WO2012008795A2 - Method for preparing an organic phase-change material from animal and plant oils - Google Patents

Abstract

The present invention relates to a method for preparing an organic phase-change material (PCM) by means of a hydrotreating reaction of animal and plant oils. More particularly, the present invention relates to a method for preparing an organic phase-change material, which involves controlling a reaction temperature, a reaction pressure, and a supporting material for a catalyst so as to selectively adjust the weight ratio of the organic phase-change material when the organic phase change material is prepared by a hydrotreating reaction of animal and plant oils, thus obtaining the organic phase-change material in an inexpensive manner.

Description

Method for preparing organic phase change material from animal and vegetable oils

The present invention, in the production of organic phase change material through the hydrotreating reaction of animal and vegetable oil, in the presence of a catalyst, by controlling the reaction temperature, the reaction pressure and the carrier of the catalyst organic phase change material having an odd carbon number of the organic having an even carbon number The present invention relates to a method for preparing an organic phase change material that is selectively adjusted to be higher than the weight of the phase change material.

A phase change material (PCM) can absorb or release a lot of heat (latent heat) as the phase changes at a certain temperature without changing the temperature so that it stores its surrounding heat and releases it when needed It is a substance. These latent heats have tens to hundreds of times more energy storage and release capacity than sensible heat, which is why they are superior to conventional sensible energy storage materials.

Because of its excellent properties, these phase-change materials have an energy industry and eco-friendly housing systems (interior materials, heating and cooling, air conditioning systems, solar systems, low cost energy utilization systems), sports clothing and jewelry (climbing, hiking backpacks, motorcycle clothing, in-line skates). , Sleeping bag), functional clothing (special military uniform), footwear (sneakers, shoes, specialization, specialization, work shoes), military industry facilities and munitions, automotive industry (interior materials, sheet), heat protection system of various digital and electric equipment, medical equipment It is an energy-saving and eco-friendly material that can be applied to various industries such as bed restraint beds for long-term inpatients and blood transportation systems.

Phase change materials are classified into organic phase change materials and inorganic phase change materials according to constituent materials. Currently, organic materials are normally used as normal-paraffins and inorganic materials are calcium chloride. In terms of physical properties, organic phase change materials are not corrosive, chemically and thermally stable, and have no sub-cooling, while the disadvantages are low phase change enthalpy, density and thermal conductivity. In contrast, inorganic phase change materials have advantages of high phase change enthalpy and density, but disadvantages include overcooling, corrosiveness, phase separation, and lack of cycle stability. As a result, in terms of physical properties, organic phase change materials are known to be superior to inorganic phase change materials.

Normal-paraffin, a representative organic phase change material, is produced from kerosene, one of the crude oil refined products. Kerosene generally contains 1-5% by weight of normal-paraffins, and the carbon number of the normal-paraffins is present in a wide range. The production of normal-paraffins from kerosene involves the steps of 1) separating the mixture of the desired carbon number using the boiling point 2) removing impurities such as sulfur, nitrogen, and oxygen in the mixture acting as a poison of the adsorbent used at the end 3) adsorbent Normal-paraffin adsorption process in the mixture using 4) adsorbed normal-paraffin desorption process using desorption material 5) It is a very complicated and expensive process to go through the desorption material and each normal-paraffin separation process using a boiling point. Moreover, since kerosene contains components having various carbon numbers and various normal-paraffin derivatives, the concentration of normal-paraffins that we need is not high, so it is difficult to effectively separate normal-paraffins from kerosene. Although U.S. Patent Application Publication No. 2010/0125162 discusses a method for improving such a normal-paraffin separation process, the method of separating normal-paraffins from kerosene is basically an expensive process, preventing the generalization of organic phase change materials. to be.

