered
Condensation material；
(2) composite obtained to step (1) carries out hot suction filtration, binary or polyhydric aliphatic until not observing melting
The seepage (vestige not soaked on filter paper) of the minimum eutectic mixture of acid and the mass loss of composite are cold less than 0.5%
But to room temperature, described phase-changing energy storage material is produced.
Binary described in step (1) or the dosage of the minimum eutectic mixture of polyhydric aliphatic acid be can at least make to be modified it is wooden
Fiber reaches adsorption saturation state；Binary or the quality of the minimum eutectic mixture of polyhydric aliphatic acid are preferably modified wood fibre matter
At least 1.5 times of amount；More preferably binary or the minimum eutectic mixture of polyhydric aliphatic acid and modified wood fibre are quality
Than 1：(2~3) match.
Heating in step (1) preferably passes through heater plate；The temperature of heating is preferably above any single fat acid phase
The temperature that 15~35 DEG C of height, the more preferably temperature higher than any 20 DEG C of single fat acid transformation temperature.
Described in step (1) vacuum suction dipping condition be preferably：The vacuum of vacuum suction dipping is -0.07
~-0.09MPa, more preferably -0.75~-0.85MPa；The time of vacuum suction dipping is 1~4h, preferably 1.5~
3h, more preferably 2.5h.
Heat described in step (3) filters preferably to be carried out at 60 DEG C；It is wooden that the purpose that heat filters is that removing is attached to
The minimum eutectic mixture of binary or polyhydric aliphatic acid that fiber surface is not entered into wood fibre hole.
Described modified wood fibre or described phase-changing energy storage material are in the field such as Solar use or building energy conservation
Application.
The present invention is had the following advantages relative to prior art and effect：
1. of the invention effectively regulated and controled the pore size of wood fibre, the complex salt solution used in the present invention by NaCl,
NaNO3、Na2SO4In at least two components form.The complex salt solution can melt plugging hole in (corrosion function) wood fibre
Extract and thylose, moreover it is possible to melt the part c h bond in wood fibre to reach the purpose of reaming.
2. the present invention improves the compatibility of supporting matrix and phase-change material.Contain one in untreated wood fibre
Extracts and its surface energy are compared relatively low a bit, and only a small amount of phase-changing energy storage material is entered in pore structure, is attached on a small quantity
Wood fibre surface.And the wood fibre after processing modified by this invention is obviously improved to the compatibility of phase-change material, phase transformation
Material can also merge well not only completely into the hole to wood fibre on its surface.Meanwhile the present invention is made
Wood fibre and the phase-change material of phase-changing energy storage material be physical bond, therefore the performance of phase-change material will not change.
The present invention, can be preferably by effects such as its hydrogen bond, capillary force, intermolecular forces using modified wood fibre as porous material
Absorbing fats acid phase-changing energy storage material, prevents its leakage, and compatibility is fine, and after wood fibre is modified, porosity increase is right
The adsorbance of aliphatic acid increases, and energy storage efficiency is more excellent.
3. present invention improves phase-changing energy storage material performance.The present invention handles wood fibre by complex salt solution, increases
The aperture of wood fibre, the pore passage structure of wood fibre is improved, it is low common to binary or polyhydric aliphatic acid to improve wood fibre
The absorption property of compound phase-change material is fused and mixed, solves existing fatty acid phase-change material because backing material aperture is small, absorption
Measure it is low caused by phase transformation enthalpy it is low the problem of, and improve latent heat of phase change.Drawn by various signs, as nanoscale aperture
Wood fibre, its aperture is bigger, and the amount of the phase-changing energy storage material of absorption is more, and effectively prevents from revealing.The present invention is with modification
Wood fibre is porous supporting matrix, and sizing phase is prepared as phase-change accumulation energy main body using binary or polyhydric aliphatic acid eutectic mixture
In change energy-storage material, percetage by weight shared by binary or the minimum eutectic mixture of polyhydric aliphatic acid is 60~80%, phase transition temperature
For 15~55 DEG C, enthalpy of phase change is 26~170J/g.
