SK86696A3 - A producing method of amines from olefins over pillared clay - 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, 2-20 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 pillared (interlayered) clays as the heterogeneous catalyst.

Description

Process for the production of amines from olefins above pillar clays

Technical field

The present invention relates to a process for the production of amines by reacting ammonia or primary and secondary amines with olefins at elevated temperatures and pressures in the presence of pillar clays.

BACKGROUND OF THE INVENTION

An overview of olefin amination methods is given in the Functionalization of Alkenes: Catalytic Amination of Monoolefins, J. J. Brunet et al., J. Mol. Catal., 49 (1989), pp. 235-259.

There are basically two mechanisms of catalysis. The olefin is coordinated through the metal complex. These activated species may be disrupted by nucleophilic amines and form a high amination product. The amine can be chemisorbed on acid centers or metal centers (via a metal amide) and reacted in this way with the olefin.

Suitable catalysts are zeolites. They are characterized by a high number of catalytically active centers, which is associated with a large surface area. The zeolites described differ in type and subsequent processing (eg heat treatment, dealumination, acid treatment, metal ion exchange, etc.). Examples are given in US-A 4375002, US-A 4536602, EP-A 305564, EP-A 101921, DE-A 4206992.

From EP-A 13938, EP-A 431451 and EP-A 132736, processes are known in which boron-, gallium-, aluminum- and iron-silicate zeolites are used for the production of amines from olefins and the possibility of doping these zeolites with alkali metals is mentioned, alkaline earth metals and transition metals.

CA-A 2092964 discloses a process for the production of amines from olefins using BETA-zeolites, which are defined as crystalline aluminosilicates of a certain composition with a pore size greater than 5 Angstroms. Metal or halogen modified beta / zeolites are preferably used.

The disadvantage of zeolites as catalysts is their costly preparation and hence their high cost.

The selective synthesis of molecular sieves (for example zeolites) in hydrothermal synthesis requires precise adherence to many parameters, such as crystallization time, crystallization temperatures, pressure or aging degree.

The structure-controlling compound (template) typically used in zeolite synthesis must be removed after crystallization. As a rule, the template is removed by calcination when the organic compound is oxidatively degraded. This is considered very disadvantageous for environmental and economic reasons.

The preparation of crystals of a certain size or morphology and the preparation of carrier zeolites, which are often desirable as catalysts in view of the advantages of the treatment process, is only possible with great expense, if at all possible.

Zeolites have a very narrow pore size distribution. The pore size varies from 4 to about 12 Angstroms depending on the type of zeolite.

In the zeolite catalyzed reaction, only those molecules that are smaller than the pore dimensions have access to the catalytically active centers within the zeolite. Reactants having large dimensions are excluded from the interior of the pores.

For the above amination reactions, this means that the catalytic centers within the zeolite are not available for the preparation of amines that are larger than the pore diameter.

It is an object of the present invention to overcome the above-mentioned disadvantages, in particular to provide olefin amination catalysts whose preparation is substantially simpler than that of zeolite catalysts and which have a favorable pore size distribution also for relatively bulky amine molecules.

The use of acid-modified montmorillonites is described in EP 469719. The use of precipitated catalysts with a combination of two or more metal oxides with the exception of the combination of Si and Al is described in JP-04082864.

All processes for the synthesis of amines from olefins on these catalysts are characterized by low amine yield or low space-time yield, or lead to rapid deactivation of the catalyst.

Accordingly, the present invention aims to overcome these disadvantages.

SUMMARY OF THE INVENTION

A new general formula (I) and an improved process for the production of amines have been found

(I) where

R ^1, R ^2, R ^3, R ^4, R ^5, R ⁶ are hydrogen, C 1 -C 20 alkyl, C2-C2Q alkenyl, C 2 to ^C 2Q ~ alkynyl, C 3 -C ₂₀ -cycloalkyl, C C ₄ -C ₂₀ -alkylcycloalkyl, C ₄ -C ₂₀ -cycloalkylalkyl, aryl, C ₇ -C ₂₀ -alkylaryl or C ₇ -C ₂₀ -aralkyl,

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

R ³ or R ⁵ represent C ₂₁ -C ₂₀₀ alkyl, C ₂₁ -C ₂₀ C-alkenyl or together a C ₂ -C ₁₂ alkylene chain, by reaction of olefins of formula II

wherein R ³ , R ⁴ , R ⁵ and R ⁶ are as defined above, with ammonia or primary or secondary amines of formula III

(III) wherein R ¹ and R ² are as defined above, at temperatures of from 200 to 200 ° C

350 ° C and pressures of 100 to 300 bar in the presence of heterogeneous catalysts, which include the use of pillar clay as a heterogeneous catalyst.