On the other hand, commonly encountered vegetable oils include coconut oil, corn oil, cottonseed oil, peanut oil, olive oil, palm oil, palm kernel oil, rapeseed oil, canola oil, sesame oil, soybean oil, sunflower oil, castor oil, linseed oil, safflower oil, Jatropha oil is used, and animal oils include fish oil, tallow, pork and confined fat. In general, the animal and vegetable oil is composed of triglyceride (triglyceride) in which three molecules of fatty acids are combined with one molecule of glycerol. Occupies. For example, palm oil is composed of 1% by weight of C14 fatty acid, 43% of C16 fatty acid, and 55% by weight of C18 fatty acid.

Hydrogenation of these triglycerides yields a mixture of high concentrations of normal-paraffinic materials. Hydrogenation of triglyceride is performed by 1) separating triglyceride into 3 molecules of fatty acid and 1 molecule of glycerol, 2) olefin saturation reaction in fatty acid, and 3) converting fatty acid into normal-paraffin through dehydration and decarboxylation reaction. This results in the production of normal-paraffins with the same carbon number as the fatty acids in triglycerides or with normal-paraffins with one carbon less than fatty acids. For example, palm oil is mainly triglycerides composed mainly of C16 and C18 fatty acids, so when the palm oil is hydrogenated, four kinds of normal-paraffins, mainly C15, C16, C17 and C18, can be obtained.

When normal-paraffin is used as a raw material for phase change material, the use of a single substance having a specific melting point is advantageous to the application of the phase change material as compared to the use of a mixture form having various melting points. Since the phase change material utilizes the latent heat of the process of coagulation and melting of normal-paraffins, the melting point of each normal-paraffin determines the use of the phase change material made from it. For example, C17 (melting point 21 degrees) and C18 (melting point 28 to 30 degrees), which have a melting point similar to the temperature of the active area, are used for housing and clothing purposes, and below C16 (18 degrees melting point). Normal-paraffins are mainly used for cold energy storage and C19 (melting point 32 ~ 34 degrees) or more. Normal-paraffins are mainly used for thermal energy storage.

Recently, the application of phase change materials to housing applications has been the most popular and is expected to form the largest market in the future. The use of phase change materials for residential applications can be divided into passive and active methods. As the term suggests, the passive method is a method of controlling the temperature of a house with only phase change material without the help of other air-conditioning devices, while the active method is a method of reducing the energy of the air conditioner by acting as a supplement to the air conditioners currently used. . Theoretically, the passive method would be the ideal method, but considering the seasonal temperature fluctuations, the limit of latent heat capacity of phase change materials, and customer convenience, the use of phase change materials in an active manner would be most appropriate. In this respect, C17 is expected to be the largest among normal-paraffins for phase change material applications. In addition, C15 normal-paraffin with a melting point of 10 degrees is expected to be in high demand because it is most suitable for cold energy storage. Therefore, it would be very commercially useful if the weight ratio of the organic phase change material having an odd carbon number such as C15 and C17 can be maximized by controlling relatively easy factors such as reaction temperature, reaction pressure and catalyst carrier.

The present invention is an organic phase change material having an odd number of carbon atoms in the presence of a catalyst in the presence of a catalyst in the production of an organic phase change material through a hydrotreating reaction of animal and vegetable oil having an even carbon number It provides a method for producing an organic phase change material that is selectively higher than the weight of the phase change material.

The method for preparing an organic phase change material according to the present invention is characterized in that the weight ratio of the organic phase change material is more effectively controlled by controlling the reaction temperature, the reaction pressure, and the carrier of the catalyst as a control factor during the hydrogenation reaction. More specifically, the method for producing an organic phase change material through the hydrotreating reaction of animal and vegetable oil according to the present invention is controlled by the reaction temperature, reaction pressure and the carrier of the catalyst in the presence of a catalyst to commercially more advantageously It is characterized in that the weight ratio R _{o / e} of the organic phase change material defined by is greater than one.

(One)

In Formula 1, n is an odd number of 13 to 21, m _(n) is the weight of the organic phase change material having n carbon atoms and m _{(n + 1)} is of the organic phase change material having (n + 1) It is weight.