The wood fibre of the present invention after treatment, its borehole enlargement, can retain more phase-change materials, so enthalpy of phase change
It is high.Meanwhile in the phase-changing energy storage material of the present invention, phase-change material is in transition temperature range without thermal degradation；It is adsorbed to wood
After in the hole of matter fiber, weight-loss ratio reduces, and reflects that the heat endurance of phase-change material produced by the present invention improves.It is prepared by the present invention
After obtained phase-changing energy storage material thermal cycle 100 times, its enthalpy of phase change is still very high, illustrates not reveal, and hot energy storage efficiency is very high,
Thermal reliability is good.Therefore all have broad application prospects in the field such as Solar use and building energy conservation.
4. the present invention effectively reduces the phase transition temperature of phase-changing energy storage material.In view of single fat acid phase transition temperature compared with
It is high, it is difficult to meet the requirement of low temperature energy-storage system, the present invention is made using the eutectic mixture of aliphatic acid binary or multicomponent system
For body of phase change material, the phase transition temperature of material can be reduced to meet to require.
5. the preparation method technique of the present invention is simple.Sizing phase-change material prepared by the present invention not only has higher phase transformation
Enthalpy and good heat endurance, and preparation technology is simple, and the wood fibre wide material sources utilized are again cheap, and raw material are not
Chemical treatment need to be passed through, be consequently belonging to environmentally friendly material；Meanwhile phase-changing energy storage material produced by the present invention is a kind of environmental protection
The material of energy-conservation, there is good application prospect.
Brief description of the drawings
Fig. 1 is the preparation flow figure that the reaming of wood fibre in embodiment 2 is modified.
Fig. 2 is the SEM figures of the wood fibre of embodiment 2, wherein, a is unmodified wood fibre, and b is modified wooden fibre
Dimension I.
Fig. 3 is the preparation flow figure of the minimum eutectic mixture of binary of fatty acids in embodiment 3.
Fig. 4 is the preparation flow figure of phase-changing energy storage material in embodiment 3.
Fig. 5 is the SEM figures of phase-changing energy storage material, wherein, a is phase-changing energy storage material I made from comparative example 1, and b is real
Apply phase-changing energy storage material made from example 3.
Fig. 6 is the XRD of phase-changing energy storage material made from embodiment 3.
Fig. 7 is the DSC curve analysis chart of each phase-changing energy storage material, wherein a be laurate-myristic acid binary of fatty acids most
Eutectic, b are phase-changing energy storage material I made from comparative example 1, and c is phase-changing energy storage material made from embodiment 3.
Fig. 8 is modified wood fibre, modified wood fibre/laurate-myristic acid phase-changing energy storage material and laurate-meat
The TG analysis charts of myristic acid.
Fig. 9 is the DSC figures before and after phase-changing energy storage material thermal cycle made from embodiment 3 100 times.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1 prepares complex salt solution
The preparation of complex salt solution I：Proportioning weighs 10g sodium nitrate, 6g sodium chloride, 4g sodium sulphate, the burning being put into mass ratio
In cup, then 80mL distilled water is poured into, stirred on 60 DEG C of magnetic stirring apparatus to being completely dissolved, room temperature cooling, obtain double salt
Solution I.
The preparation of complex salt solution II：Sodium chloride in mass ratio：Sodium nitrate=4:6 proportionings, weigh sodium chloride 6g, sodium nitrate
9g, it is put into beaker, adds 60mL distilled water, is being stirred on 60 DEG C of magnetic stirring apparatus to being completely dissolved, room temperature cools down,
Obtain complex salt solution II.
