SK86596A3 - Manufacturing process of amines from olefins on aluminium-beta-zeolites without transition metals and prepared without treatment with halogens - Google Patents

Abstract

Prepn. of amines of formula R<5>R<6>CH-CR<3>R<4>-NR<1>R<2> (I) (where R<1-6> = H, 1-20 C alkyl, 2-20 C alkenyl, 2-8 C alkynyl, 3-20 C cycloalkyl, 4-20 C alkyl-cycloalkyl, 4-20 C cycloalkyl-alkyl, aryl, 7-20 C alkylaryl or 7-20 C aralkyl; R<1>R<2> may be an (un)satd. 3-9 C alkylene di-chain; and R<3> or R<5> = 21-200 C alk(en)yl or R<3>R<5> = a 2-12 C alkylene di-chain) comprises reacting olefins of formula R<5>R<6>C=CR<3>R<4> (II) with NH3 or prim. or sec. amines of formula HNR<1>R<2> (III) at 200-350 degrees C and 100-300 bar, using Al-BETA-zeolites, free from transition metal and prepd. without halogen treatment, as zeolitic catalyst.

Description

Technical field

The present invention relates to a process for the production of amines by reaction of ammonia or primary and secondary amines with olefins at elevated temperatures and pressures in the presence of transition metal-free aluminum β-zeolites and prepared without treatment with halogens.

BACKGROUND OF THE INVENTION

CA-A 2092964 discloses a process for producing amines from olefins using β-zeolites, which are defined as crystalline aluminosilicates of a particular composition with a pore size greater than 5.10 ^-10 m. A disadvantage of this process is that the yields achieved with this zeolite class are less than 14% at low space velocities and a large excess of ammonia.

It is therefore an object of the present invention to overcome these disadvantages and in particular to achieve high space-time yields.

SUMMARY OF THE INVENTION

Accordingly, a new and improved process for the preparation of amines of formula I has been found

where

R ^1, R ^2, R ^3, R ^4, R ^5, R ⁶ are hydrogen, C ^ · - to C ₂ g alkyl, C ₂ ~ C ₂₀ alkenyl and C ₂ - to C _2Q - alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₄ - to

C ₂ -C 6 -alkylcycloalkyl, C ₄ -C 8 -cycloalkylalkyl, aryl, C ₁ -C 20 -alkyllaryl or C ₁ -C 2 -alkyl C ₂ -C ₈ -alkyl,

R ¹ and R ² together are a saturated or unsaturated C ₃ to _Cg alkylene dichain,

R ³ and R ⁵ is C ₂₁ ~ and C Q _{0 2} -alkyl, C 1 ₂ "Q-C ₂₀ alkenyl, or together C ₂ to C ₁ ~ ^2-a Y lkylé ^new dichain, by reacting olefins of the formula II

wherein R ³ , R ⁴ , R ⁵ or or primary III

R ⁶ are as defined above, with ammonia or secondary amines of the general formula

wherein R ¹ and R ² are as defined above, at temperatures of from 250 to 350 ° C and pressures of 150 to 300 bar in the presence of zeolite catalysts, wherein the zeolite used is transition metal-free aluminum-p-zeolite and prepared without treatment with halogens.

The method according to the invention can be carried out as follows:

The olefin II and ammonia or the primary or secondary amine of the formula III can be reacted at temperatures from 250 to 350 ° C, preferably 260 to 330 ° C, particularly preferably 260 to 320 ° C and pressures 150 to 300 bar, preferably 170 to 300 bar, especially preferably 200 to 300 bar in the presence of transition metal-free aluminum-p-zeolites and prepared without treatment with halogens as a catalyst, e.g. in a pressure reactor and preferably the amine obtained is separated and the unreacted starting materials are recycled.

The present invention is characterized by a very good yield with high selectivity and high space-time yield. In addition, deactivation of the catalyst is suppressed.

