FI84260C - FOERFARANDE FOER FRAMSTAELLNING AV AMINERADE PRODUKTER MED ANVAENDNING AV EN NICKEL- OCH / ELLER KOBOLTKATALYSATOR. - Google Patents

Description

84260

Process for the preparation of aminated products using a nickel and / or cobalt catalyst This application is separated from the parent application 843 514 by division.

The present invention relates to an amination process using a ruthenium-wetted nickel and / or cobalt catalyst for hydrogenation-dehydrogenation. The catalyst can be used to aminate compounds containing hydroxyl groups, such as alcohols, phenols and alkanolamines.

Catalytic amination of alcohols is a well known method. In this process, alkylene oxides, hydroxyl-containing compounds, aldehydes and ketones can be aminated by reacting said compounds with ammonia, primary amines and secondary amines in a continuous or batch process in the presence of hydrogen gas and a hydrogenation-dehydrogenation catalyst. It is possible to replace all the hydrogen atoms of the ammonia or amine types with an alkyl radical of the hydroxyl-containing compound so that a mixture of primary, secondary and tertiary amines is obtained as the reaction product.

Amination of hydroxyl-containing compounds such as ethylene glycols and ethanolamines gives not only straight-chain di- and polyamines, but also polyamines with branched molecular chains and six-ring heterocyclic amines such as piperazine, morpholine and their derivatives. In the preparation of ethyleneamines, the most desirable products are those containing predominantly primary amino groups. Ethyleneamines with tertiary amino groups and heterocyclic rings are of less commercial interest.

Various catalysts, most of which are based on nickel and / or cobalt, have been used to improve this process. A large number of activators, such as copper, magnesium, chromium, iron and zinc, have been used to improve the selectivity for the product alloy 2 84260 and to increase the reaction rate. Among the patents describing the amination of organic substances, mention may be made of U.S. Pat. Nos. 1,449,423 and 2,365,721. U.S. Pat. No. 3,766,184 describes a catalyst containing nickel and / or cobalt and iron which increases the yield of ethylenediamine and prevents the formation of piperazine. U.S. Patent No. 3,278,598 describes a Raney nickel catalyst in which rhodium, palladium or ruthenium in a carbon support is used as the Bika catalyst. However, this catalyst increases the formation of secondary amino groups at the expense of primary amino groups.

According to the present invention, a novel catalyst has been invented which promotes the formation of primary and non-cyclic amines. The catalyst is a hydrogenation-dehydrogenation catalyst containing cobalt and / or nickel on a support which is wetted with ruthenium. It contains, calculated as metal in oxide-free form and as a percentage by weight of the total weight of the catalyst, a total amount of 4-40% of cobalt and / or nickel and 0.1-5% of ruthenium on a porous metal oxide support. In addition, the catalyst is characterized by a physical configuration obtained by a) impregnating a support coated with nickel and / or cobalt in metallic or finely divided oxide form with a solution of ruthenium halide in a ruthenium metal mixture and r) drying the catalyst intermediate in ruthenium. finally reducing the nickel and / or cobalt oxides in hydrogen gas to a fine nickel and / or cobalt metal.

The use of this catalyst for the amination of hydroxyl-containing compounds such as alcohols, phenols and alkanolamines with ammonia or primary amines gives a higher yield of the desired primary amines and polyamines, while the formation of unwanted by-products in 3,84260 is greatly reduced compared to previously aminated reactions. It cannot be said with certainty whether the advantageous result obtained by such an amination process using the catalyst of the present invention depends on the way in which cobalt and / or nickel and ruthenium are deposited on the support, or whether the metals and the support have undergone a chemical reaction. chemical characteristics. However, it can be shown that catalysts prepared in the same way but using ruthenium compounds other than. halides give a lower proportion of primary amines in the amination product mixture.

