KR101655764B1 - Nickel catalyst and Hydrogenated Castor oil produced by this Nickel catalyst - Google Patents

Abstract

The present invention relates to a process for preparing an effective nickel catalyst by reducing / oxidizing a nickel catalyst to prepare a hydrogenated castor oil which meets the needs of a desired user with a higher quality surfactant and has a lower odor component, To a nickel catalyst for producing a castor oil having a low iodine value and a hydrogenated castor oil having an iodine value of 2.0 or less.
The hydrogenated castor oil having an iodine value of 2.0 or less has a low odor and a low reactivity, so that a high quality surfactant can be produced.

Description

Technical Field [0001] The present invention relates to a nickel catalyst for hydrogenation of castor oil, and a process for producing the nickel catalyst,

The present invention relates to a nickel catalyst for the hydrogenation of castor oil and a process for their preparation.

Castor is a perennial plant cultivated in hot, dry areas near the equator, India and Brazil are widely known cultivated cultures worldwide, and also cultivated in parts of China and Southeast Asia.

Castor oil can be obtained by extruding castor oil and solvent extraction method. Castor oil is also called Castor oil. Castors Today Today is a fast growing industry, and the chemical structure of castor oil has attracted attention in many areas, with a wide range of responsiveness in the field of preservative chemistry. These castor oil derivatives are now widely used in a variety of industries, which is comparable to petrochemicals. Castor oil is rated better than petrochemicals in terms of environmental friendliness, ecosystem and recycling.

This is because the retention of castor oil is very widely available commercially due to the inherent physical and chemical properties of cis-9, 12 hydroxy octadecanoic acid, known as ricinoleic acid, due to the specific content of unsaturated hydroxylated fatty acids . In addition, castor oil is used in a processed form of more than 60%, most of which are distributed in the form of hydrogenated castor oil. Hydrogenated castor oil is widely used as a raw material for surfactants. The worldwide demand for surfactants is 13 million tons, exceeding $ 22.6 billion.

The chemical structure of castor oil or castor oil is shown in the following formula (1).

[Structural formula 1]

Table 1 below shows constituent fatty acids of castor oil.

As shown in Table 1, the major fatty acid of castor oil is ricinoleic acid, and the formula of ricinoleic acid is C ₁₈ H ₃₄ O ₃ It is an unsaturated omega-9 fatty acid that exists in mature castor oil and accounts for more than 80% of its fatty acids. It is a carboxylic acid with one hydroxy group and one carbon-carbon double bond. It is a lump of crystal form and has a melting point of 5.5 ° C and a boiling point of 226 ° C (10 mmHg). It is soluble in ethanol, acetone and ether, but not in petroleum ether. Castor oil is industrially produced by fractional distillation or saponification of hydrolyzed castor oil. Zinc salts are used as deodorants. It has an anti-inflammatory and analgesic effect and is used as a raw material for dry cleaning soaps and fiber materials.

The chemical structure of ricinoleic acid is represented by the following structural formula 2.

[Structural formula 2]

Nickel, Raney nickel, copper-chromium, and copper-nickel supported on silica are mainly used for the hydrogenation process of the oil, and for the hydrogenation of a specific oil, a noble metal catalyst having excellent activity even at low temperatures is used. Nickel catalysts are mostly supported on silica and are usually prepared by precipitation.

When the margarine is produced by curing the oil, the hydrogenation selectivity of the catalyst is also as important as the activity, since all of the double bonds of the oil are not hydrogenated but partially hydrogenated until saturated. On the other hand, when preparing saturated fatty acids such as stearic acid from a fat, all the double bonds must be hydrogenated and the active material should not dissolve in the fatty acid, so that a catalyst having high acid resistance and activity is required.

Hydrogenated castor oil, which is the intermediate raw material of surfactant, is called hydrogenated castor oil and hydrogenated castor oil. Hydrogenated castor oil, which has been widely used in the market, has an iodine value of 3.0 or more indicating hydrogenation degree. Recently, however, there has been a need for a hydrogenated castor oil which has lowered the iodine value to 2.0 or less in order to meet demands of customers who desire a higher quality surfactant and to produce a hydrogenated castor oil having a low odor component. In order to prepare such low iodine castor oil, it is difficult to achieve by changing the temperature, pressure, catalyst amount, stirring speed, etc., which are main parameters of the hydrogenation process, and the efficiency of the existing nickel catalyst should be improved.

