CN111995989B - Novel functional heating fluid material and preparation method thereof - Google Patents
Novel functional heating fluid material and preparation method thereof Download PDFInfo
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- CN111995989B CN111995989B CN202010806618.2A CN202010806618A CN111995989B CN 111995989 B CN111995989 B CN 111995989B CN 202010806618 A CN202010806618 A CN 202010806618A CN 111995989 B CN111995989 B CN 111995989B
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- 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
- C09K5/08—Materials not undergoing a change of physical state when used
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Abstract
Discloses a novel functional heating fluid material, which comprises a carbon group nano material mixture of carboxylated graphene and carboxylated multi-wall carbon nano tubes, wherein the carbon group nano material mixture is chemically modified by long-chain alkyl quaternary ammonium salt. In addition, a method for preparing the novel heating fluid material is also disclosed. The new heating liquid material has high heat conductivity coefficient and high suspension stability.
Description
Technical Field
The invention belongs to the field of heat conduction and exchange materials, and particularly relates to a novel functional heating fluid material and a preparation method thereof.
Background
In various heating apparatuses, heating fluid plays a crucial role in achieving good heat transfer and exchange. The traditional heating liquid is water, and the heat transfer of the water is slow, so that the water temperature rises slowly.
Chinese patent application CN1583937A discloses a heating working medium, which is a mixed liquid prepared from the following raw materials in parts by weight: 5-9 parts of calcium chloride, 12-15 parts of magnesium chloride, 0.01-0.05 part of preservative and 14-20 parts of water. However, the concentration of the inorganic salt additive of the heating working medium is too high, and even under the condition that a proper amount of preservative is added, the additive still has great corrosivity on heating equipment.
Chinese patent application CN104962244A discloses an energy-saving heating superconducting fluid, which comprises the following components: the composition comprises, by mass, 0.5-1.1% of triethanolamine, 25-35% of ethanol, 0.1-0.9% of sodium benzoate, 0.005-0.015% of sodium metasilicate, 63-72% of dichloromethane and the balance of water. The superconducting liquid changes the structure of a product, is quick in heat transfer, energy-saving and environment-friendly, and prolongs the service life. However, as the superconducting liquid matrix mainly uses dichloromethane, the boiling point of the dichloromethane is 39.8 ℃, the superconducting liquid is easy to boil at a higher temperature, and certain potential safety hazards exist.
In general, whether water, alcohol, oil, or the like is used as the heating liquid, it is difficult to satisfy the current increasing heat transfer and exchange requirements due to low heat transfer performance. In recent years, a novel heat exchange medium, namely nanofluid, is proposed. The nano fluid is a multi-phase system formed by taking a traditional heat transfer working medium as a base liquid and adding nano-sized additives into the base liquid.
Among the nanoparticles, Ag, Cu and Al are most studied2O3、TiO2、SiO2CuO, ZnO and MgO, and carbon group nanomaterials. In particular, as the research on carbon nanotubes and graphene is deepened, they are gradually used as core nanoparticles.
In the nano fluid, because the nano particles have smaller sizes and relatively larger specific surface areas, the nano fluid is easier to be fully dispersed in a base liquid compared with a suspension of micron-sized particles, and thus has higher heat conduction performance. On the other hand, in a two-phase system of the nanofluid, the nanoparticles collide with each other, and the heat transfer performance of the nanofluid is greatly improved due to factors such as friction between the nanoparticles and the heat exchange surface and the wall surface. Finally, compared with the suspension of micron-sized particles, the nano-fluid has the mobility closer to that of the base fluid, and the loss influence on the heat exchange equipment is reduced to be lower. It can be seen that the nanofluid has many excellent characteristics, especially good thermal conductivity, due to good suspension stability.
However, when using higher contents of carbon group nanomaterials, there are still technical drawbacks of less than ideal thermal conductivity and suspension stability.
Therefore, in view of the above-mentioned drawbacks of the prior art, a new functional heating fluid material and a preparation method thereof are needed.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a new functional heating fluid material and a preparation method thereof. Compared with the prior art, the novel functional heating fluid material has higher heat conductivity coefficient and better suspension stability.
In order to achieve the purpose, on one hand, the invention adopts the following technical scheme: a novel functional heating fluid material comprises a carbon group nano material mixture of carboxylated graphene and carboxylated multi-wall carbon nano tubes, and is characterized in that the carbon group nano material mixture is chemically modified by long-chain alkyl quaternary ammonium salt.
The novel heating fluid material is characterized in that the average transverse size of the carboxylated graphene is 1-5 microns; the average thickness is 0.8-1.2 nm; the carboxyl content was 5% by weight.
