CN110129007A - A kind of efficient stable cold-storage material - Google Patents
A kind of efficient stable cold-storage material Download PDFInfo
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- CN110129007A CN110129007A CN201910416400.3A CN201910416400A CN110129007A CN 110129007 A CN110129007 A CN 110129007A CN 201910416400 A CN201910416400 A CN 201910416400A CN 110129007 A CN110129007 A CN 110129007A
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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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- 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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- 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
- Y02E70/00—Other energy conversion or management systems reducing GHG emissions
- Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
Abstract
The invention discloses a kind of efficient stable cold-storage materials, belong to refrigeration technology field.The watermelon juice that the present invention is added during fermentation material processed contains a large amount of carbohydrate, protein and various microelements and amino acid, add citric acid, yeast extract etc., improve the efficiency of synthesis bacteria cellulose, improve its mechanical performance, the compatibility between each component is improved, the loss for preventing moisture and cooling capacity is facilitated；The present invention is using sodium carboxymethylcellulose, acrylic acid, 2- acrylamide-2-methyl propane sulfonic as raw material, the stability of this cold-storage material system can be improved with the big quaternary carbon of steric hindrance and sulfonic acid group, it improves and stores up cold effect, the sour component containing sulfhydryl amino contained in the mercaptoethanol and albumen of addition, so that system is with the characteristics of not changing ice, it is not easy to melt under room temperature, the low temperature environment in itself and peripheral extent can be kept in the long period.The present invention solves the problems, such as to commonly use Macromolecule coolant cold accumulation effects at present and stability is bad.
Description
Technical field
The invention belongs to refrigeration technology fields, and in particular to a kind of efficient stable cold-storage material.
Background technique
Requirement with people to food genuineness is higher and higher, long-distance between a large amount of fresh foods and native article strange land
Transport and small mount, multi items, multifrequency degree, the commodity distribution of short time require increasingly to increase, thus, in recent years, cold chain
In Refrigerated Transport technology be developed rapidly.
Refrigerated Transport is broadly divided into mechanical cold storage system transport and cold insulation transports two major classes.If being able to achieve long-distance transportation,
The cost of the latter will be significantly lower than the former, but its core technology is to provide cold insulation time long cold-storage material.There are many kinds of cold-storage materials
Class, such as: water, inorganic salt solution, organic matter, high molecular material and compound.
Cool Storage Technology is that cooling capacity is stored in cold-storage material using effective means such as various physics, chemistry, machinery, when needing
The process that the cooling capacity of storage is released again.Cooling capacity and various objects can efficiently be stored by being produced by the technology
It manages, this substance of chemical requirements is referred to as cold-storage material.
Cold-storage material be it is a kind of by it is organic or (and) translucent (or opaque) for form of inorganic compound, sticky gluey mix
Object is closed, can absorb at low temperature and store a large amount of cooling capacity, and a large amount of cooling capacity can be released when temperature is higher, the long period keeps
The low temperature environment of itself and surrounding a small range.
Energy storage material can be divided into three classes by energy storage mode: sensible heat formula, latent heat formula and hot type partly latent, and sensible heat type energy storage material exists
While energy storage, it is unable to control environment temperature, and energy storage density is lower, device volume is larger, therefore application value is not high.Half
Hidden heat energy storage is to carry out absorbing and releasing for heat using reversible reaction, and energy storage density is larger, but technology is complicated and operates
Property is not strong, is only taken seriously at present in field of solar energy, still farther out from practical application.Hidden heat energy storage is to utilize material in phase transformation
It absorbs or heat release comes energy storage or release, not only energy density is higher for this material, and device is simple, small in size etc., Er Qiecai
Expect approximately constant temperature, the temperature of control system can be carried out with this.Therefore latent heat of phase change stored energy application is relatively broad.
Phase change cold-storage is that state of matter is changed (phase using various effective means (physics, chemistry, machinery etc.)
Become).When the thermal efficiency that generates store, the process released again when needing.The latent heat of substance is that substance carries out phase
Heat of vaporization, heat of fusion and the heat of sublimation absorbed when change, latent heat of phase change is big more than sensible heat and temperature change is small, and energy storage density is big；Phase
Become cool storage material be can be stored using the phase transformation of the material with released cold quantity and realize the material of energy space-time conversion.Cold-storage skill
Art is the charge characteristics using certain cool storage materials (cold-storage material), stores cold energy and is subject to a kind of practical energy storage skill of reasonable employment
Art.Cold-storage material is to produce efficiently store cooling capacity and various physics, chemical requirements by phase change cold-storage technology
Extraordinary substance；Main energy storage agent is to determine the main component of cold-storage material cold-storage ability, screens the stronger main energy storage agent of cold-storage ability
It is particularly important.
In existing cold-storage material technology, generally all largely using ammonium nitrate, ammonium chloride, sodium chloride, calcium chloride, urea,
The raw materials such as sodium carbonate, sodium sulphate, sodium nitrate add water to be cold-storage material, its advantage is that cold-storage speed is fast, shortcoming is the presence of analysis ice
Phenomenon, cold-storage go out that effect is not satisfactory, and cool-storage time is relatively short, application field is single, not environmentally the deficiencies of, need to research and develop one
Kind new and effective stable cold-storage material, have many advantages, such as suitable phase transition temperature, biggish latent heat of phase change, performance it is stable,.