The preparation of the modified wood fibre of embodiment 2
The preparation of modified wood fibre I：Weigh 20g and the wood fibre of 24 hours has been dried at 105 DEG C (purchased from Xu
Zhou Pucheng wood industries Co., Ltd), it is put into beaker, is slowly added into the complex salt solution I that 100mL embodiments 1 obtain and is stirred with glass bar
Mix uniformly, complex salt solution I and wood fibre are matched as 5 in mass ratio:1 mixing, immediately after with ultrasonication 1 hour
(power 280W, frequency 47KHz), vacuum drying chamber of the pretreatment modification wood fibre at 170 DEG C is bakeed 2 hours, then
It is washed with deionized water to pour into Buchner funnel and filters, this process circulates 10 times, obtains washing modified wood fibre, the filter residue of gained
Dried in 105 DEG C of air dry oven, then crushed with high speed Universal pulverizer, in 80 DEG C of vacuum drying chamber dry 24 again
Hour, the sieve for crossing 60 mesh, modified wood fibre I is made.
For the three specific preparation flows of component complex salt solution modified wood fibre as shown in figure 1,1 is sodium chloride, 2 be sodium nitrate, 3
For sodium sulphate, 4 be distilled water, and 5 be beaker, and 6 be magnetic stirring apparatus, and 7 be complex salt solution, and 8 be wood fibre, and 9 be glass bar, 10
It is pretreatment modification wood fibre for ultrasonication, 11,12 be vacuum drying chamber, and 13 be vavuum pump, and 14 be bottle,suction, and 15 are
Buchner funnel, 16 be washing modified wood fibre, and 17 be modified wood fibre.
The preparation of modified wood fibre II：Weigh 20g the wood fibre of 15 hours has been dried at 100 DEG C and (be purchased from
Xuzhou Pu Cheng wood industries Co., Ltd), it is put into beaker, is slowly added into the complex salt solution II that 100mL embodiments 1 obtain and uses glass bar
Stir, complex salt solution II and wood fibre are matched as 3 in mass ratio:1 mixing, it is small with ultrasonication 2 immediately after
When (power 330W, frequency 35KHz), vacuum drying chamber of the pretreatment modification wood fibre at 180 DEG C is bakeed 1 hour, so
After be washed with deionized water to pour into Buchner funnel and filter, this process circulates 10 times, obtains washing modified wood fibre, the filter of gained
Slag is dried in 105 DEG C of air dry oven, is then crushed with high speed Universal pulverizer, is dried again in 80 DEG C of vacuum drying chamber
24 hours, the sieve of 60 mesh excessively, are made modified wood fibre II.
To obtaining, modified wood fibre I carries out pore analysis and surface topography characterizes：Given birth to using Merck ＆ Co., Inc of the U.S.
The model ASAP2460 nitrogen adsorptions Porosimetry of production carries out pore analysis, test degassing to obtaining modified wood fibre I
Temperature is 80 DEG C, and the average pore size data result measured is as shown in table 1.Using Dutch FEI, model Quanta200 environment
SEM carries out SEM tests to the modified wood fibre I of gained, needs to handle by metal spraying before testing, as a result such as
Shown in Fig. 2.
As shown in Figure 2 and Table 1, its average pore size very little, it is 8.73nm without the wood fibre of modification；By
After the double salt processing of the present invention, aperture is substantially expanded by about one time.
The wood fibre of table 1 before modified after average pore size
The preparation of the phase-changing energy storage material of embodiment 3
(1) preparation of laurate-minimum eutectic mixture of myristic acid binary of fatty acids
Mass ratio (proportioning) between aliphatic acid phase-change material is calculated by Schroeder's formula eutectic mixture is calculated
Minimum eutectic temperature.Mass ratio by the way that laurate and palmitic acid is calculated is 67.66:32.34.Weighing quality is
6.766g laurate and 3.234g myristic acid are added in beaker, and side is heated in the magnetic stirring apparatus top that temperature is 60 DEG C
Stirring 6 hours, natural cooling, obtains described laurate-minimum eutectic mixture of myristic acid binary of fatty acids at room temperature.
Fig. 3 is the preparation flow figure of the minimum eutectic mixture of binary of fatty acids, and a is certain single fat acid, and b is another fat
Acid, c are beaker, and d is magnetic stirring apparatus, and e is the minimum eutectic mixture of binary of fatty acids.