In addition, the method for preparing an organic phase change material through a hydrotreating reaction of animal and vegetable oil according to the present invention includes a carrier of the catalyst including zirconium and controlling the reaction temperature (T, ^o C) and reaction pressure (P, bar) By adjusting to satisfy Equation 2, the weight ratio R _{o / e} of the organic phase change material may be greater than one.

P <(704.3) * e ^-0.008T (2)

      250 ℃ ≤ T ≤ 410 ℃ 10bar ≤ P ≤ 150bar

The carrier of the catalyst contains zirconium, the reaction temperature (T, ^o C) is 250 ~ 410 ^o C and the reaction pressure (P, bar) is controlled to 10 ~ 150 bar to satisfy the above formula 2, the organic phase change material The weight ratio R _{o / e} may be greater than one. That is, if R _{o / e} is greater than 1, the weight ratio of the organic phase change material having an odd carbon number is obtained at a higher ratio than the weight ratio of the organic phase change material having an even carbon number by controlling the reaction temperature and the reaction pressure within the above range. It means you can.

When the carrier of the catalyst contains zirconium and is adjusted to satisfy the equation 2 by controlling the reaction temperature and the reaction pressure, the reaction temperature (T, ^o C) in Equation 2 is 280 ℃ ≤ T ≤ 350 ℃ and the reaction pressure is 20bar It is more preferable that ≦ P ≦ 80 bar.

In addition, the method for producing an organic phase change material through the hydrotreating reaction of animal and vegetable oil according to the present invention includes a titanium of the catalyst and the reaction temperature (T, ^o C) and the reaction pressure (P, bar) by controlling the When Equation 3 is satisfied, R _{o / e, which} is a weight ratio of the organic phase change material, may be greater than one.

P <(30070) * e ^-0.023T (3)

     250 ℃ ≤ T ≤ 410 ℃ 10bar ≤ P ≤ 150bar

In the method for preparing an organic phase change material through a hydrogenation reaction of animal and vegetable oil according to the present invention, the catalyst carrier includes aluminum, and the reaction temperature (T, ^o C) and the reaction pressure (P, bar) are controlled by the following equation. When 4 is satisfied, R _{o / e, which} is a weight ratio of the organic phase change material, may be greater than 1.

P <(927.9) * e ^-0.009T (4)

   250 ℃ ≤ T ≤ 410 ℃ 10bar ≤ P ≤ 150bar

When the carrier of the catalyst is zirconium, it may be zirconium oxide or zirconium phosphate, and when the carrier of the catalyst is titanium, it may be titanium oxide or titanium phosphate, and in the case of aluminum, it may be aluminum oxide or aluminum phosphate, but is not limited thereto.

On the other hand, the catalyst used in the present invention uses a catalyst having a high durability and durability in order to obtain a simple process and a weight ratio of the organic phase change material selectively. The catalyst used in the present invention includes an active ingredient in a carrier, and may be any one or a mixture of two or more selected from the group consisting of VIB, VIIB, VIIIB, VIII, IB or IIB metals, and preferably an organic phase change material. Weight ratio R_{o / e}In terms of more selective control of The metal group VIB may be Mo or W, the metal group VIII may be Ni, Pd, or Pt and the group VIIIB may be one or more mixtures selected from the group Fe, Co, Ru, Rh, and Ir, but is not limited thereto. This is not the case.

In order to obtain the weight of the organic phase change material having an odd number of carbon atoms in the present invention selectively higher than the weight of the organic phase change material having an even number of carbon atoms, the Group VIB metal of the present invention is included in an amount of 0.1 to 70% by weight based on the carrier. However, when supported at less than 0.1% by weight, the activity of the catalyst is very low, and thus does not act as a catalyst. When the VIB group is supported, it is supported on the catalyst in an oxidized state, but it is difficult to carry at least 70% by weight based on oxide. Preferably, Group VIB metal is used in an amount of 1 wt% to 40 wt%. In order to obtain the weight of the organic phase change material having an odd number of carbon atoms in the present invention selectively higher than the weight of the organic phase change material having an even number of carbon atoms, the Group VIII metal or the Group VIIB metal of the present invention is 0.1 to It is included in 60% by weight, because when supported by 0.1% by weight or less, the activity of the catalyst is very low, it does not act as a catalyst, it is difficult to support more than 60% by weight. Group VIII metal or Group VIIB metal is preferably used in an amount of 0.1 to 20% by weight.