The new method can be performed as follows:

The olefin II and ammonia or the primary or secondary amine of formula III can be reacted at temperatures from 200 to 350 ° C, preferably 220 to 330 ° C, particularly preferably 230 to 320 ° C and pressures 100 to 300 bar, preferably 120 to 300 bar, particularly preferably 140 to 290 bar in the presence of pillar clay 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 process is characterized by a very good yield in combination with high selectivity and high spatial yield. In addition, deactivation of the catalyst is suppressed.

The novel process 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 this process comprises mixing ammonia and / or an amine of formula III with an olefin of formula II in a molar ratio of 1: 1 to 5: 1 and feeding the mixture to a fixed bed reactor at a pressure of 100 to 300 bar; at 200 to 350 ° C they react in the gas phase or in a supercritical state.

The desired product can be recovered from the reacted mixture by known methods, for example by distillation or extraction, and, if desired, brought to the desired purity by further separation operations. Unreacted starting materials are generally preferably recycled to the reactor.

Mono- or polyunsaturated olefins of the formula II can be used, in particular those having 2 to 10 carbon atoms or mixtures thereof and polyolefins as starting materials. Because of their less pronounced tendency to polymerize, monoolefins are more suitable than di- and polyolefins, which, however, can also be reacted selectively with a larger excess of ammonia or amine. The position of the equilibrium 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, in addition to the amount of both the excess ammonia / amine and the 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 selectivity is dependent upon the constitution of the olefin, the amine used and the catalyst, and is generally in the region of 200-350 ° C.

Suitable catalysts for the amination of olefins are pillar clays, such as are known from Stud.Surf.Sci.Catal., 1994, 84, 331-384.

Pillared clays (PILCs) are composed of layers, for example montmorillonite, beidelite, hectorite or saponite, among which pillar oxides are inserted. For example, the pillars may be obtained by subjecting the compound layer to an ion exchange with large cations such as [Al ₁₃ O ₄ (OH) 24 (H ₂ O) ₁₂ ] ⁷⁺ or [Zr 4 (OH) θ (H 2 O) 16] ^{8 +} followed by calcination. This leads to the formation A12O ₃ or ZrO ₂ pillars for these cations. Other oxides that may also be incorporated are, for example, TiO ₂ , Cr ₂ O ₃ , SiO ₂ , Ta ₂ O ₅ , Fe ₂ O ₃ , mixtures thereof or mixtures with other metal oxides such as MgO. Sulfides such as Fe ₂ S ₃ can also serve as pillars instead of oxides. The space between the layer structures, which is bridged by pillars, is available as pore volume for reactants. Another pore volume is created by delaumination.

Pillar clays may be molded as such or also with a binder in a ratio of 98: 2 to 40:60 wt. for extrudates or pellets. Suitable binders include various aluminas, preferably boehmite, amorphous aluminosilicates having an SiO ₂ / Al ₂ O ₃ of from 25:75 to 95: 5, silica, preferably finely divided silicon dioxide, a mixture of finely divided SiO ₂ and A1 ₂ O ₃ , finely divided TiO ₂ and clays. After forming into extrudates or moldings, they are preferably dried at 110 ° C for 16 h and calcined at 200 to 500 ° C for 2 to 16 h, whereby the calcination can also be carried out directly in the amination reactor.

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

One of the modifications of the catalysts is that unformed and formed pillar clays 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, transition metals such as e.g. Ti, Zr, Mn, Fe, Mo, Cu, Zn, Cr, rare metals and / or rare earth metals such as e.g. La, Ce or Y.

A preferred embodiment consists in that the molded pillar clays according to the invention are introduced into a flow tube and at 20 to 100 ° C, e.g. a halide, acetate, oxalate, citrate or nitrate of the metals described above. Such an ion exchange can e.g. be carried out on pillar clays in hydrogen, ammonium and alkali metals.

Another possibility of applying metal to pillar clays 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 and, if desired, repeated calcination may be added to both the ion exchange and the impregnation. For metal doping of pillar clays, subsequent treatment with hydrogen and / or water vapor may be appropriate.

