CN110003863A - A kind of micro- jelly chilled food is fresh-keeping to use phase-change material for cold storage and preparation method - Google Patents
A kind of micro- jelly chilled food is fresh-keeping to use phase-change material for cold storage and preparation method Download PDFInfo
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- CN110003863A CN110003863A CN201910251037.4A CN201910251037A CN110003863A CN 110003863 A CN110003863 A CN 110003863A CN 201910251037 A CN201910251037 A CN 201910251037A CN 110003863 A CN110003863 A CN 110003863A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Abstract
The present invention provides a kind of micro- jelly chilled food phase-change material for cold storage and preparation method thereof.Micro- jelly fruits and vegetables of the invention use phase-change material for cold storage using decyl alcohol and lauryl alcohol mixed solution as main base fluid, improve the thermal conductivity of phase-change material for cold storage using hydroxylated multi-walled carbon nanotubes and neopelex as additive.The phase transition temperature of phase-change material for cold storage is -3.2 DEG C, latent heat of phase change 171J/g, and thermal conductivity is 0.3462W/ (mK).After 100 high/low temperatures recycle, which still has excellent thermal stability.Phase-change material for cold storage obtained is applicable to the fresh-keeping of the food such as meat, vegetables.Invention further provides the preparation methods of composite phase-change cool storage material.
Description
Technical field:
It is specifically a kind of to be applicable to as meat the present invention relates to a kind of fresh-keeping phase-change material for cold storage of micro- jelly chilled food
The phase-change material for cold storage of the offer cold storing and fresh-keeping of the food such as class, vegetables.
Background technique:
In recent years, with the rapid development of economy, energy shortage and environmental problem are got worse.Therefore, energy benefit is improved
With efficiency, protecting environment is an important topic.Energy storage is the key technology for solving crisis.Storage comes from solar energy and wind
Can etc. renewable energy the energy, especially non-peak period generate the energy, for renewable energy technologies extensive use extremely
It closes important.TES (thermal energy storage) is one of the effective ways for solving the imbalance between supply and demand of the space-time energy.This technology is considered as solving
The potential solution of energy shortage and environmental problem.Thermal energy can be stored with sensible heat, latent heat storage and chemical reaction heat storage
Form storage.In these forms, LHTES (latent heat energy storage) is realized by using PCM (phase-change material), works as ambient temperature
When being raised and lowered, PCM can store during phase transition process or discharge thermal energy.PCM have high-energy density and from storage to
The small advantage of the temperature change of retrieval.These characteristics pay high attention to LHTES and are widely used in solar energy heat-storage, air conditioner condensation
Heat recovery system, temperature adjust textile, many applications such as Energy Conservation Project in Construction.
Phase change energy storage technology can be realized power grid " move paddy and fill out peak ", improves energy utilization rate, reduces the wasting of resources, and conduct
The novel energy-conserving technology that one environmental protection and energy saving, circular economy, the energy are adjusted with comprehensive utilization in one receives significant attention.Latent heat
Thermal energy storage system discharges a large amount of latent heat of phase change using material when undergoing phase transition, to realize the storage and utilization to energy.
Heat or cooling capacity are absorbed using phase-change material, can be realized the recycling of energy.Phase change energy storage technology is as a kind of efficient
Energy utilization technology be applied in cold chain industry.The technology can move paddy and fill out peak, alleviate in the energy time and space not
The problem of matching, while can solve last one kilometer dispatching, temperature fluctuation, chain rupture that Cold Chain Logistics occur during transportation
The problems such as with single temperature control.According to food refrigerated technology, if aquatic products category is housed in -2~-3 DEG C of micro- jelly storage temperature section,
Storage period is 1.5~2 times long compared to ice cube storage.Therefore cold chain transportation technology with greater need for for different product to transportational process
Implement targetedly temperature adjustment or temperature control technique, chain cleavage does not occur for guarantee.For the fruits and vegetables that different temperatures requires, for providing
The phase-change material phase transition temperature of cooling capacity is different, needs to carry out phase transition temperature stringent matching, to prevent due to phase transition temperature it is excessively high
Or it is too low to transport article damage.Therefore, it researches and develops a kind of suitable for micro- low temperature phase change cold storage material for freezing refrigeration.In phase
In change energy-storage material, nalka alcohols has biggish latent heat of phase change, there is good application prospect.Lauryl alcohol is as a kind of organic
Phase-changing energy storage material, phase transition temperature is 24 DEG C, latent heat of phase change 207J/g, and decyl alcohol phase transition temperature is 6 DEG C, latent heat of phase change is
181J/g, it is nontoxic, environmentally friendly, cheap the advantages that have been to be concerned by more and more people.By two kinds of phase-change materials with low
New mixed solution is made in eutectic method, and phase transition temperature is -3.2 DEG C, latent heat of phase change 179.7J/g, and hydroxylating multi wall carbon is added and receives
After mitron, thermal conductivity thermal conductivity is 0.3462W/ (mK).The phase-change material to applied to micro- jelly refrigeration storage and transportation domestic at present
Study less, mostly can ignore based on the organic phase change material of degree of supercooling, but potential heat value is but between 100-150J/g, heat
Conductance is even more very small.