 For this reason, the catalyst Ni used in the present invention in order to obtain the weight of the organic phase change material having an odd carbon number at a higher ratio than the weight of the organic phase change material having an even carbon number is 0.1 to 60 with respect to the carrier. It may be included in the weight percent Mo may be included in 0.1 to 70% by weight based on the carrier, most preferably Ni is included in 0.1 to 20% by weight relative to the carrier and Mo may be included in 1 to 40% by weight relative to the carrier. .

Therefore, in the method for preparing an organic phase change material according to the present invention, the active ingredient of the catalyst is a mixture of Ni and Mo, and Ni is included in an amount of 0.1 to 60% by weight based on the carrier, and Mo is included in an amount of 0.1 to 70% by weight based on the carrier. It is preferable that it is done.

In the method for preparing an organic phase change material in which the weight of the organic phase change material having an odd carbon number is selectively higher than the weight of the organic phase change material having an even carbon number, the active ingredient of the catalyst is preferably Ni and It is a mixture of Mo and the carrier of the catalyst is zirconium oxide, the reaction temperature is 280 ~ 350 ^o C and the reaction pressure (P, bar) is controlled to 20 ~ 80 bar by weight ratio of the organic phase change material defined by the formula 2 R Organic phase change materials with _{o / e} greater than 1 can be obtained.

The animal and vegetable oil is not particularly limited, but coconut oil, corn oil, cottonseed oil, peanuts, olive oil, palm oil, palm oil, rapeseed oil, canola oil, sesame oil, soybean oil, sunflower oil, castor oil, linseed oil, safflower oil, jatropha oil It may be one or two or more mixtures selected from the group consisting of fish oil, beef tallow, pork fat, poultry fat and fatty acids or waste oil thereof.

The fats and fauna-derived fats are mainly composed of triglycerides, which are fats having 4 to 36 carbon atoms constituting each chain of triglycerides, and fatty acids having 4 to 36 carbon atoms. It is preferable to use but is not limited thereto.

In the hydrogenation reaction of animal and vegetable oil according to the method for preparing an organic phase change material of the present invention, triglyceride mainly present in fat by hydrogen may be produced as propane, water, carbon monoxide, carbon dioxide, and the like as normal by-paraffins and by-products. In addition, the paraffins produced at this time are C13 to C22, preferably C15 to C18.

The method for preparing an organic phase change material according to the present invention controls the reaction temperature, the reaction pressure and the carrier of the catalyst in the presence of a catalyst in the preparation of the organic phase change material through the hydroprocessing reaction of animal and vegetable oils to reduce the weight ratio of the organic phase change material. By selectively adjusting the weight of the organic phase change material having an odd number of carbon atoms, the weight of the organic phase change material having an even number of carbon atoms can be produced.

In addition, the present invention, when preparing an organic phase change material through the hydrogenation reaction of animal and vegetable oil, in the presence of a catalyst, by controlling the reaction temperature, the reaction pressure and the carrier of the catalyst, the weight of the organic phase change material having an odd carbon number has an even carbon number There is an advantage in that an organic phase change material having a characteristic (melting point) required by manufacturing an organic phase change material that is selectively higher than the weight of the organic phase change material can be manufactured more selectively.

In addition, the organic phase change material prepared according to the present invention is manufactured by inexpensive process while being manufactured by selectively adjusting the weight of the organic phase change material that meets the requirements, so that it can be applied to various industrial fields to achieve the generalization of the organic phase change material. Can be.