Iodine Value (IV), which indicates the degree of hydrogenation, refers to the grams (g) of iodine (I ₂ ) added to 100 g of fat. Unsaturated fatty acids have a high iodine value.

 When the double bond is near the carboxyl group (-COOH), the iodine value depends on the position of the unsaturated bond in the molecule, and the iodine value is smaller than the theoretical value. Although it may have a slightly lower value, it is widely used as a method for investigating the average unsaturation of oils. As a method of measuring iodine value, a method of measuring the amount of iodine is mainly used. 0.1 to 1 g of sample is dissolved in 10 cc of carbon tetrachloride, and a glacial acetic acid solution of iodine chloride is added to the mixture. The mixture is stirred for 1 hour in a dark and cold place, Measurements are made by calculating the difference between the parallel control groups.

When the fat is heated at high temperature for a long time or the autoxidation proceeds, the unsaturated fatty acid is decomposed and the iodine level is lowered.

Oil with a high iodine value is low in melting point and high in reactivity because it has a large number of double bonds, and is easily oxidized. Low iodine oil has a high melting point and good oxidation stability.

In addition, iodine content is lowered by hydrogenation, and animal oils generally have a low iodine value and vegetable oils have a high iodine value. Low iodine produces a hard soap and high iodine produces a soft soap.

Korean Patent Laid-Open No. 10-2010096279 relates to a nickel hydrogenation catalyst, which is a catalyst containing nickel in a solid silica carrier and has a non-catalytic content of 0.4 ml / g and a catalyst having a maximum TPR peak value in the range of 360 to 420 ° C And the aim is to provide a nickel catalyst which, when calculated on the basis of the weight of the coded catalyst, can maintain the same activity on the basis of (identical) catalyst weight of the coated catalyst, while significantly reducing the nickel content I have left.

Korean Patent Laid-Open No. 10-2013-0051937 relates to the hydrogenation of fatty acids using promoted supported nickel catalysts, comprising the step of hydrogenating unsaturated fatty acids in the presence of hydrogen and supported nickel catalysts, 5 to 80 wt% of nickel calculated from atomic nickel for the catalyst, 0.1 to 10 wt% of copper calculated as atomic copper relative to the weight of the catalyst, 1 to 10 wt% of 11 to 10 wt% There is a feature that includes metal.

In the conventional technology, nickel is used as a hydrogenation catalyst. However, since the nickel dispersion is low in the dispersion of the nickel support by the precipitation method, the hydrogenation efficiency is still low.

The inventors of the present invention have developed a method for increasing the degree of hydrogenation by increasing the degree of dispersion of a nickel catalyst on a support while solving the technical problems of hydrogenation of castor oil using a conventional nickel catalyst, .

Korean Patent Publication No. 10-2014-0096279 (Aug. Korean Patent Publication No. 10-2013-0051937 (Feb.

The present invention relates to a process for preparing an effective nickel catalyst by reducing / oxidizing a nickel catalyst to prepare a hydrogenated castor oil which meets the needs of a desired user with a higher quality surfactant and has a lower odor component, To produce a castor oil having a low iodine value.

(A) placing a support in a nickel-containing solution and using the precipitant to obtain a precipitate; (b) subjecting the obtained precipitate to a primary reduction in a reducing atmosphere; (c) oxidizing the primary reduced precipitate in an oxidizing atmosphere; (d) subjecting the oxidized precipitate to a secondary reduction in a reducing atmosphere, thereby producing a nickel catalyst for hydrogenation of castor oil.

The support in step (a) may be selected from silica, alumina, silica-alumina, titania, and zirconia, and the temperature in step (b) may range from 450 ° C to 600 ° C , The temperature of step (c) may range from 400 ° C to 500 ° C, and the temperature of step (d) may range from 450 ° C to 600 ° C.

