KR102035536B1 - Hydrogenation catalyst of animal and vegetable oil for use as bio heavy fuel oil and its acid value and iodine reduction method - Google Patents

Abstract

The present invention is characterized by hydrogenation of animal and vegetable oils using a catalyst calcined by supporting nickel (Ni) and divalent metals (M ²⁺ ) on a porous support calcined by carrying a Lanternum (La) reaction promoter. The present invention relates to a hydrogenation catalyst of animal and vegetable oil for use as bio heavy oil, and a method for reducing acid value and iodine value of animal and vegetable oil using the same, including nickel (Ni) and divalent on a porous support supported by a lanternum (La) reaction promoter. metal (M ²⁺⁾ to the bearing by using a calcined catalyst, the active metal nickel (Ni) and 2 supported on the aluminum oxide porous support during plant and animal significant hydrogenation reduces the particles of the metal (M ^2+), By increasing the degree of dispersion to promote the reaction activity there is an effect that the efficiency of reducing the acid value and iodine value of animal and vegetable oil.

Description

Hydrogenation catalyst of animal and vegetable oil for use as bio heavy fuel oil and its acid value and iodine reduction method}

The present invention relates to a hydrogenation reaction of animal and vegetable oil for use as bio-heavy oil, and a method for reducing acid value and iodine value of animal and vegetable oil using the same, and more specifically, nickel on a porous support calcined by carrying a Lanteran (La) reaction promoter. It is used as bio heavy oil for use for fuel oil mixing by reducing acid and iodine values by hydrogenating animal and vegetable oil by using a catalyst calcined by supporting (Ni) and divalent metal (M ²⁺ ). The present invention relates to a hydrogenation reaction catalyst of animal and vegetable oil and an acid value and iodine value reduction method of animal and vegetable oil using the same.

Due to the recent crisis of resource depletion due to increased energy consumption and the disruption of natural ecosystems due to the increase in greenhouse gas emissions, the government is pursuing policies to promote renewable energy distribution to diversify energy sources and reduce greenhouse gases. In Korea, from January 2014, the biofuel pilot project for power generation has been implemented for two years based on the "Notice on Promotion of the Biofuel Pilot Project for Power Generation (Ministry of Industry Notice 2014-1)" and the "Petroleum and Petroleum Alternative Fuel Business Act". Promoting.

Bio heavy oil for power generation, which is being piloted in Korea, refers to a fuel produced in accordance with quality standards by mixing and manufacturing fatty acid esters made by reacting animal or vegetable fat or alcohol with fat or oil. Cashew nut shell liquid and palm oil are attracting attention because of their sustainability and low emissions of greenhouse gases and harmful pollutants such as HC, CO and NO _x . However, as the properties of biofuel for power generation differ from those of heavy oil, the oxidation and corrosion characteristics, spraying characteristics, flow characteristics, and combustion characteristics of fuel are also different. For this reason, domestic heavy fuel oil for power generation should meet the quality standards of the items listed in [Table 1] below.

Item (unit) Quality standards Flash point (℃) More than 70 Kinematic viscosity (50 ℃, ㎠ / s) 15 or more ~ 80 or less Residual Carbon (Weight%) below 10 Sulfur (weight%) 0.05 or less Ash content (% by weight) 0.10 or less Copper plate corrosion (50 ℃, 3h) 1 or less Pour point (℃) 27 or less Density (15 ℃, ㎏ / ㎥) 991 or less Moisture (% by weight) 0.30 or less Computer Value (mg KOH / g) 25 or less alkali
(mg / kg) Na 70 or less Ca 30 or less K 70 or less Iodine Value (g / 100g) 120 or less  Nitrogen (weight%) 0.3 or less Vanadium (mg / kg) 50 or less Total calorific value (kcal / kg) 9,000 or more Water and sediment (volume%) 0.5 or less Silicon + Aluminum + Iron (mg / kg) 200 or less  Phosphorus (mg / kg) 100 or less

Representative raw materials of power generation bio heavy oil include Cashew nut shell liquid (CNSL) and palm oil. However, such raw materials of bio heavy oil generally have high acid and iodoid values. . If the acid value is high, the acidity is high, so the internal combustion engine is easily corroded, or the flow of fuel oil is not smooth. If the iodine value is high, it is easily combined with oxygen, which is likely to cause acid waste.

