KR20110130022A - Metal oxide catalyst for preparing longer chain secondary dialkylamines - Google Patents

Abstract

PURPOSE: A metal oxide catalyst for manufacturing long-chain secondary dialkyl amine is provided to improve the yield of a reaction and to simplify manufacturing processes. CONSTITUTION: A metal oxide catalyst for manufacturing long-chain secondary dialkyl amine includes the following: A metal oxide catalyst is used for manufacturing the long-chain secondary dialkyl amine by reacting C8 to C13 long-chain alcohol and ammonia. The metal oxide catalyst is represented by chemical formula 1. In chemical formula 1, a, b, c, and d represent respective materials with respect to the total weight of the catalyst. The a is 40-80 weight%, the b is 1-15 weight%, the c is 0.5-10 weight%, and the d is 20-40 weight%. M is an oxide of at least one metal element selected from a group including molybdenum, tungsten, manganese, and tin.

Description

Metal Oxide Catalyst for Preparing Longer Chain Secondary Dialkylamines

The present invention relates to a metal oxide catalyst for preparing long-chain secondary dialkylamine having 8 to 13 carbon atoms, and more particularly, to a long chain which can obtain a final product having a high reaction yield, a simple process, and excellent purity and quality. A four-component metal oxide catalyst for preparing secondary dialkylamines.

Long chain secondary dialkylamine having 8 to 13 carbon atoms is a raw material of molybdenum-based lubricating oil additive used as engine oil and grease additive, and it has much better wear resistance than engine oil and grease additives, improving automobile fuel economy and improving engine life. It is an excellent high performance additive. However, since the manufacturing technology of the long-chain secondary dialkylamine is monopolized in developed countries such as the United States, Japan, and Germany, the state relies on the import of high-grade lubricant additives in its entirety.

Amine compounds are useful compounds used as pharmaceutical intermediates, agrochemical intermediates, dye intermediates, rubber chemicals, surfactants, water treatment agents, urethane raw materials, epoxy curing agents, emulsifiers and solvents. Among them, commercial applications of secondary amine derivatives, especially long chain secondary amine compounds having carbon chain lengths of 8 to 13, include corrosion inhibitors, emulsifiers, urethane raw materials, pesticides and dyes of general primary and tertiary alkylamine derivative compounds. It belongs to a unique area that distinguishes it from intermediates. The primary uses of secondary dialkyl amines having 8 to 13 carbon chains include molybdenum-based engine oils and grease additives, which act as antioxidants, antiwear agents, extreme pressure additives, and friction modifiers. It is known to show excellent performance by using a small amount of additives compared to molybdenum type. Particularly, molybdenum-based engine oil additives synthesized from long-chain secondary amines are used to improve the fuel efficiency of automobiles for CO ₂ reduction, which is noted as a major cause of global warming gas as well as international oil price hikes. It is known that it has an excellent effect of reducing energy by reducing mechanical wear and reducing fuel consumption by reducing abrasion generated, and demand is increasing rapidly around the world.

As a method for preparing a long chain secondary amine, a three-step step of preparing a fatty dinitrile from a fatty acid, hydrogenating the fatty nitrile to produce a primary fatty amine, and then reacting with an alcohol to prepare a secondary dialkyl amine in three steps Preparation method, the first step to prepare a primary amine by amination of the long-chain alcohol with ammonia, and the second step to prepare a secondary alkyl alcohol by reacting with alcohol, and the amination reaction of the long-chain alcohol with ammonia 2 There is a one-step process for preparing a class alkyl alcohol. Among the existing processes, secondary alkylamines are mostly prepared from fatty acids through a complex process of two to three stages, but recently, due to the development of amination technology, one-step long-chain alcohol amination catalyst and secondary alkyl using the catalyst The production process of amines is being actively researched and developed.