The step of obtaining the precipitate of step (a) may include stirring, filtering the precipitate, and drying and calcining the filtered precipitate. The stirring speed of the stirring step may be 300 rpm to 600 rpm Lt; / RTI >

On the other hand, the nickel content of the nickel catalyst may be 20 wt% to 50 wt%.

Another example of the present invention provides a nickel catalyst for the hydrogenation of castor oil, which is prepared by any one of the above-described methods and comprises from 20% to 50% by weight of nickel, and further comprises a nickel catalyst Wherein the nickel catalyst comprises 20 wt% to 50 wt% of nickel and can lower the iodide value to 2.0 or less by hydrogenation of the castor oil.

The nickel catalyst for lowering the iodine value and the hydrogenated castor oil produced through the nickel catalyst provided in the present invention lower the iodine value of the castor oil and lower the reactivity by repeatedly performing the reduction / oxidation reaction on the nickel catalyst, The stability is improved.

Further, it is possible to provide a hydrogenated castor oil in which the odor component is reduced and a high quality surfactant can be produced.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the structure of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions are not described in detail to avoid unnecessarily obscuring the subject matter of the present invention.

The present invention relates to a nickel catalyst for lowering iodine value and a hydrogenated castor oil produced by the process. The purpose of hydrogenation of the fat is to hydrogenate the double bond of the unsaturated fatty acid constituting the fat to lower the degree of unsaturation, And changes in the chemical and physical properties of the fat, such as changes in plasticity. As the number of double bonds decreases, the chance of self-oxidation is reduced, so the stability of the smell and quality is increased, and the physical properties of the resulting product are accompanied by a change in the physical properties.

The nickel catalyst is subjected to pretreatment by repeatedly performing the reduction and oxidation treatment to widen the degree of dispersion of nickel as compared with the case where it is produced by the precipitation method which is a conventional production method, thereby widening the degree of dispersion and thereby improving the hydrogenation activity, The degree of hydrogenation of the oil can be further increased to lower the iodine value.

The method for producing the catalyst used in the present invention is as follows.

The supported or supported silica was added to the nickel-containing aqueous solution so that the content of nickel in the hydrogenation catalyst was 20 wt% to 50 wt%, the temperature was raised to 80 to 100 ° C, and sodium carbonate (Na ₂ CO ₃ ) Precipitate. Thereafter, stirring is carried out at a constant speed of 400 to 600 rpm. The precipitate thus precipitated is filtered, dried in an oven at 100 to 150 ° C for 10 to 18 hours, and then calcined at 450 to 600 ° C for 4 to 7 hours.

In the present invention, the content of nickel is a content ratio of nickel supported on the prepared catalyst, that is, the support or the support, to the total weight of the support or support.

The catalyst prepared by the precipitation method is reduced with hydrogen at a first reduction temperature of 450 to 600 ° C to prepare a first reduction catalyst. The prepared primary reduction catalyst is oxidized at 400 to 500 ° C. using oxygen and then subjected to secondary reduction at 450 to 600 ° C. using hydrogen to produce a secondary reduction catalyst. The secondary reduction catalyst prepared above is a nickel catalyst for lowering the iodine value prepared in the present invention.

The above carrier or support is not limited to silica, and can be produced by selecting at least one of alumina, silica-alumina, titania and zirconia.

In the method of oxidizing the catalyst produced using oxygen in the present invention, the oxidizing atmosphere can be used as long as it is a gas capable of forming an oxidizing atmosphere without deteriorating physical properties of the nickel catalyst as well as oxygen.

In addition, in the method of reducing the catalyst using hydrogen in the present invention, it is possible to use a gas other than hydrogen as long as it can form a reducing atmosphere within a range that does not deteriorate the physical properties of the produced nickel catalyst. There is no restriction to hydrogen in the gas that can be present.

If the oxidation temperature is lower than 400 占 폚, the nickel oxide which causes redispersion of the nickel is sufficiently generated and the degree of dispersion is not increased, and if the oxidation temperature is lower than 400 占 폚, If the temperature is higher than 500 ° C, excessive sintering of the nickel causes difficulty in redispersion of the nickel, so that the dispersion can not be increased.