Therefore, in the case of CNSL oil, the iodine value (IV), which shows a high degree of unsaturated fatty acid and shows an unsaturated degree, needs to be improved about 2 times higher than the upper specification limit as shown in Table 2 below, and other Since palm oil as a raw material has a high fatty acid content and an acid value is about 3 to 4 times higher than the upper specification limit as shown in [Table 2], it is not suitable for mixing CNSL oil or palm oil with fuel oil as it is. Reaction treatment should be performed to reduce the

Item Test Methods unit standard Properties CNSL Palm oil Acid Number KS M ISO 6618 mgKOH / g Max. 25 9.5 86.8 Iodine Number EN 14111 g / 100g Max. 120 259 64.5

And, for example, CNSL in vegetable oil, as the main component, as shown in the following formula 1, 3-pentadicenyl phenol (3-pentadecenyl phenol, 'cardanol'), 5-pentadisenyl resorcinol (5- pentadecenyl resorcinol (called 'cardol'), 6-pentadisenyl salicylic acid (6-pentadecenyl salicylic acid, called 'anacardic acid') and 2-methyl 5-pentadisenyl resorcinol (2-methyl 5-pentadecenyl resorcinol , 2-methyl cardol).

(Formula 1)

Compounds of the four components having a structure as shown in the formula (1) has a hydrocarbon chain having 15 carbon atoms having a structure as shown in the following formula (2). There are double bonds in this hydrocarbon, with only 3% of saturated fatty acids without double bonds and the remainder being unsaturated fatty acids with one to three double bonds.

Increasing the proportion of unsaturated fatty acids in vegetable oils or animal oils increases iodine value, which is a problem for use as a fuel because it can be easily oxidized to improve the acid value and produce oxidized products such as quality and inhibit fuel flow. Therefore, in order to lower the high iodine value indicating the degree of unsaturation of CNSL oil and to increase the storage stability, various methods for the conversion of unsaturated fatty acids to saturated fatty acids through hydrogenation are required.

Traditional methods of lowering the iodine value and acid value of vegetable or animal oil for mixing in fuel oils require the conversion of double bonds contained in unsaturated fatty acids to single bonds through catalytic hydrogenation. This reaction improves the safety of fats and oils, and also removes some of the oxygen components contained in fats and oils, thereby increasing the calorific value and removing odors.

(Formula 2)

Patent document 1 is invention regarding the nickel catalyst for hydrogenating fatty carboxylic acids or esters, and patent document 2 is 2 used for efficiently converting high acid value and low grade bio oil of the acid value 10-200 range into biodiesel. the catalyst comprises a metal, that is a divalent metal ion (M ²⁺⁾ is ^{Mg 2 +, Ca 2 +,} Cu 2 +, Fe 2 +, Ni 2 +, Co 2 +, Mn 2 +, and Zn ^{+ 2} The invention relates to a homogeneous catalyst characterized in that it is a single or a mixture of two or more selected.

Patent Document 3 discloses a raw material oil containing an oxygen-containing organic compound and a water-insoluble chlorine-containing compound in the presence of hydrogen, wherein the porous inorganic oxide contains two or more elements selected from aluminum, silicon, zirconium, and the like. At least one metal selected from Ni, Co, Pt, Pd, Ru, Rh, Ir, Mo, and W, among two or more metals selected from the elements of Groups VIA and VIII of the periodic table in the carrier of the porous inorganic oxide The invention relates to a method for producing a hydrocarbon oil by hydrogenation deoxidation of the oxygen-containing organic compound by contacting a hydrogenation catalyst supporting the above, Patent Document 4 is an organic phase change material (Phase Change) through the hydrogenation reaction of animal and vegetable oil Material), and the catalyst used is an active ingredient in a carrier made of zirconium oxide, aluminum oxide or titanium oxide. As relates to the invention, including any one or a mixture of two or more selected from the VIB, VIIB, VIIIB, VIII, IB or IIB metal group consisting of a group.