According to a process for preparing alkylamines using a recently developed catalyst, in US Patent No. 5,530,127, BASF, Germany, uses a NiO—CuO—CoO—ZrO ₂ based catalyst in a tubular reactor to produce butyl alcohol having 4 carbon atoms at 30 ° C. at 180 ° C. Reaction with ammonia yielded 51% primary amine yield and 43% secondary amine yield. In addition, when trideca alcohol having 13 carbon atoms was reacted with ammonia at 200 ° C. and 200 atm using a NiO—CuO—MoO ₃ —ZrO ₃ catalyst, the yield of primary amine was 74% and the yield of secondary amine 25%. In addition, U.S. Patent No. 4,415,755, Texaco of the United States used a CuO-CrO catalyst in a tubular reactor when reacting octyl alcohol with ammonia, yielding a primary amine yield of 80% and a secondary amine yield of 15% under conditions of normal pressure and atmospheric pressure. When the reaction was performed under the condition of, 275 ° C. and 5 atmospheres, the yield was 58% for the primary amine and 33% for the secondary amine.

However, in the manufacture of BASF and Texaco, when the amination reaction is carried out in a tubular reactor, the reaction must be performed under severe reaction conditions at high pressure, and the secondary amine yield is 50% or less.

In addition, U.S. Pat. The reaction was carried out in a batch reactor at 180 ° C., 0.25 wt% catalyst, reaction time 5 hr, and ammonia flow rate of 30 L / hr, yielding a secondary amine yield of 94%. In addition, the reaction of laurylamine, a primary amine, with stearyl alcohol under Cu-Pd / Zeolite and Cu-Ni-Ru / Zeolite catalyst at 180 ° C., 1% of catalyst, reaction time of 5 hours, and primary amine flow rate of 25 L / hr The reaction was carried out under the conditions to obtain a secondary amine in a yield of 97%.

However, the result is that the use of expensive precious metal catalysts and the primary amine and various alcohols can be reacted to synthesize a variety of secondary amines in a higher yield, but there was a problem that the process is complicated by the two-step reaction.

Accordingly, the present inventors synthesized and reacted various nickel-based metal oxide catalysts in order to solve the problems of the prior art, resulting in a long chain secondary amine having a high reaction yield, simple process, and excellent purity and quality. Four-component metal oxide catalysts for preparing secondary dialkylamines have been developed.

An object of the present invention is to provide a four-component metal oxide catalyst for producing long chain secondary dialkylamine having high reaction yield.

Another object of the present invention is to provide a four-component metal oxide catalyst for preparing long chain secondary dialkylamines having a simple process.

It is another object of the present invention to provide a four-component metal oxide catalyst for preparing long-chain secondary dialkylamines capable of obtaining a final product having excellent purity and quality.

The above and other objects of the present invention can be achieved by the present invention described below.

The four-component metal oxide catalyst for preparing long-chain secondary dialkylamines of the present invention is used for the preparation of long-chain secondary dialkyl amines in a one-step reaction in which ammonia is reacted with a long-chain alcohol having 8 to 13 carbon atoms. It is characterized by being displayed.

Formula 1

NiO (a) MgO (b) M (c) Al ₂ O ₃ (d)

In Formula 1, a, b, c and d means the content relative to the total weight of the catalyst, a is 40 to 80% by weight, b is 1 to 15% by weight, c is 0.5 to 10% by weight, d is 20 to 40% by weight, and M is an oxide of at least one metal element selected from molybdenum (Mo), tungsten (W), manganese (Mn) and antimony (Sn).

In Formula 1, a is 50 to 75% by weight, b is 5 to 15% by weight, c is 1 to 7% by weight, and d is 15 to 35% by weight.

M in Formula 1 is characterized in that the molybdenum (Mo) oxide.

The long-chain alcohol having 8 to 13 carbon atoms is 2-ethylhexanol, 2-octanol, n-Octanol, or isotridecanol.

The use of the catalyst in the synthesis conditions of the long-chain secondary dialkylamine using the four-component metal oxide catalyst is 1 to 20% by weight based on the reactants, the reaction temperature is 110 to 210 ℃, the reaction pressure is carried out at 0.2 to 4 atm It is done.

