A phase change cold storage material, a preparation method and application thereof

Abstract

The present application relates to the technical field of phase change material, and provides a phase change cold storage material, a preparation method and application thereof, the phase change cold storage material comprises two or more components; the components comprise ester substances; the ester substances are selected from one or a combination of two or more of butyl valerate, ethyl butyrate and n-propyl acetate. By screening specific ester substances, a mixed medium with a eutectic temperature less than or equal to -90 DEG C can be obtained, so that the energy storage requirement in the temperature zone below -90 DEG C can be realized. The selected substances have the characteristics of high safety and excellent thermal performance, and can be used in the fields of liquefied natural gas storage, liquefied natural gas transportation, medicine storage, medicine transportation or power load management. Meanwhile, the phase change cold storage material preparation method is simple, low in cost and has a high market application prospect.

Description

Technical Field

[0001] This invention relates to the field of phase change materials technology, specifically to a phase change cold storage material, its preparation method, and its application, and more particularly to a phase change cold storage material, its preparation method, and its application. Background Technology

[0002] Cold storage technology is a highly efficient energy storage technology. Phase change cold storage materials have the characteristics of storing energy at low loads and releasing energy at high loads, making them play a pivotal role in cold storage technology.

[0003] Different fields have different requirements for phase change energy storage materials. In power load management with significant seasonal and temporal load variations, phase change energy storage materials need to have high latent heat of phase change. In cryogenic applications, such as LNG, which needs to be kept at low temperatures during storage and transportation, especially in the ultra-low temperature range of -90°C to -105°C; and pharmaceuticals such as vaccines, which need to be kept at low temperatures during storage and transportation to improve their preservation and distribution efficiency.

[0004] However, most existing phase change energy storage materials are concentrated in the medium and low temperature range. Traditional inorganic phase change materials, such as inorganic salts, although they have good thermal properties at normal temperatures, usually face solidification problems in the temperature range of -90°C and below, and cannot continue to remain in a liquid state, thus losing their energy storage function.

[0005] Therefore, a phase change energy storage material that can provide a continuous low-temperature environment, especially in the temperature range of -90°C to -105°C, can effectively store cold energy and release energy when needed, has great application potential in the above-mentioned application fields. Summary of the Invention

[0006] This invention provides a phase change energy storage material, its preparation method, and its application, in order to solve the defect that most phase change energy storage materials in the prior art are concentrated in the medium and low temperature range and cannot meet the energy storage requirements in the temperature range below -90℃.

[0007] Specifically, in a first aspect, the present invention provides a phase change cold storage material comprising: two or more components;

[0008] The components include esters;

[0009] The esters are selected from one or more of butyl valerate, ethyl butyrate, and n-propyl acetate.

[0010] The phase change cold storage material provided by the present invention, as described above, further includes alkanes;

[0011] Preferably, the alkane is selected from one or more combinations of n-hexane, 2,5-dimethylhexane, and n-heptane.

[0012] The phase change cold storage material provided by the present invention, as described above, further includes olefins;

[0013] Preferably, the olefin comprises 1-octene.

[0014] The phase change cold storage material provided by the present invention as described above further includes alkanes and olefins;

[0015] The molar ratio of alkanes, alkenes and esters is 36~55:51~64:36~62; preferably 45~46:63~64:45~46.

[0016] According to the phase change cold storage material provided by the present invention, the eutectic temperature of the phase change cold storage material is less than or equal to -90°C;

[0017] And / or, the latent heat of solid-liquid phase change of the phase change cold storage material is greater than or equal to 11500 J / mol.

[0018] The phase change cold storage material provided by the present invention is a binary mixed medium or a ternary mixed medium;

[0019] Preferably, the phase change cold storage material is a binary mixed medium composed of two esters, a binary mixed medium composed of alkanes and esters, a binary mixed medium composed of olefins and esters, a ternary mixed medium composed of alkanes and esters, or a ternary mixed medium composed of alkanes, olefins, and esters.