Another possibility of modification is that the piled clays - formed or unformed - are treated with acids such as hydrochloric acid (HCl), hydrofluoric acid (HF), sulfuric acid (H ₂ SO ₄ ), phosphoric acid (H ₃ PO ₄₎ ) or oxalic acid (HO ₂ C-CO ₂ H).

A particularly preferred embodiment is that the piled clays are refluxed with one of 0.001 N to 2N, preferably 0.05 to 0.5 N of said acids for 1 to 100 hours before being formed. After filtration and washing, they are usually dried at 100-160 ° C and calcined at 200-600 ° C. Another particularly preferred embodiment consists in processing the pillar clays after forming them with an acid binder. In this case, the pillar clays according to the invention are usually treated for 1 to 3 hours at 60 to 80 ° C with 3 to 25%, in particular 12 to 20% acid, then thoroughly washed, dried at 100 to 160 ° C and calcined at 200 to 600 ° C

Another possibility of modification is given by exchange with ammonium salts, e.g. NH ₄ Cl or mono-, di- or polyamines. In this case, the binder-shaped clay is usually exchanged at 60 to 80 ° C with a 10 to 25%, preferably 20% NH ₄ Cl solution for 2 hours continuously in a solution containing pillar clay and ammonium chloride in a weight ratio of 1: 15 and then dried at 100 to 120 ° C.

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

For example, a fluidizable material having a size of 0.1 to 0.8 mm can be obtained from the catalysts formed into extrudates by milling and sieving.

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,

- C - ^ - Q-C _2-alkyl, preferably a C - ^ - to C ₁₂ -alkyl, preferably CJ najumä to C-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl or isooctyl,

- ^_ C ₂ to C ₂ Q-alkenyl, preferably C ₂ "to C ₁₂ -alkenyl, particularly preferably C _2" to C ₈ alkenyl such as vinyl or allyl,

C ₂ -C ₂₀ -alkynyl, particularly preferably C ₂ -C 8 -alkynyl, especially -C ₂ H or propargyl,

C ₃ -C ₂₀ -cycloalkyl, preferably C ₃ -C ₁₂ -cycloalkyl, particularly preferably C ₅ -C 8 -cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl,

C ₄ -C ₂₀ alkylcycloalkyl, preferably C ₄ -C ₁₂ alkylcycloalkyl, most preferably C ₅ -C ₁₀ alkylcycloalkyl,

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

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

- · C? - to C ₂ Q-aryl, preferably C ₇ - to ^C 16 -alkylaryl, preferably a C ₇ - to C ₁₂ -alkyl-phenyl, such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3 -ethylphenyl or 4-ethylphenyl,

- C ₇ - to C ₂₀ -aralkyl, preferably _C? - to C ₁₆ -aralkyl, preferably _C? to C ₁₂ -phenalkyl 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 is

- C ₂₁ - C ₂₀₀ -alkyl, preferably C ₄₀ - C ₂₀ -alkyl, such as polybutyl, polyisobutyl, polypropyl, polyisopropyl and polyethylene, particularly preferably polybutyl and polyisobutyl,

- C ₂₁ - to C ₂₀₀ -alkenyl, preferably C ₄₀ - to C ₂₀₀ -alkenyl, particularly preferably C ₇ - to C ₁₇₀ -alkenyl,

R ³ and R ⁵

together represent a C ₂ -C ₁₂ -alkylene chain, preferably a C ₃ -C 8 -alkylene chain, particularly preferably - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, (CH ₂ ) ₅ -, - ( _{CH2) 6} -, and (CH _{2) 7} -, particularly preferably - (CH _{2) 3} - and (CH _{2) 4} -.

DETAILED DESCRIPTION OF THE INVENTION

Examples

Catalyst synthesis

Catalyst A

142.5 g of AlCl ₃ .6H ₂ O are dissolved in 2.9 L of distilled water and 50 g of NaOH in 5.5 L of water, the solutions are combined and stirred at 50 ° C for 1 hour, then a suspension of 100 g of Terrana D is added. (alumina from Sudchemie) in 4 L of water. The pH was adjusted to 5.5 with 21 g of a 25% NH 4 OH solution. The reaction mixture was stirred at 80 ° C for 3 hours and the product was filtered off, washed with distilled water, dried at 100 ° C for 2 hours and calcined in air at 200 ° C.