Accordingly, the present inventors, unlike the invention of Patent Document 1 to 4, by using a porous support calcined by supporting a Lanternum (La) group metal to promote the reaction activity during the hydrogenation reaction of animal and vegetable oils, acid value and iodine of animal and vegetable oils The present invention has been completed by reducing the efficiency efficiently.

Patent Document 1: US Patent Publication No. 5,493,037 (registered Feb. 20, 1996) Nickel catalyst Patent Document 2: Domestic Patent Publication No. 10-1247612 (registered on March 20, 2013) Homogeneous catalyst used in the reaction for producing biodiesel from high acid value bio oil Patent Document 3: Domestic Patent Publication No. 10-1451604 (October 10, 2014 registration) Patent Document 4: Korean Laid-Open Patent Publication No. 10-2012-0008460 (registered on Jan. 30, 2012) A method for preparing an organic phase change material through a hydrogenation reaction of animal and vegetable oils

The present invention uses a catalyst calcined by supporting nickel (Ni) and a divalent metal (M ²⁺ ) on a porous support calcined by carrying a Lanternum (La) reaction promoter and calcining animal and vegetable oils to give acid and iodine It is an object of the present invention to provide a hydrogenation reaction catalyst of animal and vegetable oil for use as bio heavy oil and an acid value and an iodine value reduction method of animal and vegetable oil using the same for reducing the value and using it for fuel oil mixing.

In particular, the present invention uses a porous support calcined by supporting a lanthanum (La) group metal, and is a nickel (Ni) and an active metal divalent metal (M ² ) calcined by being supported on an aluminum oxide porous support during hydrogenation of animal and vegetable oils. ⁺ ) Hydrogenation catalyst of animal and vegetable oil for use as bio heavy oil, characterized by reducing the size of particles and increasing the degree of dispersion, and the acid value and iodine of animal and vegetable oil using the same to provide a method for reducing It is a task.

The present invention for achieving the above object is used for bio heavy oil, characterized in that the calcined by carrying a nickel (Ni) and divalent metal (M ^{2 +} ) supported on the aluminum oxide porous support calcined by supporting the reaction accelerator The hydrogenation reaction catalyst of animal and vegetable oil is used as a solution of a subject.

In another aspect, the present invention provides a method for reducing acid value and iodine value of animal and vegetable oil, wherein the animal oil and iodine are reduced by hydrogenating animal and vegetable oil using the above-described hydrogenation reaction catalyst.

Meanwhile, the porous support carries 0.1 to 6.5 parts by weight of a reaction accelerator, 14.5 to 24.0 parts by weight of nickel (Ni), and 6.5 to 16.0 parts by weight of a divalent metal (M ²⁺ ), based on 100 parts by weight of the porous support. Is a lanthanum (La) group metal, and at least one selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, and divalent metal (M ²⁺⁾ is characterized by selecting from among one or ^{Fe 2 +, Co 2 +,} Cu 2 + or Zn ^{+ 2.}

In addition, the hydrogenation reaction is characterized in that carried out under the conditions of 5 ~ 80 Bar pressure, 1 ~ 10 h ^-1 space velocity and 250 ~ 400 ℃.

In addition, the animal and vegetable oils are 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, fish oil, tallow, lard, It is characterized in that it is one or more mixtures selected from the group consisting of poultry fats and fatty acids or waste oils thereof.

The present invention uses a catalyst calcined by supporting nickel (Ni) and divalent metal (M ²⁺ ) on a porous support calcined by carrying a Lanternum (La) reaction promoter, thereby increasing the aluminum oxide porosity during hydrogenation of animal or vegetable oils. Reduces the particles of nickel (Ni) and divalent metals (M ²⁺ ), which are the active metals supported on the support, and increases the dispersion so as to promote the reaction activity, thereby increasing the acid and iodine value of animal and vegetable oils. There is.

Hereinafter, with reference to the accompanying drawings for the hydrogenation reaction of animal and vegetable oils for use as bio heavy oil according to a preferred embodiment of the present invention, and the acid value and iodine value reduction method of animal and vegetable oil using the same parts necessary for understanding the technical configuration of the present invention It should be noted that the description of other parts will be omitted without departing from the scope of the present invention.