1 is a weight ratio of an organic phase change material in the production of an organic phase change material through a hydrogenation reaction of animal and vegetable oil, the catalyst carrier includes zirconium, the reaction temperature is 250 ~ 410 ^o C and the reaction pressure is 10 ~ 150 bar region It is a graph showing the reaction temperature and pressure of which R _{o / e} is 1.

Figure 2 is a graph of DSC analysis of octadecane (C18) obtained by separating the prepared organic phase change material.

Hereinafter, specific examples of the present invention will be described, but this is not intended to limit the scope of the present invention.

Example 1 Preparation of NiMo / ZrO 2 Catalyst

 A catalyst having 10 wt% Mo and 3 wt% Ni was prepared using 200 g of ZrO 2 having a diameter of 1 mm as a carrier. Ammonium heptamolybdate tetrahydrate (hereinafter referred to as “AHM”) was used as the Mo precursor used in the preparation, and Nickel nitrate hexahydrate (hereinafter referred to as “NNH”) was used as the Ni precursor. In the case of Mo and Ni metals, various precursors may be used, and the present invention is not limited thereto.

 NiMo / ZrO₂ catalysts were prepared in the following order.

 First, an aqueous solution prepared by dissolving AHM in distilled water was impregnated in a ZrO₂ carrier, and then dried at 150 ° C. for 2 hours, and subsequently calcined at 500 ° C. for 2 hours to prepare Mo / ZrO₂.

 After NNH was dissolved in distilled water, the Mo / ZrO₂ catalyst was impregnated, dried at 150 ° C. for 2 hours, and subsequently calcined at 500 ° C. for 2 hours to prepare a NiMo / ZrO₂ catalyst.

 6 cc of catalyst prepared according to the above procedure was charged to a cylindrical reactor, and then fed at a rate of 0.08 cc / min using R-LGO as a feed at room temperature, and a pressure of 45 bar and a H 2 flow of 16 cc / min. The temperature was raised to 320 ° C. while flowing at a rate, and pretreated for 3 hours when reached at 320 ° C.

Example 2: Preparation of NiMo / TiO 2 Catalyst

 A catalyst having about 10 wt% Mo and about 3 wt% Ni was prepared using 200 g of TiO 2 having a diameter of 1 mm as a carrier. AHM was used as the Mo precursor used in the preparation and NNH was used as the Ni precursor.

 In the case of Mo and Ni metals, various precursors may be used, and the present invention is not limited thereto. A catalyst was prepared and pretreated in the same manner as in Example 1.

Example 3: NiMo / Al ₂ O ₃  Preparation of the catalyst

200 g of Al ₂ O ₃ having a diameter of 1 mm was used as a carrier to prepare a catalyst having about 10 wt% Mo and about 3 wt% Ni. AHM was used as the Mo precursor used in the preparation and NNH was used as the Ni precursor.

 In the case of Mo and Ni metals, various precursors may be used, and the present invention is not limited thereto. A catalyst was prepared and pretreated in the same manner as in Example 1.

Example 4 Preparation of Organic Phase Change Material Mixture through Palm Oil Hydrotreating

NiMo / ZrO₂ catalyst prepared in Example 1, NiMo / TiO₂ catalyst prepared in Example 2, or NiMo / Al ₂ O ₃ catalyst prepared in Example 3 were reacted at a reaction temperature of 300 ° C., reaction pressure of 30 bar, and hydrogen of 100 cc / Under the condition of the introduction of min, palm oil containing 1% by weight of di-Methyl Disulfide (DMDS) was reacted at a rate of 0.1 cc / min (LHSV = 1). In the case of a feed, all animal and vegetable oils and fatty acids or waste oils thereof may be used, or a mixture of two or more thereof, but is not limited thereto.

 In the case of using animal or vegetable oil before purification or particularly waste oil as a feed, impurities contained in the feed may lower the activity of the catalyst or cause unwanted reactions. In order to solve this problem, a step of removing impurities contained in animal and vegetable oils before the hydrogenation reaction of animal and vegetable oils should be further included. Impurities in animal and vegetable oils were filtered using a filter having a pore size of 0.1-100 μm. In the case of removing impurities, any conventionally known removal method may be used, and the present invention is not limited thereto.