Summary of the invention
The technical problems to be solved by the invention: not for common efficient stable cold-storage material cold accumulation effects and stability at present
Good problem provides a kind of efficient stable cold-storage material.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of efficient stable cold-storage material, including following component: 3 ~ 7 parts of hyaluronic acids, 2 ~ 5 parts of polyacrylamides, 3 ~ 7 parts of boraxs, 1
~ 4 parts of sodium tetraborates, 15 ~ 30 parts of water, further includes: 12 ~ 20 parts of cold-storage adjuvants, 25 ~ 45 parts of cold-storage base-materials.
The preparation method of the cold-storage adjuvant, includes the following steps:
(1) according to the mass fraction, 5 ~ 8 parts of banana skins, 20 ~ 40 parts of watermelon juices, 3 ~ 5 parts of peptones, 1 ~ 4 part of disodium hydrogen phosphate, 1 are taken
~ 4 parts of potassium dihydrogen phosphates, 1 ~ 4 part of citric acid, 4 ~ 7 parts of yeast extracts, 3 ~ 6 parts of lactobacillus bulgaricus, 800 ~ 1000 parts of water mixing,
It in 25 ~ 32 DEG C of concussion shaker fermentations, discharges, sterilizing obtains fermentation material, in 70 ~ 85 DEG C, takes fermentation material 14 ~ 25:3:1 in mass ratio
Alginic acid, additive mixing is added, vacuum concentration obtains concentrate, takes concentrate 1:20 in mass ratio ~ 30 that reagent A is added
It impregnates, filters out soak in freeze-drying, obtain lyophilized products；
(2) it in 45 ~ 55 DEG C, takes carbomer 1:15 in mass ratio ~ 25 that water is added and is mixed, stand, obtain standing liquid, take standing liquid
Auxiliary material, lyophilized products, premix mixing is added in 18 ~ 25:1:1:4 in mass ratio, obtains mixture, mixture is taken to be concentrated into perseverance
Weight is to get cold-storage adjuvant.
Additive in the step (1): taking pyrroles 1:3 in mass ratio ~ 6 that aniline mixing is added, be passed through nitrogen protection, in
35 ~ 45 DEG C, stirring, concentrated by rotary evaporation is to get additive.
Reagent A in the step (1): 7 ~ 10:3:30 ~ 50 take beta -mercaptoethanol, glycerol, water mixing in mass ratio, i.e.,
Obtain reagent A.
Auxiliary material in the step (2): 3 ~ 6:0.1 in mass ratio takes polyvinylpyrrolidone, dopamine mixing to get auxiliary
Material.
Premix in the step (2): 4:1:25 ~ 45 take sodium carboxymethylcellulose, diatomite, water mixing in mass ratio
Stirring is to get premix.
The preparation method of the cold-storage base-material, includes the following steps:
S1. it in 30 ~ 45 DEG C, takes acrylic acid 1:4 in mass ratio ~ 8 that NaOH solution is added and is mixed, lead to nitrogen protection, be added third
The N of the 2- acrylamide-2-methylpro panesulfonic acid of olefin(e) acid quality 30 ~ 50%, acrylic acid quality 20 ~ 45%, N- methylene bisacrylamide
Amide mixing is warming up to 55 ~ 70 DEG C, and stirring obtains mixed liquor, takes mixed liquor that the initiation of mixed liquor quality 2 ~ 5% is added
Agent, the pre-treating fly ash mixing of mixed liquor quality 6 ~ 10%, keep the temperature, discharging obtains resin binder；
S2. resin binder, dehydrated alcohol mixing are taken for 1:30 ~ 55 in mass ratio, ultrasonic alcohol washes, then the resin binder after alcohol is washed
Water mixing, ultrasound washing is added for 1:30 ~ 50 in mass ratio, then the 1:15 in mass ratio ~ 25 of the resin binder after washing is added
Reagent B mixing is impregnated, and alkali leaching substrate is obtained, and is taken alkali leaching substrate washing, is freeze-dried to get cold-storage base-material.
Initiator in the step S1: sodium peroxydisulfate, potassium peroxydisulfate, any one in ammonium persulfate.
Pre-treating fly ash in the step S1: it takes flyash 1:15 in mass ratio ~ 25 that hydrochloric acid solution mixing is added and stirs
It mixes, filters, filter residue is taken to be washed with water, be heat-treated, it is cooling, it must be heat-treated material, take heat treatment material 7 ~ 12:3 in mass ratio that peach gum is added
Mixed grinding is to get pre-treating fly ash.