Hydrogenation catalysts of animal and vegetable oils (hereinafter, referred to as 'hydrogenation reaction catalysts') for use as bio heavy oils according to the present invention are nickel (Ni) and divalent metals (M) on an aluminum oxide porous support calcined by carrying a reaction accelerator. ²⁺ ) is supported and calcined.

The reaction accelerator reduces the size of the particles of nickel (Ni) and the active metal divalent metal (M ²⁺ ), which is calcined by being supported on an aluminum oxide porous support, and promotes the reaction activity by increasing the degree of dispersion to increase the acid value of animal and vegetable oils. And an effect of increasing the reduction efficiency of iodine value.

As the reaction accelerator, a transition metal is used. Specifically, a transition metal is a lanthanum (La) group metal, and La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb Alternatively, one or more selected from Lu are used.

As described above, the aluminum oxide porous support is prepared by supporting 0.1 to 6.5 parts by weight of a Lanternum (La) group metal, which is a reaction promoter, in 100 parts by weight of the porous support, and then calcining at a temperature of 400 to 500 ° C. for 2 to 6 hours.

When the supported amount of the reaction promoter to support the porous support is less than the range defined above, there is a fear that the reaction activity of the divalent metal (M ²⁺ ), which is an active metal, may not be sufficiently activated, and the amount of the reaction promoter supported above In the case of exceeding the limited range, the aggregation of metal particles may decrease the activity due to the increase in the average particle size.

When the lanternum (La) group metal is supported on the aluminum oxide porous support as described above, and the calcination falls below the range of the sintering conditions defined above, the lanternum (La) group metal is uniformly distributed in the aluminum oxide porous support. There is a risk that the calcination is not carried out, and if it exceeds the range of the calcination conditions defined above, the Lanternum (La) group metal may flow down to the lower portion of the porous support and not uniformly distributed in the porous support.

In addition, nickel (Ni) and divalent metal (M ²⁺ ) are supported and baked on a lanthanum (La) group-supported porous support baked by the above method.

To the divalent metal (M ²⁺⁾ is specifically selected the ^{Fe 2 +, Co 2 +,} Cu 2 + or Zn ^{2 +} 1 from the preferred.

The nickel (Ni) is known as a representative catalyst for activating the hydrogenation reaction to produce a saturated fatty acid by adding hydrogen to unsaturated fatty acid, the divalent metal (M ^{2 +} ) is a hydrogenation reaction with the nickel (Ni) metal. To act.

As such, the porous support calcined by supporting nickel (Ni) and divalent metal (M ²⁺ ) is loaded with 14.5-24.0 parts by weight of nickel and 6.5-16.0 parts by weight of divalent metal (M ²⁺ ), and then 400-500 It is prepared by baking for 2 to 6 hours at a temperature of ℃.

When nickel (Ni) and a divalent metal (M ²⁺ ) are supported on the aluminum oxide porous support as described above, and when firing falls below the range of the above-described firing conditions, nickel (Ni) and The divalent metal (M ²⁺ ) may be uniformly distributed in the aluminum oxide porous support and may not be fired. If the divalent metal (M ²⁺ ) is exceeded, the nickel (Ni) and the divalent metal (M ² ) may be exceeded. ⁺ ) May flow down to the bottom of the porous support so that it is not evenly distributed in the porous support.

As described above, the hydrogenation catalyst as described above uses a catalyst calcined by supporting nickel (Ni) and divalent metal (M ²⁺ ) on a porous support calcined by carrying a Lanternum (La) reaction promoter. During the hydrogenation of animal and vegetable ^oils , the particles of nickel (Ni) and divalent metals (M ²⁺ ), which are active metals supported on the porous support of aluminum oxide, are reduced, and the acidity and iodine of animal and vegetable oils are promoted by increasing the dispersion degree. There is an effect that the reduction efficiency can be increased.

On the other hand, using a hydrogenation catalyst according to the present invention to describe the method of reducing the acid value and iodine by hydrogenating animal and vegetable oil in detail as follows.