(2) preparation of phase-changing energy storage material
The laurate that step (1) is prepared-minimum eutectic mixture of myristic acid binary of fatty acids is made with embodiment 2
The modified wood fibre I in mass ratio 2 obtained：1 proportioning, weighs and pours into conical flask, and the conical flask uses work with iron stand
Dynamic clip is connected, and vacuum meter is provided with conical flask, for checking vacuum, then conical flask is put and is heated on hot plate
60 DEG C, with when laurate-myristic acid binary of fatty acids eutectic made from step (1) melt completely, continue heating and keep
Aliphatic acid eutectic is in molten condition, and connection vavuum pump vacuumizes 3 hours, and vacuum is -0.08MPa.It is to be modified wooden
The binary of fibers adsorption melting or the polyhydric aliphatic minimum eutectic mixture of acid close vacuum, withdraw vacuum holding to after saturation state
Put, obtain phase-changing energy storage material crude product.By phase-changing energy storage material crude product by the way that in heater box of the filter paper at 60 DEG C, heat is taken out
The minimum eutectic mixture of excessive binary of fatty acids is filtered out, the minimum congruent melting mixing of the binary of fatty acids until not observing melting
The seepage (vestige that filter paper does not soak) of thing and the mass loss of phase-changing energy storage material are less than 0.5%, are cooled to room temperature, produce
Described phase-changing energy storage material (modified wood fibre/laurate-myristic acid phase-changing energy storage material).
Fig. 4 is the preparation flow figure of phase-changing energy storage material, wherein 1) for binary or polyhydric aliphatic acid made from step (1) most
Eutectic mixture, 2) it is be be modified wood fibre made from embodiment 1,3) conical flask, 4) iron stand, 5) wooden for modification
Fibers adsorption binary or the minimum eutectic mixture of polyhydric aliphatic acid, 6) it is be vacuum meter, 7) heating plate, 8) vavuum pump, 9) be
Heater box, 10) it is phase-changing energy storage material.
The preparation of the phase-changing energy storage material II of embodiment 4
(1) preparation of capric acid-minimum eutectic mixture of stearic acid binary of fatty acids
Mass ratio (proportioning) between aliphatic acid phase-change material is calculated by Schroeder's formula eutectic mixture is calculated
Minimum eutectic temperature.It is 9.1 by the way that capric acid and stearic mass ratio is calculated:0.9, weigh capric acid and tristearin by proportioning
Acid is added in beaker, is heated while stirring 6 hours on the magnetic stirring apparatus that temperature is 60 DEG C, natural cooling, is obtained at room temperature
Described capric acid-minimum the eutectic mixture of stearic acid binary of fatty acids.
(2) preparation of phase-changing energy storage material
Made from the capric acid that step (1) is prepared-minimum eutectic mixture of stearic acid binary of fatty acids and embodiment 2
Modified wood fibre II in mass ratio 3：1 proportioning, is weighed and pours into conical flask, and the conical flask is pressed from both sides with iron stand using activity
Son is connected, and vacuum meter is provided with conical flask, for checking vacuum, then conical flask is put and is heated to step on hot plate
(1) capric acid made from-stearic acid binary of fatty acids eutectic melts completely, continues heating and keeps aliphatic acid eutectic to be in
Molten condition, connection vavuum pump vacuumize 1.5 hours, and vacuum is -0.85MPa.The two of wood fibre absorption melting to be modified
Member or the polyhydric aliphatic minimum eutectic mixture of acid close vacuum, withdraw vacuum plant, obtain phase-change accumulation energy material to after saturation state
Expect crude product.Phase-changing energy storage material crude product is removed into excessive binary by the way that in heater box of the filter paper at 60 DEG C, heat filters
The minimum eutectic mixture of aliphatic acid, the seepage of the minimum eutectic mixture of binary of fatty acids until not observing melting is (on filter paper
The vestige not soaked) and the mass loss of phase-changing energy storage material be less than 0.5%, be cooled to room temperature, produce described phase transformation storage
Can material II.