Reagent B: 12 ~ 20:1 in mass ratio in the step S2 takes potassium hydroxide solution, sodium carbonate mixing to get reagent
B。
The present invention is compared with other methods, and advantageous effects are:
(1) watermelon juice that the present invention is added during fermentation material processed contains a large amount of carbohydrate, protein and various micro members
Element and amino acid, addition citric acid, yeast extract etc., stimulation produces the growth activity of CELLULOLYTIC BACTERIUM, improves synthesis bacteria cellulose
Efficiency, then mixed with alginic acid, the regular arrangement of the biology cellulose macromolecular chain advantageously formed, so that its crystallization occurs
Variation, the composite membrane tensile strength that two components are formed become larger, and improve its mechanical performance, biology cellulose and alginic acid macromolecular it
Between hydrogen bond action so that macromolecular arrangement is closer, hydrophilic radical and hydrone form hydrogen bond and keep strand generation netted
Structure, the resin component being detained in cold-storage base-material retain moisture, and the hyaluronic acid of addition can provide better water imbibition, and be very
Good transmission carrier improves the compatibility between each component, so that cold-storage ingredient surface mesh has hyaluronic acid covering, fiber surface
There is hyaluronic acid coated again, is bonded between fiber by hyaluronic acid, facilitate the loss for preventing moisture and cooling capacity, it can be into one
Improve cold accumulation effects and its stability of the invention in step ground；
(2) for the present invention using sodium carboxymethylcellulose, acrylic acid, 2- acrylamide-2-methyl propane sulfonic as raw material, diatomite is nothing
Machine additive is prepared for diatomite/sodium carboxymethylcellulose organic and inorganic high hydroscopic resin using water solution polymerization process, wherein
A large amount of-OH is contained on diatomite surface, can form hydrogen bond with-the OH ,-COOH of Polymer Surface and be conducive to water-absorbing-retaining, and
Be capable of forming multiple crosslinking points so that crosslink density becomes larger, in addition, present invention introduces sulfonic acid group ionization property be better than carboxyl,
Ionizable Hydrophilic ionic number increases in high polymer, and osmotic pressure becomes larger inside and outside resin, and water absorption rate rises, and the season big with steric hindrance
The stability of this cold-storage material system can be improved in carbon and sulfonic acid group, and the carbomer of addition is compounded with poloxamer, can reinforce bacterium
The effect that is coupled of fibre composition and high polymer during adequately expanded in water, can constitute crosslinking body structure with borax,
It improves and stores up cold effect, the sour component containing sulfhydryl amino contained in the mercaptoethanol and albumen of addition, so that system, which has, does not change ice
The characteristics of, it is not easy to melt under room temperature, the low temperature environment in itself and peripheral extent can be kept in the long period, and combinable
Water conservation network is absorbed, the loss of cooling capacity is prevented, further, it is possible to further increase the cold accumulation effects and stability of this system, this hair
The control of bright made efficient stable cold-storage material, the promotion to cold accumulation effects, stability has good castering action, has fine
Application prospect.
Specific embodiment
Additive: taking pyrroles 1:3 in mass ratio ~ 6 that aniline mixing is added, be passed through nitrogen protection, in 35 ~ 45 DEG C, with 500 ~
800r/min 2 ~ 4h of magnetic agitation, moves to Rotary Evaporators, in 60 ~ 75 DEG C of concentrated by rotary evaporations to original volume 25 ~ 40% to get adding
Add agent.
Auxiliary material: 3 ~ 6:0.1 in mass ratio takes polyvinylpyrrolidone, dopamine mixing to get auxiliary material.
Pre-treating fly ash: it takes flyash 1:15 in mass ratio ~ 25 that the hydrochloric acid solution mixing that mass fraction is 15% is added and stirs
30 ~ 55min is mixed, is filtered, after taking filter residue to be washed with water 2 ~ 4 times, moves to Muffle furnace with 500 ~ 700 DEG C of heat treatment 1 ~ 3h, it is cold with furnace
But to room temperature, it must be heat-treated material, take heat treatment material 7 ~ 12:3 in mass ratio that peach gum is added and mixed in mortar, with 350 ~ 550r/min
1 ~ 3h is ground to get pre-treating fly ash.
Premix: 4:1:25 ~ 45 take sodium carboxymethylcellulose, diatomite, water mixing in mass ratio, with 500 ~ 800r/min
35 ~ 60min of magnetic agitation is to get premix.
Initiator: sodium peroxydisulfate, potassium peroxydisulfate, any one in ammonium persulfate.
Reagent A: 7 ~ 10:3:30 ~ 50 take beta -mercaptoethanol, glycerol, water mixing to get reagent A in mass ratio.
Reagent B: 12 ~ 20:1 in mass ratio takes the potassium hydroxide solution that mass fraction is 12%, sodium carbonate to mix to get examination
Agent B.
The preparation method of cold-storage adjuvant, includes the following steps:
(1) according to the mass fraction, 5 ~ 8 parts of banana skins, 20 ~ 40 parts of watermelon juices, 3 ~ 5 parts of peptones, 1 ~ 4 part of disodium hydrogen phosphate, 1 are taken
~ 4 parts of potassium dihydrogen phosphates, 1 ~ 4 part of citric acid, 4 ~ 7 parts of yeast extracts, 3 ~ 6 parts of lactobacillus bulgaricus, 800 ~ 1000 parts of water mixing,
In 25 ~ 32 DEG C with 200 ~ 230r/min concussion shaker fermentation 3 ~ 5 days, discharging, 12 ~ 18min of insulated sterilizing at 121 DEG C must be sent out
Ferment material takes fermentation material 14 ~ 25:3:1 in mass ratio that alginic acid, additive mixing is added, in 70 ~ 85 DEG C with 500 ~ 800r/min
2 ~ 5h of magnetic agitation is concentrated in vacuo to the 25 ~ 45% of original volume in 45 ~ 60 DEG C, obtains concentrate, take concentrate 1:20 in mass ratio ~
30 are dipped in reagent A and are standing and soaking 1 ~ 3h, filter out soak in the dry 4 ~ 8h of -40 DEG C of freeze driers, obtain lyophilized products；
(2) in 45 ~ 55 DEG C, take carbomer 1:15 in mass ratio ~ 25 that water mixing is added, with 500 ~ 900r/min magnetic agitation, 1 ~ 3h
Afterwards, in 25 ~ 35 DEG C of 15 ~ 18h of standing, standing liquid is obtained, is taken and is stood liquid 18 ~ 25:1:1:4 in mass ratio auxiliary material, lyophilized products, pre- is added
Mixing mixing, with 500 ~ 800r/min, 40 ~ 60min of magnetic agitation, obtains mixture, takes mixture to vacuumize and be concentrated into constant weight, i.e.,
Obtain cold-storage adjuvant.