The metal oxide support materials that have been shown to provide the most active and selective amination catalysts are those that contain more than 95% activated alumina. Less active but still selective catalysts can be prepared from conventional metal hydroxide supports containing at least 50% alumina. Examples of such supports are those consisting of alumina / silica, alumina / titanium dioxide, alumina / alumina, alumina / zirconia, and other combinations. The internal surface area of the catalyst support is not critical and may vary between 10 and 1000, preferably between 20 and 400 square meters per gram of support, but the size of the surface preferably adapts to the metal content having substantially one monomolecular layer of catalyst metals on the support surface. Numerous such carrier materials are known to those skilled in the art and are even commercially available.

The chemical nature of the support material greatly affects the properties of the catalyst. For example, a nickel and / or cobalt catalyst wetted with ruthenium on activated carbon does not show selectivity for primary amines but, on the contrary, promotes the formation of secondary and tertiary amines. Other 4,84260 supports, which are mainly acidic in nature, may give even better activity with the addition of ruthenium than without, but catalysts prepared from these supports are less selective than those constructed of metal oxides.

The carrier material used in the practice of the invention may be precipitated together with nickel and / or cobalt salts. These metals can also be introduced into the support by impregnation with a solution containing metal salts. Various organic and inorganic nickel and cobalt salts can be used for precipitation or impregnation. Examples of suitable salts are nickel nitrate, nickel acetate, nickel formate and nickel acetylacetonate, and the corresponding cobalt salts. Nickel chloride and / or cobalt chloride may be used, but these salts do not decompose on heating in air.

Instead, they can be converted to metals in hydrogen gas by heating. Another method of applying metals to the surface of a support is to use gaseous nickel or cobalt carbonyl, which decomposes on the surface of the support into a very fine metal. According to the present invention, nickel or cobalt can be used either alone as a metal, as an alloy with each other, or one of them can also be placed on top of the other. It is not possible to say in advance which metal and manufacturing method will give the best result in each individual case, but it must be tested experimentally. As long as known principles in the preparation of hydrogenation catalysts are applied, it has not been shown that the manner in which the support material is impregnated or coated with nickel or cobalt metal has any significant effect on the final activity or selectivity of the catalyst.

The amount of nickel and / or cobalt that should be used depends on the composition and physical properties of the catalyst support, such as surface size and porosity. In most cases, the most active catalysts have been shown to have a nickel and / or cobalt content of 5-20% of the total weight of the catalyst and a content of 5 84260 ruthenium of 0.2-3% of the total weight of the catalyst on a support having an inner surface area of 50-150 square meters per gram . The amount of nickel and / or cobalt in the support mainly affects the activity of the catalyst and only to a small extent its selectivity.

After the support material is impregnated with the desired amount of nickel and / or cobalt salt, it is dried and then calcined to decompose the salts into metal oxides. This is done by heating the catalyst, first gently and, if desired, under reduced atmospheric pressure to remove the solvent used for impregnation, then by blowing air through while raising the temperature to 300-600 ° C, depending on the decomposition temperature of the salts used. This temperature is maintained until the salt is completely converted to the oxide. It is important for the result that even small amounts of the salt used, especially nitrate, have not remained unchanged after calcination. It is also possible to convert the formed oxides to metal before the ruthenium treatment by reacting the catalyst intermediate with hydrogen gas at elevated temperature.

The ruthenium treatment of a catalyst containing nickel and / or cobalt oxide or metallic nickel and / or cobalt is carried out by impregnating the catalyst with a selected ruthenium halide dissolved in water or an organic solvent and drying at 50-100 ° C under a stream of inert gas, air or hydrogen. Impregnation can be accomplished by spraying the finely divided solution evenly onto the catalyst, adsorbing the ruthenium compound from the solution applied to the surface of the metal or oxide-coated support, or dipping the support in the solution and evaporating the solvent. To avoid hydrolysis of the ruthenium salt, the impregnation solution may contain small amounts of hydrochloric acid or some other hydrohalic acid.

The ruthenium halide is then reduced by heating the catalyst in a stream of hydrogen gas at about 150-200 ° C for 0.5-3 h.

