阅读说明：本技术 一种抗积碳热传导液及其制备方法 (Anti-carbon-deposition heat-conduction liquid and preparation method thereof ) 是由 沈秋云 刘丰敏 程键雄 胡敏达 于 2021-09-07 设计创作，主要内容包括：本发明公开了一种抗积碳热传导液及其制备方法,先以纳米棒晶凹土、聚丙烯腈和铜粉为原料,制成纳米棒晶凹土-掺杂石墨烯复合物；再在复合物的表面镀镍,得到镀镍复合物,接着利用γ-(甲基丙烯酰氧)丙基三甲氧基硅烷进行改性处理,得到改性镀镍复合物；然后将改性镀镍复合物、1-乙烯基-3-丁基咪唑双三氟甲烷磺酰亚胺盐加入基础油中,在光引发剂的作用下发生聚合反应即得。该热传导液可在高温条件下长期使用,残炭低,导热性能佳。(The invention discloses an anti-carbon deposition heat transfer liquid and a preparation method thereof, which comprises the steps of firstly, preparing a nano-rod crystalline attapulgite-doped graphene compound by taking nano-rod crystalline attapulgite, polyacrylonitrile and copper powder as raw materials; plating nickel on the surface of the compound to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxy silane to obtain a modified nickel-plated compound; and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the modified nickel-plated composite material. The heat transfer liquid can be used for a long time under the condition of high temperature, and has low carbon residue and good heat conductivity.)

1. The preparation method of the anti-carbon deposition heat transfer liquid is characterized by comprising the following specific steps of:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) plating nickel on the surface of the compound obtained in the step (1) to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxysilane to obtain a modified nickel-plated compound;

(3) and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid.

2. The preparation method according to claim 1, wherein the specific method of step (1) is as follows, in parts by weight: firstly, performing partial cyclization treatment and thermal oxidation on 1 part of polyacrylonitrile, then adding 1.2-1.3 parts of nanorod crystal attapulgite and 0.02-0.03 part of copper powder, uniformly stirring, and calcining under the protection of nitrogen to obtain the nanorod crystal attapulgite-doped graphene composite.

3. The preparation method according to claim 2, wherein the liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, and the monomer ratio is 1: 1, the relative molecular weight of the liquid polyacrylonitrile is 12000-15000.

4. The preparation method of claim 2, wherein the nanorod crystal attapulgite is subjected to activation treatment before feeding, and the specific method comprises the following steps: adding the nanorod crystal attapulgite into 1-2 mol/L hydrochloric acid solution which is 5-8 times of the weight of the nanorod crystal attapulgite, performing ultrasonic oscillation at 40-50 ℃ for 2-3 hours, filtering, and washing with deionized water to be neutral.

5. The preparation method of claim 1, wherein in the step (1), the nanorod crystalline attapulgite is prepared by the following steps in parts by weight: adding 1 part of attapulgite into 1.5-2 parts of water, extruding for 2-3 times by using a roller, transferring to a pressure-resistant closed container with a rapid pressure relief device, heating to 175-185 ℃ in a closed manner, preserving heat for 70-80 minutes, rapidly relieving pressure to normal pressure, spreading out, and naturally drying to obtain the attapulgite clay.

6. The method according to claim 1, wherein in the step (2), the nickel-plated composite is prepared by the following steps in parts by weight: adding 1 part of the composite into 6-8 parts of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated composite.

7. The preparation method according to claim 6, wherein the electroless plating solution is prepared by uniformly mixing the following components in parts by weight: 1 part of nickel nitrate, 1-1.2 parts of 30-40% formaldehyde aqueous solution, 1.4-1.6 parts of disodium ethylene diamine tetraacetate and 25-35 parts of water; the pH was adjusted to 12.

8. The preparation method according to claim 1, wherein in the step (2), the process conditions of the modification treatment are as follows in parts by weight: and adding 1 part of the nickel-plated composite into 5-6 parts of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring and reacting for 5-7 hours at 100-110 ℃, and centrifuging to obtain the modified nickel-plated composite.

9. The preparation method according to claim 1, wherein the specific method of step (3) is as follows, in parts by weight: firstly, adding 0.005-0.008 part of photoinitiator into 10-15 parts of base oil, then adding 0.1-0.2 part of modified nickel plating compound and 0.01-0.02 part of 1-vinyl-3-butylimidazole bistrifluoromethane sulfonyl imide salt, and carrying out photopolymerization reaction to obtain the heat transfer liquid; the base oil is dibenzyltoluene.