There is presently no the organic phase change materials with larger latent heat of phase change and thermal conductivity (phase transition temperature is -3.2 DEG C)
Related research result.
Improve the research of the correlative study of thermal coefficient about addition additive at present, but result can all drop significantly
Low latent heat of phase change value makes up other deficiencies to lose a part of latent heat of phase change.
Therefore one kind easy to operate, inexpensive, high yield, high performance decyl alcohol-lauryl alcohol/hydroxylating multi wall carbon is developed to receive
Mitron/neopelex composite phase-change storage cold material preparation method is of great significance.
Summary of the invention:
There is provided herein a kind of fresh-keeping phase-change materials and preparation method thereof of micro- jelly chilled food.
The micro- jelly chilled food of the present invention is fresh-keeping as follows with phase-change material for cold storage component and its mass fraction:
Decyl alcohol: 74-78 parts,
Lauryl alcohol: 22-26 parts,
Hydroxylated multi-walled carbon nanotubes: 0.002-0.01 parts,
Neopelex: 0.002-0.01 parts,
The potential heat value of composite material is maximum when the mass fraction of decyl alcohol and lauryl alcohol is than for 76:24, and phase transformation platform is most stable.
0.004 part of hydroxylated multi-walled carbon nanotubes is added, i.e. 0.08g/L is hydroxylated multi-walled carbon nanotubes in decyl alcohol/lauryl alcohol
It is decyl alcohol/lauryl alcohol that the additional proportion of best addition concentration, neopelex and hydroxylated multi-walled carbon nanotubes, which is 2:1,
In best addition concentration, that is, 0.008 part of neopelex is added.
Decyl alcohol is that analysis is pure, and purity is not less than 99%.
Lauryl alcohol is that analysis is pure, and purity is not less than 99%.
Hydroxylated multi-walled carbon nanotubes, purity be not less than 95%, internal diameter 5-10nm, outer diameter 10-20nm, 10-30 μm of length,
Specific surface area 200m2/g。
Neopelex is that analysis is pure, and purity is not less than 98%
The lowest total of the melting point proportion that capric acid and lauryl alcohol are obtained by theoretical calculation is 0.762: 0238, for proof theory value
Accuracy be configured with molal weight and carried out than different decyl alcohol-lauryl alcohol composite phase-change material near the lowest total of the melting point
Experimental verification.The fusion temperature of eutectic mixture is known as the theoretical eutectic point temperature of eutectic point alcohols binary organic phase change material
It can be determined by formula (1), latent heat of phase change value can be determined by formula (2), be determined by intersection point of two kinds of solution on liquidus curve minimum
The stoichiometric of eutectic mixture.
In formula, TmFor the eutectic point of mixture, DEG C；TmFor the latent heat of phase change value of eutectic system, J/g；TiFor two kinds of objects of A, B
The fusing point of matter, DEG C；R is gas constant, R=8.314J/ (molK)；XiFor molar ratio shared by two substance of A, B, XA+XB=1；
HiFor the heat of fusion of A, B, J/mol；A, B represents two kinds of substances.
With the phase transition temperature and latent heat of phase change of DSC200F3 measurement experiment sample；Experiment porch is built, composite phase-change is measured
The cooling curve of material；Using the thermal conductivity of TPS500 type thermal constant analyzer measurement phase-change material；Using KYKY-EM6000 type
Electronic Speculum observes the microstructure of phase-change material, uses the stability of high low temperature cycles test case test sample.Experiment equipment is shown in Table
1。
1 experiment equipment of table
Decyl alcohol-lauryl alcohol/hydroxylated multi-walled carbon nanotubes/neopelex mixed solution preparation method is such as
Under: 38g decyl alcohol, 12g lauryl alcohol, in the beaker that volume is 100mL are weighed using precision electronic balance.Fill decyl alcohol/
The beaker of lauryl alcohol mixed solution is placed on magnetic stirring apparatus, is stirred under 25~35 DEG C of heating temperatures, 250~300r/min revolving speed
5~10mins is mixed, guarantees that the two is uniformly mixed.It is more to 0.004 part of hydroxylating is added in the decyl alcohol prepared/lauryl alcohol mixed solution
Wall carbon nano tube, 0.008 part of neopelex.Ultrasonic wave dispersion, ultrasonic unit oscillation are carried out to the material prepared
30~60 minutes, one cycle ultrasound works 5 seconds, suspend 5 seconds, temperature upper limit is set as 45 DEG C, ultrasonic power 300W.It will
The uniform material of ultrasonic disperse takes out, and stands stand-by to room temperature.Prepared composite material potential heat value with higher and without mistake
Cold and phenomenon of phase separation, while thermal conductivity of material can be improved.The composite material and preparation method thereof reaction condition is controllable, and equipment is wanted
Ask simple, it is easy to accomplish batch production is conducive to steadily storage of cold, improves cold energy use rate and protection environment.
