AU2020103359A4 - Phase change cold storage agent for shiitake mushroom preservation and method for preparing the same - Google Patents
Phase change cold storage agent for shiitake mushroom preservation and method for preparing the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/36—Freezing; Subsequent thawing; Cooling
- A23L3/37—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The present invention discloses a phase change cold storage agent for shiitake mushroom
preservation and a method for preparing the same, and belongs to the technical field of cold
storage agents. The optimal formula of the phase change cold storage agent consisted the
following components: sorbitol 1.72%, nano zinc oxide 0.05%, sodium carboxymethyl
cellulose 0.10%, super absorbent resin 0.50%, and the rest was deionized water. Its phase
change temperature was 0.11°C, and its latent heat was 299.61 J/g. The source of the raw
materials involved in the present invention was convenient, the preparation process was
simpler, and the production cost was lower. And the prepared cold storage agent had a larger
latent heat, and its phase change temperature was compatible with the storage temperature
range and freezing point of shiitake mushrooms. It had no supercooling and phase separation,
and no obvious change in the latent heat after repeated cycles. It was non-toxic and tasteless,
safe and environmentally friendly. Compared with other cold storage agents with lower phase
change temperature, it was more suitable for shiitake mushroom preservation and cold chain
transportation.
14
')RAWINGS
Concentration of the substance
(mol/L)
0.0 0.1 02 03 0-A 0.5
0
-1
C
0
-2
-3
Fig. 1
295
290
285
-c
C 280
U
275
270
200 0.1 0.2 03 04 0.5
Concentration of the substance
(mol/L)
Fig. 2
Description
Concentration of the substance (mol/L) 0.0 0.1 02 03 0-A 0.5 0
-1
0 C
-2
-3
Fig. 1 295
290
285
-c C 280
275
270 200 0.1 0.2 03 04 0.5 Concentration of the substance (mol/L) Fig. 2
[0001] The present invention relates to the technical field of cold storage agent preparation, in particular to a phase change cold storage agent for shiitake mushroom
preservation and a method for preparing the same.
[0002] At present, the global cold chain is expanding uninterruptedly, especially in
developing countries. The expanded cold chain may promote changes in global diets, food
production and distribution, and shopping habits. With the growth of population and demand,
food safety has become an increasingly important issue in recent years. In order to extend and
ensure the shelf life of food, it is very important to keep its temperature during storage and
transportation within a given range. Every year, a large amount of food is transported and
sold in China without cold chain protection, causing serious deterioration and rot, and serious
losses. Therefore, with the support of logistics fresh-keeping facilities and technology,
establishing a sound logistics fresh-keeping system and reducing food losses in the process of
logistics fresh-keeping is the only way for the sustainable development of Chinese food
industry.
[0003] Cold storage technology is a process of using various physical, chemical, mechanical and other effective means to store cold energy in a cold storage agent, and then
release the stored cold energy when needed. The special materials produced by this
technology that can store cold energy efficiently and meet various physical and chemical
requirements are called cold storage agents. As a new type of functional material, the cold
storage agent plays an important role in cold chain logistics with its advantages of economy,
safety and convenience, and is the core technology to realize cold chain transportation.
[0004] Shiitake mushrooms are delicious and nutritious. However, after harvest,
shiitake mushrooms are prone to show quality deterioration such as weight loss, umbrella
opening, mushroom stalk growth, mushroom body shrinkage, softening, and browning, thus they are very intolerant to storage. They lose their freshness within 1 to 2 days at room temperature, which seriously affects their edibility and commodity value. Different foods have different transportation and storage temperatures. The temperature range of the cold storage agent should be compatible with the actual storage and transportation temperature range and freezing point of the food. Data show that the best storage temperature for edible fungi is 0~ 5C, and some researchers have measured the freezing point of the shiitake mushroom is -0.92C However, the currently disclosed cold storage agents are generally low or high in temperature, which can not meet the requirements of shiitake mushroom storage and transportation; for example, the invention patent application with publication number
CN104232024A discloses a cold storage agent which is composed of sodium chloride,
glycerol and water, and has a phase change temperature of -30.3°C~-29.5°C; the invention
patent application with publication number CN105601819A discloses a cold storage agent,
which is composed of a graft copolymer of konjac glucomannan-acrylic acid-acrylamide,
ammonium chloride, potassium nitrate and water, and has a phase change temperature of
-18~-15°C; their phase change temperatures are too low for shiitake mushrooms, which may
cause damage such as freezing damage to shiitake mushrooms. However, the invention patent
application with application number CN90109434.X discloses a cold storage agent composed
of potassium chloride and water, which has a phase separation problem, resulting in a higher
decay rate.