The preparation method of cold-storage base-material, includes the following steps:
S1. it in 30 ~ 45 DEG C, takes acrylic acid 1:4 in mass ratio ~ 8 that the NaOH solution that mass fraction is 10% is added and mixes, with 400 ~
After 30 ~ 55min of 700r/min magnetic agitation, lead to nitrogen protection, the 2- acrylamido -2- first of acrylic acid quality 30 ~ 50% is added
The mixing of the N of base propane sulfonic acid, acrylic acid quality 20 ~ 45%, N- methylene-bisacrylamide, is warming up to 55 ~ 70 DEG C, with 700 ~
1000r/min 30 ~ 55min of magnetic agitation, obtains mixed liquor, take mixed liquor be added mixed liquor quality 2 ~ 5% initiator,
The pre-treating fly ash of mixed liquor quality 6 ~ 10% is uniformly mixed, and keeps the temperature 3 ~ 5h, and discharging obtains resin binder；
S2. resin binder, dehydrated alcohol mixing is taken to surpass under the conditions of supersonic frequency is 45 ~ 55kHz for 1:30 ~ 55 in mass ratio
Sound alcohol washes 25 ~ 40min, then the resin binder after alcohol is washed is that water mixing is added in 1:30 ~ 50 in mass ratio, in 55 ~ 65kHz ultrasound
Under frequency condition, ultrasound 25 ~ 40min of washing, then reagent B is added in the 1:15 in mass ratio ~ 25 of the resin binder after washing and is mixed
Impregnate 2 ~ 4h, obtain alkali leaching substrate, after taking alkali leaching substrate to be washed with water 3 ~ 5 times, with the dry 4 ~ 8h of -40 DEG C of freeze driers to get
Cold-storage base-material.
A kind of efficient stable cold-storage material, according to the mass fraction, including following component: 3 ~ 7 parts of hyaluronic acids, 2 ~ 5 parts poly- third
Acrylamide, 3 ~ 7 parts of boraxs, 1 ~ 4 part of sodium tetraborate, 15 ~ 30 parts of water, 12 ~ 20 parts of cold-storage adjuvants, 25 ~ 45 parts of cold-storage base-materials.
A kind of preparation method of efficient stable cold-storage material, includes the following steps:
(1) according to the mass fraction, take 3 ~ 7 parts of hyaluronic acids, 2 ~ 5 parts of polyacrylamides, 3 ~ 7 parts of boraxs, 1 ~ 4 part of sodium tetraborate,
15 ~ 30 parts of water, 12 ~ 20 parts of cold-storage adjuvants, 25 ~ 45 parts of cold-storage base-materials；
(2) hyaluronic acid, polyacrylamide, water, cold-storage adjuvant in reaction kettle mix, with 400 ~ 700r/min magnetic agitation 35 ~
60min adds cold-storage base-material, borax, sodium tetraborate, with 600 ~ 1000r/min, 1 ~ 3h of magnetic agitation, obtains cold-storage material, takes storage
Cold burden cast reverse mould after, move to refrigerator, in 1 ~ 4 DEG C save 20 ~ for 24 hours to get efficient stable cold-storage material.
Embodiment 1
Additive: it takes pyrroles 1:3 in mass ratio that aniline mixing is added, is passed through nitrogen protection, in 35 DEG C, is stirred with 500r/min magnetic force
2h is mixed, Rotary Evaporators are moved to, in 60 DEG C of concentrated by rotary evaporations to original volume 25% to get additive.
Auxiliary material: 3:0.1 in mass ratio takes polyvinylpyrrolidone, dopamine mixing to get auxiliary material.
Pre-treating fly ash: it takes flyash 1:15 in mass ratio that the hydrochloric acid solution that mass fraction is 15% is added and is mixed
30min, filtering, after taking filter residue to be washed with water 2 times, moves to Muffle furnace with 500 DEG C of heat treatment 1h, cools to room temperature with the furnace, obtain hot
Processing material takes heat treatment material 7:3 in mass ratio that peach gum is added and mixes in mortar, with 350r/min grinding 1h to get pretreatment powder
Coal ash.
Premix: 4:1:25 in mass ratio takes sodium carboxymethylcellulose, diatomite, water mixing, is stirred with 500r/min magnetic force
35min is mixed to get premix.
Initiator: sodium peroxydisulfate.
Reagent A: 7:3:30 in mass ratio takes beta -mercaptoethanol, glycerol, water mixing to get reagent A.