The present invention has the effect of providing a four-component metal oxide catalyst for producing a long chain secondary dialkylamine capable of obtaining a final product having a high reaction yield, a simple process, and having excellent purity and quality.

Figure 1 shows the results of analyzing the catalyst according to an embodiment of the present invention by XRD.

The present invention relates to a technique for preparing a long chain secondary dialkyl amine in one step by reacting ammonia with a long chain alcohol having 8 to 13 carbon atoms.

As one specific example, Scheme 1 for isotridecanol having 13 carbon atoms corresponding to the long chain alcohol of the present invention is as follows.

Scheme 1

According to Scheme 1, a long chain alcohol having 8 to 13 carbon atoms is introduced into the reactor as a starting material, and then the catalyst according to the present invention is introduced into the reactor. The chemical formula of the catalyst according to the invention is as follows.

Formula 1

NiO (a) MgO (b) M (c) Al ₂ O ₃ (d)

In Formula 1, a, b, c and d means the content relative to the total weight of the catalyst, a is 40 to 80% by weight, b is 1 to 15% by weight, c is 0.5 to 10% by weight, d is 20 to 40% by weight, and M is an oxide of at least one metal element selected from molybdenum (Mo), tungsten (W), manganese (Mn) and tin (Sn).

Nickel oxide (NiO) is 40 to 80% by weight, magnesium oxide (MgO) is 1 to 15% by weight, M oxide is 0.5 to 10% by weight, and aluminum oxide (Al) as an active ingredient of the four-component metal oxide catalyst. ₂ O ₃ ) is preferably used to 20 to 40% by weight. More preferably, the nickel oxide is 50 to 75% by weight, the magnesium oxide is 3 to 12% by weight, the M oxide is 1 to 7% by weight, and the aluminum oxide is 22 to 35% by weight. When the content of nickel oxide is more than 80% by weight, the size of the nickel crystals increases, the reaction activity is rather reduced, and when the content of the nickel oxide is 40% by weight or less, the nickel crystals are small but the amination activity is low and the conversion rate is reduced. When the content of magnesium oxide is 1 or less, or the content of aluminum oxide is 20% by weight or less, high dispersion and uniformity of nickel oxide (NiO) crystals are reduced, so that the conversion rate is low due to low hydrogenation activity, and the content of magnesium oxide is high. If the content is more than 15% by weight, or the content of aluminum oxide is more than 40% by weight, the acidity and basicity of the catalyst are greatly increased, and the aldol condensation and peraminelation side reactions are increased, thereby greatly reducing the selectivity of the secondary amine and tertiary amine. By-products will increase. If the content of M oxide is 0.5% by weight or less, there is no effect of increasing the amination reaction activity or increasing the service life by repeated use of the catalyst by stabilizing inhibiting sintering of nickel oxide (NiO) crystals. Interfering with the production of nickel oxide (NiO) crystals, the catalytic activity is reduced and the conversion rate is lowered.

The long chain alcohol having 8 to 13 carbon atoms is 2-ethylhexanol, n-Octanol, or isotridecanol.

The use amount of the catalyst is 1 to 20% by weight, preferably 3 to 15% by weight, and the reaction temperature is 110 to 210 ° C based on the synthesis conditions of the long-chain secondary dialkylamine using the 4-component metal oxide catalyst. 120 to 190 캜, the reaction pressure is carried out at 0.2 to 4 atm, preferably 0.3 to 3 atm. If the amount of the catalyst is 20% by weight or more, or the reaction temperature is 210 ° C or more and the reaction pressure is 0.2 atm or less, the activity of the catalyst is excessively increased, and the amination reaction is further progressed, so that the secondary amine is converted to tertiary amine. The yield of the tertiary amine is reduced. And if the amount of the catalyst is 1% by weight or less, or the reaction temperature is 110 ℃ or less, the reaction pressure is more than 4 atm, the conversion rate is lowered, the reaction time is greatly increased, and other reaction conditions must be severely increased, the process operating cost is increased, 2 The yield of the tertiary amine is also reduced.