[0005] Therefore, in view of the storage characteristics of shiitake mushrooms, it is of
great significance to design and develop a cold storage agent with suitable phase change
temperature, economy, safety and convenience for storage, transportation and preservation of
shiitake mushrooms.
[0006] The invention provides a phase change cold storage agent for shiitake
mushroom preservation and a method for preparing the same. The phase change cold storage
agent not only has a phase change temperature (-1 10 C) suitable for shiitake mushroom
storage and transportation, but also has a higher phase change latent heat (>280J/g), and no
supercooling and phase separation, especially suitable for shiitake mushroom storage and transportation.
[0007] The specific technical solutions are as follows:
[0008] The present invention provides a phase change cold storage agent for shiitake
mushroom preservation, consisting of the following components by mass percentage:
sorbitol 1.38~2.07%;
nano zinc oxide 0.03~0.06%;
sodium carboxymethyl cellulose 0.09~0.11%;
super absorbent resin 0.40~0.60%;
[0009] and the rest being deionized water.
[0010] Among the above-mentioned phase change cold storage agents, the phase change temperature and latent heat of sorbitol are relatively stable, and are suitable as the
main cold storage material; the nanometer effect of nano zinc oxide may have antibacterial
and sterilization effects, and can increase the latent heat value of the cold storage agent
system; as a thickening agent, sodium carboxymethyl cellulose can prevent phase separation
without affecting the phase change process; super absorbent resin with its good water
retention performance and gel strength can effectively extend the low-temperature freezing
time, avoid the leakage of melted water, and also effectively alleviate the phase separation of
the cold storage agent.
[0011] Preferably, it consists of the following components by mass percentage:
sorbitol 1.55~1.89%;
nano zinc oxide 0.04~0.055%;
sodium carboxymethyl cellulose 0.095~0.105%;
super absorbent resin 0.45~0.55%;
[0012] and the rest being deionized water.
More preferably, it consists of the following components by mass percentage:
sorbitol 1.72%;
nano zinc oxide 0.05%;
sodium carboxymethyl cellulose 0.10%;
super absorbent resin 0.50%;
[0013] and the rest being deionized water.
[00141 Further, the particle size of the nano zinc oxide is 10~50 nm. The nano zinc oxide used is hydrophilic anatase with a uniform and small particle size, large specific surface
area, and strong nanomaterial effects.
[0015] Further, the viscosity of the sodium carboxymethyl cellulose is 800~1200
mpa.s. Viscosity is one of the most important technical indicators of sodium carboxymethyl
cellulose. The sodium carboxymethyl cellulose used has a moderate viscosity and can be
basically completely dissolved in water.
[00161 The super absorbent resin is a functional polymer material that contains strong hydrophilic groups and has a certain degree of cross-linking. The main component is sodium
polyacrylate with fine particles and the full gel after absorbing water, which can effectively
enhance the cold storage time.
[00171 Further, the phase change temperature of the phase change cold storage agent
is0.1~1° C, and the latent heat of phase change is 280.30~300.00 J/g.
[00181 Data show that the best storage temperature for the edible fungi is 0~5C, and
some researchers have measured the freezing point of the shiitake mushroom is -0.83°C;
therefore, the above phase change cold storage agent is particularly suitable for shiitake
mushroom storage and transportation.
[0019] The present invention also provides a method for preparing the phase change
cold storage agent for shiitake mushroom preservation, comprising the following steps:
[0020] (1) adding sorbitol and sodium carboxymethyl cellulose to deionized water
and mixing well to obtain solution I;
[0021] (2) adding nano zinc oxide to the solution I and mixing well to obtain solution
[0022] (3) adding super absorbent resin to the solution II and mixing well to obtain
the phase change cold storage agent.
[0023] Further, in steps (1)~(3), the mixing temperature is 20-25°C.
[0024] Compared with the prior art, the present invention has the following beneficial
effects:
[0025] (1) the present invention combines sorbitol, nano zinc oxide , sodium
carboxymethyl cellulose and super absorbent resin to obtain the phase change cold storage agent with a phase change temperature of 0.11~0.62°C, and latent heat of 285.30~299.61
J/g, which is suitable for shiitake mushroom preservation and cold chain transportation to
avoid freezing damage and other damage due to too low phase change temperature of the cold
storage agent Al.