10. An anti-carbon deposition heat transfer fluid obtained by the preparation method of any one of claims 1-9.

Technical Field

The invention relates to a heat transfer liquid, in particular to an anti-carbon-deposition heat transfer liquid and a preparation method thereof. Belongs to the technical field of chemical industry.

Background

With the development of modern industry, energy is increasingly tense, and energy conservation and environmental protection are more and more paid attention by people. The heat transfer fluid is a heat transfer medium, has high-temperature and low-pressure heat transfer performance, accurate temperature control, high heat efficiency and uniform heat transfer, and is widely applied to the fields of petroleum processing, chemical industry, food industry, textile industry, pharmaceutical industry, coating industry and the like.

The heat transfer fluid is generally used under high temperature conditions for a long time, and thermal cracking, polycondensation, oxidation, and the like, such as: the thermal cracking reaction generates low boiling point substances, and the low boiling point substances are further polymerized or condensed to form high molecular substances, so that the viscosity of the heat transfer liquid is obviously increased, the carbon residue is increased, the heat transfer efficiency is greatly reduced, and the energy consumption is increased; the oxidation reaction generates an organic acid, which increases the acid value of the heat transfer fluid, generates insoluble acid sludge, and also increases the viscosity of the heat transfer fluid. That is, these chemical reactions can significantly shorten the useful life of the heat transfer fluid, even further damaging the equipment or causing safety hazards.

In addition, in order to improve the heat conductivity of the heat transfer fluid, it has been attempted to add solid particles of high thermal conductivity such as metals to the heat transfer fluid, but the solid particles have poor compatibility with the heat transfer fluid and are liable to precipitate, which causes clogging of the piping and damage to the equipment.

In conclusion, how to reduce the carbon residue and take into account the improvement and stability of the heat conduction performance is beneficial to the long-term use of the heat conduction liquid, and also conforms to the current concept of energy conservation and environmental protection.

Patent CN106010462B discloses a preparation method of an environment-friendly durable type total-synthesis heat transfer fluid, which comprises two steps of base oil synthesis and base oil and auxiliary agent mixing, wherein the base oil is (3-alkyl-1-methyl-imidazole) hexafluorophosphate, and the auxiliary agent comprises a high-temperature antioxidant, a pour point depressant, a composite coke inhibitor and an antirust agent. The heat conduction liquid obtained in the patent has good performance, but the use temperature is only limited below 410 ℃, the use requirement in a high-temperature environment of more than 500 ℃ is difficult to meet, the carbon deposition resistant effect is general, and the requirement for long-term use under a high-temperature condition is difficult to meet.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide the carbon deposition resistance heat conduction liquid and the preparation method thereof, wherein the carbon deposition resistance heat conduction liquid has low carbon residue and good heat conduction performance when used for a long time under the high-temperature condition.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) plating nickel on the surface of the compound obtained in the step (1) to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxysilane to obtain a modified nickel-plated compound;

(3) and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid.

Preferably, the specific method of step (1) is as follows, in parts by weight: firstly, performing partial cyclization treatment and thermal oxidation on 1 part of polyacrylonitrile, then adding 1.2-1.3 parts of nanorod crystal attapulgite and 0.02-0.03 part of copper powder, uniformly stirring, and calcining under the protection of nitrogen to obtain the nanorod crystal attapulgite-doped graphene composite.

Preferably, the liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, the monomer ratio is 1: 1, and the relative molecular weight of the liquid polyacrylonitrile is 12000-15000.

Preferably, the nanorod crystal attapulgite is subjected to activation treatment before feeding, and the specific method comprises the following steps: adding the nanorod crystal attapulgite into 1-2 mol/L hydrochloric acid solution which is 5-8 times of the weight of the nanorod crystal attapulgite, performing ultrasonic oscillation at 40-50 ℃ for 2-3 hours, filtering, and washing with deionized water to be neutral.

Further preferably, the process conditions of the partial cyclization treatment are as follows: stirring and reacting for 16-18 hours at 220-230 ℃.

Further preferably, the thermal oxidation process conditions are as follows: stirring and reacting for 5-7 hours at 280-290 ℃.

Further preferably, the calcination process conditions are as follows: calcining at 1100-1200 ℃ for 6-8 hours.

