KR100738232B1 - Method of preparing mixed metal oxide catalyst and method of producing long chain aliphatic tertiary amine using the catalyst - Google Patents

Abstract

A method for preparing a long chain aliphatic tertiary amine is provided to produce the aliphatic tertiary amine from a long chain aliphatic alcohol in high yield under a milder condition using a heterogeneous catalyst having good reaction stability, reaction selectivity, and activity. The method for preparing a long chain aliphatic tertiary amine consists of aminating a C8-36 long chain aliphatic alcohol into a dimethyl amine in the presence of a hydrocalumite-like mixed metal oxide catalyst represented by a formula 1 of [M3Al(OH)6]3NO3.nH2O. In the formula, M comprises a metal element of Cu, Ni, Zn, and Ca having an oxidation number of 2, wherein the M comprises 0.5-1.5 parts by mole of Cu, 0.05-0.15 parts by mole of Ni, 0.2-0.4 parts by mole of Zn, and 0.9-2.0 parts by mole of Ca, based on 4 parts by mole of the total metal elements including Al, and n is the number of combined water and has a value of 0.2-4.

Description

METHODS OF PREPARING MIXED METAL OXIDE CATALYST AND METHOD OF PRODUCING LONG CHAIN ALIPHATIC TERTIARY AMINE USING THE CATALYST}

1 is an X-ray diffraction spectroscopy (XRD) spectrum of a mixed metal hydroxide having a hydrocalcite structure.

The present invention relates to a method for preparing a long-chain aliphatic tertiary amine and a method for preparing a catalyst that can be used in the above method, and more particularly, to perform an amination reaction using a heterogeneous solid catalyst having excellent reaction stability, reaction selectivity and activity. Thereby, the present invention relates to a method for producing a long-chain aliphatic tertiary amine in high yield under milder conditions and to a method for preparing a catalyst that can be effectively used in the method.

Aliphatic tertiary amines based on bovine oil, palm oil, palm oil, rapeseed oil and the like are intermediates such as domestic or industrial cationic surfactants, amphoteric surfactants, and amine oxides. In this regard, in particular, dimethyl long-chain alkylamine is made of a quaternary amine and is widely used for fabric softeners, antistatic agents, rinse products, cosmetic emulsifiers, dye additives, antimicrobial agents, etc. Various methods for preparing such aliphatic tertiary amines are also known. Of these, in view of the purity and economical efficiency of the synthesized aliphatic tertiary amines, the method of amination of aliphatic alcohols in the presence of a catalyst is most preferred.

Tertiary amines are synthesized by reacting aliphatic alcohols using dimethylamine, methylamine, ammonia, or the like as an amination agent in the presence of an amination catalyst. In the reaction, by-products such as primary amines and secondary amines may be produced by transalkylation or disproportionation, and thus, dimethylamine is mainly used as an amine agent when preparing tertiary amines.

In the process of aminating aliphatic alcohols to produce tertiary amines, Cu (copper), Ni (nickel), Co (cobalt), Cr (chromium) catalysts and the like having hydrogenation and dehydrogenation functions are used. French Patent 780,028 discloses a process for preparing diethyldodecylamine from dodecyl alcohol and diethylamine using a Cu / Ba supported catalyst. In a similar manner, German Patent No. 2,749,064 describes a method of using a Cu / Re supported catalyst. However, since the catalysts have relatively low activity and selectivity, a large amount of catalysts must be used, and strict reaction conditions such as high reaction pressure and reaction temperature are required. In addition, since the use of a large amount of catalyst, such as 2.5 to 8.5% by weight in order to increase the yield of the product, there is also a problem of increased catalyst cost, filtration and recovery of the catalyst. Accordingly, in order to increase the activity and selectivity of the catalyst, US Patent No. 4,138,437 and Japanese Patent No. 1977-19604 proposed a copper-chromite catalyst and US Patent No. 3,390,184 proposed a Ni / Cu / Cr catalyst, respectively. In the case of the Cr-containing catalyst, the amination activity and selectivity were high, but there was a problem in that the metal component of the catalyst was dissolved during the reaction, thereby gradually decreasing the activity, and also difficult to separate and purify Cr having carcinogenic toxicity contained in the product. There was this.