[0026] (2) The raw material sources involved in the phase change cold storage agent of the present invention are universal, the production cost is lower, and the preparation
process is simple. And the prepared cold storage agent has larger latent heat, no supercooling
and phase separation, and no obvious change in the latent heat after repeated cycles. It is
non-toxic and tasteless, safe and environmentally friendly. Compared with other cold storage
agents with lower phase change temperature, it is more suitable for shiitake mushroom
preservation and cold chain transportation.
[00271 Fig. 1 is the relationship curve between the concentration of the sorbitol
aqueous solution and the phase change temperature in example 1.
[0028] Fig. 2 is the relationship curve between the concentration of the sorbitol
aqueous solution and the latent heat in example 1.
[0029] Fig. 3 is the DSC curve diagram of the phase change cold storage agent
prepared in example 2.
[0030] Fig. 4 is the DSC curve diagram of the phase change cold storage agent
prepared in example 3.
[0031] Fig. 5 is the DSC curve diagram of the phase change cold storage agent
prepared in example 4.
[0032] Fig. 6 is the DSC curve diagram of the phase change cold storage agent
prepared in example 5.
[0033] Fig. 7 is the T-t curve of the phase change cold storage agent prepared in
example 5.
[0034] The present invention will be further described below in conjunction with specific embodiments. The following are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto.
[0035] Zinc oxide
[00361 Example 1
[0037] In this example, sorbitol was prepared into aqueous solutions with
corresponding concentration gradients respectively, which were prepared for immediate use,
and the phase change temperature and latent heat of each solution were measured by the DSC
method.
[0038] The specific steps were as follows:
[0039] A. sorbitol was formulated into an aqueous solution according to the following concentration gradient:
[0040] sorbitol: 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.4 mol/L;
[0041] B. the phase change temperature and latent heat of each solution were
measured by the DSC method.
[0042] The results were shown in Fig. 1. The phase change temperature of the sorbitol
aqueous solution remained between -3.7 and -3.5°C with the increase in concentration, which
was relatively stable and was a better monomer cold storage material for compound phase
change cold storage agents.
[0043] As shown in Fig. 2, the latent heat of the sorbitol aqueous solution was above
270J/g with the increase in concentration, which met the requirements of the main cold
storage substance selected as the phase change cold storage agent.
[0044] Therefore, sorbitol was selected as the main cold storage substance of the
phase change cold storage agent, but it could not be used alone. Its phase change temperature
did not meet the requirements of -1~1°C in this patent, and its latent heat need to be further
increased to above 280J/ g, therefore it was chosen to compound with other substances.
[0045] Example 2
[0046] The sorbitol selected according to example 1 was used as the main cold
storage material, and 0.05mol/L sorbitol (mass percentage was 1.72%) aqueous solution with
the largest latent heat (289.24J/g), nanoparticles (nano zinc oxide, the mass percentage was
0.01%) and sodium carboxymethyl cellulose (mass percentage was 0.10%) were compounded.
The phase change temperature and latent heat of the compound solution were measured by
the DSC method.
[00471 Wherein the steps of compounding sorbitol, nano zinc oxide and sodium carboxymethyl cellulose were as follows:
[00481 A. at room temperature, adding the sorbitol and sodium carboxymethyl cellulose to deionized water according to the concentration requirements, mixing and stirring
well to obtain a clear solution I;
[0049] B. adding the weighed nano zinc oxide to the solution I according to the mass
percentage (0.01%), and stirring to make it evenly dispersed to obtain the required compound
solution, namely solution II;
[0050] C. the phase change temperature and the latent heat of the compound solution
obtained in step B were measured by the DSC method.
[0051] As shown in Fig. 3, the phase change temperature of the obtained compound solution was 0.56°C, and the latent heat was 271.11 J/g.
[0052] In addition, judging from the state of the cold storage agent compound solution, the compound solution added with 0.50% super absorbent resin (by mass percentage)
was evenly dispersed and had enhanced its gel properties.
[0053] Example 3
[0054] The sorbitol selected according to example 1 was used as the main cold
storage material, and sorbitol (mass percentage was 1.72%) aqueous solution, nanoparticles
(nano zinc oxide, the mass percentage was 0.03%) and sodium carboxymethyl cellulose
(mass percentage was 0.10%) were compounded. The phase change temperature and latent
heat of the compound solution were measured by the DSC method.