6 84260

To reduce the nickel and / or cobalt oxides, the temperature is then raised, preferably to 300-600 ° C, and maintained at this temperature in a stream of hydrogen gas until the desired degree of reduction is achieved. In general, a high degree of reduction is preferred, but due to the melting of the support material and the nickel and / or cobalt flour upon extended heating, which results in a reduction in the catalyst surface, a lower degree of reduction is sometimes accepted. If the cobalt and / or nickel is in metallic form when impregnated with ruthenium halide, only the reduction of ruthenium is required.

The activated catalyst is preferably stored in an airtight state to prevent reoxidation of nickel or cobalt. The catalyst can also be stabilized by mild oxidation, carbon dioxide treatment, or some other conventional stabilization technique for pyrophoric catalysts and can then be stored in air until used.

According to the present invention, various ruthenium halides can be used in the ruthenium treatment step. Examples of suitable salts are the soluble forms of: ruthenium chloride, ruthenium ammonium chloride, ruthenium potassium chloride, ruthenium nitrosyl chloride, ruthenium potassium nitrosyl chloride, chloro-ruthenic acid, ruthenium red (hydroxychlorotetra) The preferred ruthenium compound in terms of availability, price, and efficacy is ruthenium chlorohydrate. Non-halides such as ruthenium dioxide, ruthenium sulphate, ruthenium nitrate, ruthenium nitrosyl nitrate, ruthenium ammonium nitrate, ruthenium acetylacetonate and potassium perruthenate also have a significant improvement in selectivity compared to the corresponding catalysts without ruthenium.

Accordingly, they are not included in the present invention.

The ruthenium-wetted nickel / cobalt catalysts of the invention can be further improved by the addition of other 7,84260 components. Examples of such components are metals and metal oxides of antimony, bismuth, cerium, chromium, copper, iron, manganese, molybdenum, rhenium, thorium, titanium, tungsten, uranium, vanadium, zirconium, and precious metals other than ruthenium. Other examples are phosphorus and boron compounds.

As mentioned, the catalyst according to the invention is particularly suitable for use in amination reactions. In the amination process, alkylene oxides, hydroxyl-containing compounds such as alcohols, phenols and alkanolamines can be converted to the corresponding amines by reacting said compounds with ammonia, primary amines or secondary amines in a continuous or batch process.

All hydrogen atoms of the amino nitrogen can be replaced by an alkyl radical of the reacting hydroxyl compound so that a mixture of primary, secondary and tertiary amines is obtained as the reaction product. Amination of ethylene compounds, such as ethylene glycols and ethanolamines, results in ring formation such that, in addition to straight-chain and branched di- and polyamines, six-ring heterocyclic amines such as piperazine and morpholine and their derivatives are also obtained.

In the preparation of ethyleneamines, the most desirable products are those which contain predominantly primary amino groups. By-products containing tertiary amino groups and heterocyclic rings are of lesser commercial importance. The present catalyst has a surprisingly high selectivity for the formation of primary and non-cyclic compounds at high reaction rates.

The amination of ethylene glycol with ammonia can be illustrated by the following reaction equations, which describe only a small number of all possible reactions: 8 84260

Vaf a 1 HOC2H4OH + NH3 ---> HOC2H4NH2 + H2O monoethylene ammonia monoethanol water glycol amine hoc2h4nh2 + nh3 ----- 1 -> h2nc2h4nh2 + h2o monoethanol ammonia ---- ethyl 2 water4h2n2 -> h2nc2h4nhc2h4nh2 + h2o monoethylene diethylene water ethanol diamine triamine amine C_H.

/ 2 4 \ HOC2H4NHC2H4NH2 kata1- · -> HN NH + H 2 O

Nc2h4 aminoethanolamine piperazine water

Each of the above reactions comprises three consecutive steps: a) dehydration of the hydroxyl-containing compound to the corresponding aldehyde or ketone b) addition of a scavenger to the reaction product to form an imine c) hydrogenation of this imine to the corresponding amine.