[0020] According to the phase change cold storage material provided by the present invention as described above, the binary mixed medium composed of the two ester substances is ethyl butyrate (C6H4O3). 12 O2) and n-propyl acetate (C5H) 10 The composition includes O2); preferably, the molar percentage of ethyl butyrate is 50-55%, more preferably 51.5%;

[0021] The binary mixture of alkanes and esters consists of 2,5-dimethylhexane (C8H2O). 18 ) and n-propyl acetate (C5H 10 The composition includes O2; preferably, the molar percentage of 2,5-dimethylhexane is 40-45%, more preferably 43.2%;

[0022] The binary mixture of olefins and esters consists of 1-octene (C8H4O3). 16 ) and butyl valerate (C9H 18 The composition is O2); preferably, the molar percentage of 1-octene is 60-65%, more preferably 63.9%;

[0023] The ternary mixed medium composed of alkanes and esters consists of n-hexane (C6H4O3). 14 ), n-Heptane (C7H) 16 ) and butyl valerate (C9H 18 The composition (O2) preferably includes n-hexane at a molar percentage of 47% to 66%, n-heptane at a molar percentage of 34% to 51%, and butyl valerate at a molar percentage of 50% to 52%.

[0024] The ternary mixed medium composed of alkanes, alkenes, and esters is made of 2,5-dimethylhexane (C8H2O). 18 ), 1-octene (C8H) 16 ) and ethyl butyrate (C6H 12 The composition (O2) preferably includes 2,5-dimethylhexane at a molar percentage of 23% to 55%, 1-octene at a molar percentage of 45% to 92%, and ethyl butyrate at a molar percentage of 8% to 77%.

[0025] Secondly, the present invention also provides a method for preparing the phase change cold storage material as described above, wherein the components constituting the phase change cold storage material are mixed.

[0026] Preferably, the components constituting the phase change cold storage material are mixed to obtain a mixed solution, and the mixed solution is stirred under sealed conditions to obtain the phase change cold storage material.

[0027] More preferably, the mixing temperature is room temperature.

[0028] More preferably, the stirring temperature is room temperature.

[0029] Thirdly, the present invention also provides the application of the phase change cold storage material as described above or the phase change cold storage material prepared by the preparation method as described above for energy storage in a temperature range of -90℃ to -105℃.

[0030] According to the applications provided by the present invention as described above, the phase change cold storage material is used for liquefied natural gas storage, liquefied natural gas transportation, pharmaceutical storage, pharmaceutical transportation, or power load management.

[0031] This invention provides a phase change energy storage material, its preparation method, and its applications. By screening specific ester substances, a mixed medium with a eutectic temperature of -90℃ or less, or even 170K or less, and a latent heat of phase change of 11500 J / mol or higher can be obtained, thereby meeting the energy storage requirements in the temperature range below -90℃. The substances selected in this invention possess characteristics such as high safety and excellent thermal performance, and can be used in fields such as liquefied natural gas storage, liquefied natural gas transportation, pharmaceutical storage, pharmaceutical transportation, or power load management. Furthermore, the preparation method of the phase change energy storage material of this invention is simple, low-cost, and has high market application prospects. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0033] Figure 1 This is the solid-liquid equilibrium phase diagram of the phase change cold storage material of Embodiment 1 provided by the present invention.

[0034] Figure 2 This is the solid-liquid equilibrium phase diagram of the phase change cold storage material of Embodiment 2 provided by the present invention.

[0035] Figure 3 This is the solid-liquid equilibrium phase diagram of the phase change cold storage material of Embodiment 3 provided by the present invention.

[0036] Figure 4 This is the solid-liquid equilibrium phase diagram of the phase change cold storage material of Embodiment 4 provided by the present invention.

[0037] Figure 5 This is the solid-liquid equilibrium phase diagram of the phase change cold storage material of Embodiment 5 provided by the present invention. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0039] The following is combined Figures 1-5 This invention describes a phase change cold storage material, its preparation method, and its application.