The process according to the invention is characterized in that a high selectivity of the desired reaction product is already achieved with a low excess of ammonia or amine and the dimerization and / or oligomerization of the olefin used is prevented.

One embodiment of the process is that the ammonia and / or the amine of formula III together with the olefin of formula II in a molar ratio of 1: 1 to 5: 1 are fed to a fixed bed reactor at a pressure of 100 to 300 bar and temperature. 200 to 350 ° C react in the gas phase or in the supercritical state.

From the final reaction mixture, the product can be obtained by known methods, for example by distillation or extraction and, if necessary, brought to the desired purity by further separating operations. Unreacted starting materials are generally preferably recycled to the reactor.

Monounsaturated or polyunsaturated olefins of the formula II can be used, in particular those having 2 to 10 carbon atoms or mixtures thereof and polyolefin mixtures as starting materials. Because of their less pronounced tendency to polymerize, monoolefins are more suitable than di- and polyolefins, which, however, can also react selectively with a larger excess of ammonia or amine. The position of the equilibrium point and hence the conversion to the desired amine is very strongly dependent on the reaction pressure. Higher pressure favors the addition product and a pressure range of up to 300 bar is the optimum for technical and operational reasons. The selectivity of the reaction, regardless of the amount of excess ammonia / amine and catalyst, is greatly influenced by temperature. Although the reaction rate of the addition reaction increases strongly with increasing temperature, it simultaneously promotes competitive cracking and recombination reactions of the olefin. In addition, temperature increase is not advantageous from a thermodynamic point of view. The position of the temperature optimum relative to the reaction and the selectivity is dependent on the constitution of the olefin, the amine used and the catalyst, and is generally in the region of 200-350 ° C.

In the molded or unformed state, the aluminum-p-zeolites of the invention are not treated with halogen-containing reagents such as hydrochloric acid (HCl), hydrofluoric acid (HF) or ammonium fluoride (NH ₄ F). Furthermore, the aluminum β-zeolites of the invention do not contain transition metals of groups IB, VB, VIB, VIIB, and VIII such as chromium, manganese, iron, nickel, palladium, platinum or copper.

Suitable olefin amination catalysts are transition metal free p-zeolites or alternatively NU-1-zeolites prepared without treatment with halogens, such as described in US-A 3308069 or US-A 4060590.

Transition metal free p-zeolites and prepared without treatment with halogens, which are preferably used in the H form, are usually formed as extrudates or pellets using a binder agent in a ratio of 98: 2 to 40: 60 wt. are useful in various aluminas, preferably boehmite, amorphous aluminosilicates having an SiO ₂ / Al ₂ O ₃ from 25: 75-95: 5, silica, preferably finely divided silicon dioxide, a mixture of microdisperse _SiO2 and microdisperse A1 ₂ O _3, high-dispersive TiO ₂ as well as clay. After molding, the extrudates or compacts are preferably dried at 110 ° C / 16h and calcined at 300-500 ° C / 16h, whereby calcination can also be carried out directly in the amination reactor.

Various modifications of the zeolite catalysts can be made to increase selectivity, durability and the number of possible regenerations.

One of the modifications of the catalysts is that unformed and formed zeolites can be ionically exchanged or doped with alkali metals such as Na and K, alkaline earth metals such as Ca, Mg, rare metals such as TI, and rare metals and / or rare earth metals for example. La, Ce or Y.

A preferred embodiment is that the molded transition metal-free aluminum-8-zeolites and prepared without treatment with halogens are introduced into a flow tube and are passed in dissolved form at 20 to 100 ° C, e.g. halogen, acetate, oxalate, citrate or nitrate of the metals described above. Such an ion exchange can e.g. be carried out on zeolites in hydrogen, ammonium and alkaline forms.

A further possibility of applying metal to the zeolite material is that the material is impregnated e.g. with a halide, acetate, oxalate, citrate, nitrate or oxide of the metals described above in an aqueous or alcoholic solution.