The purpose of the present invention can be achieved through the following technical solutions:
(1) stoichiometric of composite phase-change material is determined by theoretical calculation；
(2) lauryl alcohol of weighing and decyl alcohol are mixed and is placed in beaker；
(3) mixture is placed in a beaker, is stirred 5 minutes with glass bar；
(4) mixture stirred evenly is heated 20 minutes under 30 DEG C of constant temperatures of heated at constant temperature slot, is melted to limpid
Transparency liquid；
(5) mixture is stirred 5 minutes under 35 DEG C of constant temperatures through magnetic force thermostatic mixer；
(6) hydroxylated multi-walled carbon nanotubes and neopelex are added in the mixed solution being stirred, is placed in
It is stood after being shaken 1 hour in ultrasonic unit.
The mass ratio of decyl alcohol and lauryl alcohol in above-mentioned steps (2) is 0.762/0.238.
Being stirred 2~5 minutes with glass bar in above-mentioned steps (3), to be dispersed in lauryl alcohol in decyl alcohol.
25~35 DEG C of heating temperature in above-mentioned steps (4), hot bath liquid level are higher than the highest point of mixture, prevent
Remain on wall of cup.
The heating water bath time is 15~20mins in above-mentioned steps (4), to guarantee that material can melt completely.
Speed of agitator in above-mentioned steps (5) is 250~300r/min.
Ultrasonic unit duration of oscillation is 30~60 minutes in above-mentioned steps (6), one cycle ultrasound works 5 seconds, suspends 5
Second.Temperature upper limit is set as 45 DEG C.
With prior art phase transformation, the invention has the following advantages that
(1) present invention prepares compound organic phase change material, no supercooling and phenomenon of phase separation, and phase transition temperature is -3.2 DEG C, phase
Change latent heat is 179.7J/g, and after hydroxylated multi-walled carbon nanotubes are added, thermal conductivity is 0.3462W/ (mK), improves
17.4%.It is domestic at present less to the research for being applied to micro- phase-change material for freezing refrigeration storage and transportation, mostly degree of supercooling can be ignored
Based on organic phase change material, but potential heat value, but between 100-150J/g, thermal conductivity is even more very small.Heat before and after material modification
Conductance is shown in Table 2.
Table 2
(2) present invention is during preparing composite phase-change material without phenomenon of phase separation.
(3) reaction condition is mildly controllable, and the equipment needed is fairly simple, it is easy to accomplish low cost is produced in enormous quantities.
(4) low in the pollution of the environment, preparation process whole process is environmentally protective.
(5) in the decyl alcohol/lauryl alcohol composite material prepared after 100 cyclic tests, phase-change thermal storage performance is still excellent.
Detailed description of the invention:
Fig. 1 is the differential scanning calorimetry figure of optimum proportioning decyl alcohol/lauryl alcohol phase-change material prepared by the present invention.
Fig. 2 is decyl alcohol-lauryl alcohol/hydroxylated multi-walled carbon nanotubes/neopelex phase transformation prepared by the present invention
The differential scanning calorimetry figure of energy storage material.
Fig. 3 is decyl alcohol-lauryl alcohol/hydroxylated multi-walled carbon nanotubes prepared by the present invention/neopelex circulation
Differential scanning calorimetry figure after 100 times.
Fig. 4 is five kinds of different ratio decyl alcohol/lauryl alcohol phase-change material cooling curve figures of invention preparation.
Specific embodiment:
Below in conjunction with specific embodiment, the invention will be further described, and following embodiment is mass fraction.