[0040] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0041] Example 1

[0042] This embodiment provides a phase change cold storage material, which is a binary mixed medium composed of ethyl butyrate and n-propyl acetate.

[0043] This embodiment also provides a method for preparing the above-mentioned phase change cold storage material, which involves mixing ethyl butyrate and n-propyl acetate, and then stirring the mixture under sealed and room temperature conditions. The solid-liquid equilibrium phase diagram of the phase change cold storage material in this system is as follows: Figure 1 As shown, when the molar percentage of ethyl butyrate is 51.5%, this binary mixture can reach a minimum eutectic temperature of 162.59 K. The latent heat of solid-liquid phase transition at this temperature is measured to be 11869.50 J / mol.

[0044] Example 2

[0045] This embodiment provides a phase change cold storage material, which is a binary mixed medium composed of 2,5-dimethylhexane and n-propyl acetate.

[0046] This embodiment also provides a method for preparing the above-mentioned phase change cold storage material, which involves mixing 2,5-dimethylhexane and n-propyl acetate, and then stirring the mixture under sealed and room temperature conditions. The solid-liquid equilibrium phase diagram of the phase change cold storage material in this system is as follows: Figure 2 As shown, when the molar percentage of 2,5-dimethylhexane is 43.2%, this binary mixture can reach the lowest eutectic temperature of 165.75 K. The latent heat of solid-liquid phase transition at this temperature is measured to be 11957.60 J / mol.

[0047] Example 3

[0048] This embodiment provides a phase change cold storage material, which is a binary mixed medium composed of 1-octene and butyl valerate.

[0049] This embodiment also provides a method for preparing the above-mentioned phase change cold storage material, which involves mixing 1-octene and butyl valerate, and then stirring the mixture under sealed and room temperature conditions. The solid-liquid equilibrium phase diagram of the phase change cold storage material in this system is as follows: Figure 3 As shown, when the molar percentage of 1-octene is 63.9%, this binary mixture can reach the lowest eutectic temperature of 164.59 K. The latent heat of solid-liquid phase transition at this temperature is measured to be 15529.26 J / mol.

[0050] Example 4

[0051] This embodiment provides a phase change cold storage material, which is a ternary mixed medium composed of n-hexane, n-heptane and butyl valerate.

[0052] This embodiment also provides a method for preparing the above-mentioned phase change cold storage material, which involves mixing n-hexane, n-heptane, and butyl valerate, and then stirring the mixture under sealed and room temperature conditions. The solid-liquid equilibrium phase diagram of the phase change cold storage material in this system is as follows: Figure 4As shown, when the molar percentages of n-hexane, n-heptane, and butyl valerate are 47%~66%, 34%~51%, and 50%~52%, respectively, the eutectic temperature of this ternary mixed medium is in the temperature range below 170K.

[0053] A ternary mixture containing 40%, 30%, and 30% molar percentages of n-hexane, n-heptane, and butyl valerate was tested, and the eutectic temperature of this ternary mixture was 161.98 K. The latent heat of solid-liquid phase transition at this temperature was measured to be 14214.44 J / mol.

[0054] Example 5

[0055] This embodiment provides a phase change cold storage material, which is a ternary mixed medium composed of 2,5-dimethylhexane, 1-octene and ethyl butyrate.

[0056] This embodiment also provides a method for preparing the above-mentioned phase change cold storage material, which involves mixing 2,5-dimethylhexane, 1-octene, and ethyl butyrate, and then stirring the mixture under sealed and room temperature conditions. The solid-liquid equilibrium phase diagram of the phase change cold storage material in this system is shown below. Figure 5 As shown, when the molar percentages of 2,5-dimethylhexane, 1-octene, and ethyl butyrate are 23%~55%, 45%~92%, and 8%~77%, respectively, the eutectic temperature of this ternary mixed medium is in the temperature range below 170K.