Aliphatic alcohols that can be aminated by the process of the present invention include saturated aliphatic monohydric and polyhydric alcohols having 1 to 30 carbon atoms, including, for example, saturated monohydric alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, and the like. butanol, tert-butanol, isobutanol, n-pentanol, isopentanol, neopentanol, n-hexanol, isohexanol, 2-ethylhexanol, cyclohexanol, n-heptanol, n-octanol, 2-octanol, isooctanol, tert-octanol , various isomers of nonanol, decanol, hendecanol, dodecanol, tridecanol, tetradecanol, hexadecanol and octadecanol and arachidyl alcohol. Further divalent aliphatic alcohols having from 2 to about 30 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and higher polyethylene glycols, 1,2- and 1,3-propylene glycol, dipropylene glycol, dipropylene glycol, tripropylene 2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, dibutylene glycol, tributylene glycol and higher polybutylene glycols, as well as pentanediol, hexanediol, octanediol, decanediol, nonanediol, decanediol, , isomers of tridecanediol, tetradecanediol, pentacecanediol, hexadecanediol, octadecanediol, eicosanediol, and higher polyoleins having 3 to about 30 carbon atoms, such as glycerol, erythritol, heptritol, pentaerythritol, sorbitol, mannitol, trimethyll, trimethynyl

10 84260

Among the phenols suitable for amination may be mentioned phenol, o-cresol, m-cresol, p-cresol, pyrocatechol, resorcinol, hydroquinone and isomers of xylenol, and among aliphatic amino alcohols having from 2 to 30 carbon atoms, such as monoethanolamine, diethanolamine , aminoethylethanolamine, propanolamines, butanolamines, pentanolamines, hexanolamines, heptanolamines, octanolamines, decanolamines, dodecanolamines, tetradecanolamines, hexadecanolamines, octadecanolamines and eicosanolines. In addition, mixtures of the abovementioned alcohols can be used, for example mixtures of ethylene glycol and monoethanolamine or mixtures of alkanolamines obtained by the reaction of alkylene oxides with ammonia.

The aminating agent is ammonia or primary amines or secondary amines. Such amines generally have alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 5 to 3 carbon atoms, and aryl or arylalkyl groups having 6 to 40 carbon atoms. Examples of suitable amines are methylamine, ethylamine, n-butylamine, isobutylamine, ethylenediamine, benzylamine, dimethylamine and diethylamine. Aminating agents as well as hydroxyl-containing compounds can be used alone or in combination with each other.

The reaction between the aminating agent and the aminating compound is carried out in the presence of hydrogen gas to ensure a good yield of the desired aliphatic amines. In general, the amount of hydrogen gas required is relatively small, corresponding to about 0.1 to about 2 moles per mole of hydroxyl. Higher amounts of hydrogen can be used, but usually do not provide any significant benefit. The amination agent, such as ammonia, should be present in the mixture in excess, for example in the range of about 2 to about 30 moles of amination agent per mole of compound to be aminated, and preferably in the range of about 5 to about 15 moles per mole. The amount of catalyst is not critical, but is usually 0.1 to 25, preferably 1 to 15% by weight of the reactants in the batch process.

11 84260

Elevated temperature should be used for amination. Temperatures in the range of about 120-300 ° C are suitable. Particularly good yields and good selectivity are achieved when temperatures in the range of about 175 to about 225 ° C are used.

The amination is performed at a relatively high pressure. The pressure used depends on the molar ratios of the reactants, the temperature, the amount of hydrogen gas and the type of reaction. In general, the pressure should be high enough to keep most of the reactants in the solution phase. Normally this pressure is in the range of about 8 to about 40, preferably 15 to about 30 MPa.

The equipment used to perform the aminations of this invention may be any conventional high temperature / pressure equipment for batch or continuous run. For example, a pressure vessel such as an autoclave equipped with a stirrer and a heating device can be used in the batch process. The process can be carried out as a continuous process in which gaseous or solution reactants pass under pressure through a solid catalyst column maintained at the desired reaction temperature. The catalyst may also be on a liquid support or may flow countercurrently against the reaction mixture. The reaction mixture is further treated first by separating ammonia and hydrogen-sun and then the various products are separated by fractional distillation.

The invention is further illustrated by the following examples.