Embodiment 1
The lowest total of the melting point proportion that capric acid and lauryl alcohol are obtained by theoretical calculation is 0.762: 0238, for proof theory value
Accuracy be configured with molal weight than being respectively 74: 26,75: 25,76: 24,77: 23,78 near the lowest total of the melting point:
22 decyl alcohol-lauryl alcohol composite phase-change material carries out experimental verification.The experiment sample of certain mass is weighed using precision electronic balance
Product, every group of sample quality are 50g, in the beaker that volume is 100mL.Filling decyl alcohol-lauryl alcohol mixed solution beaker
It is placed on magnetic stirring apparatus, 20mins is stirred under 35 DEG C of heating temperatures, 300r/min revolving speed, guarantee that the two is uniformly mixed, then
Mixture is naturally cooled into room temperature, obtains decyl alcohol-lauryl alcohol Binary-phase variant system.From the cooling curve of Fig. 4 as it can be seen that decyl alcohol
Freezing point temperature when with the mass fraction of lauryl alcohol than for 76:24 is minimum, as the eutectic point of mixed solution.Decyl alcohol/ten
Degree of supercooling is not present in glycol, and phase transformation initial temperature is -3.1 DEG C, solidifies phase transition process for about 900s, phase transformation platform stable.
Embodiment 2
Weighing 30g mass ratio is the DA-LA of 76:24 as base fluid, then successively weighing mass fraction is 0.002 part, 0.004
Part, 0.006 part, 0.008 part, 0.01 part of hydroxylated multi-walled carbon nanotubes are added in decyl alcohol/lauryl alcohol solution.To what is prepared
Material carries out ultrasonic wave dispersion.The parameter of ultrasonic wave separating apparatus is set, and ultrasonic unit vibrates 360 times, one cycle ultrasound work
Make 5 seconds, suspends 5 seconds, temperature upper limit is set as 45 DEG C, ultrasonic power 300W.The uniform material of ultrasonic disperse is taken out, it is quiet
It is stand-by to set room temperature.Configured nano-composite phase-changing material stands 48h at room temperature, observes its sedimentation phenomenon, finds five groups
Solution is uniformly dispersed, and does not occur significantly to settle.After nano material is added to certain mass fraction, nano material will not be complete
It is scattered in solution entirely, but partly precipitated occurs, the raising of cool storage material thermal coefficient of this phenomena impair.In order to overcome
This phenomenon improves the degree of scatter of nano material, improves this feelings by adding the method for dispersing agent into cool storage material
Condition.For the optimal addn for determining dispersing agent, 0.002 part, 0.004 part, 0.008 part, 0.01 part of detergent alkylate sulphur are weighed
Sour sodium and hydroxylated multi-walled carbon nanotubes are added in decyl alcohol/lauryl alcohol solution, and it is dense that different quality is formed after being dispersed with ultrasonic wave
The nano-composite phase-changing material suspension of degree.
For decyl alcohol-lauryl alcohol/hydroxylated multi-walled carbon nanotubes nano-composite phase-changing material, when hydroxylating multi-wall carbon nano-tube
From when increasing to 0.004 part for 0.002 part, the thermal conductivity of solution increases sharply the concentration of pipe；When hydroxylated multi-walled carbon nanotubes
When concentration is greater than 0.004 part, thermal conductivity is on a declining curve.Excessive nanoparticle is added, nanoparticle can be made in the solution
Reunion and sedimentation phenomenon occurs, is unfavorable for forming uniform and stable suspension.Therefore, 0.004 part is selected to receive for hydroxylating multi wall carbon
Best addition concentration of the mitron in decyl alcohol/lauryl alcohol.It is compound when the concentration of hydroxylated multi-walled carbon nanotubes is 0.004 part
The thermal conductivity of material is 0.3231W/ (mK), improves 11.5% compared to decyl alcohol/lauryl alcohol.To the hydroxyl of different quality containing
Base multi-walled carbon nano-tube/neopelex mixed solution carries out Determination of conductive coefficients.Work as neopelex
Concentration from when increasing to 0.008 part for 0.002 part, the thermal conductivity of solution increases sharply；When the concentration of neopelex
When being 0.008 part, thermal conductivity is 0.3462W/ (mK), improves 17.4% than decyl alcohol/lauryl alcohol thermal conductivity.As it can be seen that point
Powder and the additional proportion of nano material are that 2:1 is best addition concentration in decyl alcohol/lauryl alcohol.