The novel heating fluid material is characterized in that the average pipe diameter of the carboxylated multi-wall carbon nano-tube is 10-20 nm; the average length is 10-30 μm; the carboxyl content was 2% by weight.
The novel heating fluid material is characterized in that the weight ratio of the carboxylated graphene to the carboxylated multi-walled carbon nanotube is (0.2-0.6): 1.
the novel heating fluid material further comprises free long-chain alkyl quaternary ammonium salt and polyethyleneimine.
The novel heating fluid material is characterized in that the free long-chain alkyl quaternary ammonium salt is selected from dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, tetradecyl pyridinium chloride, hexadecyl pyridinium chloride, didodecyl dimethyl ammonium chloride, ditetradecyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, didodecyl dimethyl ammonium bromide, ditetradecyl dimethyl ammonium bromide and dicetyl dimethyl ammonium bromide.
The new heating fluid material is characterized in that the average molecular weight Mn of the polyethyleneimine is 1200-3500; the primary amine content was 35 mol%; the secondary amine content was 35 mol%; the tertiary amine content was 30 mol%.
The novel heating fluid material further comprises base fluid consisting of ethylene glycol and water; advantageously, the volume ratio of ethylene glycol to water is 1: 4.
the novel heating fluid material provided by the invention is characterized in that the content of the carbon family nano material mixture chemically modified by the long-chain alkyl quaternary ammonium salt is 0.05-0.5 wt%; the content of the free long-chain alkyl quaternary ammonium salt is 0.01-0.1 wt%; the content of the polyethyleneimine is 0.02-0.15 wt% based on the weight of the new heating fluid material.
In another aspect, the present invention further provides a method for preparing the new heating fluid material, including:
adding a mixture of carboxylated graphene and carboxylated multi-walled carbon nanotubes into water, and performing ultrasonic treatment to uniformly disperse the mixture; according to the weight ratio of 8-12:1, adding long-chain alkyl quaternary ammonium salt, and reacting for 1-6h at 80-95 ℃; washing with anhydrous methanol and water for several times, and drying at 60-80 deg.C to obtain long chain alkyl quaternary ammonium salt chemically modified carbon family nanometer material mixture;
according to the formula, the carbon family nano material mixture chemically modified by the long-chain alkyl quaternary ammonium salt is uniformly mixed with the free long-chain alkyl quaternary ammonium salt, the polyethyleneimine and the base liquid to obtain the novel heating fluid material.
The invention has the beneficial effects that: compared with the prior art, the novel heating fluid material has higher heat conductivity coefficient and better suspension stability.
Without wishing to be bound by any theory, the present invention achieves the above-described benefits by using a specific carbon family nanomaterial mixture in combination with a specific dispersant.
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods described and claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for.
Parts are parts by weight unless otherwise indicated, and are calculated based on the total weight of the fire extinguishing agent. The temperatures are all expressed in degrees celsius or at ambient temperature and the pressure is at or near atmospheric pressure. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Example 1
According to the weight ratio of 0.4: 1, forming a mixture of the carboxylated graphene and the carboxylated multi-walled carbon nanotubes. The average lateral dimension of the carboxylated graphene is between 1 and 5 microns; the average thickness is 0.8-1.2 nm; the carboxyl content was 5% by weight. The average pipe diameter of the carboxylated multi-wall carbon nano-tube is 10-20 nm; the average length is 10-30 μm; the carboxyl content was 2% by weight.
Adding the mixture of the carboxylated graphene and the carboxylated multi-walled carbon nanotubes into water, and performing ultrasonic treatment to uniformly disperse the mixture; according to the following steps of 10: 1, adding hexadecyl trimethyl ammonium bromide according to the weight ratio, and reacting for 2 hours at 90 ℃; washing with anhydrous methanol and water for 3 times, and drying at 70 deg.C to obtain long chain alkyl quaternary ammonium salt chemically modified carbon family nanometer material mixture.
In addition to the above chemically modified carbon group nanomaterial mixture, free cetyltrimethylammonium bromide, polyethyleneimine and a base solution were prepared. The average molecular weight Mn of the polyethyleneimine is 1800; the primary amine content was 35 mol%; the secondary amine content was 35 mol%; the tertiary amine content was 30 mol%. The volume ratio of the base liquid is 1:4, mixing the ethylene glycol and water.
The formula of the new heating liquid material is as follows: the content of the chemically modified carbon family nano material mixture is 0.2 wt%; the content of hexadecyl trimethyl ammonium bromide is 0.05 wt%; the content of polyethyleneimine is 0.08 wt%; the balance being base liquid.