Comparative example 1
The step of embodiment 3 (1) is prepared into mass ratio as 67.66:32.34 laurate-myristic acid binary is minimum common
It is fused and mixed compound and is not modified the wood fibre in mass ratio 2 of processing:1 proportioning, weighs and pours into conical flask, the taper
Bottle is connected with iron stand using movable clip, and vacuum meter is provided with conical flask, for checking vacuum, then conical flask is put
It is completely molten that laurate made from the step of embodiment 3 (1)-myristic acid binary of fatty acids eutectic is heated on hot plate
Melt；Continuing heating keeps aliphatic acid eutectic be in molten condition, and connection vavuum pump vacuumizes 3 hours, and vacuum is-
0.08MPa.Treat laurate-minimum eutectic mixture of myristic acid binary that the wood fibre absorption for not being modified processing melts
To after saturation state, vacuum is closed, vacuum plant is withdrawn, obtains phase-changing energy storage material crude product.Phase-changing energy storage material is slightly produced
Product remove the minimum congruent melting mixing of excessive laurate-myristic acid binary by the way that in heater box of the filter paper at 60 DEG C, heat filters
Thing, (do not soaked on filter paper until not observing the seepage of laurate-minimum eutectic mixture of myristic acid binary of melting
Vestige) and the mass loss of phase-changing energy storage material be less than 0.5%, be cooled to room temperature, produce described phase-changing energy storage material I (not
Modified wood fibre/laurate-myristic acid phase-changing energy storage material).
Comparative example 2
The wood fibre (being purchased from Xuzhou Pu Cheng wood industries Co., Ltd) that 20g has dried 24 hours at 105 DEG C is weighed,
It is put into beaker, is slowly added into the complex salt solution I that 100mL embodiments 1 obtain and is stirred with glass bar, by the He of complex salt solution I
Wood fibre matches as 5 in mass ratio:1 mixing, immediately after with ultrasonication 1 hour, by pretreatment modification wood fibre
Vacuum drying chamber at 90 DEG C bakees 2 hours, is then washed with deionized water to pour into Buchner funnel and filters, this process circulation 10
It is secondary, obtain washing modified wood fibre, the filter residue of gained is dried in 105 DEG C of air dry oven, then with the omnipotent powder of high speed
The sieve that broken machine crushes, dries 24 hours in 80 DEG C of vacuum drying chamber again, crossing 60 mesh, the modified wood fibre of gained.
Because the double salt method of the present invention is for part c h bond, the extract in wood fibre based on double salt at high temperature
With thylose erode effect and the combination of reaming, temperature and double salt be the vital factor of drilling of the present invention it
One.Temperature too low (such as 90 DEG C) can not corrode the skeleton, extract and thylose of wood fibre, can reach the expansion of the present invention
Hole effect；And temperature is too high, wood fibre may be carbonized, and skeleton is destroyed serious, therefore pore passage structure is also destroyed, can not
The phase-changing energy storage material of the present invention is prepared.
Effect example
Material made from above-described embodiment is characterized and performance test.
(1) SEM phenetic analysis
Using Dutch FEI, model Quanta200 environmental scanning electron microscope is to modified wooden fibre in embodiment 3
Unmodified wood fibre laurate-nutmeg made from dimension/laurate-myristic acid phase-changing energy storage material and comparative example 1
Sour phase-changing energy storage material I carries out SEM phenetic analysis.
As shown in Figure 5, unmodified wood fibre/laurate-myristic acid phase-changing energy storage material made from comparative example 1
In I, due to unmodified wood fibre contain some extracts and its surface energy compare it is relatively low, as shown in Fig. 5 (a), only
A small amount of phase-changing energy storage material is entered in pore structure, is attached to wood fibre surface on a small quantity.As shown in Fig. 5 (b), modification is wooden
The wood fibre matrix of fiber/laurate-myristic acid phase-changing energy storage material and the compatibility of phase-change material substantially improve, phase transformation
Material can also merge well not only completely into the hole to wood fibre on its surface.