In order to improve the filtration and recovery of the amination catalyst, US Patent Nos. 2,953,601, US Patent Nos. 3,152,185 and US Patent Nos. 3,223,734 used Raney nickel catalysts having a high specific gravity of the catalyst, and US Patent No. 4,152,353. The arc used a catalyst having 20 to 49 mol% of nickel, 36 to 79 mol% of copper, and 1 to 15 mol% of mixed metals such as iron, zinc, and zirconium based on the absence of oxide. As the specific gravity of the catalyst increased, the recovery and reuse performance of the catalyst was improved, while the production cost of the catalyst was increased, and the yield of aliphatic tertiary amine was also 70% or less, and the activity was still insufficient.

U. S. Patent No. 4,210, 605 and U. S. Patent No. 4, 254, 060 disclose methods of using Cu / Ni / Ba catalysts in the form of homogeneous colloids. In this method, a three-way catalyst consisting of copper stearate, nickel acetyl acetate, barium stearate (0.1% by weight of copper metal, 0.02% by weight of nickel metal, 0.04% by weight of barium metal) was used as a catalyst, and thus 210 ° C. The aliphatic alcohol conversion was 100% when reacted at a temperature of 2 hours and at atmospheric pressure. In this method, the yield of the tertiary amine was 96%, and the purity of the tertiary amine after distillation was 99%. As such, the catalyst exhibits higher activity and selectivity than the conventional copper metal and copper oxide catalysts. The catalyst particles are in the form of colloids having a very small size, and are also mono-unsaturated by polymerization of aldehydes and disproportionation of dimethylamine. It is believed that the production of methylamine and trimethylamine was suppressed. However, in spite of such excellent reaction characteristics, the catalyst was easily poisoned by trace impurities such as carbon monoxide contained in the reactants or amine by-products in the product, and thus the activity was reduced. In addition, since the reaction system is a homogeneous system, the catalyst is not separated from the product by filtration, so that the catalyst can be separated by distillation together with the high boiling by-product, and the reuse of the catalyst is also limited due to the accumulation of the high boiling point.

Accordingly, the present inventors have tried to produce a mixed metal oxide catalyst having an increased reaction rate to alleviate the reaction conditions and at the same time reducing the amount of catalyst used and improving reaction stability. As a result, we devised a method for producing a mixed metal oxide catalyst material capable of uniformly increasing the catalytically active site concentration on the surface, and the surface distribution of the metal ions serving as the active site of the amination reaction on the surface of the solid catalyst material. In order to maintain the uniformity, the present invention was completed by preparing a mixed metal oxide catalyst in the form of hydrochalumite in the preparation step of the catalyst and adjusting the composition ratio of the metal component included in the catalyst to a specific numerical range.

It is an object of the present invention to provide a method for producing a long-chain aliphatic tertiary amine from a long-chain aliphatic alcohol in high yield under milder conditions by using a heterogeneous solid catalyst having excellent reaction stability, reaction selectivity and activity.

Another object of the present invention is to provide a method for preparing a catalyst which can be effectively used in the above method.

In the method for preparing an aliphatic tertiary amine of the present invention for achieving the above object, the method is an aliphatic alcohol having a carbon number of 8 to 36 in the presence of a mixed metal oxide catalyst of the hydrochalumite type represented by the following formula (1) Amination with dimethylamine comprises:

[Formula 1]

_{[M 3 Al (OH) 6} ] 3NO 3 · nH 2 O

(Wherein M is a metal element of Cu, Ni, Zn and Ca of divalent oxidized water, and M is 0.5 to 1.5 moles of Cu, 0.05 to 0.15 moles, relative to 4 moles of all metal elements including Al). Part Ni, 0.2 to 0.4 mole part Zn, and 0.9 to 2.0 mole part Ca, n has a value of 0.2 to 4 in the number of crystallized water).

The long-chain aliphatic alcohols include octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, bihenyl alcohol, oleyl alcohol, Ziegler alcohol produced in the Ziegler process, oxo alcohol produced in the oxo synthesis process, and the like. This can be used.