The present invention uses the hydrogenation catalyst as described above to hydrogenate animal and vegetable oil at a pressure of 5 ~ 80 Bar and reaction conditions of 250 ~ 400 ℃ while supplying the animal and vegetable oil in the reactor at a space velocity (LHSV) of 1 ~ 10 h ^-1 Conduct the reaction.

When the reaction conditions are out of the range of the reaction conditions defined above, there is a fear that the reduction efficiency of acid value and iodine is reduced.

In addition, the animal and vegetable oils are 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, fish oil, tallow, lard, It is characterized in that it is one or more mixtures selected from the group consisting of poultry fats and fatty acids or waste oils thereof.

Hereinafter, an acid value and an iodine value reduction method of animal and vegetable oil using a hydrogenation catalyst according to a preferred embodiment of the present invention will be described in more detail with reference to the following examples. However, the following examples are only examples for describing the present invention in more detail, and the present invention is not limited to the following examples.

1. Preparation of catalyst for hydrogenation of animal and vegetable oils

(Production of Catalyst 1)

Hydrogenation catalyst of animal and vegetable oil is supported by lanthanum (La) group metal support on aluminum oxide porous support in the weight ratio as described in [Table 3] and [Table 4] below and then calcined at 500 ° C. for 2 hours. A (La) group-supported aluminum oxide porous support was prepared, and then nickel and divalent metals (M ²⁺ ) were supported thereon in a weight ratio as described in Tables 3 and 4 below, followed by a temperature of 400 ° C. It was calcined for 6 hours at to prepare a hydrogenation catalyst of animal and vegetable oil.

(Production of Catalyst 2)

The hydrogenation reaction of animal and vegetable oil is carried out by supporting a lanthanum (La) group metal on an aluminum oxide porous support at a weight ratio as shown in [Table 5] below, and then firing at a temperature of 400 ° C. for 6 hours to lanternum (La) group metal. A supported aluminum oxide porous support was prepared, and then nickel and divalent metals (M ²⁺ ) were supported at a weight ratio as shown in Table 5 below, and then calcined at a temperature of 500 ° C. for 2 hours to hydrogenate animal and vegetable oils. Catalyst was prepared.

(Production of Catalyst 3)

The hydrogenation reaction of animal and vegetable ^oils is carried out by supporting nickel and divalent metals (M ²⁺ ) on an aluminum oxide porous support in a weight ratio as shown in the following [Table 3], and then calcining for 6 hours at a temperature of 400 ° C. Catalyst was prepared.

(Production of Catalyst 4)

Hydrogenation catalyst of animal and vegetable oil was supported on aluminum porous support by weight ratio as described in [Table 3] to [Table 5] below and then calcined at 400 ° C. for 6 hours to prepare a hydrogenation catalyst of animal and vegetable oil. .

2. Hydrogenation treatment of animal and vegetable oils

Using the hydrogenation reaction catalysts 1 to 4 of animal and vegetable oils prepared by the method of 1 above, as shown in Tables 3 to 5 below, animal and vegetable oils have a space velocity (LHSV) of 1 to 10 h ⁻¹ . Animal and vegetable oils were hydrogenated for 3 hours under pressure of 5 to 80 Bar and reaction conditions of 250 to 400 ° C. while being fed into the reactor.

(Examples 1 to 4 and Comparative Examples 1 to 4)

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[Table 3] shows the acid value and iodine value as a result of hydrogenation reaction using a mixed oil of cashew nut shell oil and palm oil as a raw material as a raw material.