Reagent B: 12:1 in mass ratio takes the potassium hydroxide solution that mass fraction is 12%, sodium carbonate to mix to get reagent B.
The preparation method of cold-storage adjuvant, includes the following steps:
(1) according to the mass fraction, 5 parts of banana skins, 20 parts of watermelon juices, 3 parts of peptones, 1 part of disodium hydrogen phosphate, 1 part of di(2-ethylhexyl)phosphate are taken
Hydrogen potassium, 1 part of citric acid, 4 parts of yeast extracts, 3 parts of lactobacillus bulgaricus, 800 parts of water mixing, are shaken in 25 DEG C with 200r/min concussion
Bed fermentation 3 days, discharging, insulated sterilizing 12min, obtains fermentation material at 121 DEG C, in 70 DEG C, takes fermentation material 14:3:1 in mass ratio
Alginic acid, additive mixing is added, with 500r/min magnetic agitation 2h, is concentrated in vacuo to the 25% of original volume in 45 DEG C, must be concentrated
Object takes concentrate 1:20 to be in mass ratio dipped in reagent A and is standing and soaking 1h, and it is dry in -40 DEG C of freeze driers to filter out soak
Dry 4h, obtains lyophilized products；
(2) in 45 DEG C, take carbomer 1:15 in mass ratio that water mixing is added, it is quiet in 25 DEG C after 500r/min magnetic agitation 1h
15h is set, standing liquid is obtained, takes and stands liquid 18:1:1:4 in mass ratio addition auxiliary material, lyophilized products, premix mixing, with 500r/min
Magnetic agitation 40min, obtains mixture, takes mixture to vacuumize and is concentrated into constant weight to get cold-storage adjuvant.
The preparation method of cold-storage base-material, includes the following steps:
S1. it in 30 DEG C, takes acrylic acid 1:4 in mass ratio that the NaOH solution that mass fraction is 10% is added and mixes, with 400r/min magnetic
After power stirs 30min, lead to nitrogen protection, 2- acrylamide-2-methylpro panesulfonic acid, the acrylic acid of acrylic acid quality 30% is added
The mixing of the N of quality 20%, N- methylene-bisacrylamide, is warming up to 55 DEG C, with 700r/min magnetic agitation 30min, obtains mixture
The pre-treating fly ash of liquid, the initiator, mixed liquor quality 6% that take mixed liquor addition mixed liquor quality 2% is uniformly mixed,
3h is kept the temperature, discharging obtains resin binder；
S2. resin binder, dehydrated alcohol mixing are taken for 1:30 in mass ratio, under the conditions of supersonic frequency is 45kHz, ultrasonic alcohol is washed
25min, then resin binder after alcohol is washed is that water mixing, under the conditions of 55kHz supersonic frequency, ultrasound is added in 1:30 in mass ratio
25min is washed, then the 1:15 in mass ratio of the resin binder after washing is added reagent B and mixed and impregnates 2h, alkali leaching substrate is obtained, takes alkali
After leaching substrate is washed with water 3 times, with the dry 4h of -40 DEG C of freeze driers to get cold-storage base-material.
A kind of efficient stable cold-storage material, according to the mass fraction, including following component: 3 parts of hyaluronic acids, 2 parts of polyacrylamides
Amine, 3 parts of boraxs, 1 part of sodium tetraborate, 15 parts of water, 12 parts of cold-storage adjuvants, 25 parts of cold-storage base-materials.
A kind of preparation method of efficient stable cold-storage material, includes the following steps:
(1) according to the mass fraction, 3 parts of hyaluronic acids, 2 parts of polyacrylamides, 3 parts of boraxs, 1 part of sodium tetraborate, 15 parts of water, 12 are taken
Part cold-storage adjuvant, 25 parts of cold-storage base-materials；
(2) hyaluronic acid, polyacrylamide, water, cold-storage adjuvant are mixed in reaction kettle, with 400r/min magnetic agitation 35min, then
Cold-storage base-material, borax, sodium tetraborate is added, cold-storage material is obtained with 600r/min magnetic agitation 1h, after taking cold-storage material casting reverse mould,
Refrigerator is moved to, in 1 DEG C of preservation 20h to get efficient stable cold-storage material.
Embodiment 2
Additive: it takes pyrroles 1:5 in mass ratio that aniline mixing is added, is passed through nitrogen protection, in 40 DEG C, is stirred with 700r/min magnetic force
3h is mixed, Rotary Evaporators are moved to, in 65 DEG C of concentrated by rotary evaporations to original volume 30% to get additive.
Auxiliary material: 5:0.1 in mass ratio takes polyvinylpyrrolidone, dopamine mixing to get auxiliary material.
Pre-treating fly ash: it takes flyash 1:20 in mass ratio that the hydrochloric acid solution that mass fraction is 15% is added and is mixed
45min, filtering, after taking filter residue to be washed with water 3 times, moves to Muffle furnace with 600 DEG C of heat treatment 2h, cools to room temperature with the furnace, obtain hot
Processing material takes heat treatment material 10:3 in mass ratio that peach gum is added and mixes in mortar, with 450r/min grinding 2h to get pretreatment powder
Coal ash.
Premix: 4:1:35 in mass ratio takes sodium carboxymethylcellulose, diatomite, water mixing, is stirred with 700r/min magnetic force
50min is mixed to get premix.
