WO2013093354A1

WO2013093354A1 - Use of organic compounds comprising aromatic groups and ketone or carbonyl functions for energy storage

Info

Publication number: WO2013093354A1
Application number: PCT/FR2012/053013
Authority: WO
Inventors: Jean-Pierre Lallier; Frederick Mantisi; Guillaume Le
Original assignee: Arkema France
Priority date: 2011-12-21
Filing date: 2012-12-20
Publication date: 2013-06-27
Also published as: FR2984908A1

Abstract

The present invention relates to the use of organic compounds comprising aromatic groups and ketone or carbonyl functions for energy storage.

Description

Use of organic compounds comprising aromatic groups and ketone functions or

carbonyls for energy storage.

The present invention relates to the use of organic compounds comprising aromatic groups and ketone or carbonyl functions for storing energy.

Phase change materials (or MCPs) are materials that can latently store energy during a reversible physical state change. The energy density and compactness of the energy storage elements made from these materials make them significantly more competitive than sensible heat storage materials, which store energy as a rise in temperature (unchanged). phase).

Specifically, MCPs have the ability to absorb a certain amount of heat as they move from one physical state to another, usually during their fusion, with a moderate change in their temperature and that of their environment. restore heat by returning to their original physical state, including recrystallizing. These materials are all the more interesting that the amount of heat exchanged during these phase changes, is great. In the case of a solid / liquid transition, this is expressed by their enthalpy of melting or crystallization. The melting and crystallization temperatures of PCMs also determine their possible applications. Of these, one These include the cooling of food products or heat-sensitive pharmaceuticals, textile materials, motors, electronic components and circuits, or waste combustion plants. On an industrial scale, MCPs are also a means of recovering the heat released or available contained in containers or equipment (such as chemical reactors, electrical or mechanical energy generators) or in "process" streams or fluids. (For example cooling / heating circuits, effluents), especially during certain exothermic chemical reactions. The heat released can then be reused to provide energy for other reactions, which reduces the industrial consumption of fossil or electric energy. The use of MCPs in air conditioning (heating / cooling) cycles is also an example of an application where heat energy can be efficiently stored and then returned in the desired time and quantity.

The most common MCP material is water. During its solid / liquid transition (and therefore implicitly liquid / solid), it can absorb or release significant amounts of heat. Thus, tanks or pools of water at a temperature close to 0 ° C., free (in the form of an ice / liquid water mixture) or encapsulated, for example in plastic balls or other materials, constitute an example a simple MCP system capable of storing (when melting ice) and returning (when crystallizing liquid water) large quantities of energy per unit water mass. However, the water, although abundant, available, not toxic, can not solve all the possible problems in heat exchange efficiency because of its limited range of use (towards 0 ° C) and problems related to the high volume expansion of the ice during of his training.

Other common CMPs include paraffins and fatty acids, such as dodecanoic acid, used for air conditioning of buildings, hydrated salts such as Mn (NO ₃ ) ₂ .H ₂ O, MnCl ₂ .H ₂ O, ₂ S ₂ O ₃ .5H ₂ O and CH ₂ COONa .3H ₂ O, and eutectic mixtures, especially of capric acid and lauric acid. These compounds generally have relatively low melting temperatures, ranging from about 15 to about 48 ° C. At around 150 ° C, adipic acid (C ₆ H ₁₀ O ₄ , 152 ° C) or maltitol (d ₂ H ₂₄ O n, 145 ° C) is known and for melting temperatures close to 300 ° C, mention may in particular be made of salts such as NaN0 ₃ (307 ° C) and KN0 ₃ (333 ° C). However, these MCPs have many disadvantages hindering their industrial development. In particular, organic PCMs may be flammable, have low thermal conductivity in the solid state, require large heat transfer during the freeze cycle, and have low volumetric latent heat. In addition, paraffins can pose problems of supply, cost and C0 ₂ generation due to their fossil origin. Inorganic PCMs, on the other hand, generate significant supercooling phenomena. In addition, their phase transition temperatures are not constant due in particular to their hygroscopy. Finally, they are likely to lead to corrosion of the metals with which they are in contact, resulting in unacceptable maintenance costs. To overcome some of the aforementioned drawbacks, it has been proposed to use vegetable or animal waxes, such as beeswax, sugar alcohols such as erythritol, and linear fatty acids or diacids of plant origin which offer a choice of transition temperatures (from 20 to 155 ° C) and latent heat of fusion (from 140 to 240 J / g) according to their chain length, their degree of unsaturation and their acid functions, related to their crystallinity. (See Investigation of Phase Change Materials for Elevated Temperatures, J. Waschull, R. Miiller and S. Römer, Institute for Air Conditioning and Dresden Refrigeration (ILK Dresden), Stockton University, Energy Studies, 2009) Nevertheless, the temperatures of use of these compounds remain modest while there remains a need for MCPs whose operating temperature range is much higher, typically 200-350 ° C and which remain stable at these temperatures well beyond their melting temperature. One can without limitation mention the applications in the field of solar thermodynamics. In addition, compounds which are good thermal conductors, whose density is as high as possible, have a good latent heat of fusion and are resistant to fire.