Drying may be added to both the ion exchange and the impregnation, as necessary, by repeated calcination. Following the metal doping of the zeolites, subsequent treatment with hydrogen and / or water vapor may be advantageous.

Another possibility of modification involves performing an exchange with ammonium salts, for example NH ₄ NO ₃ or with mono-, di- or polyamines. In this case, the zeolite, after shaping with the binder, is subjected to a continuous exchange, usually at 60-80 ° C, with a 10-25%, preferably 20% NH ₄ NO _{3 solution} for 2 h in a 1: 15 zeolite / ammonium nitrate solution (by weight ) and then dried at 100 to 120 ° C.

Yet another possibility of modification is that the zeolites - formed or unformed - are treated with halogen-free acids such as sulfuric acid (H ₂ SO ₄ ), phosphoric acid (H ₃ PO ₄ ) or oxalic acid (H ₂ C-C0) ₂ H).

Another modification that can be made to the zeolites of the present invention is dealumination in which the aluminum content of the zeolites is reduced, e.g. hydrothermal treatment. The hydrothermal dealumination is preferably followed by extraction with acids or complexing agents to remove non-lattice aluminum.

The catalysts can be used for the amination of olefins as extrudates with a diameter of e.g. 1 to 4 mm or as pellets e.g. with a diameter of 3 to 5 mm.

The shaped catalyst, for example in the form of extrudates, can be milled and sieved to obtain a fluid bed material of 0.1 to 0.8 mm in size.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the compounds of formulas I, II and III each have the following meanings:

- hydrogen,

C1- _C20- alkyl, preferably C1- _C12- alkyl, particularly preferably C1-C8-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec. -butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl and isooctyl,

- C ₂ - to C ₂ Q-alkenyl, preferably C ₂ - to C ₁₂ -alkenyl, particularly preferably C ₂ - to C alkenyl such as vinyl and allyl,

C ₂ -C ₂₀ -alkynyl, particularly preferably C ₂ -C 8 -alkynyl, in particular -C ₂ H and propargyl,

C ₃ -C ₂ -cycloalkyl, preferably C ₃ -C ₁₂ -cycloalkyl, particularly preferably C ₅ -C 8 -cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl,

- C ₄ -C ₁₂ alkylcycloalkyl, preferably C ₄ -C ₁₂ -alkyl-cycloalkyl, particularly preferably C ₅ -C 12 -alkyl-cycloalkyl,

C ₄ -C ₂₀ -cycloalkylalkyl, preferably C ₄ -C ₁₂ cycloalkylalkyl, particularly preferably C ₅ -C ₁₀ cycloalkyl-alkyl,

aryl, such as phenyl, 1-naphthyl and 2-naphthyl, preferably phenyl,

- C ₇ - to C ₂₀ -alkylaryl, preferably a _C? C ₁ -C ₁₆ -alkylaryl, preferably C ₇ -C ₁₂ -alkylphenyl such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl and 4-ethylphenyl, and

- C ₇ - to C ₂₀ -arylkyl, preferably a C ₇ ~ ^C 16 -aralkyl and preferably C? To C ₁₂ phenylalkyl such as phenylmethyl, 1-phenylethyl, 2-phenylethyl,

R ¹ and R ²

together represent a saturated or unsaturated C ₃ to C 8 -alkylene chain, preferably - (CH ₂ ) ₄ -, (CH ₂ ) ₅ -, - (CH ₂ ) ₇ and -CH = CH-CH = CH-,

R ³ or R ⁵

C ₂₁ -C ₂₀ -alkyl, preferably C ₄ -C ₂₀ -alkyl, such as polybutyl, polyisobutyl, polypropyl, polyisopropyl and polyethyl, particularly preferably polybutyl and polyisobutyl,

- C ₂₁ - to C ₂₀₀ -alkenyl, preferably C _Q4 - to C ₂₀₀ -alkenyl, particularly preferably C _7Q - to C _7Q ^ alkenyl,

R ³ and R ⁵

together represent a C ₂ -C ₁₂ -alkylene chain, preferably

C ₃ -C 8 -alkylene chain, particularly preferably - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - and (CH ₂ ) ₇ -, especially preferably

- (CH ₂ ) ₃ - and (CH ₂ ) ₄ -.