[0057] A ternary mixture containing 26%, 38%, and 36% molar percentages of 2,5-dimethylhexane, 1-octene, and ethyl butyrate was tested. The eutectic temperature of this ternary mixture was 157.28 K. The latent heat of solid-liquid phase transition at this temperature was measured to be 13685.76 J / mol.

[0058] In summary, the eutectic temperature of the above-mentioned mixed medium of the present invention is less than or equal to 170K, and the latent heat of solid-liquid phase change is above 11500J / mol, which can effectively meet the needs of liquefied natural gas cold energy storage, ultra-low temperature experimental environment control, and low temperature cold chain transportation.

[0059] The phase change energy storage material of this invention contains specific components that give it excellent cycle stability, thermal performance, and high energy storage efficiency. It is also non-toxic, harmless, does not deplete the ozone layer, is non-corrosive, does not cause supercooling, and does not exhibit phase separation, meeting environmental protection requirements. Furthermore, it is non-flammable, highly safe, and classified as a non-hazardous chemical. Compared to existing organic cryogenic energy storage materials, it offers advantages in safety, thermal conductivity, and cost, and its preparation method is simple, easy to implement, and convenient to operate.

[0060] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A phase change cold storage material, characterized in that, The phase change cold storage material is a binary mixed medium composed of two ester substances, a binary mixed medium composed of alkanes and ester substances, a binary mixed medium composed of olefins and ester substances, a ternary mixed medium composed of alkanes and ester substances, or a ternary mixed medium composed of alkanes, olefins, and ester substances. The binary mixture of the two esters consists of ethyl butyrate and n-propyl acetate; the molar percentage of ethyl butyrate is 50-55%. The binary mixture of alkanes and esters consists of 2,5-dimethylhexane and n-propyl acetate, wherein the molar percentage of 2,5-dimethylhexane is 40-45%. The binary mixed medium composed of olefins and esters consists of 1-octene and butyl valerate, wherein the molar percentage of 1-octene is 60-65%. The ternary mixed medium composed of alkanes and esters consists of n-hexane, n-heptane, and butyl valerate, with n-hexane comprising 47% to 66% molar percentage, n-heptane comprising 34% to 51% molar percentage, and butyl valerate comprising 50% to 52% molar percentage. The ternary mixed medium composed of alkanes, alkenes and esters consists of 2,5-dimethylhexane, 1-octene and ethyl butyrate, with 2,5-dimethylhexane having a molar percentage of 23% to 55%, 1-octene having a molar percentage of 45% to 92%, and ethyl butyrate having a molar percentage of 8% to 77%.

2. The phase change cold storage material according to claim 1, characterized in that, The binary mixture of the two esters consists of ethyl butyrate and n-propyl acetate, wherein the molar percentage of ethyl butyrate is 51.5%. The binary mixture of alkanes and esters consists of 2,5-dimethylhexane and n-propyl acetate, wherein the molar percentage of 2,5-dimethylhexane is 43.2%. The binary mixed medium composed of olefins and esters consists of 1-octene and butyl valerate, wherein the molar percentage of 1-octene is 63.9%.

3. The phase change cold storage material according to claim 1 or 2, characterized in that, The eutectic temperature of the phase change cold storage material is less than or equal to -90℃; And / or, the latent heat of solid-liquid phase change of the phase change cold storage material is greater than or equal to 11500 J / mol.

4. A method for preparing the phase change cold storage material according to any one of claims 1 to 3, characterized in that, The components constituting the phase change cold storage material are mixed.

5. The preparation method according to claim 4, characterized in that, The components constituting the phase change cold storage material are mixed to obtain a mixed solution, and the mixed solution is stirred under sealed conditions to obtain the phase change cold storage material.

6. The phase change energy storage material according to any one of claims 1 to 3 or the phase change energy storage material prepared by the preparation method according to claim 4 or 5, for energy storage in a temperature range of -90℃ to -105℃.

7. The application according to claim 6, characterized in that, The phase change cold storage material is used for liquefied natural gas storage, liquefied natural gas transportation, pharmaceutical storage, pharmaceutical transportation, or power load management.

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