In the amination reaction, the catalyst is supplied to the reactor at 1.0 to 5% by weight relative to the long chain aliphatic alcohol, and the dimethylamine may be supplied to the reactor at a ratio of 1.05 to 1.2 equivalents based on the long chain aliphatic alcohol. In addition, the amination reaction may be carried out at a temperature of 210 ℃ to 240 ℃ and a pressure of 0.8 to 2.0 atm.

After performing the amination reaction, the catalyst can be separated from the product using a decantation or filtration separation method, and then the separated catalyst can be reused in subsequent amination reactions.

In the method for preparing a catalyst according to the present invention for achieving the above another object, the method maintains the pH of an aqueous solution and an aqueous alkali solution containing Cu, Ni, Zn and Ca, their mixed aqueous solution at 7 to 9 Simultaneously and simultaneously, preparing a mixed metal hydroxide in the form of hydrochalumite represented by Chemical Formula 1; Separating the hydroxide from the reaction solution, and washing and drying; And heat-treating the dried hydroxide at a temperature of 500 ° C to 700 ° C.

Hereinafter, the present invention will be described in more detail.

In the method for producing an aliphatic tertiary amine according to the present invention, a mixed metal oxide catalyst in the form of hydrochalumite represented by the following formula (1) is used.

[Formula 1]

_{[M 3 Al (OH) 6} ] 3NO 3 · nH 2 O

In Formula 1, M includes metal elements of Cu, Ni, Zn, and Ca, and Cu, Ni, Zn, and Ca each have a divalent oxidation number. N represents the number of crystallized water and has a value of 0.2 to 4.

M includes 0.5 to 1.5 mole parts of Cu with respect to 4 mole parts of all metal elements including Al. When the M contains more than 1.5 mole parts of Cu, the initial activity may be high, but as the solubility of the copper component increases, the deactivation of the catalyst may be increased as a result, and the M is less than 0.5 mole parts of Cu. This is because, when it contains, the catalytic activity is greatly reduced, which is undesirable.

M includes 0.05 to 0.15 moles of Ni with respect to 4 moles of all metal elements including Al. This is because when the Ni is more than 0.15 mole parts, the disproportionation side reaction of dimethylamine increases and the high boiling by-products are greatly increased, and when it is less than 0.05 mole parts, the activity in the amination reaction is reduced.

M includes 0.2 to 0.4 mol parts of Zn and 0.9 to 2.0 mol parts of Ca with respect to 4 mol parts of the total metal elements including Al. When the ratio of Zn is more than 0.4 mol part or the ratio of Ca is more than 2.0 mol part and the ratio of Al is more than 1.2 mol part, since the active copper and nickel components are reduced, the reaction activity may be greatly reduced, which is not preferable. In addition, when the ratio of Zn is less than 0.2 mole parts, or the ratio of Ca is less than 0.9 mole parts and the ratio of Al is less than 0.9 mole parts, since the copper and nickel components are not synthesized in the form of hydrocalumite, the structure of the catalyst becomes unstable, and thus the active ingredient It is not preferable because the distribution of is not uniform, and the reaction stability is also reduced along with the decrease in the reaction selectivity, which greatly reduces the filtration separability of the catalyst.

According to the present invention, the mixed metal oxide catalyst of the hydrochalumite type represented by Chemical Formula 1 is an aqueous solution containing Cu, Ni, Zn and Ca and an aqueous alkali solution while maintaining the pH of the mixed aqueous solution at 7-9. After preparing a mixed metal hydroxide by adding (step 1), the hydroxide is separated from the reaction solution, washed and dried (step 2), and the dried hydroxide is heat-treated at 500 ° C to 700 ° C ( Third step). Hereinafter, the method for preparing the catalyst will be described in more detail at each step.

First, the first step is to prepare a mixed metal hydroxide of the crystalline hydrocalumite form represented by the formula (1). According to the present invention, the mixed metal hydroxide of the hydrochalumite type represented by Formula 1 is prepared by simultaneously adding an aqueous solution containing a mixed metal component and an aqueous alkali solution, which is a mixed metal component which is a commonly known precipitation method. Precipitation method of adding alkali component to aqueous solution containing [ Reactivity of Solids , 5 , 219-228 (1988)] and hydrothermal methods [see US Pat. No. 5,250,279].