Example 1

A concentrated aqueous solution of metal nitrate containing the amount of metals given in Table 1 was added to 90 grams of activated alumina catalyst support in tablet form, 3 mm in length and diameter and having a surface area of about 100 square meters per gram of support. The excess solution was evaporated in vacuo at about 75 ° C, the tablets dried and the nitrates decomposed into the corresponding oxides by heating at 500 ° C in a stream of dry air. After cooling, the tablets were saturated with a 2% solution of ruthenium compound 12,84260, the composition and amount of which are shown in Table 1, and dried at 100 ° C in air.

The tablets were then heated in a stream of hydrogen gas, first for one hour at about 150-200 ° C to convert the ruthenium compound to ruthenium metal, and then for four hours at 400 ° C to reduce the metal oxides to a fine metal.

table 1

Cat. Metal nitrate Ruthenium compound No. Metal Quantity, Type Quantity, grams grams AI nickel 10 ruthenium chloride 0,5 hydride

B1 nickel 10 - A2 nickel 7,5 ruthenium chloro 0,5 copper 2,2 rhydrate chromium 0,3 B2 nickel 7,5 copper 2,2 chromium 0,3 A3 cobalt 10 ruthenium chloro 0,5 rhydrate B3 cobalt 10 - A4 nickel 4 ruthenium chloro-0.25 cobalt 4 ride hydrate iron 4 A5 nickel 4 ruthenium chloro-0.5. Ride Hydrate Cobalt 4 1 Iron 4 A6 Nickel 4 Ruthenium Chloride 1.0 Cobalt 4 Ride Hydrate Iron 4 B4 Nickel 4 Cobalt 4 Iron 4 - 84260

Table 1 (continued)

Ratal. Metal nitrate Ruthenium compound No. Metal Quantity, Type Quantity, grams grams B5 nickel 4 ruthenium nit- 0,5,,,. cobalt 4 iron 4 B6 nickel 4 ruthenium nit- 1,0,,, .... cobalt 4 iron 4 A7 nickel 10 ruthenium bromide 0,5 midi B7 nickel 10 A8 nickel 10 ruthenium potassium 0,5 chloride A9 nickel 10 ruthenium nitro 0,5 silyl chloride AIO nickel 10 ruthenium potassium 0,5 nitrosyl chloride

Aliquinium 10 ruthenium ammonium chloride 0.5

Bll nickel 10 ruthenium ammonium 0.5 nitrate

Example 2

A 300 ml autoclave equipped with a stirrer and temperature control was purged with nitrogen gas. Eight grams of one of the catalysts prepared in Example 1, 25 g of monoethanolamine, 3.5 g of water and 65 g of running ammonia were charged to the autoclave. The autoclave was sealed and hydrogen gas was introduced at a pressure of 5.5 MPa. The contents of the autoclave were heated to 200 ° C and maintained at this temperature with constant stirring until the experiment was stopped.

During the reaction, autoclaved samples were taken and 14,84260 were analyzed by gas chromatography. The conversion of the added amination-capable compounds was calculated, as was the amount of compounds formed in the reaction. The results obtained are shown in Table 2.

Conversion is defined as the ratio of the amount consumed in the reaction of the amination-capable compounds to the amount initially added.

Example 3

A mixture of 6.25 g of ethanolamine and 18.75 g of monoethanolamine reacted with ammonia in the same manner as described in Example 2. Catalyst A1 described in Example 1 was used as a catalyst and Catalyst B1 was used as a reference. The results obtained are shown in Table 3.

Example 4

A mixture of 6.25 g of aminoethylethanolamine and 18.75 g of monoethanolamine reacted with ammonia in the same manner as in Example 3. The result is shown in Table 3.

Example 5

A mixture of 12.5 g of monoethylene glycol and 12.5 g of monoethanolamine reacted with ammonia in the same manner as in Example 3. The results are shown in Table 3.

The results shown in Tables 2 and 3 show that the catalysts of the invention promote the formation of primary amino groups.

84260

Abbreviations EDA = ethylenediamine MEA = monoethanolamine PIP = piperazine DETA = diethylenetriamine AEP = araminoethylpiperazine AEEA = aminoethylethanolamine HEP = hydroxyethylpiperazine DEA = diethanolamine

Table 2

Kata- Kon- Mole-% amino- lysate- ver- Weight% of products formed groups_ tori sio% EDA DETA AEEA PIP AEP HEP Prim. Sec. Tert.