 In the hydrotreating reaction for the purpose of refining crude oil, since the sulfur itself is contained in the feed itself, the activity of the catalyst is maintained without mixing sulfur compounds separately. However, in the case of the hydroprocessing reaction of animal and vegetable oils, animal and vegetable oils used as feeds do not contain sulfur, but rather have oxygen, which is a sulfur-like group, so that the catalyst is easily deactivated by reaction with oxygen. To overcome this, 1% by weight of di-Methyl Disulfide (DMDS) sulfur compound was mixed with the feed and treated.

 Sampling was performed every 8 hours, and the reaction properties of the obtained product were confirmed by simdist analysis, and the results are shown in Table 1.

Table 1

The results shown in Table 1 show that the conversion of triglycerides to normal-paraffins (C15-C18) in palm oil was 97-98% for both NiMo / ZrO₂ and NiMo / TiO₂ and NiMo / Al ₂ O ₃ catalysts. In addition, in the order of NiMo / ZrO ₂ , NiMo / Al ₂ O ₃ , and NiMo / TNi _M catalysts, the decarboxylation reaction was superior to the dehydration reaction. there was.

Example 5 Control of the Weight Ratio of Organic Phase Change Materials According to Reaction Temperature and Reaction Pressure Under NiMo / ZrO 2 Catalyst

 The reaction was carried out in the same manner as in Example 4 except that the reaction pressure was changed to 20, 30, 70, and 100 bar at a reaction temperature of 300 ° C., and the results are shown in Table 2.

TABLE 2

The results shown in Table 2 show that the higher the reaction pressure at the same reaction temperature under the NiMo / ZrO₂ catalyst, the more dehydration reaction is superior to the decarboxylation reaction, resulting in more C16 and C18 components than C15 and C17 components. Could.

The reaction was carried out in the same manner as in Example 4 except that the reaction temperature was changed to 280, 290, 300, 310, 320, 350, and 380 ° C. at a reaction pressure of 30 bar. Table 3 shows.

TABLE 3

The results shown in Table 3 show that the higher the reaction temperature at the same reaction pressure under the NiMo / ZrO₂ catalyst, the more dehydrated reactions are superior to the carboxyl leaving reactions, resulting in more C16 and C18 components than C15 and C17 components. Could.

After interpolating the results of Table 2, the reaction temperature was 300 ℃ the reaction pressure of about 69bar or more smaller than R _{o / e} is 1, is approximately 69bar or less was confirmed that R is greater than the _{o / e} is 1. In the same way, a reaction pressure of R _{o / e} = 1 at each reaction temperature of 280, 290, 310, 320, 350, and 380 ° C. was obtained, and the results are shown in FIG. 1. In addition, as shown in FIG. 1, the reaction temperature (T, ^o C) and the reaction pressure (P) when R _{o / e} = 1 through the trend of the reaction pressure values R _{o / e} = 1 at each temperature , bar) can be obtained as follows.

P = (704.3) * e ^-0.008T

Therefore, when P <(704.3) * e ^-0.008T , R _{o / e} is greater than 1, and conversely, when P> (704.3) * e ^-0.008T , R _{o / e} is less than 1. From these results, it was also found that by controlling the reaction temperature, the reaction pressure, and the carrier of the catalyst, the weight of the organic phase change material having an odd carbon number can be selectively obtained at a weight higher than that of the organic phase change material having an even number.

Therefore, R _{o / e} was larger than 1 in the case of, whereas R _{o / e} was smaller than 1 in the case of. From these results, the reaction temperature, reaction pressure and the carrier of the catalyst were It was also found that the weight of the organic phase change material can be selectively obtained at a weight higher than that of the even numbered organic phase change material.