In the present invention, the temperature at which the nickel oxide is reduced in the second reducing atmosphere is preferably 450 to 600 ° C. If the reducing temperature is lower than 450 ° C., it is difficult to sufficiently redispersion of the nickel oxide produced in the oxidation process, If the temperature is higher than < RTI ID = 0.0 > ° C, < / RTI > the redispersion by reduction and the sintering due to heat occur at the same time,

The nickel content of the prepared catalyst is preferably 20 wt% to 50 wt%, and more preferably 30 wt% to 40 wt%. When the nickel content is out of the range of 20 wt% to 50 wt%, the effect as a nickel catalyst can be reduced because the nickel is not evenly dispersed in the support silica.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

[Comparative Example 1]

550 g of nickel nitrate (Ni (NO ₃ ) ₂ ) was dissolved in water (H ₂ O) 100 and poured into 165 g of silica (SiO ₂ ) (nickel content 40 wt%), precipitated with a precipitant, filtered, Dried for 12 hours, and then calcined at 500 ° C for 5 hours. In this way, 50 g of the nickel catalyst prepared by the precipitation method was reduced at 450 ° C. for 5 hours while flowing hydrogen at a rate of 4,500 ml / min to finally prepare the nickel catalyst.

[Comparative Example 2]

550 g of nickel nitrate was dissolved in 100 g of water and poured into 165 g of silica (nickel content: 40 wt%), precipitated with a precipitant, filtered and dried in an oven at 120 ° C for 12 hours and then calcined at 500 ° C for 5 hours. 50 g of the nickel catalyst prepared by the precipitation method was hydrogenated at 450 ° C. for 5 hours while flowing hydrogen at a rate of 4,500 ml / min, oxidized at 300 ° C. for 5 hours while flowing oxygen at a rate of 4,500 ml / min, And the mixture is reduced at 450 DEG C for 5 hours to finally produce a nickel catalyst.

The evaluation of the hydrogenation reaction of the castor oil was carried out in the same manner as in Comparative Example 1.

[Comparative Example 3]

Comparative Example 2 was carried out in the same manner as in Comparative Example 2 except that the temperature was adjusted to 600 ° C under the oxidation condition of Comparative Example 2. The hydrogenation reaction of the castor oil was evaluated in the same manner as in Comparative Example 1.

[Comparative Example 4]

The hydrogenation reaction of castor oil was evaluated in the same manner as in Comparative Example 1, except that the temperature was adjusted to 400 ° C under the oxidation condition of Comparative Example 2, and the temperature was adjusted to 350 ° C under the reducing condition. .

[Comparative Example 5]

The hydrogenation reaction of the castor oil was evaluated in the same manner as in Comparative Example 1, except that the temperature was adjusted to 400 ° C under the oxidation condition of Comparative Example 2, and the temperature was adjusted to 700 ° C under the reducing condition. .

[Comparative Example 6]

In Comparative Example 1, 100 g of nickel nitrate and 180 g of silica (nickel content of 10 wt%) were used in order to make the nickel content different. To 50 g of the nickel catalyst prepared by the precipitation method, hydrogen was fed at 4,500 ml / The catalyst was oxidized at 400 ° C for 5 hours while flowing oxygen at a rate of 4,500 ml / min. The catalyst was then reduced at 450 ° C for 5 hours while flowing hydrogen at a rate of 4,500 ml / min. Finally, a nickel catalyst was prepared. The evaluation of the hydrogenation reaction is carried out in the same manner as in Comparative Example 1.

[Comparative Example 7]

610 g of nickel nitrate and 100 g of silica (nickel content of 55 wt%) were used in order to make nickel content different from Comparative Example 6, and the hydrogenation reaction of the castor oil was evaluated in the same manner as in Comparative Example 1.

[Example 1]

Comparative Example 2 was carried out in the same manner as in Comparative Example 2 except that the temperature was adjusted to 400 ° C under the oxidation condition of Comparative Example 2. The hydrogenation reaction of the castor oil was performed in the same manner as in Comparative Example 1.

[Example 2]

The hydrogenation reaction of castor oil was evaluated in the same manner as in Comparative Example 1 except that the temperature was adjusted to 500 ° C under the oxidizing conditions of Comparative Example 2 and the temperature was adjusted to 600 ° C under the reducing conditions. .