In Examples 1 to 4 of Table 3 below, a catalyst prepared according to the method of Catalyst 1 was used, Comparative Examples 1 and 2 were catalysts prepared according to the method of Catalyst 3, and Comparative Examples 3 and 4 were Catalyst 4 The hydrogenation reaction was performed using the catalyst prepared by the method of each.

division catalyst
(Parts by weight) Reaction condition Property evaluation
(% Reduction) Ni
M ²⁺ La family
metal Al ₂ O ₃
Support Pressure (Bar) Space velocity (h ^-1 ) Temperature
(℃) Iodine Value (g / 100g) Acid
(mg-KOH / g) Raw material
(Plant oil mixed oil) Untreated hydrogenation 186.3 42.9 Comparative example
One 20.0 6.5
(Fe) -  100 30 One 400 73.7
(60.4) 14.7
(65.7) Comparative example
2 20.0 8.0
(Co) - 30 5 350 97.9
(47.5) 18.2
(57.6) Comparative example
3 24.0 - - 30 One 300 114.0
(38.9) 23.8
(44.5) Comparative example
4 24.0 - - 30 5 250 127.9
(31.3) 25.2
(41.3) Example
One 14.5 6.5
(Fe) 0.1
(La) 30 One 350 57.8
(69.0) 13.6
(68.3) Example
2 16.0 8.0
(Co) 0.5
(La) 30 5 350 54.2
(70.9) 9.8
(77.2) Example
3 18.0 10.0
(Cu) 1.0
(Pr) 30 One 350 42.8
(77.0) 2.7
(93.7) Example
4 20.0 12.0
(Zn) 2.0
(Pr) 30 5 350 41.0
(78.0) 3.2
(92.5)

As described in [Table 3], as a result of the hydrogenation reaction of the mixed oil mixed with cashew nut shell oil and palm oil, Examples 1 to 4 using the catalyst according to the present invention had an acid value and It was confirmed that the reduction efficiency of iodine value was excellent.

In Comparative Examples 1 and 2, it was found that the reduction efficiency of the acid value and the iodine value was superior to Comparative Examples 3 and 4 using only Ni alone as Ni and Fe or Co metals were used together as the catalyst.

(Examples 5 to 20 and Comparative Examples 5 to 8)

[Table 4] below shows the acid value and iodine value of the palm oil as a raw material, as shown in Table 4 below.

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In Examples 5 to 20 of Table 4 below, a catalyst prepared according to the method of Catalyst 1 was used, and Comparative Examples 5 to 8 performed a hydrogenation reaction using a catalyst prepared according to the method of Catalyst 4.

division catalyst
(Parts by weight) Reaction condition Property evaluation
(% Reduction) Ni M ²⁺ La family Al ₂ O ₃
Support Pressure (Bar) Space velocity (h ^-1 ) Temperature
(℃) Iodine Value (g / 100g) Acid
(mg-KOH / g) Raw material
(Palm oil) Untreated hydrogenation 64.5 86.8 Comparative example
5 20.0 - - 100 5 One 400 43.5
(32.6) 45.6
(47.5) Comparative example
6 20.0 - - 10 One 350 41.4
(35.8) 43.9
(49.4) Comparative example
7 24.0 - - 30 5 300 38.5
(40.3) 39.7
(54.3) Comparative example
8 24.0 - - 80 10 250 39.7
(38.4) 38.4
(55.8) Example
5 20 14.0
(Cu) 3.0
(La) 100 30 One 400 23.0
(64.3) 14.6
(83.2) Example
6 30 One 350 22.8
(64.7) 10.0
(88.5) Example
7 30 One 300 22.9
(64.5) 18.4
(78.8) Example
8 30 One 250 26.1
(59.5) 20.2
(76.7) Example
9 10 One 400 21.0
(67.4) 17.6
(79.7) Example
10 5 One 400 18.5
(71.0) 13.6
(84.3) Example
11 10 One 350 18.1
(71.9) 20.2
(76.7) Example
12 5 One 350 19.8
(69.3) 17.5
(79.8) Example
13 10 One 300 18.9
(70.7) 18.4
(78.8) Example
14 5 One 300 20.8
(67.8) 17.6
(79.7) Example
15 30 5 350 18.1
(71.9) 14.5
(83.3) Example
16 30 10 350 16.5
(74.4) 16.9
(80.5) Example
17 80 One 300 19.8
(69.3) 15.1
(82.6) Example
18 80 One 350 18.7
(71.0) 9.5
(89.1) Example
19 80 5 350 15.9
(75.3) 6.7
(92.3) Example
20 80 10 350 15.3
(76.3) 8.5
(90.2)

As described in the above [Table 4], as a result of the hydrogenation reaction of palm oil, Examples 5 to 20 using the catalyst according to the present invention confirmed that the reduction efficiency of acid value and iodine value was superior to Comparative Examples 5 to 8. Could.