Example 6: Control of the weight ratio of organic phase change material according to reaction temperature and reaction pressure under NiMo / TiO₂ catalyst

The reaction was carried out in the same manner as in Example 5 except that the NiMo / TiO₂ catalyst was used instead of the NiMo / ZrO₂ catalyst, and through the trend of the reaction pressure values R _{o / e} = 1 at each temperature, R _{o /} The relationship between reaction temperature (T, ^o C) and reaction pressure (P, bar) when _e = 1 was obtained as follows.

P = (30070) * e ^-0.023T

Therefore, when P <(30070) * e ^-0.023T , R _{o / e} is greater than 1. On the contrary, when P> (30070) * e ^-0.023T , R _{o / e} is less than 1. there was.

Example 7: NiMo / Al ₂ O ₃  Control of Weight Ratio of Organic Phase Change Materials by Reaction Temperature and Reaction Pressure under Catalyst

The reaction was carried out in the same manner as in Example 5 except that the NiMo / Al ₂ O ₃ catalyst was used instead of the NiMo / ZrO₂ catalyst, and through the trend of reaction pressure values such that R _{o / e} = 1 at each temperature, The relation between reaction temperature (T, ^o C) and reaction pressure (P, bar) when R _{o / e} = 1 was obtained as follows.

P = (927.9) * e ^-0.009T

Therefore, when P <(927.9) * e ^-0.009T , R _{o / e} is greater than 1. On the contrary, when P <(927.9) * e ^-0.009T , R _{o / e} is less than 1. there was.

As described above, when the organic phase change material was prepared through the hydroprocessing reaction of animal and vegetable oil, it was found that it is possible to selectively control the weight ratio of the organic phase change material by controlling the reaction temperature, the reaction pressure, and the carrier of the catalyst.

Example 8 Separation of Organic Phase Change Materials with Selectively Controlled Weight Ratio

 1 wt% C14, 24 wt% C15, 19 wt% C16, 31 wt% C17, 23 wt% C18 and 2, obtained by carrying out the same reaction as in Example 4 using the NiMo / ZrO catalyst prepared in Example 1 A phase change material mixture having a composition by weight of unconverted oil was separated into each phase change material through a distillation method.

In the case of a feed of 10,000 kg / hr, the results of the separation of each component in 93% purity is shown in Table 4, and the results of the separation in 99% purity is shown in Table 5, respectively.

In the case of product separation, all conventionally known separation methods can be used and are not limited to the above distillation methods.

Table 4

[Revision 11.08.2011 under Rule 26]
Table 5

When the mixture of the organic phase change material obtained by selectively controlling the weight ratio of the organic phase change material by controlling the reaction temperature, the reaction pressure and the carrier of the catalyst is separated in 93% purity, In the case of using four distillation towers and separating them with 99% purity, it was found that high purity phase change materials could be prepared by using a relatively simple method.

Example 9 Characterization of Organic Phase Change Materials

In Example 8, octadecane (C18) having a purity of 99% in each normal-paraffin (C15-C18) prepared and isolated from palm oil was analyzed using DSC, and the results are shown in FIG. 2. DSC experiments were carried out in a nitrogen atmosphere at a temperature of minus 10 degrees to 60 degrees at a rate of 5 K / min and then maintained for 5 minutes, after which the temperature was lowered to the same rate at minus 10 degrees and then maintained for 5 minutes. The same experiment was repeated 10 times in order to evaluate the stability of the phase change material during the temperature change.

2, the octadecane (C18) obtained from palm oil started melting at 27.7 degrees in the case of temperature rise, and the melting proceeded mainly around 30 degrees, and the latent heat absorbed at this time was 212.6 J / g. On the other hand, in the case of temperature drop, solidification started at 26.6 ° C, and solidification proceeded mainly at 26 ° C, and the latent heat released at this time was 212.3 J / g. Melting point, freezing point and latent heat amount at that time did not change even in 10 repeated evaluations.

As described above, it was confirmed that the phase change material prepared and separated from palm oil has properties suitable for the phase change material such as phase change in a narrow temperature range, high latent heat and high stability.

