US20110056656A1

US20110056656A1 - Method for Producing a Latent Heat Storage Material and Dialkyl Ether as a Latent Heat Storage Material

Info

Publication number: US20110056656A1
Application number: US12/863,643
Authority: US
Inventors: Holger Ziehe; Achim Weitze; Thoralf Gross
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-01-23
Filing date: 2009-01-15
Publication date: 2011-03-10
Also published as: EP2242734A2; US10654765B2; ES2650473T3; PL2242734T3; WO2009092349A3; KR20160032256A; DE102008005721B4; EP2242734B1; TWI400227B; JP2011510140A; DE102008005721C5; JP5670202B2; KR101710016B1; US20160257628A1; TW200940492A; DE102008005721A1; WO2009092349A2; KR20100106593A

Abstract

The invention relates to a method for producing latent heat storage material from linear alcohols by dehydrating to dialkyl ethers or to olefins, and hydrating to paraffins and dialkyl ether as a latent heat storage material.

Description

FIELD OF THE INVENTION

The invention relates to a method for producing a latent heat storage material from linear alcohols and dialkyl ether as a latent heat storage material.

BACKGROUND OF THE INVENTION

Phase change materials (PCMs) may release or absorb, respectively, or store, respectively, heat by melting or solidifying, respectively, within a defined temperature range, and thus function as latent heat storage materials. This principle of heat storage may also be used, for example, in the wall insulation of buildings. Such latent heat storage materials are, e.g. in the form of micro-capsules, introduced into the wall plaster or into gypsum plasterboards and liquefy during the day with high heat input. The heat absorbed is stored in the wall and keeps the interior cool. Following cooling during the evening hours and at night, the liquid storages solidify and release the crystallization heat to the environment. In that, the interior is warmed up.
As latent heat storage materials, predominantly paraffins and paraffin mixtures are used. Commercially available paraffin mixtures for PCM applications are, for example, Rubitherm® 27 and Rubitherm® 31. The main component of the above Rubitherm® mixtures is C₁₈paraffin with a content of only 59 or 39% by mass, respectively. These paraffin mixtures consist of even- and odd-numbered linear paraffins in the chain length range of C₁₇to C₂₁or C₁₇to approx. C₃₀, respectively, however, have a portion of linear chains of 98.0 or 95.6% by mass, respectively.
Paraffins may also be produced by hydrating commercially available alpha-olefins. These, however, only have linearities of approx. 90 to less than 95% by mass in the C₁₆to C₁₈range, and have the disadvantage that due to the branched side products, their melting enthalpy is clearly lower in comparison to that of highly linear paraffins.
It was found, that mixtures of even-numbered and odd-numbered paraffins, such with different chain lengths and/or higher branched portions have the disadvantage that these have wide or several different melting peaks, wherein, when these peaks are too far apart with regard to the temperature, normally only part of the possible melting enthalpy can actually be used.

SUMMARY OF THE INVENTION

The object of the present invention therefore is the provision of highly linear compounds, like paraffins, with a defined chain length for use as latent heat storage materials. Herewith, the following advantages are achieved: on the one hand, the melting range of highly pure paraffins is clearly narrower compared to paraffin mixtures, and thus the full storage capacity can be used at low temperature differences already. On the other hand, the melting enthalpy of the pure substance is clearly higher than that of the mixtures.
The invention is defined by the subject matter of the independent claims. Preferred embodiments are the subject matter of the dependent claims or described hereinafter.

DESCRIPTION OF PREFERRED EMBODIMENT

Pure substances, in particular linear paraffins with defined chain lengths, have higher melting heats and narrower melting ranges than branched paraffins or paraffin mixtures. Via the selection of the structure and chain length of the paraffin, the melting temperature of the PCM can be set across a wide temperature range.
The paraffins preferably fulfill the following specification independent from each other:

a) they have even-numbered chain lengths at more than 95 by mass, in particular more than 98 by mass,
b) they exclusively have a certain C-number at more than 95% by mass, in particular more than 97% by mass,
c) they are linear at more than 95% by mass.

The dialkyl ethers respectively have two residues R, so that the limit values are respectively lower. The dialkyl ethers preferably fulfill the following specification independent from each other:

a) they have even-numbered chain lengths at more than 91% by mass, in particular more than 95% by mass,
b) they exclusively have a certain C-number at more than 91% by mass, in particular more than 94% by mass, and
c) they are linear at more than 91% by mass, in particular more than 95% by mass.