Decyl alcohol prepared by the present invention/lauryl alcohol composite phase-change material phase transition temperature and latent heat of phase change are as shown in Figure 1, phase transformation
Temperature is -3.2 DEG C, latent heat of phase change 179.7J/g, no degree of supercooling.After hydroxylated multi-walled carbon nanotubes and dispersing agent is added, phase
Become the thermal coefficient of material as 0.3462W/ (mK), improves 17.4%.The latent heat of phase change and Xiang Bianwen of nanocomposite
Degree is as shown in Fig. 2, -3.2 DEG C of phase transition temperature, latent heat of phase change 171J/g.After circulation 100 times, the phase of nano-composite phase-changing material
Become latent heat and phase transition temperature as shown in figure 3, -3.1 DEG C of phase transition temperature, latent heat of phase change 170.2J/g.In general, circulation front and back
The hot physical property fluctuation range of composite phase-change material is smaller, shows preferable stability.To sum up, decyl alcohol/ten prepared by the present invention
Glycol composite phase-change material can steadily store cooling capacity in sub-zero low temperature environment, and improve the phase of raising
Become energy-storage property, and process is simple, it is convenient and practical.
Claims (6)
1. a kind of micro- jelly chilled food is fresh-keeping to use phase-change material for cold storage, it is characterised in that including following component and its mass fraction:
Decyl alcohol: 74-78 parts,
Lauryl alcohol: 22-26 parts,
Hydroxylated multi-walled carbon nanotubes: 0.002-0.01 parts,
Neopelex: 0.002-0.01 parts.
2. micro- jelly chilled food according to claim 1 is fresh-keeping to use phase-change material for cold storage, which is characterized in that the decyl alcohol is
Analyze it is pure, purity be not less than 99%.
3. micro- jelly chilled food according to claim 1 is fresh-keeping to use phase-change material for cold storage, which is characterized in that the lauryl alcohol
Pure to analyze, purity is not less than 99%.
4. micro- jelly chilled food according to claim 1 is fresh-keeping to use phase-change material for cold storage, which is characterized in that the hydroxylating
Multi-walled carbon nanotube, purity be not less than 95%, internal diameter 5-10nm, outer diameter 10-20nm, 10-30 μm of length, specific surface area 200m2/
g。
5. micro- jelly chilled food according to claim 1 is fresh-keeping to use phase-change material for cold storage, which is characterized in that the dodecane
Base benzene sulfonic acid sodium salt is that analysis is pure, and purity is not less than 98%.
6. micro- jelly chilled food according to claim 1 is fresh-keeping to use phase-change material for cold storage, it is characterised in that including following step
It is rapid:
Step 1: it is determined according to the theoretical eutectic point temperature of alcohols binary organic phase change material by formula (1), latent heat of phase change value is logical
It crosses formula (2) to determine, the lowest total of the melting point proportion that capric acid and lauryl alcohol are obtained by theoretical calculation is 0.762: 0.238, in order to verify
The accuracy of theoretical value is configured with molal weight than being respectively 74: 26,75: 25,76: 24,77 near lowest total of the melting point:
23,78: 22 decyl alcohol-lauryl alcohol composite phase-change material carries out experimental verification, determines the optimum proportioning of base fluid；
Step 1: the lauryl alcohol of weighing and decyl alcohol are mixed and are placed in beaker；
Step 2: mixture is placed in a beaker, and is stirred 5~10 minutes with glass bar；
Step 3: the mixture stirred evenly is heated 5~10 minutes under 25~35 DEG C of constant temperatures of heated at constant temperature slot, is melted
To as clear as crystal liquid；
Step 4: mixture is stirred 5~10 minutes under 35 DEG C of constant temperatures through magnetic force thermostatic mixer；
Step 5: the mass ratio being stirred is decyl alcohol/lauryl alcohol of 76:24 as base fluid, then successively weighs 0.002 part, 0.004
Part, 0.006 part, 0.008 part, 0.01 part of hydroxylated multi-walled carbon nanotubes be added in decyl alcohol/lauryl alcohol solution, be placed in ultrasound
In wave apparatus concussion 30~stand after sixty minutes, be determined by experiment the optimal addn of hydroxylated multi-walled carbon nanotubes；
Step 6: 0.004 part of hydroxylating multi wall is added as base fluid in decyl alcohol/lauryl alcohol that the mass ratio being stirred is 76:24
Carbon nanotube, then successively weigh mass fraction be 0.002 part, 0.004 part, 0.008 part, 0.01 part of dodecyl benzene sulfonic acid
Sodium, with ultrasonic wave dispersion 30~after sixty minutes formed different quality concentration nano-composite phase-changing material suspension.Pass through experiment
Determine the optimal addn of neopelex.
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| CN113637460A (en) * | 2021-08-26 | 2021-11-12 | 杭州鲁尔新材料科技有限公司 | Accurate temperature control phase-change material for short-distance transportation of medicines and folding cold storage bag using same |
| CN113930220A (en) * | 2021-11-24 | 2022-01-14 | 华中科技大学 | Steel slag-based binary composite phase change material capable of melting snow and removing ice and preparation method thereof |
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