Claims (12)

1. In the preparation of organic phase change material through hydrogenation of animal and vegetable oils,

   In the presence of a catalyst, a method for producing an organic phase change material, characterized in that, by controlling the reaction temperature, the reaction pressure, and the carrier of the catalyst, R _{o / e, which} is a weight ratio of the organic phase change material defined by Equation 1 below, is greater than one: .

   (One)

   In formula 1, n is an odd number of 13 to 21, m _(n) is the weight of the organic phase change material having a carbon number _n and m _{(n + 1)} is of the organic phase change material having a carbon number (n + 1) It is weight.
2. The method of claim 1,

   When the carrier of the catalyst includes zirconium and satisfies Equation 2 by controlling the reaction temperature (T, ^o C) and the reaction pressure (P, bar), the weight ratio of the organic phase change material R _{o / e} is 1 Method for producing an organic phase change material, characterized in that larger.

   P <(704.3) * e ^-0.008T (2)

         250 ℃ ≤ T ≤ 410 ℃ 10bar ≤ P ≤ 150bar
3. The method of claim 1,

   When the carrier of the catalyst comprises titanium and controls the reaction temperature (T, ^o C) and the reaction pressure (P, bar) to satisfy the following formula 3, the weight ratio of the organic phase change material R _{o / e} is 1 Method for producing an organic phase change material, characterized in that larger.

   P <(30070) * e ^-0.023T (3)

         250 ℃ ≤ T ≤ 410 ℃ 10bar ≤ P ≤ 150bar
4. The method of claim 1,

   When the catalyst carrier includes aluminum and the reaction temperature (T, ^o C) and the reaction pressure (P, bar) to satisfy the following formula 4, the weight ratio of the organic phase change material R _{o / e} is 1 Method for producing an organic phase change material, characterized in that larger.

   P <(927.9) * e ^-0.009T (4)

         250 ℃ ≤ T ≤ 410 ℃ 10bar ≤ P ≤ 150bar
5. The method of claim 2,

   Zirconium is a method for producing an organic phase change material, characterized in that the zirconium oxide or zirconium phosphate.
6. The method of claim 3,

   Titanium is a method for producing an organic phase change material, characterized in that the titanium oxide or titanium phosphate.
7. The method of claim 4, wherein

   Aluminum is an aluminum oxide or aluminum phosphate method for producing an organic phase change material, characterized in that.
8.  The method of claim 1,

    The catalyst is a method for producing an organic phase change material, characterized in that it comprises any one or a mixture of two or more selected from the group consisting of VIB, VIIB, VIIIB, VIII, IB or Group IIB metal as an active ingredient in the carrier.
9.  The method of claim 8,

    The metal group VIB is Mo or W, the metal group VIII is Ni, Pd, or Pt, the metal group VIIIB is Fe, Co, Ru, Rh, or Ir manufacturing method of an organic phase change material.
10. The method of claim 1,

    The catalyst is a method for producing an organic phase change material, characterized in that Ni is contained in 0.1 to 60% by weight based on the carrier and Mo is 0.1 to 70% by weight relative to the carrier.
11. The method of claim 1,

    The active component of the catalyst is an organic phase change material of Ni and a mixture of Mo and characterized in that the R _{o / e} ratio of the organic phase change material which is defined by the following is a carrier of the catalyst is zirconium oxide type 2 is greater than 1 Manufacturing method.

    P <(704.3) * e ^-0.008T (2)

          280 ℃ ≤ T ≤ 350 ℃ 20bar ≤ P ≤ 80bar
12.  The method of claim 1,

    The animal and vegetable oils include coconut oil, corn oil, cottonseed oil, peanuts, olive oil, palm oil, palm oil, rapeseed oil, canola oil, sesame oil, soybean oil, sunflower oil, castor oil, linseed oil, safflower oil, jatropha oil, fish oil, tallow oil, pork Method for producing a phase change material, characterized in that one or more mixtures selected from the group consisting of poultry fat and fatty acids or waste oil thereof.

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