In particular, the alcohols are purified or selected, respectively, such that they already fulfill the above limit values for the paraffins, for producing the dialkyl ethers as well as for producing the paraffins.
The latent heat storage material is obtainable by dehydrating linear fatty alcohols to dialkyl ethers or to olefins, wherein the latter are subsequently hydrated to paraffins. Fatty alcohols in terms of this invention are alcohols with C-numbers higher than or equal to 6 and preferably with terminal hydroxy groups. Particularly suitable starting materials in case of the paraffins are cetyl alcohol or stearyl alcohol, and in case of the dialkyl ethers lauryl alcohol or myristyl alcohol.
It was thus surprisingly found that particularly paraffins are suited as linear paraffins for PCM applications, which can be produced by dehydrating linear alcohols to linear olefins and their subsequent hydration. The linear alcohols used are easily available as single sections and are preferably based on renewable vegetable or animal raw materials, in particular vegetable ones, like e.g. palm oil, palm kernel oil, coconut oil, rapeseed oil or other vegetable oils.
Alcohols obtainable from natural raw materials are characterized by an increased linearity of e.g. >98% by mass. The paraffins produced therefrom are therefore surprisingly well suited for application in PCMs. Beside native sources for the alcohols, ethylene oligomerisation according to the Ziegler synthesis, too, is a source for the alcohols used according to the invention.
Alternatively, paraffins may also be used, which can be produced by dehydrating synthetic alcohols. In the chain length range C₁₆to C₁₈, however, normally these frequently only have linearities from 93 to 99%.
The use of linear paraffins as PCMs is known, just like the production of paraffins from fatty alcohols. So far, however, no paraffins have been described for this application as latent heat storage material, which are produced from dehydrated alcohols, in particular such ones, which are available from renewable raw materials.
In the past, the skilled person always assumed that the production of alcohols from paraffins is a refinement step, in which the alcohol has a higher value than the paraffin. Now, it was not to be expected that the reverse path, i.e. the production of paraffin from an alcohol, is economically reasonable. However, it was now demonstrated that paraffins from alcohol dehydration result in particularly pure paraffins, and that these pure paraffins have clearly better characteristics, even compared to only slightly contaminated paraffins.
For this special application, the prices of the paraffins are higher than the prices of fatty alcohols. The required quantities of latent heat storage used directly correlate with the melting heat used, i.e. that substances which have a 20% higher melting heat, also accordingly have to be used in lesser quantities in order to achieve the same effect. For example, textiles can be produced with the same storage capacity with a lesser weight, and thus the wearing comfort can be clearly increased.
A further dehydration product of linear fatty alcohols are dialkyl ethers. These are likewise very non-polar and are characterized by sharp melting peaks and a high melting heat. In particular didodecyl ether and ditetradecyl ether have similar melting temperatures like e.g. C₁₈or C₂₂paraffins, respectively. Suitable catalysts for the dehydration to dialkyl ethers are clays, including boehmitic clays.
In the comparison of products produced by means of dehydrating fatty alcohol, dialkyl ethers and olefins/paraffins, the dialkyl ethers have the advantage that they can be produced economically, since for every 2 mol of fatty alcohol, only 1 mol of water has to be eliminated. As far as desired, the ethers may be stabilized against peroxide formation by means of antioxidants, wherein it is assumed, that in the micro- or macro-capsules, in which PCMs are frequently used, a decomposition of the ethers is sufficiently minimized by the capsule layer (frequently a polymer layer).
The latent heat storage material is preferably encapsulated by a polymer material as the capsule wall in micro-capsules with average particle sizes in the range from 1 to 200 μm, or in macro-capsules with average particle sizes in the range of more than 200 μm to 2 cm. Suitable polymer materials are, e.g., styrene divinylbenzene polymers or unsaturated polyesters. Preferred wall materials, since they are very resistant to ageing, particularly are thermoset polymers. Suitable thermoset polymer materials are, for example, cross-linked formaldehyde resins, cross-linked polyureas and cross-linked polyurethanes as well as cross-linked methacrylic acid ester polymers.
Melting temperature and melting heat are determined by means of DSC analytics. With a defined heating and cooling rate, the onset temperature (melting temperature) and the area below the curve (melting heat) are determined. The melting temperatures and heats of the paraffins and paraffin mixtures determined by means of DSC are respectively represented in the experiment part.

