WO2012008797A2

WO2012008797A2 - Method for preparing an organic phase change material by means of a hydrotreating reaction of animal and plant oils

Info

Publication number: WO2012008797A2
Application number: PCT/KR2011/005232
Authority: WO
Inventors: 김도완; 김도경; 이상일; 전희중; 강신영; 유재욱; 오승훈
Original assignee: 에스케이이노베이션 주식회사
Priority date: 2010-07-16
Filing date: 2011-07-15
Publication date: 2012-01-19
Also published as: WO2012008797A3; WO2012008797A9

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. The method for preparing an organic phase-change material according to the present invention can enable the preparation of a high-purity organic phase-change material in an inexpensive manner as compared to conventional preparation methods in which organic phase-change materials are obtained from kerosene through absorption and desorption processes.

Description

Process for preparing organic phase change material through hydrogenation of animal and vegetable oils

The present invention relates to a method for producing an organic phase change material (PCM) through the hydrotreating reaction of animal and vegetable oil, and more particularly, to a mixture of the organic phase change substance through the hydrotreating reaction of animal and vegetable oil in the presence of a catalyst. It relates to a method for preparing an organic phase change material by separating the mixture of the organic phase change material obtained after the preparation.

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 fatty acids are bonded to one molecule of glycerol, and the fatty acids constituting each chain are mainly 4 carbon atoms (butyric acid) to 28 carbon atoms (octacoseno). Iksan) up to fatty acids. The types of fatty acids that make up one species of animal or vegetable oil are generally simple, with most fatty acids in the three species being the majority. 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.

When the triglyceride is hydrogenated, a mixture composed of a high concentration of normal-paraffin material is obtained, and then a normal-paraffin having each phase change material property can be obtained simply and inexpensively through a separation method such as distillation. 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. Therefore, it is possible to produce a phase change material in the range of melting point −188 ° C. (C3 propane melting point) to 65 ° C. (C28 octacosene melting point) through a hydrogenation process of a main animal or vegetable oil composed of fatty acids having 4 to 28 carbon atoms. .

US Patent No. 6,574,971 discusses triglycerides of animal and vegetable oil and methods of using fatty acids in triglycerides as phase change materials. Although this method is also a method of preparing a phase change material using animal and vegetable oil, the oxidation stability is lower than that of the present patent for preparing a phase change material using normal-paraffin which has undergone the hydrogenation process of animal and vegetable oil. It has a disadvantage.

Therefore, in the present invention, a relatively inexpensive organic phase change material is prepared through a method of preparing an organic phase change material by preparing a mixture of organic phase change materials through a hydrogenation reaction of animal and vegetable oil in the presence of a catalyst and then separating the outputs thereof. In addition, it was confirmed that it is possible to generalize the phase change material applied to various industries.

In order to overcome the above problems, the present invention provides a method for preparing an organic phase change material by separating a mixture of organic phase change materials obtained after preparing a mixture of organic phase change materials through a hydrogenation reaction of animal and vegetable oil in the presence of a catalyst. To provide.

One embodiment of the present invention for achieving the above object is a method for producing an organic phase change material through a hydrogenation reaction of animal and vegetable oil,

(a) preparing a mixture of organic phase change materials in the presence of a catalyst through a hydrotreating reaction of animal or vegetable oils;

(b) separating the organic phase change material from the mixture of step (a); to prepare an organic phase change material.

The animal and vegetable oil is not particularly limited, but coconut oil, corn oil, cottonseed oil, peanuts, 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 It may be any one or a mixture of two or more selected from the group consisting of fish oil, tallow, pork, poultry fat and fatty acids or waste oil thereof.

In the case of the fat, the number of carbons constituting each chain of the triglyceride is 4 to 36 fats, and in the case of the fatty acid, it is preferable to use fatty acids having 4 to 36 carbons, but is not limited thereto.

In addition, before step (a), the animal and vegetable oil used in the present invention may further include a step of removing impurities contained therein. The step of removing the impurities may be performed using a conventional method, but the pore size is 0.1. It is preferable to use a filter of ˜100 μm.

The present invention uses a catalyst having a high durability and durability in the step (a) to produce an organic phase change material through a simple process.

Such catalysts may comprise any one or two or more mixtures selected from the group consisting of VIB, VIIB, VIIIB, VIII, IB or IIB metals as active ingredients in the carrier, more specifically the metal VIB group is Mo or W, The metal group VIII may be Ni, Pd, or Pt, and the group VIIIB may be Fe, Co, Ru, Rh, or Ir, but is not limited thereto.