DETAILED DESCRIPTION OF THE INVENTION

Examples

Catalyst A

To 150 g of β-zeolite (available from Degussa) are added 7.5 g of Aerozil 200 (Degussa), 12 g of NH ₄ OH 25% and 5 g of starch. The mixture was compacted in a kneader and kneaded with the careful addition of water (no more than 125 ml). The kneading time was 60 min. In an extruder operating at an extrusion pressure of 120 bar, 2 mm extrudates were produced, which were then dried for 16 h at 110 ° C and calcined for 16 h at 500 ° C.

Catalyst B

To 60 g of β-zeolite (available from Uetikon) was added 40 g of bomite and 2 g of formic acid. The mixture is compacted in a kneader and kneaded with the careful addition of water (no more than 65 ml). The kneading time was 60 min. In an extruder operating at an extrusion pressure of 80 bar, 2 mm extrudates are produced, which are then dried for 16 hours at 120 ° C and calcined for 16 hours at 500 ° C.

Catalyst C

To 60 g of β-zeolite (available from Degussa) was added 40 g of bomite and 2 g of formic acid. The mixture was compacted in a kneader and kneaded with the careful addition of water (no more than 64 ml). The kneading time was 40 min. In an extruder operating at an extrusion pressure of 55 bar, 2 mm extrudates are produced, which are then dried for 16 hours at 120 ° C and calcined for 16 hours at 500 ° C.

Catalyst D

To 100 g of β-zeolite (available from Degussa) are added 6.7 g of silica sol (AS40 available from Bayer), 8 g of NH ₄ OH 25% and 5 g of starch. The mixture was compacted in a kneader and kneaded with the careful addition of water (no more than 85 ml). The kneading time was 50 min. In an extruder operating at an extrusion pressure of 80 bar, 2 mm extrudates are produced, which are then dried for 4 hours at 120 ° C and calcined for 16 hours at 500 ° C.

Catalyst E

To 10 g of β-zeolite (available from Degussa) is added 10 g of Aerosil ^R 200 Aerosil 200 (available from Degussa) and 5.5 g of starch. The mixture was compacted in a kneader and kneaded with the careful addition of water (no more than 110 ml). The kneading time was 40 min. In an extruder operating at an extrusion pressure of 75 bar, 2 mm extrudates are produced, which are then dried for 4 hours at 110 ° C and calcined for 16 hours at 500 ° C.

Catalyst F

To 180 g of β-zeolite (available from Uetikon) was added 120 g of bomite and 6 g of formic acid. The mixture was compacted in a kneader and kneaded with careful addition of water (no more than 210 ml). The kneading time was 45 min. In an extruder operating at an extrusion pressure of 70 bar, 2 mm extrudates are produced, which are then dried at 110 ° C for 4 hours and calcined at 500 ° C for 16 hours.

Catalyst G

To 480 g of β-zeolite (available from Uetikon) was added 120 g of bomite and 12 g of formic acid. The mixture is compacted in a kneader and kneaded with the careful addition of water (not more than 500 ml). The kneading time was 45 min. In an extruder operating at an extrusion pressure of 80 bar, 2 mm extrudates are produced, which are then dried at 110 ° C for 4 hours and calcined at 500 ° C for 16 hours.

Comparative example (doped β-zeolites)

The catalyst Hg of the leaf catalyst is placed in a 500 ml flask and a solution of 10 ml of water and 0.5 g of NH ₄ F is added. After half an hour, the water was evaporated at 80 ° C (15 mbar). The catalyst was dried at 120 ° C for 16 h.

Catalyst I

100 g of zeolite (available from Degussa) in powder form is treated with 3 g of NH ₄ F in 100 ml of water. After half an hour, the water was evaporated at 80 ° C (15 mbar). The catalyst was dried at 110 ° C for 14 h.