Initiator: potassium peroxydisulfate.
Reagent A: 8:3:40 in mass ratio takes beta -mercaptoethanol, glycerol, water mixing to get reagent A.
Reagent B: 18:1 in mass ratio takes the potassium hydroxide solution that mass fraction is 12%, sodium carbonate to mix to get reagent B.
The preparation method of cold-storage adjuvant, includes the following steps:
(1) according to the mass fraction, 7 parts of banana skins, 30 parts of watermelon juices, 4 parts of peptones, 3 parts of disodium hydrogen phosphates, 3 parts of di(2-ethylhexyl)phosphates are taken
Hydrogen potassium, 3 parts of citric acids, 6 parts of yeast extracts, 5 parts of lactobacillus bulgaricus, 900 parts of water mixing, are shaken in 30 DEG C with 210r/min concussion
Bed fermentation 4 days, discharging, insulated sterilizing 16min, obtains fermentation material at 121 DEG C, in 75 DEG C, takes fermentation material 20:3:1 in mass ratio
Alginic acid, additive mixing is added, with 700r/min magnetic agitation 4h, is concentrated in vacuo to the 35% of original volume in 50 DEG C, must be concentrated
Object takes concentrate 1:25 to be in mass ratio dipped in reagent A and is standing and soaking 2h, and it is dry in -40 DEG C of freeze driers to filter out soak
Dry 6h, obtains lyophilized products；
(2) in 50 DEG C, take carbomer 1:20 in mass ratio that water mixing is added, it is quiet in 30 DEG C after 700r/min magnetic agitation 2h
17h is set, standing liquid is obtained, takes and stands liquid 20:1:1:4 in mass ratio addition auxiliary material, lyophilized products, premix mixing, with 700r/min
Magnetic agitation 50min, obtains mixture, takes mixture to vacuumize and is concentrated into constant weight to get cold-storage adjuvant.
The preparation method of cold-storage base-material, includes the following steps:
S1. it in 35 DEG C, takes acrylic acid 1:6 in mass ratio that the NaOH solution that mass fraction is 10% is added and mixes, with 500r/min magnetic
After power stirs 45min, lead to nitrogen protection, 2- acrylamide-2-methylpro panesulfonic acid, the acrylic acid of acrylic acid quality 40% is added
The mixing of the N of quality 35%, N- methylene-bisacrylamide, is warming up to 60 DEG C, with 800r/min magnetic agitation 45min, obtains mixture
The pre-treating fly ash of liquid, the initiator, mixed liquor quality 8% that take mixed liquor addition mixed liquor quality 4% is uniformly mixed,
4h is kept the temperature, discharging obtains resin binder；
S2. resin binder, dehydrated alcohol mixing are taken for 1:45 in mass ratio, under the conditions of supersonic frequency is 50kHz, ultrasonic alcohol is washed
30min, then resin binder after alcohol is washed is that water mixing, under the conditions of 50kHz supersonic frequency, ultrasound is added in 1:40 in mass ratio
30min is washed, then the 1:20 in mass ratio of the resin binder after washing is added reagent B and mixed and impregnates 3h, alkali leaching substrate is obtained, takes alkali
After leaching substrate is washed with water 4 times, with the dry 6h of -40 DEG C of freeze driers to get cold-storage base-material.
A kind of efficient stable cold-storage material, according to the mass fraction, including following component: 5 parts of hyaluronic acids, 4 parts of polyacrylamides
Amine, 5 parts of boraxs, 3 parts of sodium tetraborates, 20 parts of water, 18 parts of cold-storage adjuvants, 30 parts of cold-storage base-materials.
A kind of preparation method of efficient stable cold-storage material, includes the following steps:
(1) according to the mass fraction, 5 parts of hyaluronic acids, parts of polyacrylamides, 5 parts of boraxs, parts of sodium tetraborates, 20 parts of water, 18 are taken
Part cold-storage adjuvant, 30 parts of cold-storage base-materials；
(2) hyaluronic acid, polyacrylamide, water, cold-storage adjuvant are mixed in reaction kettle, with 500r/min magnetic agitation 20min, then
Cold-storage base-material, borax, sodium tetraborate is added, cold-storage material is obtained with 700r/min magnetic agitation 2h, after taking cold-storage material casting reverse mould,
Refrigerator is moved to, in 2 DEG C of preservation 22h to get efficient stable cold-storage material.
Embodiment 3
Additive: it takes pyrroles 1:6 in mass ratio that aniline mixing is added, is passed through nitrogen protection, in 45 DEG C, is stirred with 800r/min magnetic force
4h is mixed, Rotary Evaporators are moved to, in 75 DEG C of concentrated by rotary evaporations to original volume 40% to get additive.
Auxiliary material: 6:0.1 in mass ratio takes polyvinylpyrrolidone, dopamine mixing to get auxiliary material.
Pre-treating fly ash: it takes flyash 1:25 in mass ratio that the hydrochloric acid solution that mass fraction is 15% is added and is mixed
55min, filtering, after taking filter residue to be washed with water 4 times, moves to Muffle furnace with 700 DEG C of heat treatment 3h, cools to room temperature with the furnace, obtain hot
Processing material takes heat treatment material 12:3 in mass ratio that peach gum is added and mixes in mortar, with 550r/min grinding 3h to get pretreatment powder
Coal ash.