Group VIB, VIIB, VIIIB, VIII, IB or IIB metal of the present invention is included in 0.1 to 70% by weight with respect to the carrier, when supported by 0.1% by weight or less, the activity of the catalyst is very low and does not act as a catalyst, This is because it is difficult to support at 70% by weight or more. Preferably it is supported by 1 to 40% by weight.

Carriers used in the present invention are not particularly limited, but aluminum oxide, zirconium oxide, silica-alumina, titanium oxide, carbon, alkaline earth metal oxide, alkali metal oxide, aluminum phosphate, niobia, ceria, lantania, zirconium phosphate, Titanium phosphate, silicon carbide or mixtures thereof can be used.

In addition, the method for producing an organic phase change material of the present invention is more preferably the carrier is zirconium oxide, aluminum oxide or titanium oxide, the active ingredient of the catalyst is a mixture of Ni and Mo and the hydrogenation reaction is a temperature of 250 ~ 410 ℃ It can be carried out at 10-150 bar air pressure.

In addition, step (b) of the present invention may be carried out using fractional distillation, but it is preferable to use four or more distillation columns to produce a higher purity organic phase change material.

On the other hand, animal and vegetable oil is mainly composed of triglycerides (Triglyceride), in the general hydrotreating reaction conditions, triglycerides are produced by the hydrogen-propane, H ₂ O, CO, CO ₂ and the like as a by-paraffin and by-products.

The organic phase change material produced according to the present invention may be composed of normal-paraffins having 13 to 22 carbon atoms, preferably composed of normal-paraffins having 15 to 18 carbon atoms, and having a purity of 98% or more. Can be.

In addition, the organic phase change material may be composed of normal-paraffin having a melting point at a temperature of -5 ℃ to 42 ℃ and preferably composed of normal-paraffin having a melting point at a temperature of 9 ℃ 31 ℃.

In the presence of a catalyst according to the present invention, a mixture of organic phase change materials may be prepared through a hydrogenation reaction of animal and vegetable oil, and then, the output may be separated to prepare an organic phase change material. It is a high process, simple process, and low cost process, so it can be applied to various industrial fields to achieve generalization of organic phase change materials.

1 is a flowchart of an organic phase change material production process in the case of using a hydroprocessing reaction of animal and vegetable oil.

Figure 2 is a graph of DSC analysis of octadecane (C18) prepared and separated from palm oil in Example 7.

Hereinafter, a method of preparing a mixture of organic phase change materials through a hydrogenation reaction of animal and vegetable oil using a catalyst prepared using the technique of the present invention, and distilling the same will be described in detail as follows. I would like to.

The organic phase change material manufacturing process includes removing impurities contained in the feed, pretreating the feed through hydrogenation, separating the unreacted hydrogen after the hydrodeoxidation, and cooling and separating the produced hydrocarbon. It can be included as a step to add a step to, but can be added or subtracted one or two steps according to any purpose, of course.

Although the process of using the hydroprocessing reaction of animal and vegetable oil as a feed is illustrated by way of example in FIG. 1, this invention is not limited to this.

Example 1 Preparation of NiMo / ZrO 2 Catalyst

A catalyst having about 10 wt% molybdenum and about 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 into a cylindrical reactor, and then fed at a rate of 0.08 cc / min with R-LGO as a feed at room temperature, and a pressure of 45 bar and a H₂ 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: Preparation of Organic Phase Change Material Mixture through Palm Oil Hydrotreating

Palm oil containing 1% by weight of di-Methyl Disulfide (DMDS), which is a feed of NiMo / ZrO₂ and NiMo / TiO₂ catalysts prepared by the above method at a reaction temperature of 300 ° C., reaction pressure of 30 bar, and 100 cc / min of hydrogen. Were each reacted at a rate of 0.1 cc / min (LHSV = 1). In the case of feed, any one or more of all animal and vegetable oils and fatty acids or waste oils thereof may be used, but is not limited to the palm oil.

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 group such as sulfur, 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

In the results shown in Table 1, the conversion of triglyceride in palm oil to normal-paraffin (C15-C18) was 98% for both NiMo / ZrO₂ and NiMo / TiO₂ catalysts. In addition, when the NiMo / TiO ₂ catalyst was used, the dehydration reaction was superior to the carboxylization reaction compared to the NiMo / ZrO ₂ case, and it was found that the C16 and C18 components were generated relatively more than the C15 and C17 components.