In the first step, an aqueous solution (A) in which copper, nickel, zinc, calcium and aluminum salts are dissolved, and an alkaline precipitant aqueous solution (B) are added together to coprecipitate them into particles in the form of hydroxide, wherein the copper, nickel, zinc The concentration of the aqueous solution of calcium and aluminum salts (A) may be in the range of 30 to 50% by weight, and the concentration of the aqueous solution of the alkaline precipitant may be in the range of 5 to 15% by weight, in which case the volume of each aqueous solution is the same. During the addition, the pH of the mixed aqueous solution is preferably maintained at 7 to 9, the pH can be adjusted by adjusting the amount of the precipitant aqueous solution. The temperature of the aqueous solution during coprecipitation is preferably kept constant in the range of 15 ° C to 30 ° C to maintain the hydrogel form, the coprecipitation time is preferably about 0.5 to 10 hours.

The precursors of copper, nickel, zinc, calcium and aluminum components usable in the present invention include nitrates and hydrochlorides, and the anions remaining after the nitrates are washed can be effectively removed during the firing process. .

As the alkaline precipitant according to the present invention, sodium hydroxide may be used. The amount of the alkaline precipitant is adjusted so that the pH of the aqueous metal hydroxide solution in the first step can be maintained at 7 to 9, preferably 7.5 to 8.5. When the pH of the aqueous solution exceeds 9, a mixture of metal hydroxides other than the hydrocalcite type hydroxide may be formed, and when the pH is lower than 7, precipitation of components such as copper, nickel, and zinc may be completely made. Because you may not lose.

Subsequently, the aqueous solution obtained as above is aged at a temperature of 40 ° C. to 80 ° C. for 3 to 30 hours. The hydrochalumite-type mixed metal hydroxide prepared in this manner has a layered structure, and the layered structure is formed of an intermediate metal surface formed by mixing divalent metal ions and trivalent metal ions, and a combination of OH groups on and below the metal surface. It may include a side made of. In particular, the mixed metal hydroxide is in the form of a crystalline substance in which divalent metal ions and trivalent metal ions are uniformly mixed at a molecular level, and combines the divalent metal component as a component that is active in the amination reaction of an aliphatic alcohol. There is an advantage that can be synthesized.

The second step is a process of separating the intermediate composite material of hydrochalumite form obtained in the first step by vacuum filtration or centrifugation, followed by washing with deionized water and drying. In this step, it is important to control the residual amount of the cationic material such as sodium derived from the alkaline precipitant added in the first step, preferably the concentration of the cationic material is 1,000 ppm or less for the catalyst in the oxide state Is adjusted. The drying consists of a first drying step of drying at room temperature for 12 hours or more, and a second drying step of drying for 2 to 12 hours at a temperature of 100 ° C to 120 ° C.

The third step is a process of baking by drying the dried intermediate composite material at 500 ℃ to 700 ℃ for 3 to 10 hours. If the firing temperature is too high, more than 700 ℃ metal oxide particles are sintered and the catalytic activity is reduced, if the firing temperature is too low below 500 ℃ metal hydroxides such as calcium and aluminum is not sufficiently converted to oxide. In addition, since the binding property of copper and nickel, which is an active metal component, is reduced, the reaction stability of the catalyst may be reduced, which is not preferable. The catalyst material in the form of dark brown fine powder produced after firing is a mixed metal oxide catalyst having a uniform distribution of the surface active ingredient used in the present invention.

As such, the mixed metal oxide catalyst prepared by heat-treating the hydrocalcite-type hydroxide exhibits excellent catalytic activity in the amination reaction of the long-chain aliphatic alcohol. Hereinafter, the amination reaction of the aliphatic alcohol to which the catalyst of the present invention is used is described. It explains in detail.

First, a long chain aliphatic alcohol and a mixed metal oxide catalyst are injected into the reactor.

The long-chain aliphatic alcohols used in the present invention are straight or branched aliphatic alcohols having 8 to 36 carbon atoms. Examples of the long-chain aliphatic alcohol include octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, bihenyl alcohol, oleyl alcohol, and the like. In particular, the branched alcohol may be Ziegler alcohol produced in the Ziegler process, Oxo alcohol produced during the oxo synthesis step. These may be used alone or in combination of one or more of them. The catalyst may be used in the range of 0.5 to 8% by weight, preferably in the range of 1.0 to 5% by weight relative to the aliphatic alcohol.