[Example 3]

Comparative Example 6 Hydrogenation of castor oil was evaluated in the same manner as in Comparative Example 1 except that the content of nickel was changed to 300 g of nickel nitrate and 140 g of silica (nickel content 30 wt%). .

Hydrogenation reaction experiment

Evaluation of hydrogenation reaction of castor oil using the nickel catalysts prepared in the above Comparative Examples and Examples proceeds as follows.

2500 g of castor oil was charged into a 5 L batch reactor and stirred at a rate of 355 rpm while raising the temperature of the reactor to 140 캜. When the temperature reached 140 캜, 35 g of the nickel catalyst prepared after purging with hydrogen was introduced through the inlet, and the inlet valve was closed. Fill the hydrogen to 9 bar and start the reaction.

2 hours and 4 hours later, samples were taken from the sample collection part at the bottom of the reactor to measure the iodine value. The results of the physical property evaluation are shown in Table 2 below.

The iodine value, which is the above property evaluation, is measured by the KS H ISO 3961 method.

The evaluation of the physical properties of the examples and comparative examples shown in Table 2 is as follows. In Comparative Example 1, the oxidation and the second reduction treatment were not performed. The iodine value was as high as 3,0, It can be seen that the preferred degree of nickel dispersion is not achieved.

Comparative Example 2 and Comparative Example 3 show the effect of the oxidation temperature at the first and second reduction temperatures of 450 캜. When the oxidation treatment was performed at 300 캜 and 600 캜, the iodine value was 2.5 and 2.3, And the iodine shown in Example 3 is higher than 2.0 and 1.9.

Comparative Example 4 and Comparative Example 5 show the effect of the reduction temperature at the oxidation temperature of 400 ° C. When the reduction treatment was performed at 350 ° C and 700 ° C, the iodine value was 2.8 and 2.7, Show iodine is higher than 2.0, 1.9.

In addition, Comparative Example 6 and Comparative Example 7 show effects according to the content of nickel at an oxidation temperature of 400 ° C. and a reduction temperature of 450 ° C. When the content of nickel is 10 wt% and 55 wt%, the iodine value is 2.2 and 2.3, This is higher than the iodine shown in Examples 1 and 3 of 2.0 and 1.9.

The nickel catalysts of the hydrogenation catalysts produced by the above-mentioned Comparative Examples and Examples were 30 wt% to 50 wt%, the reduction temperature was 450 ° C to 600 ° C, and the oxidation temperature was 400 ° C to 500 ° C. A hydrogenated castor oil having a low iodine value of 2.0 or less can be produced.

When the castor oil is hydrogenated using the nickel catalyst produced by the present invention, the hydrogenation reaction activity of the castor oil is higher than that of the castor oil. Thus, a hydrogenated castor oil having an iodine value of 2.0 or less can be produced. The low-hydrogenated castor oil is useful for producing high-quality surfactants, and it can be seen that the oil is commercially applicable.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments, It will be apparent that the scope is not limited. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

(a) placing a support in a nickel-containing solution and using a precipitant to obtain a precipitate;
(b) subjecting the obtained precipitate to a first reduction at 450 to 600 占 폚 in a reducing atmosphere;
(c) oxidizing the primary reduced precipitate at 400 to 500 占 폚 in an oxidizing atmosphere;
(d) subjecting the oxidized precipitate to a secondary reduction at 450 to 600 占 폚 in a reducing atmosphere; ≪ / RTI > wherein the catalyst is a catalyst. The method according to claim 1,
Wherein the support in step (a) is selected from at least one of silica, alumina, silica-alumina, titania, and zirconia. delete delete delete The method according to claim 1,
Wherein the step of obtaining the precipitate of step (a) comprises the step of stirring, filtering the precipitate, and drying and calcining the filtered precipitate. The method according to claim 6,
Wherein the agitation speed of the agitating step is 300 rpm to 600 rpm. The method according to claim 1,
Wherein the nickel content of the nickel catalyst is 20 wt% to 50 wt%. A nickel catalyst for the hydrogenation of castor oil, produced by the process of any one of claims 1, 2, 6 to 8 and comprising from 20% to 50% by weight of nickel. delete