Catalyst J

To 19 g of catalyst B is added a solution of 20 ml of water, 1.9 g of oxalic acid and 0.1 g of Pd acetate. After 30 min, the water was evaporated at 80 ° C (15 mbar). The catalyst was dried at 120 ° C for 16 h and calcined at 500 ° C for 16 h.

Catalyst K

To 20 g of catalyst I is added a solution of 20 ml of water, 2 g of oxalic acid and 0.1 g of Pd acetate. After 0.5 h, the water was evaporated at 80 ° C (15 mbar). The catalyst is dried at 120 ° C for 16 hours and calcined at 500 ° C for 16 hours.

Comparative Example 2 (other zeolites).

Catalyst L

To 525 g of H-Y-type zeolite (BASF) was added 225 g of bomite and 15 g of formic acid. The mixture was compacted and kneaded with the careful addition of water (590 mL). The kneading time is 45 min. In an extruder operating at an extrusion pressure of 90 bar, 2 mm extrudates are produced, which are then dried for 16 hours at 120 ° C and calcined for 16 hours at 500 ° C.

Catalyst M

To 525 g of type 5 zeolite (available from vereinigte Aluminum Werke) was added 40 g of bomite and 2 g of formic acid. The mixture was compacted and kneaded with careful addition of water (55 mL). The kneading time is 40 min. In an extruder operating at an extrusion pressure of 55 bar, 2 mm extrudates are produced, which are then dried for 16 hours at 120 ° C and calcined for 16 hours at 400 ° C.

An example of the amination of ml of each of the above catalysts is placed in separate tests in a stirred autoclave having a capacity of 0.3 L. The olefins and ammonia are then introduced into a closed autoclave. The amount of feedstock was calculated by maintaining the desired pressure at the reaction temperature as the autogenous pressure of the reactants.

The output was analyzed by gas chromatography separately for liquid and gas phase. The conversions given in the tables always refer to olefin; the mentioned extracts relate to the main products: cyclohexylamine from cyclohexene, cyclopentylamine from cyclopentene, tert-butylamine from isobutene.

A high pressure reactor having a length of 2 m and an inner diameter of 24 mm was used for continuous preparation and heated by an aluminum block type heating unit and equipped with three internal temperature monitors as well as a pressure unit. In each case, 60 ml of catalyst was charged and the top of the reactor tube was filled with porcelain rings. Feeding of olefin and ammonia was carried out downwards.

Output analysis was performed by gas chromatography and possibly further distillation.

The experiments were optionally carried out in a tubular reactor (6 mm ID) under isothermal conditions at 270 ° C to 340 ° C and a pressure of 280 bar with a mixture of olefins and ammonia in a molar ratio of 1: 1.5 to 1: 2. The reaction products were analyzed by gas chromatography.

The results obtained are summarized in Tables 1-4.

Table 1 tert-butylamine (NH ₃ : C ₄ Hg = 1.5)

catalyst extr. prostr. (%) Α1 ₂ θ3 SiO ₂ pressure (Bar) tert -butylamine weight per liter (kg / 1) the (° C) (% by weight) WHSV 0.7 g / g.h WHSV 1.5 g / g.h WHSV 3 g / g.multidot.h A 5 280 270 21.71 21.20 19.15 0.42 B 40 280 270 21.52 19.96 16,15 0.5 C 40 280 270 21.62 19.88 16.26 0.53 D 2 280 270 21.15 20.42 16.38 0.45 E 9 280 270 22,03 20.57 19.69 0.41 F 40 280 270 21.79 19.76 16.49 0.55 G 20 280 270 22.48 21.08 18.38 0.49 H 40 280 270 21.44 19.61 16.84 0.50 I 40 280 270 21.17 19.20 16.32 0.52 J 40 280 270 21.53 18.79 16,11 0.58 K 40 280 270 20.79 18.58 15.82 0.55 L 30 280 270 20.58 13.54 8.6 0.49 M 40 280 270 20.44 17.77 13.69 0.55

It has been found that treating the catalyst with palladium and / or flora does not provide any improvement. In several cases, the damage was obvious. In the case of Pd processing, undesirable polymer formation occurred. Comparative catalysts I and J also show a lower space-time yield.