Subsequently, after replacing the reactor with an inert gas such as nitrogen (N ₂ ), the reactor was again replaced with hydrogen (H ₂ ) while heating the reactor to a temperature of 120 ° C. The hydrogen pressure was charged at 0.5 atmosphere (gauge pressure), the reaction temperature was raised to a temperature of 210 ° C to 240 ° C, and then 1.05 to 1.2 equivalent ratio of dimethylamine gas was supplied to the reactor with respect to aliphatic alcohol, and 0.8 to 2.0 atmospheres. The reaction proceeds for 2 to 6 hours at a reaction pressure of. Hydrogen, unreacted amine gas, water produced in the reaction, small amounts of unreacted aliphatic alcohol and produced aliphatic amines are continuously removed from the reactor as exhaust gas and fed to the condenser. In the condenser the materials are separated into water and organic layer, the double organic layer is recycled to the reactor, and hydrogen and unreacted amine gas are also recycled to the reactor. After the reaction, the catalyst is separated from the product using a decantation or filtration method, and the resulting aliphatic tertiary amine is purified by distillation under reduced pressure or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it is to be understood that the following examples are intended to illustrate the invention and are not intended to limit the invention.

Example  One

(1-1) Mixed Metal Oxide Catalyst Preparation

Copper nitrate [Cu (NO ₃ ) ₂ · 3H ₂ O] 48.3 g, nickel nitrate [Ni (NO ₃ ) ₂ · 6H ₂ O] 5.8 g, zinc nitrate [Zn (NO ₃ ) ₂ · 6H ₂ O] 23.8 g , 70.8 g of calcium nitrate [Ca (NO ₃ ) ₂ .4H ₂ O] and 74.9 g of aluminum nitrate [Al (NO ₃ ) ₃ .9H ₂ O] were dissolved in deionized water to prepare a 500 ml solution (solution A). On the other hand, was prepared a 500ml solution (solution B) by dissolving [NaOH] 40g of sodium hydroxide in deionized water, a solution (solution C) of 100ml is dissolved sodium hydroxide [NaOH] 4g and sodium nitrate [NaNO _3] 55g of deionized water Prepared.

The solution C was added to a 2 L beaker equipped with a pH electrode and stirred. When the solution C had a pH of 8, the solution A and the solution B were added at the same flow rate for 1 hour, and the flow rate of the solution B was adjusted so that the pH of the mixed solution was maintained at 8. Subsequently, the mixed solution was aged at a temperature of 60 ° C. for 12 hours, and then filtered. At this time, 800 ml of deionized water was added to disperse, stir and filter the mixture four times. The filtered hydroxide was dried at a temperature of 100 ℃ for 10 hours _{[Cu 1 .0 Ni 0 .1 Zn} 0 .4 Ca 1 .5 Al (OH) 6] 3NO 3 · hydro of light blue powder represented by the nH ₂ O Mixed metal hydroxides in the form of kalumite were synthesized. By analyzing the dried hydroxide by X-ray diffraction spectroscopy (XRD), it was confirmed that the hydroxide has a structure of hydrokalumite, the results are shown in FIG. Subsequently, the dried powder was calcined at a temperature of 550 ° C. for 6 hours to prepare a mixed metal oxide catalyst of dark brown powder.