According to the formula, the components are uniformly mixed to obtain the novel heating fluid material.
Comparative example 1
The mixture of carboxylated graphene and carboxylated multiwall carbon nanotubes was used directly, with the same conditions as in example 1.
Comparative example 2
The chemically modified carbon group nanomaterial mixture is replaced by the chemically modified carboxylated graphene with the same weight, and the rest conditions are the same as in example 1.
Comparative example 3
The chemically modified carbon family nanomaterial mixture is replaced with the chemically modified carboxylated carbon nanotubes in equal weight, and the rest of the conditions are the same as in example 1.
Performance testing
First, the thermal conductivity of the base liquid (ethylene glycol and water in a volume ratio of 1: 4) at 50 ℃ was measured according to the transient hot wire method, and then the thermal conductivity of the new materials for heating liquids of example 1 and comparative examples 1 to 3 was measured under the same conditions, and the final results were evaluated using the ratio of the latter to the former as the respective relative thermal conductivity (%).
The suspension stability is judged by whether obvious sedimentation appears after different standing days. See table 1 for results.
TABLE 1
+ + no obvious macroscopic precipitation
+ a small amount of visible precipitation
+ a large amount of visually observable precipitate
As can be seen from Table 1, the novel heating fluid material of example 1 of the present invention has not only higher thermal conductivity but also better suspension stability than those of comparative examples 1 to 3.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (3)
1. A new functional heating fluid material comprises a carbon group nano material mixture of carboxylated graphene and carboxylated multi-walled carbon nanotubes, a base fluid consisting of free long-chain alkyl quaternary ammonium salt, polyethyleneimine, ethylene glycol and water in a volume ratio of 1: 4; wherein the average molecular weight Mn of the polyethyleneimine is 1200-; the primary amine content was 35 mol%; the secondary amine content was 35 mol%; the tertiary amine content is 30 mol%;
the method is characterized in that the carbon family nano material mixture is chemically modified by long-chain alkyl quaternary ammonium salt, and the specific method is as follows: adding a mixture of carboxylated graphene and carboxylated multi-walled carbon nanotubes into water, and performing ultrasonic treatment to uniformly disperse the mixture; adding long-chain alkyl quaternary ammonium salt according to the weight ratio of 8-12:1, and reacting for 1-6h at the temperature of 80-95 ℃; washing with anhydrous methanol and water for several times, and drying at 60-80 deg.C to obtain long chain alkyl quaternary ammonium salt chemically modified carbon family nanometer material mixture;
wherein the average lateral dimension of the carboxylated graphene is between 1 and 5 μm; the average thickness is 0.8-1.2 nm; the carboxyl content was 5 wt%;
the average pipe diameter of the carboxylated multi-wall carbon nano-tube is 10-20 nm; the average length is 10-30 μm; the carboxyl content was 2 wt%;
the weight ratio of the carboxylated graphene to the carboxylated multi-walled carbon nanotubes is 0.2-0.6: 1;
the content of the carbon family nanometer material mixture chemically modified by the long-chain alkyl quaternary ammonium salt is 0.05 to 0.5 weight percent; the content of the free long-chain alkyl quaternary ammonium salt is 0.01-0.1 wt%; the content of the polyethyleneimine is 0.02-0.15 wt% based on the weight of the new heating fluid material.
2. The new heating fluid material according to claim 1, wherein the free long-chain alkyl quaternary ammonium salt is selected from dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, tetradecyl pyridinium chloride, hexadecyl pyridinium chloride, didodecyl dimethyl ammonium chloride, ditetradecyl dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, didodecyl dimethyl ammonium bromide, ditetradecyl dimethyl ammonium bromide, and dicetyl dimethyl ammonium bromide.
3. A method of preparing a new heating fluid material of claim 1 or 2, comprising:
adding a mixture of carboxylated graphene and carboxylated multi-walled carbon nanotubes into water, and performing ultrasonic treatment to uniformly disperse the mixture; adding long-chain alkyl quaternary ammonium salt according to the weight ratio of 8-12:1, and reacting for 1-6h at the temperature of 80-95 ℃; washing with anhydrous methanol and water for several times, and drying at 60-80 deg.C to obtain long chain alkyl quaternary ammonium salt chemically modified carbon family nanometer material mixture;
according to the formula, the carbon family nano material mixture chemically modified by the long-chain alkyl quaternary ammonium salt is uniformly mixed with the free long-chain alkyl quaternary ammonium salt, the polyethyleneimine and the base liquid to obtain the novel heating fluid material.
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