Preferably, in the step (1), the preparation method of the nanorod crystalline attapulgite comprises the following steps in parts by weight: adding 1 part of attapulgite into 1.5-2 parts of water, extruding for 2-3 times by using a roller, transferring to a pressure-resistant closed container with a rapid pressure relief device, heating to 175-185 ℃ in a closed manner, preserving heat for 70-80 minutes, rapidly relieving pressure to normal pressure, spreading out, and naturally drying to obtain the attapulgite clay.

Preferably, in the step (2), the preparation method of the nickel-plated composite comprises the following steps: adding 1 part of the composite into 6-8 parts of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated composite.

Further preferably, the chemical plating solution is prepared by uniformly mixing the following components in parts by weight: 1 part of nickel nitrate, 1-1.2 parts of 30-40% formaldehyde aqueous solution, 1.4-1.6 parts of disodium ethylene diamine tetraacetate and 25-35 parts of water; the pH was adjusted to 12.

Further preferably, the process conditions of the ultrasonic oscillation treatment are as follows: and carrying out 300-400W ultrasonic oscillation for 20-30 minutes at the temperature of 75-85 ℃.

Further preferably, the process conditions for hydrogen reduction are as follows: treating for 2-3 hours at 400-420 ℃ under the condition of introducing hydrogen; the flow rate of hydrogen is 5 to 7 m/s.

Preferably, in the step (2), the process conditions of the modification treatment are as follows in parts by weight: and adding 1 part of the nickel-plated composite into 5-6 parts of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring and reacting for 5-7 hours at 100-110 ℃, and centrifuging to obtain the modified nickel-plated composite.

Preferably, the specific method of step (3) is as follows, in parts by weight: firstly, adding 0.005-0.008 part of photoinitiator into 10-15 parts of base oil, then adding 0.1-0.2 part of modified nickel plating compound and 0.01-0.02 part of 1-vinyl-3-butylimidazole bistrifluoromethane sulfonyl imide salt, and carrying out photopolymerization reaction to obtain the heat transfer liquid; the base oil is dibenzyltoluene.

Further preferably, the photoinitiator is any one of the photoinitiators 651, 2100, or 2959.

Further preferably, the photopolymerization reaction process conditions are as follows: and under the nitrogen atmosphere, irradiating for 30-40 minutes by 365nm ultraviolet light.

The anti-carbon-deposition heat-conduction liquid is prepared by the preparation method.

The invention has the beneficial effects that:

firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials; plating nickel on the surface of the compound to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxy silane to obtain a modified nickel-plated compound; and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid. The heat transfer liquid can be used for a long time under the condition of high temperature, and has low carbon residue and good heat conductivity.

According to the invention, after the modified nickel plating compound and the 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt are added into the base oil, the photopolymerization reaction improves the compatibility of the system, so that the stability of the heat transfer liquid is improved, the heat transfer performance is ensured, the viscosity is prevented from increasing, and the carbon deposition phenomenon is further reduced.

The 1-vinyl-3-butylimidazole bistrifluoromethane sulfonyl imide salt is an ionic liquid, on one hand, the solubility is improved, on the other hand, double bonds in the ionic liquid can be polymerized with double bonds (gamma- (methacryloyloxy) propyl trimethoxy silane is used for modifying a nickel-plated composite and introducing the double bonds) in the modified nickel-plated composite, so that the dispersibility of the modified nickel-plated composite in a system is improved, the stability of a heat conduction liquid is improved, the heat conduction performance is ensured, the viscosity is prevented from being increased, and the carbon deposition phenomenon is reduced.

The nickel-plated composite is prepared by preparing a nanorod crystal attapulgite-doped graphene composite by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials, and plating nickel on the surface of the nanorod crystal attapulgite-doped graphene composite, wherein the nanorod crystal attapulgite and copper are doped to effectively inhibit the agglomeration of graphene, the stability of a heat transfer liquid is influenced after the surface is added, the specific surface area is increased, micro particles in a system can be adsorbed, and carbon deposition is avoided. The copper, the graphene, the nickel and the like have synergistic effect, so that the heat conducting performance is improved, and the stability of the heat conducting liquid is further improved.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.

In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified. The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.

Example 1:

a preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) plating nickel on the surface of the compound obtained in the step (1) to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxysilane to obtain a modified nickel-plated compound;

(3) and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid.

The specific method of the step (1) is as follows: firstly, performing partial cyclization treatment and thermal oxidation on 1g of polyacrylonitrile, then adding 1.2g of nano-rod crystalline attapulgite and 0.03g of copper powder, uniformly stirring and calcining under the protection of nitrogen to obtain the nano-rod crystalline attapulgite-doped graphene composite.