Hereinafter, embodiments of the present invention will be described in detail. The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

Example 1:

(1-1) Amination Catalyst NiO (63), MgO (7) MoO ₃ (5), Al ₂ O ₃ (25) Preparation

2,094 g of nickel nitrate [Ni (NO ₃ ) ₂ · 6H ₂ O], 385 g of magnesium nitrate [Mg (NO ₃ ) ₂ · 6H ₂ O] and 1,576 g of aluminum nitrate [Al (NO ₃ ) ₃ · 9H ₂ O] It was dissolved in deionized water to prepare a 7L solution (A solution). 1,120 g of sodium hydroxide [NaOH] was dissolved in deionized water to prepare a 7 L solution (B solution). 212 g of sodium carbonate [Na ₂ CO ₃ ] was dissolved in deionized water to prepare a 2 L solution (C solution). C solution was added to a 30L reactor equipped with a pH electrode and stirred. A and B solutions were added for 5 hours at the same flow rate at pH 9 of the C solution, and the B solution was adjusted to bring the final pH of the dispersion to pH 9. 73 g of Na ₂ MoO ₄ .2H ₂ O was added to the C solution slurry, and the mixture was stirred for 1 hour. Then, the mixture was stirred at 80 ° C. for 12 hours and filtered. Next, 15 L deionized water was added, the dispersion and stirring were repeated three times. The filtered hydroxide was dried at 100 ° C. for 10 hours. The dried hydroxide was ground to a size of 10 to 60 micrometers in a mill and calcined in air at 600 ° C. for 6 hours. The calcined oxide powder was reduced under hydrogen flow at 500 ° C. for 5 hours in a reduction kiln. As a result of analyzing the calcined catalyst in air by XRD, crystals of nickel oxide were confirmed, and magnesium oxide, molybdenum oxide and aluminum oxide were fine amorphous (FIG. 1). The reduced catalyst powder was stabilized by flowing nitrogen gas containing 5% of carbon dioxide at 30 ° C. for 6 hours and used as a catalyst.

(1-2) hydrogenation reaction

70 kg of isotridecanol was added to a 200 L stainless reactor, and 6 kg of NiO (63) .MgO (7) .MoO ₃ (5) .Al ₂ O ₃ (25) catalyst was added. Thereafter, nitrogen gas was injected into the reactor, and the depressurization was repeated to replace the reactor with nitrogen. After nitrogen substitution, the ammonia gas (NH ₃ ) was charged to 1.0 atm while raising the temperature to 90 ° C, and the temperature was raised to 160 ° C to perform the amination reaction for 10 hours. After the reaction, the mixture was cooled to 60 DEG C, depressurized, replaced with nitrogen, left to stand, and the catalyst layer was precipitated. The amine layer corresponding to the upper layer was sent to a distillation step to obtain a long chain secondary amine having a purity of 96%. The secondary amine after the catalyst was separated and the amine sample after distillation were analyzed by GC (gas chromatography). The reaction results are shown in Table 1 below.

Examples 2 to 3:

In the composition of the NiO (a), MgO (b), WO ₃ (c), Al ₂ O ₃ (d) catalyst, a is 40 to 80% by weight, b is 1 to 15% by weight, and c is 0.5 to 10% by weight. and d were synthesized in the same manner as in Example (1-1) except that the values were changed as in Table 1 within the range of 20 to 40% by weight, and the reaction was the same as in Example (1-2). The reaction results are shown in Table 1.