Premix: 4:1:45 in mass ratio takes sodium carboxymethylcellulose, diatomite, water mixing, is stirred with 800r/min magnetic force
60min is mixed to get premix.
Initiator: ammonium persulfate.
Reagent A: 10:3:50 in mass ratio takes beta -mercaptoethanol, glycerol, water mixing to get reagent A.
Reagent B: 20:1 in mass ratio takes the potassium hydroxide solution that mass fraction is 12%, sodium carbonate to mix to get reagent B.
The preparation method of cold-storage adjuvant, includes the following steps:
(1) according to the mass fraction, 8 parts of banana skins, 40 parts of watermelon juices, 5 parts of peptones, 4 parts of disodium hydrogen phosphates, 4 parts of di(2-ethylhexyl)phosphates are taken
Hydrogen potassium, 4 parts of citric acids, 7 parts of yeast extracts, 6 parts of lactobacillus bulgaricus, 1000 parts of water mixing, are shaken in 32 DEG C with 230r/min
Shaker fermentation 5 days, discharging, insulated sterilizing 18min, obtained fermentation material at 121 DEG C, in 85 DEG C, took fermentation material 25:3 in mass ratio:
1 is added alginic acid, additive mixing, with 800r/min magnetic agitation 5h, is concentrated in vacuo to the 45% of original volume in 60 DEG C, obtains dense
Contracting object takes concentrate 1:30 to be in mass ratio dipped in reagent A and is standing and soaking 3h, filters out soak in -40 DEG C of freeze driers
Dry 8h, obtains lyophilized products；
(2) in 55 DEG C, take carbomer 1:25 in mass ratio that water mixing is added, it is quiet in 35 DEG C after 900r/min magnetic agitation 3h
18h is set, standing liquid is obtained, takes and stands liquid 25:1:1:4 in mass ratio addition auxiliary material, lyophilized products, premix mixing, with 800r/min
Magnetic agitation 60min, obtains mixture, takes mixture to vacuumize and is concentrated into constant weight to get cold-storage adjuvant.
The preparation method of cold-storage base-material, includes the following steps:
S1. it in 45 DEG C, takes acrylic acid 1:8 in mass ratio that the NaOH solution that mass fraction is 10% is added and mixes, with 700r/min magnetic
After power stirs 55min, lead to nitrogen protection, 2- acrylamide-2-methylpro panesulfonic acid, the acrylic acid of acrylic acid quality 50% is added
The mixing of the N of quality 45%, N- methylene-bisacrylamide, is warming up to 70 DEG C, with 1000r/min magnetic agitation 55min, must mix
Feed liquid takes mixed liquor that the initiator of mixed liquor quality 5% is added, the pre-treating fly ash of mixed liquor quality 10% mixes
It is even, 5h is kept the temperature, discharging obtains resin binder；
S2. resin binder, dehydrated alcohol mixing are taken for 1:55 in mass ratio, under the conditions of supersonic frequency is 55kHz, ultrasonic alcohol is washed
40min, then resin binder after alcohol is washed is that water mixing, under the conditions of 65kHz supersonic frequency, ultrasound is added in 1:50 in mass ratio
40min is washed, then the 1:25 in mass ratio of the resin binder after washing is added reagent B and mixed and impregnates 4h, alkali leaching substrate is obtained, takes alkali
After leaching substrate is washed with water 5 times, with the dry 8h of -40 DEG C of freeze driers to get cold-storage base-material.
A kind of efficient stable cold-storage material, according to the mass fraction, including following component: 7 parts of hyaluronic acids, 5 parts of polyacrylamides
Amine, 7 parts of boraxs, 4 parts of sodium tetraborates, 30 parts of water, 20 parts of cold-storage adjuvants, 45 parts of cold-storage base-materials.
A kind of preparation method of efficient stable cold-storage material, includes the following steps:
(1) according to the mass fraction, 7 parts of hyaluronic acids, 5 parts of polyacrylamides, 7 parts of boraxs, 4 parts of sodium tetraborates, 30 parts of water, 20 are taken
Part cold-storage adjuvant, 45 parts of cold-storage base-materials；
(2) hyaluronic acid, polyacrylamide, water, cold-storage adjuvant are mixed in reaction kettle, with 700r/min magnetic agitation 60min, then
Cold-storage base-material, borax, sodium tetraborate is added, cold-storage material is obtained with 1000r/min magnetic agitation 3h, after taking cold-storage material casting reverse mould,
Refrigerator is moved to, is saved in 4 DEG C for 24 hours to get efficient stable cold-storage material.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking cold-storage adjuvant.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking cold-storage base-material.
Comparative example 3: the efficient stable cold-storage material of Wuxi City company production.
Embodiment and comparative example are tested according to GB/T 22232-2008 standard, test result is as shown in table 1.
