LU502456B1 - Preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel and application in thermal storage - Google Patents

Preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel and application in thermal storage Download PDF

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Publication number
LU502456B1
LU502456B1 LU502456A LU502456A LU502456B1 LU 502456 B1 LU502456 B1 LU 502456B1 LU 502456 A LU502456 A LU 502456A LU 502456 A LU502456 A LU 502456A LU 502456 B1 LU502456 B1 LU 502456B1
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Prior art keywords
chitin
phase change
change material
microporous carbon
aerogel
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LU502456A
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French (fr)
Inventor
Junchi Wang
Xiaobo Yan
Wenyao Guo
Lingbin Kong
Hui Li
Xiaomin Deng
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Univ Shandong Jianzhu
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/048—Elimination of a frozen liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A process is disclosed for preparation and application of shape stabilized phase change material via microporous carbon derived from chitin aerogel, belonging to the technical field of thermal storage. Chitin is the largest production next only to cellulose as a natural polysaccharide, it exhibits the characteristics of broad source and low cost. Chitin is dissolved in NaOH-urea solution, and then freeze-drying to obtain chitin aerogel in present invention. The microporous carbon is synthesized by the carbonization of chitin aerogel in a non-oxidizing atmosphere, which is used as support material of the shape stabilized phase change material. As for prepared shape stabilized phase change material could resolve the problems of low thermal conductivity and leakage during the thermal storage process.