Comparative Examples 1 to 4:

In the composition of the NiO (a), MgO (b), WO ₃ (c), Al ₂ O ₃ (d) catalyst, a is 40 to 80% by weight, b is 1 to 15% by weight, and c is 0.5 to 10% by weight. , d was synthesized in the same manner as in Example (1-1) except that it was changed as shown in Table 1 outside the range of 20 to 40% by weight, and the reaction was the same as in Example (1-2). In addition, Raney 2800 (nickel) catalyst of WR Grace was reacted as in Example (1-2). The reaction results are shown in Table 1.

Example 4:

NiO (63) · MgO (9 ) · WO 3 (3) · Al 2 O _3, but the 25 catalyst Example 1-1 in the same manner as Synthesis ₂ MoO ₄ 2H ₂ O instead of Na in Na ₂ WoO ₄ 2H ₂ O was used and the reaction was the same as in Example (1-2). The reaction results are shown in Table 1.

Example 5:

A catalyst of NiO (63), MgO (9), MnO (3), Al ₂ O ₃ (25) was synthesized in the same manner as in Example (1-1), except that Na ₂ MoO ₄ Manganese nitrate [Mn (NO ₃ ) ₂ .6H ₂ O] was used instead of 2H ₂ O, and the reaction was the same as in Example (1-2). The reaction results are shown in Table 1.

Example 6:

A catalyst of NiO (63), MgO (9), SnO ₂ (3), Al ₂ O ₃ (25) was synthesized in the same manner as in Example (1-1), except that tin chloride [Sn was used instead of Na ₂ MoO ₄ 2H ₂ O. (Cl) ₄ .5H ₂ O] was used and the reaction was the same as in Example (1-2). The reaction results are shown in Table 1.

Example Catalyst composition (wt%) % Alcohol conversion Primary amine
yield(%) Secondary amine yield (%) Tertiary amine yield (%) Example 1 NiO (63), MgO (7), MoO ₃ (5), Al ₂ O ₃ (25) 93 8 83 3 Example 2 NiO (73), MgO (5), MoO ₃ (2), Al ₂ O ₃ (20) 96 6 85 5 Example 3 NiO (53), MgO (10), MoO ₃ (5), Al ₂ O ₃ (32) 91 9 80 2 Comparative Example 1 NiO (60), MgO (7), MoO ₃ (11), Al ₂ O ₃ (22) 98 5 55 38 Comparative Example 2 NiO (38) MgO (7) MoO ₃ (5) Al ₂ O ₃ (50) 54 19 33 2 Comparative Example 3 NiO (63) MgO (1) MoO ₃ (0.4) Al ₂ O ₃ (35.6) 65 27 37 One Comparative Example 4 Raney Ni (Ni 89%), W. R. Grace. # 2800 88 28 53 7 Example 4 NiO (63), MgO (9), WO ₃ (3), Al ₂ O ₃ (25) 94 9 80 5 Example 5 NiO (63), MgO (9), MnO (3), Al ₂ O ₃ (25) 92 10 80 2 Example 6 NiO (63) MgO (9) SnO ₂ (3) Al ₂ O ₃ (25) 92 6 81 5

In the composition of the NiO (a), MgO (b), WO ₃ (c) Al ₂ O ₃ (d) catalyst as in Examples 1 to 3, a is 40 to 80% by weight, b is 1 to 15% by weight %, c is in the range of 0.5 to 10% by weight, d is in the range of 20 to 40% by weight conversion of 91% or more, the yield of primary amines of 9% or less, the yield of secondary long-chain amines of 80% or more When the distillation was a high-quality long chain secondary amine of more than 96% purity. However, as in Comparative Examples 1 to 4, in the catalyst composition, a is 40 to 80% by weight, b is 1 to 15% by weight, c is 0.5 to 10% by weight, and d is 20 to 40% by weight of the catalyst. The yield of the secondary amine was 30%, or the yield of the tertiary amine was more than 30%, resulting in very low production yields. In addition to the addition of molybdenum, the addition of tungsten, manganese, and tin oxides yielded excellent yields of secondary amines of 80% or more.