The Applicant has found that compounds comprising aromatic rings and ketone or carbonyl functions meet these needs. These compounds have melting points of up to 350 ° C, maintain their stability at temperatures up to 100 ° C above their melting point. These compounds are fire resistant, have good latent heat of fusion, have densities higher than 1.2 and are good thermal conductors.

Summary of the invention

The invention relates to the use of at least one organic compound comprising at least one aromatic group and at least one ketone or carbonyl functional group for the storage of thermal energy.

Detailed description :

Aromatic group is understood to mean the groups of the phenyl, naphthyl, anthracyl, phenanthryl or benzophenanthryl type, or more generally the so-called "polyaromatic" groups, which may or may not be substituted. This can be used to finely adjust the melting and crystallization temperatures

Preferably it is the phenyl or naphthyl group and more preferably the phenyl group. The aromatic groups may optionally carry any type of substituent, allowing adjustment of the melting and / or crystallization temperatures.

In a preferred form, the organic compounds used in the invention contain at least one phenyl ether moiety. In another preferred form, the organic compounds contain at least one biphenyl entity.

The aromatic groups are linked together by at least one ketone or carbonyl function. According to one variant, the organic compounds may contain in addition of the ketone or carbonyl function (s), an ether or thio ether function. This ether or thio ether function may be located adjacent to the ketone or carbonyl (ester or thioester) function or not.

The organic compounds used in the invention may also contain amide, imide, sulfone, sulfoxide, or a combination of all or parts of the above functions. According to another preferred form of the invention, the organic compounds used in the invention contain at least one functional terminal group such as acid, ester, hydroxyl, nitrile, nitro, amide or ester. Finally, the organic compounds used in the invention may also contain ionic groups.

The organic compounds used in the invention have a density greater than 1, and preferably greater than 1.2.

The inventors have demonstrated that these compounds have a combination of very advantageous characteristics for use in the storage of thermal energy, namely:

a melting temperature, as measured by DSC, of between 200 and 400 ° C., more particularly between 300 and 400 ° C.

- optionally, a crystallization temperature, as measured by DSC, between 150 and 380 ° C, more particularly between 200 and 350 ° C.

a thermal stability up to 100 ° C. beyond the melting point. a melting enthalpy, as measured by DSC, of at least 100 J / g, more particularly at least 120 J / g or even at least 135 J / g, for example up to 350 J / g; boy Wut,

- optionally, an enthalpy of crystallization, as measured by DSC, of at least 80 J / g, more particularly at least 100 J / g and for example up to 350 J / g,

a good thermal stability, resulting in a capacity to undergo at least 5 cycles, in particular at least 10 cycles, or even at least 50 cycles, of successive melting / crystallization without:

1- the variation of their melting point during the cycles, as measured by DSC, does not exceed 10 "6 VOï 5% and / or

2- the variation of their crystallization temperature during the cycles, as measured by DSC, does not exceed 20% or even 10%, and / or

3- the variation of their enthalpy of fusion during the cycles, as measured by DSC, does not exceed 10 ~ 6;

5%, and / or

The variation of their enthalpy of crystallization during the cycles, as measured by DSC, does not exceed 10% or even 7%, and / or

Their weight loss between the first and the last cycle does not exceed 10%, preferably 5% or even 1%,

as measured, for example, using a ramp rate (heating / cooling) for DSC ranging from 1 to 20 ° C / min, especially 10 ° C / min.

They are characterized by good fire resistance and good thermal conductivity. The organic compounds used in the invention may respond in a nonlimiting manner to the following formulas in Table 1; the positions of the groups on the aromatic rings which may be ortho, meta or para, preferably being in the para position:

Table 1

The organic compounds used in the invention may especially be suitable for the cooling of food products, heat-sensitive pharmaceutical products, motors, electronic components and circuits, buildings, textile materials, chemical reactors, combustion of waste, or included in solar energy storage devices. The heat captured can then be restored to allow the heating of a wall such as a chemical reactor chamber or a fluid.

The organic compounds used in the invention can be used in a mixture, in particular to form eutectic mixtures. they may also contain various additives such as thermal stabilizers or UV, fillers, agents for limiting supercooling such as nucleating agents. Mention may in particular be made of metal oxides, silicates, carbon nanotubes and carbon fibers, metal salts, alumina, talcs, short fibers.

Example 1

Preparation of EKKE (1, 4-phenoxybenzoyl) benzene) according to US4816556:

EKKE is prepared from diphenyl ether (DPE) and terephthaloyl chloride (ATC1) by a Friedel & Craft reaction with aluminum trichloride (AlCl3) in 1,2-dichlorobenzene (oDCB).