[0055] The steps of compounding sorbitol, nano zinc oxide and sodium
carboxymethyl cellulose were as follows:
[0056] A. at room temperature, adding the sorbitol and sodium carboxymethyl
cellulose to deionized water according to the concentration requirements, mixing and stirring
well to obtain a clear solution I;
[00571 B. adding the weighed nano zinc oxide to the solution I according to the mass
percentage (0.03%), and stirring to make it evenly dispersed to obtain the required compound solution, namely solution II;
[00581 C. the phase change temperature and the latent heat of the compound solution obtained in step B were measured by the DSC method.
[0059] As shown in Fig. 4, the phase change temperature of the obtained compound solution was 0.46°C, and the latent heat was 292.45J/g.
[0060] In addition, judging from the state of the cold storage agent compound solution, the compound solution added with 0.50% super absorbent resin (by mass percentage)
was evenly dispersed and had enhanced its gel properties.
[0061] Example 4
[0062] The sorbitol selected according to example 1 was used as the main cold
storage material, and sorbitol (mass percentage was 1.72%) aqueous solution, nanoparticles
(nano zinc oxide, the mass percentage was 0.05%) and sodium carboxymethyl cellulose
(mass percentage was 0.10%) were compounded. The phase change temperature and latent
heat of the compound solution were measured by the DSC method.
[0063] The steps of compounding sorbitol, nano zinc oxide and sodium
carboxymethyl cellulose were as follows:
[0064] A. at room temperature, adding the sorbitol and sodium carboxymethyl cellulose to deionized water according to the concentration requirements, mixing and stirring
well to obtain a clear solution I;
[0065] B. adding the weighed nano zinc oxide to the solution I according to the mass
percentage (0.05%), and stirring to make it evenly dispersed to obtain the required compound
solution;
[0066] C. the phase change temperature and the latent heat of the compound solution
obtained in step B were measured by the DSC method.
[00671 As shown in Fig. 5, the phase change temperature of the obtained compound solution was 0.04637°C, and the latent heat was 296.56J/g.
[0068] In addition, judging from the state of the cold storage agent compound solution, the compound solution added with 0.50% super absorbent resin (by mass percentage)
was evenly dispersed and had enhanced its gel properties.
[0069] Example 5
[00701 The phase change temperature and the latent heat of the compound solution in example 4 met the expected requirements, and compared to examples 2 and 3, its phase
change temperature was lower and the latent heat of phase change was higher. However, it
was still water-like and had poor gel properties, which may cause leakage of melted water
and phase separation during transportation.
[00711 In order to improve the state of the cold storage agent, 0.50% (by mass percentage) super absorbent resin was added to the compound solution of example 4 for
compounding to prepare a phase change cold storage agent.
[0072] This kind of phase change cold storage agent consisted the following component ratios:
sorbitol 1.72% (by mass percentage),
nano zinc oxide 0.05% (by mass percentage),
sodium carboxymethyl cellulose 0.10% (by mass percentage),
super absorbent resin 0.50% (by mass percentage),
[0073] and the rest was deionized water.
[0074] The method for preparing the phase change cold storage agent, comprising the
following steps:
[00751 A. at room temperature, adding the sorbitol and sodium carboxymethyl
cellulose to deionized water, mixing and stirring well to obtain a clear solution;
[0076] B. adding the weighed nano zinc oxide to the solution obtained in step A
according to the mass percentage, and stirring to make it evenly dispersed;
[00771 C. Adding the weighed super absorbent resin to the liquid obtained in step B
according to the mass percentage, and stirring to make it evenly dispersed to obtain the phase
change cold storage agent.
[0078] As shown in Fig. 6, the phase change temperature of the phase change cold
storage agent was 0.11°C, and the latent heat was 299.61J/g. Its phase change temperature
met the phase change temperature range (-1 1°C) of the cold storage agent to be developed,
and the latent heat also exceeded 280J/g. And its dispersion was uniform, and the gel state
was good, therefore it met the requirements of the phase change cold storage agent to be
developed.
[00791 The following tested the supercooling, phase separation and the changes in phase change temperature and latent heat after repeated freezing and thawing.