The Figures Show:

FIG. 1 C-chain distribution, of paraffins Rubitherm® 27 and Rubitherm® 31;

FIG. 2 DSC diagram of C16 to C22 paraffins (pure);

FIG. 3 DSC diagram for comparison of Rubitherm® 31/Di-C12 ether/C20 paraffin;

FIG. 4 DSC diagram for comparison of Rubitherm® 27/C18 paraffin/C16 paraffin;

FIG. 5 DSC diagram Di-C12/C14/C16/C18 ethers, and

FIG. 6 DSC diagram for comparison of hexadecane from a synthetic/native source.

EXPERIMENT PART

The evaluation of the DSC analyses for the determination of melting enthalpy [J/g] and onset temperature was performed according to DIN 53765. All DSC curves were measured with the device DSC 204 F1 of the company Netzsch with heating and cooling rates of 10 K/min.

Comparative Example

Commercially available PCMs are Rubitherm® 27 and Rubitherm® 31: Rubitherm® 27 and Rubitherm® 31 have the composition as apparent from FIG. 1 (determined via GC) and furthermore show the following characteristic determined via DSC:

TABLE 1

Paraffin	Rubitherm ® 27	Rubitherm ® 31

n-paraffin content [%]	98.0	95.6
Onset 1 [° C.]	4	−2
Onset 2 [° C.]	26	27
Melting heat 1 [J/g]	22.0	17.9
Melting heat 2 [J/g]	156.3	147.8

As an example for dehydrating linear fatty alcohols, the dehydration of hexadecanol to linear olefins (Experiment 1) and the hydration of hexadecene (Experiment 2) are described in the following.

Experiment 1

Dehydrating fatty alcohols to linear olefins 2474 g of NACOL® 16-99 (purity 99.5%, based on renewable raw materials) were mixed with 500 g of Al₂O₃and 60 ml of xylene in a 6 l flask and heated at up to 295° C. at the water separator for 4.5 hours. In that, 180 ml of water were formed. The hexadecene formed was distilled in vacuum. The yield was a mixture of alpha- and internal olefins.

Experiment 2

Hydrating linear olefins to linear paraffins 685 g of the hexadecene obtained in Experiment 1 were hydrated for 7 hours at 98° C. according to a known method over a heterogeneous Ni-containing catalyst at 20 bar H₂pressure and filtrated after cooling.
Fatty alcohols with chain lengths of C₁₆to C₂₂were used according to Experiments 1 and 2, and the following paraffins were obtained:

TABLE 2

Paraffin	Hexadecane	Octadecane	Eicosane	Docosane

n-paraffin (main	99.6	98.8	93.2	97.4
component) [%]
n-paraffin	99.8	98.9	96.8	98.6
(total) [%]
iso-paraffin [%]	0.2	0.1	1.8	1.2
Onset [° C.]	17.4	27.4	32.5	40.6
Melting heat [J/g]	245.6	250.7	247.2	270.5

Experiment 3

Experiments 1 and 2 were repeated, however, a synthetic fatty alcohol (hexadecanol) from the Ziegler process with a purity of 95.6% was used as the alcohol.

Experiment 4

Experiment 2 was repeated, however, a synthetic olefin (hexadecene ex Chevron Phillips) with a purity of 94.2% was used as the olefin.
A comparison of the onset temperatures and melting heats for paraffins of different purity due to different production methods are compiled in the following table for hexadecane by way of example.

TABLE 3

Paraffin	Hexadecane	Hexadecane	Hexadecane

Test number

	1	2	3
Source	Native alcohol	Synth. alcohol	Synth. olefin
n-C₁₆paraffin [%]	99.6	91.8	92.3
n-paraffin (total) [%]	99.8	93.1	93.2
iso-paraffin (total) [%]	0.2	6.3	6.2
Onset [° C.]	17.4	13.6	14.3
Melting heat [J/g]	245.6	224.2	207.8

Experiment 5-7

Octadecane and Docosane were mixed at weight ratios of 1:1, 2:1, and 3:1, and the DSC curves were measured again.

	TABLE 4

	Paraffin mixture
	[weight ratio]

C₁₈/C₂₂paraffin	C₁₈/C₂₂paraffin	C₁₈/C₂₂paraffin
1:1	2:1	3:1

Onset 1 [° C.]	−1.6	−1.2	−0.5
Onset 2 [° C.]	28.5	26.6	26.7
Melting	17.67	21.64	19.93
heat 1 [J/g]
Melting	123.9	128.7	123.4
heat 2 [J/g]

As an example for the partial dehydration of linear fatty alcohols, the dehydration of dodecanol to linear dialkyl ethers is described in the following.
Experiment 8-11: Dehydrating linear fatty alcohols dialkyl ethers
10 kg/h of NACOL® 12-99 (purity 99.2%, based on renewable raw materials) were led over Al₂O₃beads in a fixed bed reactor (Ø=60 mm, l=900 mm) at 260° C. according to a known method. The didodecyl ether formed was subsequently distilled in vacuum.