(1-2) Amination Reaction

12 g of the mixed metal oxide catalyst prepared above and 600 g of stearyl alcohol were charged into a 1 L stainless flask reactor, and the mixture was stirred three times with nitrogen while stirring the mixture. After repeating the process of supplying and decompressing three times in this way, the reactor was heated to a temperature of 120 ° C., and the process of supplying hydrogen again and depressurizing was repeated twice. Subsequently, hydrogen was charged to 0.5 atm, heated to a temperature of 200 ° C. and maintained for 15 minutes, after which the temperature was again raised to 220 ° C., and then 1.1 equivalent ratio of dimethylamine gas was supplied to the reactor for aliphatic alcohol, The reaction was carried out for 3 hours at a reaction pressure of 1.0 atm. Hydrogen, unreacted amine gas, water produced in the reaction, a small amount of unreacted aliphatic alcohol and produced aliphatic amine were continuously removed from the reactor as exhaust gas and fed to the condenser. In the condenser, the condensate was separated into water and an organic layer, of which the organic layer was recycled to the reactor, and hydrogen and unreacted amine gas were also recycled to the reactor. After the reaction, the catalyst was decanted or filtered off from the product, and the aliphatic tertiary amine was purified by distillation under reduced pressure. The separated catalyst was stirred with the addition of stearyl alcohol, recharged into the reactor, and used repeatedly for amination reaction. The amination reaction product thus prepared was analyzed by GC (gas chromatography), and the results are shown in Table 1 below. The reaction results are expressed in% of GC area. The amount of metal residue contained in the purified aliphatic tertiary amine after distillation was measured by acid decomposition of the sample, followed by quantitative analysis using an Inductively Coupled Plasma Atomic Emission Spectrometer. The contents of copper, nickel, zinc, calcium and aluminum were less than 1 ppm in the purified samples after the first and ten reactions, respectively.

Example  2 and 3

In the mixed metal oxide catalyst, a catalyst was prepared in the same manner as in Example (1-1) except that the composition of Cu, Ni, Zn, and Ca was partially different (see Table 1 for the composition ratio of specific catalysts). ), The preparation reaction of the long chain aliphatic tertiary amine was carried out in the same manner as in Example (1-2). The reaction results are shown in Table 1.

Comparative example  1 to 3

In the mixed metal oxide catalyst, a catalyst was prepared in the same manner as in Example (1-1) except that the composition of Cu, Ni, Zn, and Ca was partially different (see Table 1 for the composition ratio of specific catalysts). ), The preparation reaction of long chain aliphatic tertiary amine was carried out in the same manner as in Example (1-2). The reaction results are shown in Table 1.

Comparative example  4

A catalyst was prepared in the same manner as in Example (1-1) except that sodium carbonate was used instead of sodium hydroxide as the alkali precipitater (the specific composition ratio of the catalyst is shown in Table 1 below), and the same as in Example (1-2). The reaction of long chain aliphatic tertiary amine was carried out by the method. The reaction results are shown in Table 1 below.

Catalyst composition Reaction Recovery Aliphatic tertiary amine analysis Filtration yield (%) Distillation yield (%) Purity (%)  Example 1 _{Cu 1 .0 Ni 0 .1 Zn 0} .4 Ca 1 .5 Al One 98.2 95.0 98.2 2 98.2 95.0 98.2 5 98.0 94.8 98.0 10 97.5 94.6 98.0 Example 2 _{Cu 0 .7 Ni 0 .05 Zn 0} .35 Ca 1 .9 Al One 98.0 94.7 98.0 5 97.8 94.5 98.0 Example 3 _{Cu 1 .4 Ni 0 .1 Zn 0} .4 Ca 1 .1 Al One 98.4 95.0 98.2 5 98.2 95.0 98.0 Comparative Example 1 _{Cu 1 .09 Ni 0 .01 Zn 0} .4 Ca 1 .5 Al One 98.0 90.6 96.5 3 96.5 86.6 90.3 Comparative Example 2 _{Cu 0 .4 Ni 0 .1 Zn 0} .2 Ca 2 .3 Al One 97.5 92.6 95.6 3 91.5 80.3 92.3 Comparative Example 3 _{Cu 0 .6 Ni 0 .1 Zn 0} .1 Ca 1 .5 Al 1 .7 One 97.6 91.2 96.8 3 86.6 78.6 86.6 Comparative Example 4 CuO-NiO-ZnO-CaCO ₃ -Al ₂ O ₃ (1-0.1-0.4-1.5-0.5, molar ratio) One 95.0 92.3 95.8 3 85.9 81.7 87.8

From Table 1, when the catalyst is used once, it can be confirmed that the aliphatic tertiary amines prepared in Examples 1 to 3 of the present invention are superior in purity and yield to the aliphatic tertiary amines prepared in Comparative Examples 1 to 4. In addition, in Examples 1 to 3, even when the catalyst is repeatedly reused about 5 or 10 times, excellent filtration yield, distillation yield and purity are maintained, whereas Comparative Examples 1 to 4 maintain the activity of the catalyst according to the number of reactions. And the like. The filter yields, distillation yields and purity of the aliphatic tertiary amines of Comparative Examples 1 to 4, which were prepared by repeatedly using the catalyst three times, were significantly reduced, and the examples prepared by using the catalyst repeatedly about five or ten times. It can be seen that the lower level than the aliphatic tertiary amine of 1-3.