The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, the monomer ratio is 1: 1, and the relative molecular weight of the liquid polyacrylonitrile is 12000.

The method comprises the following steps of (1) carrying out activation treatment on the nanorod crystal attapulgite before feeding, and specifically comprises the following steps: adding the nanorod crystal attapulgite into 1mol/L hydrochloric acid solution with the weight 8 times that of the nanorod crystal attapulgite, ultrasonically oscillating for 2 hours at 50 ℃, filtering, and washing with deionized water until the solution is neutral.

The process conditions of the partial cyclization treatment are as follows: the reaction was stirred at 230 ℃ for 16 hours.

The process conditions of the thermal oxidation are as follows: the reaction was stirred at 290 ℃ for 5 hours.

The calcination process conditions are as follows: calcining at 1200 ℃ for 6 hours.

In the step (1), the preparation method of the nanorod crystal attapulgite comprises the following steps: adding 1g of attapulgite into 2g of water, extruding for 2 times by using a roller, transferring to a pressure-resistant closed container with a rapid pressure relief device, heating to 185 ℃ in a closed manner, preserving heat for 70 minutes, rapidly relieving pressure to normal pressure, spreading out, and naturally drying to obtain the attapulgite clay.

In the step (2), the preparation method of the nickel-plated composite is as follows: adding 1g of the compound into 8g of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated compound.

The chemical plating solution is prepared by uniformly mixing the following components: 1g of nickel nitrate, 1.2g of a 30% formaldehyde aqueous solution, 1.4g of disodium ethylenediamine tetraacetic acid and 35g of water; the pH was adjusted to 12.

The process conditions of the ultrasonic oscillation treatment are as follows: the mixture was ultrasonically shaken at 400W for 20 minutes at 75 ℃.

The process conditions of hydrogen reduction are as follows: treating for 2 hours at 420 ℃ under the condition of introducing hydrogen; the hydrogen flow rate was 7 m/s.

In the step (2), the process conditions of the modification treatment are as follows: adding 1g of nickel-plated composite into 5g of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring at 110 ℃ for reaction for 5 hours, and centrifuging to obtain the modified nickel-plated composite.

The specific method of the step (3) is as follows: firstly, 0.008g of photoinitiator is added into 10g of base oil, then 0.2g of modified nickel plating compound and 0.01g of 1-vinyl-3-butylimidazole bis (trifluoromethanesulfonyl) imide salt are added, and the thermal conduction liquid is obtained after photopolymerization reaction; the base oil is dibenzyltoluene.

The photoinitiator is photoinitiator 651. The technological conditions of the photopolymerization are as follows: under nitrogen atmosphere, 365nm ultraviolet light is irradiated for 40 minutes.

Example 2:

a preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) plating nickel on the surface of the compound obtained in the step (1) to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxysilane to obtain a modified nickel-plated compound;

(3) and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid.

The specific method of the step (1) is as follows: firstly, performing partial cyclization treatment and thermal oxidation on 1g of polyacrylonitrile, then adding 1.3g of nano-rod crystalline attapulgite and 0.02g of copper powder, uniformly stirring and calcining under the protection of nitrogen to obtain the nano-rod crystalline attapulgite-doped graphene composite.

The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, the monomer ratio is 1: 1, and the relative molecular weight of the liquid polyacrylonitrile is 15000.

The method comprises the following steps of (1) carrying out activation treatment on the nanorod crystal attapulgite before feeding, and specifically comprises the following steps: adding the nanorod crystal attapulgite into a 2mol/L hydrochloric acid solution with the weight 5 times that of the nanorod crystal attapulgite, ultrasonically oscillating for 3 hours at 40 ℃, filtering, and washing with deionized water until the solution is neutral.

The process conditions of the partial cyclization treatment are as follows: the reaction was stirred at 220 ℃ for 18 hours.

The process conditions of the thermal oxidation are as follows: the reaction was stirred at 280 ℃ for 7 hours.

The calcination process conditions are as follows: calcining at 1100 deg.C for 8 hr.

In the step (1), the preparation method of the nanorod crystal attapulgite comprises the following steps: adding 1g of attapulgite into 1.5g of water, extruding the mixture for 3 times by using a roller, transferring the mixture into a pressure-resistant closed container with a rapid pressure relief device, heating the mixture to 175 ℃ in a closed manner, preserving the heat for 80 minutes, rapidly relieving the pressure to normal pressure, and naturally drying the mixture after spreading the mixture out to obtain the attapulgite clay.