(2) XRD phenetic analysis
Using the model Ultima IV x-ray powder diffraction instruments of Rigaku company manufacture to modified in embodiment 3
Wood fibre/laurate-myristic acid phase-changing energy storage material carries out XRD phenetic analysis, wherein the angular range tested be 0~
40 °, speed is 10 °/min.
It will be appreciated from fig. 6 that modified wood fibre/laurate-myristic acid phase-changing energy storage material appearance in XRD characterization results
The diffraction maximum diffraction maximum comprising modified wood fibre and the diffraction maximum of laurate-myristic acid, i.e., occur without new diffraction maximum,
Illustrate that wood fibre and phase-change material are physical bonds, therefore the performance of phase-change material will not change.Wood fibre simultaneously
, can more preferable absorbing fats acid phase-change accumulation energy material by effects such as its hydrogen bond, capillary force, intermolecular forces for porous material
Material, prevents its leakage, and compatibility is fine, after wood fibre is modified, porosity increase, the adsorbance of aliphatic acid is increased,
Energy storage efficiency is more excellent.
(3) phase-change material thermal property is tested
It is right using the model STA-449C differential scanning calorimeters (DSC) and thermogravimetric analyzer (TG) of German Nai Chi companies
Phase-changing energy storage material I carries out thermal property phenetic analysis, wherein DSC in phase-changing energy storage material and comparative example 1 in embodiment 3
The temperature range of test is 0~80 DEG C, and heating rate is 10 DEG C/min, and nitrogen is protected, air-flow 20mL/min, and rate of temperature fall is
10℃/min.30~800 DEG C of heating rates of temperature range of TG tests are 10 DEG C/min, and nitrogen is protected, air-flow 40mL/min.
The thermal physical property parameter of the phase-changing energy storage material of table 2
As shown in Fig. 7 each phase-changing energy storage material DSC curve, a is laurate-minimum congruent melting of myristic acid binary of fatty acids
Thing, b are the phase-changing energy storage material I of comparative example 1, and c is the phase-changing energy storage material of embodiment 3.Because wood fibre does not have in itself
There is enthalpy of phase change, so the size of phase-changing energy storage material enthalpy of phase change is minimum to laurate-myristic acid binary of fatty acids depending on it
The adsorbance of eutectic phase-change material, adsorbance is bigger, and enthalpy of phase change is higher.From the phase transformation of the peak area and table 2 of melting endothermic peak
It is unmodified wood fibre that the hot physical performance parameter of energy storage material, which can be seen that matrix, and it is to laurate-myristic acid binary fat
The adsorbance of the minimum eutectic phase-change material of fat acid is seldom, causes enthalpy of phase change very low, therefore energy storage efficiency is not also high.And wooden fibre
Dimension passes through modified, its borehole enlargement, can retain the minimum eutectic phase transformation material of more laurate-myristic acid binary of fatty acids
Material, cause enthalpy of phase change high, therefore energy storage efficiency is also relatively high.
As shown in Fig. 8 TG analysis results, pure aliphatic acid phase-change material weight-loss ratio is up to 100%, when it is adsorbed to
After in the hole of modified wood fibre, weight-loss ratio reduces, and illustrates that heat endurance improves.
Fig. 9 is the DSC figures before and after modified wood fibre/laurate-myristic acid phase-changing energy storage material thermal cycle 100 times,
It can be seen that after 100 circulations, its enthalpy of phase change is still very high, illustrates not reveal, hot energy storage efficiency is very high, thermal reliability
It is good, all have broad application prospects in the field such as Solar use and building energy conservation.