Example 4 Composition Change of the Organic Phase Change Material Mixture According to Reaction Pressure

Except for changing the reaction pressure to 20, 30, 70, 100 bar, the reaction was carried out in the same manner as in Example 3 for the NiMo / ZrO 2 catalyst, the results are shown in Table 2.

TABLE 2

From the results shown in Table 2, the higher the reaction pressure at the same reaction temperature, it was found that the dehydration reaction is superior to the carboxylization reaction to generate more C16 and C18 components than the C15 and C17 components.

Example 5 Composition Change of Organic Phase Change Material Mixture with Different Reaction Temperatures

The reaction was carried out in the same manner as in Example 3 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 the dehydration reaction is superior to the decarboxylation reaction, resulting in the generation of more C16 and C18 components than the C15 and C17 components. Could.

From the results of Tables 1 to 3, the conversion rate of triglyceride to normal-paraffin (C15-C18) in palm oil in the presence of the prepared catalyst was a high level of 98%, and also the reaction temperature, reaction pressure and catalyst It was found that a phase change material having a desired property (melting point) in a mixture of phase change materials can be prepared more selectively by controlling a relatively easy control factor such as a carrier.

Example 6 Separation of Organic Phase Change Material Mixture

Distilling a phase change material mixture having a composition of 1 wt% C14, 24 wt% C15, 19 wt% C16, 31 wt% C17, 23 wt% C18 and 2 wt% unconverted oil, obtained by the same reaction as in Example 3 The phase separation material was separated by the 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

Table 5

In the results of Tables 4 to 5, four distillation towers were used for separation of 93% purity and five distillation towers for separation of 99% purity to prepare phase change materials of high purity in a relatively simple manner. Could see.

Example 7 Characterization of Organic Phase Change Materials

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

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

(a) preparing a mixture of organic phase change materials in the presence of a catalyst through a hydrotreating reaction of animal or vegetable oils;

(b) separating the organic phase change material from the mixture of step (a).
The method of claim 1,

The animal and vegetable oils are coconut oil, corn oil, cottonseed oil, peanuts, 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, fish oil, tallow oil, pork Method for producing an organic phase change material, characterized in that any one or two or more selected from the group consisting of poultry fat and fatty acids or waste oil thereof.
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 two or more mixtures selected from the group consisting of VIB, VIIB, VIIIB, VIII, IB or group IIB metal as an active ingredient in the carrier.
The method of claim 3

The metal group VIB is Mo or W, the metal group VIII is Ni, Pd, or Pt and the group VIIIB is Fe, Co, Ru, Rh, or Ir manufacturing method of an organic phase change material.
The method of claim 3, wherein

The VIB, VIIB, VIIIB, VIII, IB or group IIB metal is prepared in an organic phase change material, characterized in that containing 0.1 to 70% by weight based on the carrier.
The method of claim 3, wherein

The carrier is aluminum oxide, zirconium oxide, silica-alumina, titanium oxide, carbon, alkali metal oxide, alkali metal oxide, aluminum phosphate, niobia, ceria, lanthania, zirconium phosphate, titanium phosphate, silicon carbide or mixtures thereof Method for producing an organic phase change material, characterized in that.
The method of claim 1,

The carrier is zirconium oxide, aluminum oxide or titanium oxide, the active ingredient of the catalyst is a mixture of Ni and Mo and the hydroprocessing reaction is carried out at an atmospheric pressure of 10 ~ 150 bar temperature of 250 ~ 410 ℃ Method of preparation of the substance.
The method of claim 1,

Before the step (a), further comprising the step of removing impurities contained in animal and vegetable oil.
The method of claim 8,

Removing the impurities is a method of producing an organic phase change material, characterized in that using a filter having a pore size of 0.1 ~ 100 μm.
The method of claim 1,

Step (b) is a method for producing an organic phase change material is carried out using fractional distillation.
The method of claim 1,

The organic phase change material separated in step (b) is a method for producing an organic phase change material, characterized in that the purity is 98% or more.
The method of claim 1,

The organic phase change material is a method for producing an organic phase change material, characterized in that consisting of normal-paraffins having 13 to 22 carbon atoms.
The method of claim 12,

The organic phase change material is a method for producing an organic phase change material, characterized in that consisting of normal-paraffins having from 15 to 18 carbon atoms.
The method of claim 1,

The organic phase change material is a method for producing an organic phase change material, characterized in that consisting of normal-paraffins having a melting point at a temperature of -5 ℃ to 42 ℃.
The method of claim 14,

The organic phase change material is a method for producing an organic phase change material, characterized in that consisting of normal-paraffins having a melting point at a temperature of 9 ℃ to 31 ℃.