In the step (2), the preparation method of the nickel-plated composite is as follows: adding 1g of the compound into 6g of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated compound.

The chemical plating solution is prepared by uniformly mixing the following components: 1g of nickel nitrate, 1g of a formaldehyde water solution with the mass concentration of 40%, 1.6g of ethylene diamine tetraacetic acid and 25g of water; the pH was adjusted to 12.

The process conditions of the ultrasonic oscillation treatment are as follows: the mixture was ultrasonically shaken at 300W for 30 minutes at 85 ℃.

The process conditions of hydrogen reduction are as follows: treating for 3 hours at 400 ℃ under the condition of introducing hydrogen; the hydrogen flow rate was 5 m/s.

In the step (2), the process conditions of the modification treatment are as follows: adding 1g of nickel-plated composite into 6g of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring and reacting for 7 hours at 100 ℃, and centrifuging to obtain the modified nickel-plated composite.

The specific method of the step (3) is as follows: firstly, 0.005g of photoinitiator is added into 15g of base oil, then 0.1g of modified nickel-plated compound and 0.02g of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt are added, and the thermal conduction liquid is obtained after photopolymerization reaction; the base oil is dibenzyltoluene.

The photoinitiator is photoinitiator 2100. The technological conditions of the photopolymerization are as follows: and under the nitrogen atmosphere, 365nm ultraviolet light is used for 30 minutes.

Example 3:

a preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) plating nickel on the surface of the compound obtained in the step (1) to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxysilane to obtain a modified nickel-plated compound;

(3) and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid.

The specific method of the step (1) is as follows: firstly, performing partial cyclization treatment and thermal oxidation on 1g of polyacrylonitrile, then adding 1.25g of nano-rod crystalline attapulgite and 0.025g of copper powder, uniformly stirring and calcining under the protection of nitrogen to obtain the nano-rod crystalline attapulgite-doped graphene composite.

The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, the monomer ratio is 1: 1, and the relative molecular weight of the liquid polyacrylonitrile is 13000.

The method comprises the following steps of (1) carrying out activation treatment on the nanorod crystal attapulgite before feeding, and specifically comprises the following steps: adding the nanorod crystal attapulgite into 1.5mol/L hydrochloric acid solution with the weight 7 times that of the nanorod crystal attapulgite, ultrasonically oscillating for 2.5 hours at 45 ℃, filtering, and washing with deionized water to be neutral.

The process conditions of the partial cyclization treatment are as follows: the reaction was stirred at 225 ℃ for 17 hours.

The process conditions of the thermal oxidation are as follows: the reaction was stirred at 285 ℃ for 6 hours.

The calcination process conditions are as follows: calcining at 1150 deg.C for 7 hr.

In the step (1), the preparation method of the nanorod crystal attapulgite comprises the following steps: adding 1g of attapulgite into 1.8g of water, extruding the mixture for 3 times by using a roller, transferring the mixture into a pressure-resistant closed container with a rapid pressure relief device, heating the mixture to 180 ℃ in a closed manner, preserving the heat for 75 minutes, rapidly relieving the pressure to normal pressure, and naturally drying the mixture after spreading the mixture out.

In the step (2), the preparation method of the nickel-plated composite is as follows: adding 1g of the compound into 7g of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated compound.

The chemical plating solution is prepared by uniformly mixing the following components: 1g of nickel nitrate, 1.1g of formaldehyde water solution with the mass concentration of 35%, 1.5g of ethylene diamine tetraacetic acid and 30g of water; the pH was adjusted to 12.

The process conditions of the ultrasonic oscillation treatment are as follows: the mixture was ultrasonically shaken at 400W for 25 minutes at 80 ℃.

The process conditions of hydrogen reduction are as follows: treating at 410 deg.C for 2.5 hr under hydrogen gas condition; the hydrogen flow rate was 6 m/s.

In the step (2), the process conditions of the modification treatment are as follows: adding 1g of nickel-plated composite into 5.5g of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring and reacting for 6 hours at 105 ℃, and centrifuging to obtain the modified nickel-plated composite.

The specific method of the step (3) is as follows: firstly, 0.006g of photoinitiator is added into 13g of base oil, then 0.15g of modified nickel plating compound and 0.015g of 1-vinyl-3-butylimidazole bis (trifluoromethanesulfonyl) imide salt are added, and the thermal conduction liquid is obtained after photopolymerization reaction; the base oil is dibenzyltoluene.