In a 2L glass reactor, oDCB (450 g), ATCl (34.5 g) and diphenyl ether (72.6 g) are introduced. The temperature is then decreased to -5 ° C. With nitrogen flushing and stirring, AlCl 3 (105g) is slowly introduced to maintain the temperature between -5 ° C and 5 ° C. The reaction medium is then brought to 20 ° C. and maintained for 15 minutes. MeOH (575 g), previously cooled to -20 ° C, is then slowly added to keep the temperature below 50 ° C. The reaction medium is then cooled to ambient temperature and left stirring for 1 hour. The reaction medium is filtered and solid obtained is then resuspended in MeOH (575 g) at room temperature and stirred for 1 hour. The medium is then filtered and rinsed on the filter with a little methanol (200 g). The product is then dried in a vacuum oven at 120 ° C. overnight. A sample of the solid is purified by recrystallization from N, -dimethylacetamide and the product is dried in a vacuum oven at 120 ° C overnight. The measurement of the density at 20 ° C. is carried out in cyclohexane with a pycnometer: d = 1.196.

A DSC analysis of the EKKE obtained according to the following protocol is carried out:

The sample is introduced into a drilled aluminum capsule, then is characterized on the apparatus DSC TA Q2000 cooling Intracooler with the following program under a nitrogen sweep of 50ml / min according to the standard ISO 11357: 1: stabilization at 20 ° C

2: Heating ramp at 20.00 ° C / min up to 260 ° C

3: Cooling at 20.00 ° C / min up to 20.00 ° C

4: Heating ramp at 20.00 ° C / min up to 260.00 ° C

5: Cooling at 20 ° C / min

This program from step 4 is repeated several times in order to evaluate the thermal stability during several heating cycles followed by cooling.

In the table below, melting temperatures (Tf), melting enthalpies and recrystallization temperatures (Te) are grouped together:

The first firing temperature is 215.5 ° C. enthalpy

Tf of fusion Tc

cycle (° C) (J / g) (° C)

1,215.5 137 179, 1

2,216 135,184.7

3,216, 1,136,177, 6

4 216, 2135 205.2

5,216, 3,136,182, 9

6,216, 2,135,177.7

7,216, 4,135,195, 8

8,216, 4,135,177.3

9,216, 3,135,204.5

10 216, 4 136 176, 4

Example 2

EKKE di-Nitro, or 1,4-bis [4- (4-nitrophenoxy) benzoyl] benzene is prepared according to the procedure described in the article "Synthetic

Communications, 21 (2), 229-234 (1991).

The terephthaloyl chloride (10.15 g) is dissolved at 50 ° C. in 50 ml of nitrobenzene under a nitrogen sweep. This solution is added slowly (in 15 minutes) to a solution of 4-phenoxynitrobenzene (21.5 g) and AlCl 3 (14.7 g) in 50 ml of nitrobenzene with stirring and under a nitrogen sweep. The reaction medium is maintained at 75 ° C. for 30 minutes and is then cooled to ambient temperature. An aqueous solution of HC1 is then added to 10% (200mL) while maintaining the temperature below 70 ° C.

The nitrobenzene is removed by steam distillation. The medium is then filtered and washed several times with water and three times with methanol. The product obtained is then recrystallized with 250 ml of N, -dimethylacetamide. The product is dried in a vacuum oven at 120 ° C. overnight. The measurement of the density at 23 ° C. in cyclohexane is 1.21.

In the table below, the melting temperatures (Tf), the fusion enthalpies and the recrystallization temperatures (Te) are grouped together during the different cycles:

enthalpy

Te fusion tf

cycle (° C) (J / g) (° C)

1,268, 9,136,245

2,269,136 240.2

3,269, 5,135,204.4

4,269, 4,135,204, 9

5,269, 4,134,208.8

6,269, 4,135,215, 9

7,269, 4,135,211.3

8,269, 4,135,209, 4

9,269, 4,135 205.3

10,269, 4,135,204.5 Example 3

EKKE diNitrile is prepared according to the same procedure as above starting from 4-phenoxybenzonitrile while respecting the molar ratios of all products.

The measurement of the density at 23 ° C. in cyclohexane is 1.13.

enthalpy

Te fusion tf

cycle (° C) (J / g) (° C)

1,299,5,148,259

2,298, 9,145,254, 5

3,299,114,259,5

4,298, 9,143,254, 4

5,298, 9,143,254, 9

6,298, 9,143,256, 9

7,298, 8,143,256, 5

8,298, 9,143,254, 3

9,298, 9,143,251.2

10,298, 8,143,252, 4

Claims

claims

Use of at least one organic phase-change compound capable of absorbing a certain amount of heat as it passes from one physical state to another comprising at least one aromatic group and at least one ketone or carbonyl function for storage of thermal energy in which at least one organic compound has a group selected from the following entities:

- phenyl ether

- biphenyl

- biphenyl ether and biphenyl

Use according to Claim 1, in which at least one organic compound has at least one functional group chosen from acid, nitrile, nitro, amide and ester functional groups.

Use according to claim 1 wherein at least one organic compound has a melting point of between 200 and 350 ° C.

Use according to claim 1 wherein at least one organic compound has amide, imide, sulfone, sulfoxide functions.

Use according to any one of claims 1 to 8 in the fields of cooling foodstuffs, heat-sensitive pharmaceuticals, motors, electronic components and circuits, buildings, textile materials, chemical reactors, waste combustion plants, or included in solar energy storage devices.