Description

PREPARATION METHOD OF SHAPE STABILIZED PHASE CHANGE MATERIAL VIA MICROPOROUS CARBON DERIVED FROM CHITIN AEROGEL AND APPLICATION IN THERMAL STORAGE CROSS-REFERENCE TO RELATED APPLICATIONS
FIELD OF THE DISCLOSURE The invention relates to that the technical field of phase change thermal storage, which is specifically concerned with a preparation process of microporous carbon derived from chitin gel and application in phase change thermal storage.
BACKGROUND OF THE DISCLOSURE Thermal storage can be realized in large-scale applications from the angle of technology and economy. Thereinto, phase change thermal storage has received wide application prospects in solar energy, building material, and waste heat recovery due to its characteristics of high thermal storage density, superior stability and stable phase change temperature. Organic solid-liquid phase change material is one of the potential to be employed in thermal storage owing to its non-toxic, low supercooling degree, and no phase separation. Nevertheless, the practical application of organic PCM is severely restrained by poor thermal conductivity and leakage during the thermal storage process. Therefore, shape stabilized phase change material 1s recognized as an ideal thermal storage material in practical application.
As a natural renewable resource, chitin is generated about 10 billion tons in nature per annum, which is mainly found in crustacean shells, insects, and microorganisms (the shrimp and crab shells are contented with as high as 15%~30% of chitin). However, the inventor found that chitin exhibits the question of low load capacity and single application form in thermal storage.
SUMMARY OF THE DISCLOSURE To overcome the above shortcomings, chitin is used as a precursor, which is dissolved in the NaOH-urea solution, then the mixture is freeze-dried to obtain the chitin aerogel. Next, chitin aerogel is carbonized in a non-oxidizing atmosphere to synthesize microporous carbon with a high load capacity and low density.
To achieve the technical purpose, the invention adopts the following technical scheme: The first aspect of the present invention provides a shape stabilized phase change material via microporous carbon derived from chitin aerogel, which comprises: Support material, Support material is loaded by phase change material, Wherein, microporous carbon derived from chitin aerogel is used as support material.
The research of invention found that at present, chitin as abundant biomass in nature could prepare the chitin aerogel. Microporous carbon could be obtained by direct carbonized chitin aerogel, which is applied in the preparation of shape stabilized phase change material not only exhibiting a higher thermal storage density but also reducing the cost of production.
Compared with the traditional porous biochar, microporous carbon derived from chitin aerogel display the advantage of a favorable load capacity, low density, lightweight, and simple production. Therefore, microporous carbon is recognized desirable material using in building materials and environmental fields.
The second aspect of the present invention provides a method of preparing shape stabilized phase change material via microporous carbon derived from chitin aerogel, which comprises: Chitin is dissolved in the NaOH-urea solution, then the mixture is freeze-dried to obtain the chitin aerogel; Chitin aerogel is carbonized in a non-oxidizing atmosphere to synthesize microporous carbon, Microporous carbon derived from chitin is loaded by phase change material to prepare the shape stabilized phase change material.
The third aspect of the present invention provides the use of a shape stabilized phase change material as described above for the application of thermal storage.
The invention has the advantages that: (1) Chitin is an abundant polysaccharide in nature with the characteristics of broad source and eases carbonization; chitin aerogel could be prepared to shape stabilized phase change material with high thermal storage efficiency; microporous carbon derived from chitin aerogel shows the advantage of low cost and simple preparation process.
(2) The preparation method of the invention has the advantages of simple method, low cost, generality, and easy large-scale applications.
DETAILED DESCRIPTION In particular, the following detailed description is exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meanings as commonly understood by ordinary technicians in the technical field to which this invention belongs.
Noted that the terminology used here is only for describing specific embodiments, and is not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, when the terms "comprising" and/or "comprising" are used in this specification, they indicate the presence of features, steps, operations, devices, components and/or combinations.
A preparation process of shape stabilized phase change material via microporous carbon derived from chitin aerogel and application thereof in thermal storage comprises the following steps: (1) Chitin power is immersed in 2wt.%-10wt.% NaOH solution for 8h-12h. Next, chitin power it is treated by 5%(v/v)-10%(v/v) HCI solution for 8h-12h. Finally, chitin power is immersed in 1wt.%-2wt.% NaClO2 at 80°C for 4h-8h to obtain purified chitin.
(2) The 1wt.%-3wt.% purified chitin obtained in step (1) is dispersed into the NaOH-urea solution (the mass fraction of NaOH and urea are 6wt.%-12wt.% and 3wt.%-6wt.%, respectively), then the mixture 1s refrigerated at -25°C--40°C for two freezing-thawing cycles to prepare the chitin solution.
(3) The chitin solution obtained in step (2) is stirred by a homogenizer with 5000r/min-10000r/min to form a milky dispersion, next the milky dispersion is dialyzed and freeze-dried to achieve chitin aerogel.
(4) The chitin aerogel obtained in step (3) is heated from 20°C to 600°C-1200°C according to the linear heating rate of 1°C/min-50°C/min with the non-oxidizing atmosphere flow rate to be 100mL/min in tube furnace. Keeping the temperature for 1h-6h and then naturally cooling to room temperature to obtain the microporous carbon.
(5) The phase change material is completely melted at 90°C for 30min, and then microporous carbon obtained in step (4) is immersed into the melted phase change material (the mass ratio of phase change material: microporous carbon of 1:100-100:1) and stirred for 30min-240min. The generated mixture is treated in an ultrasonic field at 90°C for Smin-60min, and then it is cooled to room temperature. After that, the solidified mixture is smashed by a crusher.
(6) The melting process, ultrasonic treatment, cooling process, and crush in step (5) are repeated 2-10 cycles, then the acquired mixture is melted at 60°C-120°C and followed by vacuum infiltration (-0.01MPa --0.1MPa) for 4h-48h.
(7) The mixture obtained in step (6) is cooled at room temperature and smashed by a crusher to obtain the power of shape stabilized phase change material.
(8) The power obtained in step (7) is pressed into a tablet at 0 5MPa-30MPa for Smin to obtain the shape stabilized phase change material via microporous carbon derived from chitin aerogel.
In some embodiments, chitin is smashed by a crusher to obtain the chitin power.
In some embodiments, chitin power is immersed in NaOH, HCI, and NaClO» solution to remove impurities such as the protein, minerals and pigments.
In some embodiments, in step (2), the 1wt.%-3wt.% purified chitin obtained in step (1) is dispersed into the NaOH-urea solution (the mass fraction of NaOH and 5 urea are 6wt.%-12wt.% and 3wt.%-6wt.%, respectively), then the mixture is refrigerated at -25°C--40°C for two freezing-thawing cycles to prepare the chitin solution.
In some embodiments, in step (3), the chitin solution obtained in step (2) is stirred by homogenizer with 5000r/min -10000r/min to form a milky dispersion, next the milky dispersion is dialyzed and freeze-dried to achieve chitin aerogel.
In some embodiments, the phase change material is single or multiple organic matters and is not limited to the type and amount of phase change material.
In some embodiments, the phase change material is organic matter, including, without limitation stearic acid, polyethylene glycol, paraffin wax, et. al, to achieve the high thermal storage density of shape stabilized phase change material.
In some embodiments, chitin aerogel is carbonized in a tube furnace at 600°C-1200°C.
In some embodiments, the heating rate of a tube furnace is in the range of 1°C-50°C, the soaking time is in the range of 1h-6h.
The non-oxidizing atmosphere including, without limitation argon, nitrogen, helium, or krypton.
In some embodiments, the mass ratio between phase change material and microporous carbon is 1:100-100:1. In some embodiments, the stirring time is 30min-240min after immersing the microporous carbon.
The ultrasonic time of mixture is in the range of Smin -60min.
In some embodiments, the melting process, ultrasonic treatment, cooling process, and crush repeat 2-10 cycles.
In some embodiments, the vacuum infiltration including, both the phase change material and support material is mixed in a vacuum oven at 60°C-120°C, and then the pressure of vacuum oven 1s reduced to -0.01MPa--0.1MPa for 4h-48h.
In some embodiments, the power of shape stabilized phase change material 1s placed in a mold to process the desirable shape at a certain temperature and pressure.
In some embodiments, the temperature is in the range of 5°C-120°C, and the pressure is in the range of 0.5MPa -30MPa during the shaping process.
Then, the present invention will be further explained in detail with specific embodiment. It should be pointed out that the specific embodiment explains the present invention rather than limits it.
EMBODIMENT 1 The preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel includes the following steps: (1) Chitin power is immersed in Swt.% NaOH solution for 10h, and then, it is treated by 7%(v/v) HCI solution for 10h. Finally, chitin power is immersed in 1.7wt.% NaClO; at 80°C for 6h to obtain purified chitin.
(2) The 2wt.% purified chitin obtained in step (1) is dispersed into the NaOH-urea solution (the mass fraction of NaOH and urea are 8wt.% and 4wt.%, respectively), then the mixture is refrigerated at -30°C for two freezing-thawing cycles to prepare the chitin solution.
(3) The chitin solution obtained in step (2) is stirred by homogenizer with 10000r/min to form a milky dispersion, next milky dispersion is dialyzed and freeze-dried to achieve chitin aerogel.
(4) The chitin aerogel obtained in step (3) is heated from 20°C to 800°C according to the linear heating rate of 5°C/min with the non-oxidizing atmosphere flow rate to be 100mL/min in tube furnace. Keeping the temperature for 2h and then naturally cooling to room temperature to obtain the microporous carbon labeled as CNC.
(5) The phase change material is completely melted at 90°C for 30min, and then microporous carbon obtained in step (4) is immersed into the melted stearic acid (the mass ratio of stearic acid/CNC of 3:2) and stirred for 60min. The generated mixture is treated in an ultrasonic field at 90°C for 10min, and it is cooled to room temperature. After that, the solidified mixture is smashed by a crusher.
(6) The melting process, ultrasonic treatment, cooling process, and crush in step (5) are repeated 3 cycles, then the acquired mixture is melted at 90°C and followed by vacuum infiltration (-0.08MPa) for 6h.
(7) The mixture obtained in step (6) is cooled at room temperature and smashed by a crusher to obtain the power of shape stabilized phase change material.
(8) The power obtained in step (7) is pressed into a tablet at 10MPa for Smin to obtain the shape stabilized phase change material via microporous carbon derived from chitin aerogel labeled as CNC-SA.
The shape stabilized phase change material obtained in embodiment 1 is used in thermal storage, the corresponded thermal storage performance is shown in Table 1. Table 1 Thermal storage performance of shape stabilized phase change material Melting Freezing Melting Freezing Thermal Embodiment sample temperature temperature enthalpy enthalpy Storage CC) CC) we ap no (%0) 1 CNC-SA 66.86 70.85 112.90 113.25 85.34 Ultimately, it should be noted that the above description is only the preferred embodiment of the present invention, and is not used to limit the present invention. Although the present invention has been described in detail with the foregoing embodiments, those in the field can still modify the technical solutions described in the foregoing embodiments, or replace some of them equivalently. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of protection of the present invention. Although the specific embodiments of the present invention have been described above, it is not a limitation on the scope of protection of the present invention. Therefore, the technicians in the field should understand: On the basis of the technical scheme of the invention, various modifications or deformations that can be made by technicians in the field without creative labor are still within the scope of protection of the invention.