Example  4 and 5

In the (1-2) amination reaction of Example 1, except that bihenyl alcohol (Example 4) and oleyl alcohol (Example 5) were used instead of stearyl alcohol in the same manner as in Example 1 Long chain aliphatic tertiary amines were prepared. The bihenyl alcohol was reacted at a temperature of 230 ℃, the oleyl alcohol was reacted at a temperature of 215 ℃. The reaction results are shown in Table 2 below.

Reactant Reaction Recovery Aliphatic tertiary amine analysis Filtration yield (%) Distillation yield (%) Purity (%) Example 4 Bihenyl alcohol One 98.2 94.8 98.0 5 98.0 94.6 97.8 Example 5 Oleyl alcohol One 98.3 94.7 98.3 5 98.0 94.5 98.1

According to the present invention, by carrying out the amination reaction using a heterogeneous solid catalyst having excellent reaction stability, reaction selectivity and activity, a long-chain aliphatic tertiary amine can be produced in a high yield stably under milder conditions. In addition, the catalyst is very economical because it can be easily separated and reused from the product through a method such as decantation.

Claims (6)

     A method for preparing an aliphatic tertiary amine, characterized by amination of a long chain aliphatic alcohol having 8 to 36 carbon atoms with dimethylamine in the presence of a mixed metal oxide catalyst in the form of hydrochalumite represented by Formula 1 below: [Formula 1] _{[M 3 Al (OH) 6} ] 3NO 3 · nH 2 O (Wherein M is a metal element of Cu, Ni, Zn and Ca of divalent oxidized water, and M is 0.5 to 1.5 moles of Cu, 0.05 to 0.15 moles, relative to 4 moles of all metal elements including Al). Part Ni, 0.2 to 0.4 mole part Zn, and 0.9 to 2.0 mole part Ca, n has a value of 0.2 to 4 in the number of crystallized water). The method of claim 1, The long chain aliphatic alcohol is selected from the group consisting of octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, bihenyl alcohol, oleyl alcohol, Ziegler alcohol produced in the Ziegler process, and oxo alcohol produced in the oxo synthesis process. And at least one alcohol. The method of claim 1, During the amination reaction, the catalyst is supplied to the reactor at 1.0 to 5% by weight relative to the long chain aliphatic alcohol, and the dimethylamine is supplied to the reactor at a ratio of 1.05 to 1.2 equivalents based on the long chain aliphatic alcohol. . The method of claim 1, The amination reaction is characterized in that it is carried out at a temperature of 210 ℃ to 240 ℃ and a pressure of 0.8 to 2.0 atm. The method of claim 1, After performing the amination reaction, further comprising decanting or filtration of the catalyst from the product for reuse in the amination reaction. A process for preparing a catalyst used in the process for preparing the long chain aliphatic tertiary amine of claim 1, comprising the following steps: Simultaneously adding an aqueous solution containing Cu, Ni, Zn and Ca and an aqueous alkali solution while maintaining the pH of the mixed aqueous solution at 7 to 9 to prepare a mixed metal hydroxide in the form of hydrochalumite represented by the following Chemical Formula 1 , [Formula 1] _{[M 3 Al (OH) 6} ] 3NO 3 · nH 2 O (Wherein M is a metal element of Cu, Ni, Zn and Ca of divalent oxidized water, and M is 0.5 to 1.5 moles of Cu, 0.05 to 0.15 moles, relative to 4 moles of all metal elements including Al). Part Ni, 0.2 to 0.4 mole part Zn, and 0.9 to 2.0 mole part Ca, n has a value of 0.2 to 4 in the number of crystallized water); Separating the hydroxide from the reaction solution, and washing and drying; And Heat-treating the dried hydroxide at a temperature of 500 ° C to 700 ° C.

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