(Examples 21 to 28 and Comparative Examples 9 and 10)

[Table 5] below shows the acid value and iodine value as a result of hydrogenation reaction using juvenile oil as a raw material.

Examples 21 to 28 in Table 5 below used a catalyst prepared according to the method of Catalyst 2, and Comparative Examples 9 and 10 were subjected to a hydrogenation reaction using a catalyst prepared according to the method of Catalyst 4.

division catalyst
(Parts by weight) Reaction condition Property evaluation
(% Reduction) Ni
M ²⁺
La family
metal Al ₂ O ₃
Support Pressure (Bar) Space velocity (h ^-1 ) Temperature
(℃) Iodine Value (g / 100g) Acid
(mg-KOH / g) Raw material
(Fish
Fish oil) Untreated hydrogenation 148.6 10.9 Comparative example
9 20.0 - - 100 30 One 250 92.3
(37.9) 8.6
(21.1) Comparative example
10 24.0 - - 30 One 400 87.5
(41.1) 7.4
(32.1) Example
21 22.0 14.0
(Zn) 5.0
(La)  100 30 One 400 34.3
(77.0) 2.0
(81.7) Example
22 30 One 350 29.9
(79.9) 2.4
(78.0) Example
23 30 One 300 34.6
(76.7) 3.6
(67.0) Example
24 30 One 250 37.9
(74.5) 4.2
(61.5) Example
25 24.0 16.0
(Fe) 6.5
(Pr) 30 One 400 33.8
(77.3) 2.8
(74.3) Example
26 30 One 350 34.5
(76.7) 3.5
(67.9) Example
27 30 One 300 28.7
(80.7) 3.3
(69.7) Example
28 30 One 250 32.2
(78.3) 2.2
(79.8)

As described in [Table 5], as a result of hydrogenating the juvenile oil, Examples 21 to 28 using the catalyst according to the present invention confirmed that the reduction efficiency of acid value and iodine value was superior to Comparative Examples 9 and 10. Could.

As a result of the hydrogenation of the mixed oil, palm oil and juvenile oil in which cashew nut shell oil and palm oil were mixed using the hydrogenation reaction catalyst according to the present invention, the examples using the catalyst according to the present invention were compared to the comparative examples. It turned out that the reduction efficiency of acid value and iodine value is excellent.

As described above, the hydrogenation reaction of animal and vegetable oil for use as bio heavy oil according to a preferred embodiment of the present invention, and the acid value and iodine value reduction method of animal and vegetable oil using the same have been described, but this is only described for example and the present invention Those skilled in the art will appreciate that various changes and modifications can be made without departing from the technical spirit.

Claims (7)

Nickel (Ni) was formed on an aluminum oxide porous support calcined by supporting 0.1 to 6.5 parts by weight of reaction accelerator, 14.5 to 24.0 parts by weight of nickel (Ni), and 6.5 to 16.0 parts by weight of divalent metal (M ²⁺ ), based on 100 parts by weight of the porous support. ) And the ^bivalent metal (M ^{2 +} ) to support the firing,
The reaction promoter is a Lanternum (La) group metal, and at least one selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu and,
The divalent metal (M ²⁺ ) is a hydrogenation catalyst of animal and vegetable oil for use as bio heavy oil, characterized in that one selected from Fe ²⁺ , Co ²⁺ , Cu ²⁺ or Zn ²⁺ .
delete delete delete Using the hydrogenation catalyst according to claim 1 to reduce the acid value and iodine by hydrogenating the animal and vegetable oil at a pressure of 5 ~ 80 Bar, a space velocity of 1 ~ 10 h ^-1 and 250 ~ 400 ℃ conditions Method for reducing acid value and iodine value of animal and vegetable oils.
delete The method of claim 5,
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, fish oil, tallow, pork and poultry fat. And one or more mixtures selected from the group consisting of fatty acids or waste oils thereof.