Claims (8)

WHAT IS CLAIMED IS:
1. A preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel, characterized by comprising: support material; support material is loaded by phase change material; wherein, microporous carbon derived from chitin aerogel is used as support material.
2. The preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel according to claim 1, characterized in that the microporous carbon derived from chitin aerogel is obtained by directly carbonized chitin aerogel, especially, chitin derivatives (chitosan and chitosan oligosaccharide) could be used to replace chitin.
3. The preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel according to claim 1, the phase change material is organic matter, including, without limitation stearic acid, polyethylene glycol, paraffin wax.
4. The preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel according to claim 1, the mass ratio between phase change material and microporous carbon is 1:100-100:1.
5. A preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel, characterized by comprising: chitin is dissolved in the NaOH-urea solution, which is freeze-dried to obtain the chitin aerogel, then carbonized in a non-oxidizing atmosphere to synthesize microporous carbon.
microporous carbon derived from chitin aerogel is loaded by phase change material to achieve shape stabilized phase change material.
6. The preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel according to claim 1, chitin aerogel is carbonized in a non-oxidizing atmosphere including, without limitation argon, nitrogen, helium, or krypton.
7. The practical application of the shape stabilized phase change material via microporous carbon derived from chitin aerogel in claim 1.
LU502456A 2022-07-04 2022-07-04 Preparation method of shape stabilized phase change material via microporous carbon derived from chitin aerogel and application in thermal storage LU502456B1 (en)

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