Table 2

Comparative Example of CA 2092964, Ex. 1 tert-butylamine (NH ₃ : C ₄ H ₈ = 2: 1)

Claims (11)

PATENT CLAIMS A process for the preparation of amines of formula I R ⁵ R ³ R ¹ \ 1 / CH - c - N (I) / First \ ₂ R ² where R ^1, R ^2, R ^3, R ^4, R ^5, R ⁶ are hydrogen, C -, - to C ₂₀ -alkyl, C ₂ - to C ₂₀ -alkenyl, C ₂₀ -cycloalkyl, C ₄ to ~ -Cykloalkylalkyl C ₂₀ aryl, and C ₂ q aralkyl, C ₂ - to C ₂₀ -alkynyl, C ₃ - C ₂₀ alkylcycloalkyl, C ₄ to ~ C ₇ - to C ₂₀ -alkylaryl or C ₇ - Ί 9 R R together are a saturated or unsaturated C ₃ to C _g - alkylene dichain, and R ³ or R ⁵ denote C 21 - C 200 -alkyl, C 21 - ^C 200 ^{-alkenyl or} together a C ₂ - C ₁₂ -alkylene chain by reaction of olefins of formula II (II) wherein R ³ , R ⁴ , R ⁵ and R ⁶ have the above meanings, with ammonium- or primary formula III or secondary amines of the R ¹ H - (III) \ _r 2 wherein R ¹ and R ² are as defined above, at temperatures of from 250 to 350 C and pressures of 150 to 300 bar in the presence of zeolite catalysts, characterized in that aluminum-p-zeolites without transition metals and prepared without halogen treatment. A process for the preparation of an amine of formula I according to claim 1, characterized in that the aluminum β-zeolites are used in the H-form. ^à A process for the preparation of amines of the formula I according to claims 1 and 2, characterized in that the amine I formed is separated and the unreacted starting materials I and II are recycled. A process for the preparation of amines of formula I according to any one of claims 1 to 3, characterized in that the zeolite catalyst used is aluminum-p-zeolite which has been binder-shaped and calcined at a temperature of from 300 to 600 ° C. A process for the preparation of amines according to any one of claims 1 to 4, characterized in that the olefin of the formula II is isobutene, diisobutene, cyclopentene, cyclohexene or polyisobutene. * A process for the preparation of amines according to any one of claims 1 to 5, characterized in that the zeolite catalyst used is aluminum-p-zeolite which has been prepared without treatment with a halogen-containing reagent selected from the group consisting of hydrochloric acid, hydrofluoric acid and NH ₄ F. A process for the production of amines according to any one of claims 1 to 6, characterized in that a zeolite catalyst, which is an aluminum-p-zeolite, which is unsupported, is used. A process for the preparation of amines of formula I according to any one of claims 1 to 7, characterized in that a zeolite catalyst is used in which the aluminum-p-zeolite is doped with one or more rare earth metals. A process for the production of amines according to any one of claims 1 to 8, characterized in that a zeolite is used as the zeolite catalyst, which is an aluminum-p-zeolite doped with one or more of an alkali metal, alkaline earth metal or noble metal selected from the group consisting of sodium, potassium, calcium, magnesium and thallium. * A process for the production of amines according to any one of claims 1 to 9, characterized in that the zeolite catalyst to be used is aluminum-p-zeolite in ammonium form. A process for producing amines according to any one of claims 1 to 11 10, characterized in that an aluminum-p-zeolite which has been treated with a halogen-free acid, in particular selected from the group consisting of sulfuric acid, phosphoric acid, oxalic acid or mixtures thereof, is used as the zeolite catalyst.