[0080] The method for testing the supercooling was as follows: 150mL of the cold storage agent formula was put into a 400 mL beaker, which was put in the refrigerator at
-20°C. The probe of the thermal resistance thermometer was fixed at the center of the solution,
and the temperature was measured and recorded every 1 minute to obtain the
temperature-time (T-t) curve of the cold storage agent.
[0081] Fig. 7 was the T-t curve of this example. It could be seen from the figure that
the cold storage agent of this example had no supercooling, and a phase change temperature
of 0.10°C, which was in good agreement with the result measured by DSC.
[0082] The method for testing the phase separation and phase change temperature and
latent heat curve after repeated freezing and thawing was as follows: 150 mL of the cold
storage agent formula was put into a 400 mL beaker which was put in the refrigerator at
-20°C. Repeated freezing and thawing (every 7 days) were performed to observe whether
there was a phase separation, and the melted cold storage agent was tested by DSC to
determine the phase change temperature and latent heat after repeated freezing and thawing.
[0083] After repeated freezing and thawing, it was observed that the phase change
cold storage agent of this example had no phase separation, and had good gel properties and
good dispersion uniformity.
[0084] Table 1 Changes in phase change temperature and latent heat over time in
example 3 of the present invention after repeated freezing and thawing
Time (d) Phase change temperature (C) Latent heat (J/g) 0 0.11 299.61 7 0.14 298.48
14 0.13 294.77
21 0.11 291.35
28 0.12 289.12
[0085] It could be seen from Table 1 that the phase change temperature after repeated
freezing and thawing only showed a slight change, and could basically maintain stability; the
latent heat after repeated freezing and thawing only showed a slight change, and could be stable greater than 280J/g. It could be seen that the cold storage agent of this example had the characteristics that the latent heat after repeated freezing and thawing cycles did not change significantly, and it could always remain in a higher range for a long time.
Time (d) Phase change temperature (C) Latent heat (J/g) 0 0.11 299.61 7 0.14 298.48
14 0.13 294.77
21 0.11 291.35
28 0.12 289.12
Claims (8)
1. A phase change cold storage agent for shiitake mushroom preservation, consisting of the
following components by mass percentage:
sorbitol 1.38~2.07%;
nano zinc oxide 0.03~0.06%;
sodium carboxymethyl cellulose 0.09~0.11%;
super absorbent resin 0.40~0.60%;
and the rest being deionized water.
2. The phase change cold storage agent for shiitake mushroom preservation according to
claim 1, consisting of the following components by mass percentage:
sorbitol 1.55~1.89%;
nano zinc oxide 0.04~0.055%;
sodium carboxymethyl cellulose 0.095~0.105%;
super absorbent resin 0.45~0.55%;
and the rest being deionized water.
3. The phase change cold storage agent for shiitake mushroom preservation according to
claim 1, consisting of the following components by mass percentage:
sorbitol 1.72%;
nano zinc oxide 0.05%;
sodium carboxymethyl cellulose 0.10%;
super absorbent resin 0.50%;
and the rest being deionized water.
4. The phase change cold storage agent for shiitake mushroom preservation according to
claim 1, wherein a particle size of the nano zinc oxide is 10~50 nm.
5. The phase change cold storage agent for shiitake mushroom preservation according to
claim 1, wherein a viscosity of the sodium carboxymethyl cellulose is 800~1200 mpa.s.
6. The phase change cold storage agent for shiitake mushroom preservation according to any
one of claims 1~5, wherein a phase change temperature of the phase change cold storage
agentis0.1~1° C, and latent heat is 280.30~300.00 J/g.
7. A method for preparing the phase change cold storage agent for shiitake mushroom preservation according to any one of claims 1~5, comprising the following steps:
(1) adding sorbitol and sodium carboxymethyl cellulose to deionized water and mixing well
to obtain solution I;
(2) adding nano zinc oxide to the solution I and mixing well to obtain solution II;
(3) adding super absorbent resin to the solution II and mixing well to obtain the phase change
cold storage agent.
8.The method for preparing the phase change cold storage agent according to claim 7,
wherein in steps (1) to (3), a mixing temperature is 20~25° C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386347A (en) * | 2022-08-25 | 2022-11-25 | 昆山徽虎冰袋有限公司 | Quick-matching gel type high enthalpy phase change cold storage agent suitable for temperature below 0 DEG C |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115386347A (en) * | 2022-08-25 | 2022-11-25 | 昆山徽虎冰袋有限公司 | Quick-matching gel type high enthalpy phase change cold storage agent suitable for temperature below 0 DEG C |
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