Table 1:
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Phase transition temperature (DEG C) | -36.5 | -34.3 | -35.6 | -32.7 | -31.6 | -20.5 |
| Latent heat of phase change (KJ/g) | 354 | 351 | 353 | 337 | 326 | 280 |
| Cold storage capacity attenuation rate/7d(%) | 1.5 | 2.7 | 1.9 | 5.7 | 6.1 | 13.9 |
In conclusion the phase transition temperature of efficient stable cold-storage material of the invention is low, latent heat of phase change is high, and cold accumulation effects are more preferably more steady
Fixed, the scope of application is wider.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of efficient stable cold-storage material, according to the mass fraction, including following component: 3 ~ 7 parts of hyaluronic acids, 2 ~ 5 parts of polypropylene
Amide, 3 ~ 7 parts of boraxs, 1 ~ 4 part of sodium tetraborate, 15 ~ 30 parts of water, which is characterized in that further include: 12 ~ 20 parts of cold-storage adjuvants, 25 ~
45 parts of cold-storage base-materials.
2. a kind of efficient stable cold-storage material according to claim 1, which is characterized in that the preparation method of the cold-storage adjuvant,
Include the following steps:
(1) according to the mass fraction, 5 ~ 8 parts of banana skins, 20 ~ 40 parts of watermelon juices, 3 ~ 5 parts of peptones, 1 ~ 4 part of disodium hydrogen phosphate, 1 are taken
~ 4 parts of potassium dihydrogen phosphates, 1 ~ 4 part of citric acid, 4 ~ 7 parts of yeast extracts, 3 ~ 6 parts of lactobacillus bulgaricus, 800 ~ 1000 parts of water mixing,
It in 25 ~ 32 DEG C of concussion shaker fermentations, discharges, sterilizing obtains fermentation material, in 70 ~ 85 DEG C, takes fermentation material 14 ~ 25:3:1 in mass ratio
Alginic acid, additive mixing is added, vacuum concentration obtains concentrate, takes concentrate 1:20 in mass ratio ~ 30 that reagent A is added
It impregnates, filters out soak in freeze-drying, obtain lyophilized products；
(2) it in 45 ~ 55 DEG C, takes carbomer 1:15 in mass ratio ~ 25 that water is added and is mixed, stand, obtain standing liquid, take standing liquid
Auxiliary material, lyophilized products, premix mixing is added in 18 ~ 25:1:1:4 in mass ratio, obtains mixture, mixture is taken to be concentrated into perseverance
Weight is to get cold-storage adjuvant.
3. a kind of efficient stable cold-storage material according to claim 2, which is characterized in that the additive in the step (1): take
Aniline mixing is added in pyrroles 1:3 in mass ratio ~ 6, is passed through nitrogen protection, and in 35 ~ 45 DEG C, stirring, concentrated by rotary evaporation is to get addition
Agent.
4. a kind of efficient stable cold-storage material according to claim 2, which is characterized in that the reagent A in the step (1): press
Mass ratio 7 ~ 10:3:30 ~ 50 take beta -mercaptoethanol, glycerol, water mixing to get reagent A.
5. a kind of efficient stable cold-storage material according to claim 2, which is characterized in that the auxiliary material in the step (2): pressing matter
Amount takes polyvinylpyrrolidone, dopamine mixing to get auxiliary material than 3 ~ 6:0.1.
6. a kind of efficient stable cold-storage material according to claim 2, which is characterized in that the premix in the step (2): press
Mass ratio 4:1:25 ~ 45 take sodium carboxymethylcellulose, diatomite, water to be mixed to get premix.
7. a kind of efficient stable cold-storage material according to claim 1, which is characterized in that the preparation method of the cold-storage base-material,
Include the following steps:
S1. it in 30 ~ 45 DEG C, takes acrylic acid 1:4 in mass ratio ~ 8 that NaOH solution is added and is mixed, lead to nitrogen protection, be added third
The N of the 2- acrylamide-2-methylpro panesulfonic acid of olefin(e) acid quality 30 ~ 50%, acrylic acid quality 20 ~ 45%, N- methylene bisacrylamide
Amide mixing is warming up to 55 ~ 70 DEG C, and stirring obtains mixed liquor, takes mixed liquor that the initiation of mixed liquor quality 2 ~ 5% is added
Agent, the pre-treating fly ash mixing of mixed liquor quality 6 ~ 10%, keep the temperature, discharging obtains resin binder；
S2. resin binder, dehydrated alcohol mixing are taken for 1:30 ~ 55 in mass ratio, ultrasonic alcohol washes, then the resin binder after alcohol is washed
Water mixing, ultrasound washing is added for 1:30 ~ 50 in mass ratio, then the 1:15 in mass ratio ~ 25 of the resin binder after washing is added
Reagent B mixing is impregnated, and alkali leaching substrate is obtained, and is taken alkali leaching substrate washing, is freeze-dried to get cold-storage base-material.
8. a kind of efficient stable cold-storage material according to claim 7, which is characterized in that the initiator in the step S1: mistake
Sodium sulphate, potassium peroxydisulfate, any one in ammonium persulfate.
9. a kind of efficient stable cold-storage material according to claim 7, which is characterized in that the pretreatment fine coal in the step S1
Ash: taking flyash 1:15 in mass ratio ~ 25 that hydrochloric acid solution is added and be mixed, and filtering takes filter residue to be washed with water, and is heat-treated, cooling,
It must be heat-treated material, take heat treatment material 7 ~ 12:3 in mass ratio that peach gum mixed grinding is added to get pre-treating fly ash.
10. a kind of efficient stable cold-storage material according to claim 7, which is characterized in that the reagent B in the step S2: press
12 ~ 20:1 of mass ratio takes potassium hydroxide solution, sodium carbonate mixing to get reagent B.
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