The photoinitiator was photoinitiator 2959. The technological conditions of the photopolymerization are as follows: under nitrogen atmosphere, 365nm ultraviolet light was irradiated for 35 minutes.

Comparative example 1

A preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, plating nickel on the surface of graphene to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxy silane to obtain a modified nickel-plated compound;

(2) and then adding the modified nickel-plated compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid.

In the step (1), the preparation method of the nickel-plated composite is as follows: adding 1g of graphene into 8g of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated composite.

The chemical plating solution is prepared by uniformly mixing the following components: 1g of nickel nitrate, 1.2g of a 30% formaldehyde aqueous solution, 1.4g of disodium ethylenediamine tetraacetic acid and 35g of water; the pH was adjusted to 12.

The process conditions of the ultrasonic oscillation treatment are as follows: the mixture was ultrasonically shaken at 400W for 20 minutes at 75 ℃.

The process conditions of hydrogen reduction are as follows: treating for 2 hours at 420 ℃ under the condition of introducing hydrogen; the hydrogen flow rate was 7 m/s.

In the step (1), the process conditions of the modification treatment are as follows: adding 1g of nickel-plated composite into 5g of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring at 110 ℃ for reaction for 5 hours, and centrifuging to obtain the modified nickel-plated composite.

The specific method of the step (2) is as follows: firstly, 0.008g of photoinitiator is added into 10g of base oil, then 0.2g of modified nickel plating compound and 0.01g of 1-vinyl-3-butylimidazole bis (trifluoromethanesulfonyl) imide salt are added, and the thermal conduction liquid is obtained after photopolymerization reaction; the base oil is dibenzyltoluene.

The photoinitiator is photoinitiator 651. The technological conditions of the photopolymerization are as follows: under nitrogen atmosphere, 365nm ultraviolet light is irradiated for 40 minutes.

Comparative example 2

A preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) carrying out modification treatment on the compound obtained in the step (1) by using gamma- (methacryloyloxy) propyl trimethoxy silane to obtain a modified compound;

(3) and then adding the modified compound and 1-vinyl-3-butylimidazole bis (trifluoromethane) sulfonyl imide salt into base oil, and carrying out polymerization reaction under the action of a photoinitiator to obtain the heat transfer fluid.

The specific method of the step (1) is as follows: firstly, performing partial cyclization treatment and thermal oxidation on 1g of polyacrylonitrile, then adding 1.2g of nano-rod crystalline attapulgite and 0.03g of copper powder, uniformly stirring and calcining under the protection of nitrogen to obtain the nano-rod crystalline attapulgite-doped graphene composite.

The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, the monomer ratio is 1: 1, and the relative molecular weight of the liquid polyacrylonitrile is 12000.

The method comprises the following steps of (1) carrying out activation treatment on the nanorod crystal attapulgite before feeding, and specifically comprises the following steps: adding the nanorod crystal attapulgite into 1mol/L hydrochloric acid solution with the weight 8 times that of the nanorod crystal attapulgite, ultrasonically oscillating for 2 hours at 50 ℃, filtering, and washing with deionized water until the solution is neutral.

The process conditions of the partial cyclization treatment are as follows: the reaction was stirred at 230 ℃ for 16 hours.

The process conditions of the thermal oxidation are as follows: the reaction was stirred at 290 ℃ for 5 hours.

The calcination process conditions are as follows: calcining at 1200 ℃ for 6 hours.

In the step (1), the preparation method of the nanorod crystal attapulgite comprises the following steps: adding 1g of attapulgite into 2g of water, extruding for 2 times by using a roller, transferring to a pressure-resistant closed container with a rapid pressure relief device, heating to 185 ℃ in a closed manner, preserving heat for 70 minutes, rapidly relieving pressure to normal pressure, spreading out, and naturally drying to obtain the attapulgite clay.

In the step (2), the process conditions of the modification treatment are as follows: adding 1g of the compound into 5g of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring and reacting for 5 hours at 110 ℃, and centrifuging to obtain the modified compound.

The specific method of the step (3) is as follows: firstly, 0.008g of photoinitiator is added into 10g of base oil, then 0.2g of modified compound and 0.01g of 1-vinyl-3-butylimidazole bis (trifluoromethanesulfonyl) imide salt are added, and the thermal conduction liquid is obtained after photopolymerization reaction; the base oil is dibenzyltoluene.