Catalyst B

77.1 g of bomite and 3.9 g of formic acid are added to 115.7 g of catalyst A. It is compacted in a kneader and kneaded with the careful addition of water (100 ml). In an extruder, 4 mm extrudates are produced at a pressure of 50 bar, dried at 120 ° C for 16 h and then calcined for 5 h at 500 ° C.

The catalyst has a BET surface of 216 m ² / g and exhibits a 001 reflection at about 18.4 Å in the X-ray pattern.

Catalyst C

315 g A1 (NO _{3) 3} 9H ₂ O was dissolved in 3.9 1 of distilled water and 70 g of NaOH in 7.6 1 of water were combined and then a suspension of 140 g Terrana D (alumina by Sudchemie) in 1.4 l of water. The pH was adjusted to 5.5 with 32.5 g of a 25% NH ₄ OH solution. The reaction mixture was stirred at 80 ° C for 3 hours and the product was filtered off, washed with distilled water, dried at 100 ° C for 2 hours and calcined in air at 200 ° C for 5 hours.

Catalyst D

103.9 g of bomite and 5.2 g of formic acid are added to 155.9 g of catalyst C. It is compacted in a kneader and kneaded with careful addition of water (138 ml). In an extruder, 4 mm extrudates are produced at a pressure of 55 bar, dried at 120 ° C for 16 hours and then calcined for 5 hours at 300 ° C.

The catalyst has a BET surface area of 167 m ² / g.

Catalyst E

426.6 g of titanium tetraisopropylate are added dropwise to 6 µM

HCl, stirred at 20-25 ° C for 3 hours and combined with a suspension of 120 g of Terrana D (alumina from Sudchemie) in 12 L of 1: 1 water / acetone with stirring. The mixture is stirred for an additional 3 hours at 20-25 ° C and the product is filtered off, washed with distilled water, dried at 100 ° C for 2 hours and calcined in air for 3 hours at 300 ° C.

Catalyst F

31.3 g of bomite and 3.2 g of formic acid are added to 125 g of catalyst E. The mixture is compacted in a kneader and kneaded with the careful addition of water (75 ml). On a 60 bar extruder, 4 mm extrudates are produced and dried for 16 hours at 110 ° C and calcined for 12 hours at 300 ° C,

BET: 227 m ² / g

Catalyst G

426.6 g of titanium tetraisopropylate were added dropwise to 61 ml of 1M HCl, stirred at 20-25 ° C for 3 hours and combined with a suspension of 120 g of K10 (modified alumina from Sudchemie) in 12 1 of 1: 1M HCl / acetone with stirring. . The mixture is stirred for an additional 3 hours at 20-25 ° C and the product is filtered off, washed with distilled water, dried at 100 ° C for 2 hours and calcined in air for 3 hours at 300 ° C.

Catalyst F

27.7 g of bomite and 2.8 g of formic acid are added

110.7 g of catalyst G. The mixture was compacted in a kneader and kneaded with the careful addition of water (87 ml). The kneading time is 60 minutes. On a 45 bar extruder, 4 mm extrudates are produced and dried for 12 hours at 120 ° C and calcined for 12 hours at 500 ° C.

BET: 229 m ² / g

Catalyst I

96.8 g of zinc oxychloride are dissolved in 2900 g of distilled water and combined with a suspension of 120 g of K10 (treated alumina from Sudchemie) in 12 l of water with stirring. The mixture is stirred for an additional 24 hours at 20-25 ° C and the product is filtered off, washed with distilled water, dried at 100 ° C for 2 hours and air-dried for 12 hours at 200 ° C.

Catalyst J

29.5 g of bomite and 3 g of formic acid are added to 117.9 g of catalyst I. In a kneader, the mixture is compacted and kneaded with careful addition of water (87 ml). 4 mm extrudates are produced on a 65 bar extruder and dried for 12 hours at 120 ° C and calcined for 12 hours at 500 ° C.

BET: 250 m ² / g

Catalyst K of catalyst D is placed on a frit in a heated glass tube and 2 L of a 20% NH ₄ Cl solution is circulated through the catalyst at 80 ° C for 3 hours. The NH 4 Cl solution is then replaced with fresh NH ₄ Cl solution and the process is repeated. The catalyst is then washed with water passing through it and then dried at 110 DEG C. for 2 hours and calcined at 300 DEG C. for 3 hours.