Examples 7-11:

NiO (63), MgO (7), MoO ₃ (5), Al ₂ O ₃ (25) catalyst of Example 1-1 was used, but the reaction conditions were changed as shown in Table 2, but the reaction was performed in Example (1 Was the same as -2). The reaction results are shown in Table 2.

Example Catalytic amount
(weight%) Reaction temperature (℃) Reaction pressure (atmospheric pressure) Response time (hours) % Alcohol conversion Primary amine
Selectivity (%) Secondary amine selectivity (%) Tertiary amine selectivity (%) Example 7 12 160 0.7 8 95 6 81 8 Example 8 8 150 0.8 15 93 9 81 3 Example 9 8 160 2.0 12 98 25 70 3 Example 10 8 180 0.8 8 98 4 83 11 Example 11 5 160 1.0 10 93 7 82 4

As in Examples 7 to 11, the amount of the catalyst used was 1 to 20% by weight, the reaction temperature was 110 to 210 ° C, the reaction pressure was 0.2 to 4 atm, and the yield of the secondary long-chain amine was 81%. It was able to synthesize | combine with high yield above.

Examples 12-13

NiO (63), MgO (7), MoO ₃ (5), Al ₂ O ₃ (25) catalysts of Example (1-1) were used, but the reaction was carried out in isotridecanol to normal octane as shown in Table 3. It was reacted with Nol and 2-ethylhexanol as in Example (1-2). The reaction results are shown in Table 3.

Example Reaction alcohol Alcohol conversion
(%) Primary amine yield
(%) Secondary amine yield
(%) Tertiary Amine Yield
(%) Example 12 Normal Octanol 98 7 86 5 Example 13 2-ethylhexanol 94 10 78 6

As a result of the amination reaction using normal octanol and 2-ethylhexanol having 8 carbon atoms as in Examples 12 to 13, the yield of secondary long-chain amine was 80% or more, which was synthesized in high yield. .

Therefore, when preparing the secondary dialkylamine from the long-chain alcohol using the catalyst according to the present invention, the engine oil additive and grease additive having excellent quality since the process is simple and can produce a product having excellent reaction yield, purity and quality. There is an advantage that can be used as.

Claims (6)

A four-component metal for producing long-chain secondary dialkylamines, which is used to prepare long-chain secondary dialkyl amines in a one-step reaction in which ammonia is reacted with a long-chain alcohol having 8 to 13 carbon atoms. Oxide catalyst:
Formula 1
NiO (a) MgO (b) M (c) Al ₂ O ₃ (d)
In Formula 1, a, b, c and d means the content relative to the total weight of the catalyst, a is 40 to 80% by weight, b is 1 to 15% by weight, c is 0.5 to 10% by weight, d is 20 to 40% by weight, and M is an oxide of at least one metal element selected from molybdenum (Mo), tungsten (W), manganese (Mn) and tin (Sn). The long chain according to claim 1, wherein in Formula 1, a is 50 to 75% by weight, b is 3 to 12% by weight, c is 1 to 7% by weight, and d is 22 to 35% by weight. Metal oxide catalyst for the preparation of secondary dialkylamines. The metal oxide catalyst of claim 1, wherein M in Formula 1 is a molybdenum (Mo) oxide. The long-chain alcohol having a carbon number of 8 to 13 is 2-ethylhexanol, n-octanol, or isotridecanol. Metal oxide catalyst for the production of long chain secondary dialkylamines. According to claim 1, Long chain secondary dialkylamine synthesis conditions using the catalyst is 1 to 20% by weight based on the reactants, the reaction temperature is 110 to 210 ℃, reaction pressure is 0.2 to 4 atm, characterized in that the long chain 2 Metal oxide catalyst for preparing dialkylamines. According to claim 1, Long chain secondary dialkylamine synthesis conditions using the catalyst is 3 to 15% by weight based on the reactants, the reaction temperature is 120 to 190 ℃, the reaction pressure is 0.3 to 3 atmospheres, characterized in that the long chain 2 Metal oxide catalyst for preparing dialkylamines.

Images