The photoinitiator is photoinitiator 651. The technological conditions of the photopolymerization are as follows: under nitrogen atmosphere, 365nm ultraviolet light is irradiated for 40 minutes.

Comparative example 3

A preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) plating nickel on the surface of the compound obtained in the step (1) to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxysilane to obtain a modified nickel-plated compound;

(3) and then adding the modified nickel-plated compound and the 1-vinyl-3-butylimidazole bis (trifluoromethanesulfonyl) imide salt into the base oil, and uniformly stirring to obtain the heat transfer fluid.

The specific method of the step (1) is as follows: firstly, performing partial cyclization treatment and thermal oxidation on 1g of polyacrylonitrile, then adding 1.2g of nano-rod crystalline attapulgite and 0.03g of copper powder, uniformly stirring and calcining under the protection of nitrogen to obtain the nano-rod crystalline attapulgite-doped graphene composite.

The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, the monomer ratio is 1: 1, and the relative molecular weight of the liquid polyacrylonitrile is 12000.

The method comprises the following steps of (1) carrying out activation treatment on the nanorod crystal attapulgite before feeding, and specifically comprises the following steps: adding the nanorod crystal attapulgite into 1mol/L hydrochloric acid solution with the weight 8 times that of the nanorod crystal attapulgite, ultrasonically oscillating for 2 hours at 50 ℃, filtering, and washing with deionized water until the solution is neutral.

The process conditions of the partial cyclization treatment are as follows: the reaction was stirred at 230 ℃ for 16 hours.

The process conditions of the thermal oxidation are as follows: the reaction was stirred at 290 ℃ for 5 hours.

The calcination process conditions are as follows: calcining at 1200 ℃ for 6 hours.

In the step (1), the preparation method of the nanorod crystal attapulgite comprises the following steps: adding 1g of attapulgite into 2g of water, extruding for 2 times by using a roller, transferring to a pressure-resistant closed container with a rapid pressure relief device, heating to 185 ℃ in a closed manner, preserving heat for 70 minutes, rapidly relieving pressure to normal pressure, spreading out, and naturally drying to obtain the attapulgite clay.

In the step (2), the preparation method of the nickel-plated composite is as follows: adding 1g of the compound into 8g of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated compound.

The chemical plating solution is prepared by uniformly mixing the following components: 1g of nickel nitrate, 1.2g of a 30% formaldehyde aqueous solution, 1.4g of disodium ethylenediamine tetraacetic acid and 35g of water; the pH was adjusted to 12.

The process conditions of the ultrasonic oscillation treatment are as follows: the mixture was ultrasonically shaken at 400W for 20 minutes at 75 ℃.

The process conditions of hydrogen reduction are as follows: treating for 2 hours at 420 ℃ under the condition of introducing hydrogen; the hydrogen flow rate was 7 m/s.

In the step (2), the process conditions of the modification treatment are as follows: adding 1g of nickel-plated composite into 5g of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring at 110 ℃ for reaction for 5 hours, and centrifuging to obtain the modified nickel-plated composite.

The specific method of the step (3) is as follows: adding 0.2g of the modified compound and 0.01g of 1-vinyl-3-butylimidazole bis (trifluoromethanesulfonyl) imide salt into 10g of base oil, and stirring and uniformly mixing to obtain the modified compound; the base oil is dibenzyltoluene.

Comparative example 4

A preparation method of an anti-carbon deposition heat transfer liquid comprises the following specific steps:

(1) firstly, preparing a nanorod crystal attapulgite-doped graphene compound by using nanorod crystal attapulgite, polyacrylonitrile and copper powder as raw materials;

(2) plating nickel on the surface of the compound obtained in the step (1) to obtain a nickel-plated compound, and then performing modification treatment by using gamma- (methacryloyloxy) propyl trimethoxysilane to obtain a modified nickel-plated compound;

(3) and then adding the modified nickel-plated compound into the base oil, and uniformly stirring to obtain the heat conduction liquid.

The specific method of the step (1) is as follows: firstly, performing partial cyclization treatment and thermal oxidation on 1g of polyacrylonitrile, then adding 1.2g of nano-rod crystalline attapulgite and 0.03g of copper powder, uniformly stirring and calcining under the protection of nitrogen to obtain the nano-rod crystalline attapulgite-doped graphene composite.

The liquid polyacrylonitrile is a copolymer of acrylonitrile and methyl methacrylate, the monomer ratio is 1: 1, and the relative molecular weight of the liquid polyacrylonitrile is 12000.