	TABLE 5

	Dialkyl ether

Didodecyl	Ditetradecyl	Dihexadecyl	Dioctadecyl
ether	ether	ether	ether

Purity [%]	93.4	95.2	94.8	91.2
Onset [° C.]	30.4	41.8	51.5	59.3
Melting heat [J/g]	209.4	227.4	231.2	207.9

Claims

1-17. (canceled)

18. New. A method for absorbing heat by liquefying a latent heat storage material and emitting the heat stored in the latent heat storage material following cooling by solidifying, by using a latent heat storage material produced from linear fatty alcohols, comprising dehydrating linear fatty alcohols, wherein more than 95% by mass of the fatty alcohols used are linear, to produce;

(a) olefins, wherein the olefins are hydrated to paraffins, the paraffins comprising exclusively a certain C-number at more than 95% by mass, or

(b) dialkyl ethers of the formula R₁—O—R₂, wherein R₁and R₂, independent of one another, are hydrocarbon residues with 6 to 22 carbon atoms, wherein more than 95% by mass of the sum of all residues R₁and R₂comprise the same C-number, and the residues R₁and R₂are equal.

19. New. The method according to claim 18, characterized in that said paraffins comprise even-numbered chain lengths at more than 95% by mass.

20. New. The method according to claim 18, characterized in that said paraffins exclusively comprise a certain C-number at more than 97% by mass.

21. New. The method according to claim 18, characterized in that said dialkyl ethers comprise even-numbered chain lengths at more than 91% by mass.

22. New. The method according to claim 18, characterized in that said dialkyl ethers exclusively comprise a certain C-number at more than 94% by mass.

23. New. The method according to claim 18, characterized in that said fatty alcohols, in the case of the producing olefins are cetyl alcohol or stearyl alcohol, and in case of producing dialkyl esters are lauryl alcohol or myristyl alcohol.

24. New. The method according to claim 18, characterized in that said fatty alcohols are obtained from native vegetable raw materials.

25. New. The method according to claim 18, characterized in that said fatty alcohols are produced by ethylene oligomerisation according to the Ziegler synthesis.

26. New. The method according to claim 18, characterized in that one or more of said latent heat storage materials are encapsulated by a polymer material as the capsule wall into micro-capsules with average particle sizes in the range from 1 to 200 um, or into macro-capsules with average particle sizes in the range from more than 200 um to 2 cm.

27. New. A method for storing heat by liquefying and emitting heat by solidifying as in a latent heat storage material comprising using as said latent heat storage material dialkyl ethers of the formula R₁—O—R₂, wherein R₁and R₂, independent of one another, are hydrocarbon residues with 6 to 22 carbon atoms, and wherein

more than 95% by mass of the sum of all residues R₁and R₂are linear,

more than 95% by mass of the sum of all residues R₁and R₂have the same C-number, and

the residues R₁and R₂are equal.

28. New. The method according to claim 27, characterized in that more than 98% by mass of the sum of all residues R₁and R₂are linear.

29. New. The method according to claim 27, characterized in that more than 95% by mass, of the sum of all residues R₁and R₂are even-numbered.

30. New. The method according to claim 27, characterized in that more than 97% by mass of the sum of all residues R₁and R₂comprise the same C-number.

31. New. The method according to claim 27, characterized in that said dialkyl ethers are derived from the hydration of fatty alcohols, in particular lauryl alcohol or myristyl alcohol.

32. New. The method according to claim 31, characterized in that fatty alcohols are obtained from native vegetable raw materials.

33. New. The method according to claim 27, characterized in that said latent heat storage material is encapsulated by a polymer material as the capsule wall into micro-capsules with average particle sizes in the range from 1 to 200 um, or into macro-capsules with average particle sizes in the range from more than 200 um to 2 cm.

34. New. The method according to claim 24, comprising dehydrating said fatty alcohols to produce said alcohols having at least one of the following characteristics:

more than 95% by mass of said alcohols are linear or

the alcohols comprise even-numbered chain lengths at more than 95% by mass; or

the alcohols comprises a certain C-number at more than 97% by mass.