BET: 193 m ² / g

Catalyst L

1.1 L of a 0.33 M ZrOCl ₂ solution is refluxed for 24 hours. After diluting 4.5 L of distilled water, 20 g of Terana D is added at 20-25 ° C and stirred for 1 hour. The powder was filtered off, washed twice with 1.5 L of hot, distilled water, dried at 110 ° C for 2 hours and calcined at 250 ° C for 3 hours.

Catalyst M

24.5 g of bomite and 2.5 g of formic acid are added to 98 g of catalyst L. In a kneader, the mixture is compacted and kneaded with the careful addition of water (50 ml). 1.5 mm extrudates are produced on a 90 bar extruder and dried for 16 hours at 120 ° C and calcined for 5 hours at 300 ° C.

Example of amination

The tests were carried out in a tubular reactor (6 mm ID) under isothermal conditions at 270 ° C to 300 ° C and a pressure of 280 bar from a 1: 1.5 molar ratio of isobutene and ammonia. The reaction products were analyzed by gas chromatography.

The results obtained are summarized in Table 1.

Table 1 tert-Butylamine (NH ₃ : C ₄ H _g = 1.5)

catalyst amount of extrusion pom. substances ai ₂ o ₃ (%) pressure bar temperature 'C tert-butylamine (% by weight) density (Kg / 1) WHSV 0.7 (G / g.multidot.h) WHSV 1.5 (G / g.multidot.h) WHSV 3 (G / g.multidot.h) B 40 280 300 13.26 10.38 7.72 0.7 D 40 280 300 11.33 5.91 2.86 0.71 F 20 280 300 13.25 9.04 5.65 0.80 H 20 280 300 13.16 10.80 J 20 280 300 14.01 11.34 7.20 0.62 The 40 280 300 12.52 7.95 5.79 0.7 M 20 280 300 12.95 9.89 6.96 0.96

Pv m-k

Claims (9)

PATENT CLAIMS A process for the preparation of amines of formula I wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each hydrogen, C 1 -C ₂₀ -alkyl, C ₂ -C ₂ -alkenyl, C ₂ -C ₂₀ -alkynyl, C ₃ - C ₂₀ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ alkylcycloalkyl, C ₄ -C ₂₀ cycloalkylalkyl, aryl, C 1 -C ₂₀ alkylaryl or C 6 -C ₂₀ aralkyl, Rl and ^R2 together are a saturated or unsaturated C ₃ to _Cg alkylene chain, and R ³ or R ⁵ represent C 21 -C 20 -alkyl, C 21 -C 20 -alkenyl or R ³ and R ⁵ together are a C ₂ -C ₁₂ -alkylene chain, by reaction of olefins of formula II wherein R ³ , R ⁴ , R ⁵ and ^R6 are as defined above, with ammonia or primary or secondary amines of formula III H - N (III) wherein R ¹ and R ² are as defined above, at temperatures from 200 to 350 ° C and pressures of 100 to 300 bar in the presence of heterogeneous catalysts, which comprises using pillared clay as a heterogeneous catalyst. A process for the preparation of amines according to claim 1, characterized in that the amine I formed is isolated and unreacted starting materials II and III are recycled. Process for the preparation of amines according to claims 1 and 2, characterized in that the olefin of the formula II used is isobutene, diisobutene, cyclopentene, cyclohexene or polyisobutene. A process for the preparation of amines according to any one of claims 1 to 3, characterized in that aluminum, zirconium, titanium, chromium, gallium, iron, tantalum or silicon piled clay are used as heterogeneous catalysts. A process for the preparation of amines according to any one of claims 1 to 4, characterized in that piled clays which have been treated with an acid, in particular selected from the group consisting of hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, phosphoric acid, are used as heterogeneous catalysts. oxalate and mixtures thereof. A process for the preparation of amines according to any one of claims 1 to 6 5, characterized in that pillar clays which have been doped with one or more transition metals are used as heterogeneous catalysts. A process for the preparation of amines according to any one of claims 1 to 7 6, characterized in that pillar clays which have been doped with one or more rare earth elements are used as heterogeneous catalysts. A process for the preparation of amines according to any one of claims 1 to 8 7, characterized in that pillar clays in ammonium form are used as heterogeneous catalysts. A process for the preparation of amines according to any one of claims 1 to 10 8, characterized in that pillar clays which have been binder-shaped and calcined at 200 to 600 ° C are used as heterogeneous catalysts.