η-adsorbance
△HIt is multiple- phase-changing energy storage material enthalpy of phase change
The minimum eutectic enthalpy of phase change of △ H-laurate-myristic acid binary of fatty acids
The data of table 2 are brought into formula (1), adsorbance of the wood fibre to phase-change material is calculated respectively.Knot
Fruit shows that obtained unmodified wood fibre only adsorbs 39.1% phase-change material in comparative example 1, and embodiment 3 is made
The wood fibre of the modification obtained can adsorb up to 60.3% phase-change material；Meanwhile the phase transformation of the phase-changing energy storage material of embodiment 3
Enthalpy is 98.2J/g, and the value is of a relatively high, is suitable for various fields.After wood fibre is modified simultaneously, extract or thylose
It is removed, the effect such as its hydrogen bond, capillary force, intermolecular force increase, therefore can more preferable absorbing fats acid phase-change accumulation energy
Material, prevent its leakage.
In summary, at least expanded than the aperture of unmodified wood fibre by the wood fibre of modification of the present invention
1 times, after wood fibre is modified, it is removed with the extract or thylose of phase-change material poor compatibility, can not only expands aperture,
Maximum phase-change material retains space, and also improves their compatibility, so substantially increases the absorption of phase-change material
Amount.And the phase transition temperature of the phase-changing energy storage material be room temperature (28.3 DEG C) and higher enthalpy of phase change more suitable for utilizing, especially
It is in building energy saving field；Meanwhile after phase-change material is immersed in modified wood fibre, its heat endurance improves a lot, warp
After crossing repeatedly circulation, its thermal property seldom changes, and illustrates that its thermal reliability is fine, therefore wood fibre phase prepared by the present invention
Change energy-storage material is a kind of phase-changing energy storage material of superior performance.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified wood fibre, it is characterised in that comprise the following steps：
After pretreated wood fibre is mixed with complex salt solution, it is ultrasonically treated, then high temperature bakees, and washing filters, and dries
After crush, then be dried in vacuo；Produce described modified wood fibre.
2. the preparation method of modified wood fibre according to claim 1, it is characterised in that：
Described wood fibre and the proportioning of complex salt solution in mass ratio 1:(2~5) match.
3. the preparation method of modified wood fibre according to claim 1, it is characterised in that：
Described complex salt solution is the complex salt solution for including at least two sodium salts in sodium chloride, sodium nitrate, sodium sulphate.
4. the preparation method of modified wood fibre according to claim 1, it is characterised in that：
Described ultrasonic power parameter is 100~450W；
The described ultrasonic time is 0.5~2h.
5. the preparation method of modified wood fibre according to claim 1, it is characterised in that：
The temperature that described high temperature bakees is 150~200 DEG C；
The time that described high temperature bakees is 0.5~3 hour.
A kind of 6. modified wood fibre, it is characterised in that：
It is prepared by the preparation method of the modified wood fibre described in any one of Claims 1 to 5.
7. a kind of phase-changing energy storage material, including modified wood fibre described in claim 6 and binary or polyhydric aliphatic acid it is minimum
Eutectic mixture, wherein described binary or the percetage by weight of the minimum eutectic mixture of polyhydric aliphatic acid are 60~80%.
8. the preparation method of the phase-changing energy storage material described in claim 7, it is characterised in that comprise the following steps：
(1) heating makes described binary or the minimum eutectic mixture of polyhydric aliphatic acid melt completely, and it is wooden to add described modification
Fiber, enter vacuum adsorbed dipping in the case where holding binary or the minimum eutectic mixture of polyhydric aliphatic acid are in molten condition, until
The binary or the minimum eutectic mixture of polyhydric aliphatic acid of described wood fibre absorption melting reach saturation state, obtain composite wood
Material；
(2) composite that is obtained to step (1) carries out hot suction filtration, until do not observe melting binary or polyhydric aliphatic acid most
The seepage of eutectic mixture and the mass loss of composite are less than 0.5%, are cooled to room temperature, produce described phase-change accumulation energy
Material.
9. the preparation method of described phase-changing energy storage material according to claim 8, it is characterised in that institute in step (1)
State vacuum suction dipping condition be：
The vacuum of vacuum suction dipping is -0.07~-0.09MPa；
The time of vacuum suction dipping is 1~4h.
10. the phase-changing energy storage material described in modified wood fibre or claim 7 described in claim 6 in Solar use or
Application in building energy saving field.
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