The method comprises the following steps of (1) carrying out activation treatment on the nanorod crystal attapulgite before feeding, and specifically comprises the following steps: adding the nanorod crystal attapulgite into 1mol/L hydrochloric acid solution with the weight 8 times that of the nanorod crystal attapulgite, ultrasonically oscillating for 2 hours at 50 ℃, filtering, and washing with deionized water until the solution is neutral.

The process conditions of the partial cyclization treatment are as follows: the reaction was stirred at 230 ℃ for 16 hours.

The process conditions of the thermal oxidation are as follows: the reaction was stirred at 290 ℃ for 5 hours.

The calcination process conditions are as follows: calcining at 1200 ℃ for 6 hours.

In the step (1), the preparation method of the nanorod crystal attapulgite comprises the following steps: adding 1g of attapulgite into 2g of water, extruding for 2 times by using a roller, transferring to a pressure-resistant closed container with a rapid pressure relief device, heating to 185 ℃ in a closed manner, preserving heat for 70 minutes, rapidly relieving pressure to normal pressure, spreading out, and naturally drying to obtain the attapulgite clay.

In the step (2), the preparation method of the nickel-plated composite is as follows: adding 1g of the compound into 8g of chemical plating solution containing nickel nitrate, carrying out ultrasonic oscillation treatment, filtering, washing, drying and hydrogen reduction to obtain the nickel-plated compound.

The chemical plating solution is prepared by uniformly mixing the following components: 1g of nickel nitrate, 1.2g of a 30% formaldehyde aqueous solution, 1.4g of disodium ethylenediamine tetraacetic acid and 35g of water; the pH was adjusted to 12.

The process conditions of the ultrasonic oscillation treatment are as follows: the mixture was ultrasonically shaken at 400W for 20 minutes at 75 ℃.

The process conditions of hydrogen reduction are as follows: treating for 2 hours at 420 ℃ under the condition of introducing hydrogen; the hydrogen flow rate was 7 m/s.

In the step (2), the process conditions of the modification treatment are as follows: adding 1g of nickel-plated composite into 5g of gamma- (methacryloyloxy) propyl trimethoxy silane, stirring at 110 ℃ for reaction for 5 hours, and centrifuging to obtain the modified nickel-plated composite.

The specific method of the step (3) is as follows: adding 0.2g of the modified nickel-plated compound into 10g of base oil, and uniformly stirring to obtain the modified nickel-plated composite; the base oil is dibenzyltoluene.

Test examples

The performance of the heat transfer fluids obtained in examples 1 to 3 and comparative examples 1 to 4 was examined, and the results are shown in Table 1.

And detecting the heat conductivity coefficient by using a heat conductivity coefficient tester.

The thermal stability was examined as follows: the heat transfer fluid was allowed to stand at 500 ℃ for 6 months, and the stability of the heat transfer fluid was observed.

Carbon residue determination is carried out with reference to GB/T268-1987.

TABLE 1 Performance test results

	Thermal conductivity (40 ℃, W (m.K))	Standing at 500 deg.C for 6 months	Carbon residue (%)
				Example 1	0.201	Uniform, no floc, no precipitate, no delamination	0.0009
Example 2	0.204	Uniform, no floc, no precipitate, no delamination	0.0008
				Example 3	0.211	Uniform, no floc, no precipitate, no delamination	0.0006
Comparative example 1	0.145	A small amount of floccule appears without sediment	0.0324
				Comparative example 2	0.149	A small amount of floccule appears without sediment	0.0152
Comparative example 3	0.161	A large amount of floccules appear and a small amount of precipitates	0.0273
				Comparative example 4	0.153	Delamination occurred	0.0395

As is clear from Table 1, the heat conductive fluids obtained in examples 1 to 3 were excellent in heat conductivity, thermal stability, carbon residue and performance.

The comparative example 1 is that the nano-rod crystalline attapulgite-doped graphene composite is replaced by graphene, the comparative example 2 omits surface nickel plating treatment, the comparative example 3 omits a photopolymerization reaction step, and the comparative example 4 omits 1-vinyl-3-butylimidazole bistrifluoromethane sulfimide salt, so that the stability of the obtained heat transfer liquid is poor, the heat transfer performance is poor, and the residual carbon is high, which indicates that after the graphene is subjected to doping and surface nickel plating treatment, the heat transfer performance and stability of the heat transfer liquid are improved and the residual carbon is reduced by combining the improvement and synergistic effect of ionic liquid on compatibility.

Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.