AI 76 60, '20 20.3 6.1 9.9 2.3 1.4 82 17 0.9

Bl 76 54.4 14.2 4.4 20.8 4.4 1.5 74 24 1.5 A2 40 81 7.7 4.1 6.7 0.2 0.3 91 9 0.1 B2 40 75 4.5 2.8 15.5 1.5 0.7 85 15 0.6 A3 88 56 7.9 5.3 25.5 3.1 1.3 73 26 1 B3 88 43 7.7 6, 5 33.8 5.5 2.4 62 36 2 A4 60 67 7.7 8.5 12.8 2.0 2.0 83 16 1 A5 60 72 7.9 8.0 7.7 1.0 1 , 4 88 12. 1 A6 60 71 10.2 6.9 9.2 1.4 1.3 86 13 1 B4 60 58 9.9 19.9 14.1 2.5 3.3 77 22 1 B5 60 61 9.2 10.1 13.9 2.6 3.2 80 19 1 B6 60 62 10.0 7.1 16.0 2.4 2.5 79 19 1 A7 60 60 14.5 5.5 8 , 1 1.7 1.2 86 13 1 B7 60 63 11.2 7.3 13.8 2.5 2.2 81 18 1 A8 60 69 14.7 5.4 8.1 1.7 1.2 86 13 1 A9 60 69 13.9 5.5 9.0 1.6 1.0 86 13 1 AIO 60 70 12.3 5.3 9.3 2.0 1.1 86 13 1

Ali 60 69 13.2 5.8 8.4 2.3 1.3 86 13 1

Bll 60 63 10.5 6.1 14.0 3.6 2.8 80 18 2 16 84260 μ

M

α>

E- · H N rH ro ro (N

: RO

•B

e o \ o JC I 44

> 1 -H QJ N OI CO CO O CO

V-t I — I CO i— (CN i — i CN rH

0 o c o H g e e

C -H

μ co co o co o σ '.

Oi CO <D CO fO 00 C ro ro O O I — I o u «· - -

Q "3 · H” O O O O

CORPORATION

o C Pj r ^ LD I ^ -CO 0) 03 HU - - -

H) I O (N rHC \ 1 OH

qj

G

O) <1 σ> rsi o o QJ U *> * «

44 U fN ro ro <D

iH <H (N rH -te -K

rt • ro

G

ro 0¾ co (N o (N oo <—l • HU - - - * · · O 4-i <O ro Oro rs) (N>, 44 44 -p x rt -p 3 QJ Q>

rH μ -P

3 C O) n ro co -H

(Ö UJ Eh * * - u

Eh 3 u h · o * *: rj 6 Q: 3

3 S

+)

(Λ O

O -P

O Cu o> r ^ m · o> o co o) 44 H ν '' '- o

CU Γ- H · ('' H · N CO C

CQ rH f-H H

QJ n3

UJ

M -H

O C 3 (UU h · ro oo in r »U) 2 (N (N roro cn (N rö

0 H

• H 34 -P rö

44 -P

nj <C

Q) Q in ro o r ~ oo C

¢ 3 U tn ro rorsi oi ro qj

•B

m

X

• 3

> GJ

G X

O df> OO OO OO H

r- o o in in cö>

•B

1 I m 1 03 -P>, 444403 rH i-H rH i I i — I '—I> 1 m rt) cm cm cm -h qj rd in oi

H -ro>, - h C

• H i — I H C

ui -h m o

[jJ ^ -p-prO H · uo -K

Claims (2)

A process for preparing aminated products by reacting a hydroxyl group-containing compound with ammonia or a primary or secondary amine at a temperature of 120-300 ° C in the presence of hydrogen and a catalyst, characterized in that the catalyst is a ruthenium doped nickel. and / or cobalt catalyst containing 4-40, preferably 5-20 wt.% nickel and / or cobalt and 0.1-5 wt.% ruthenium and a porous support consisting of at least 50 wt.% alumina, which can be obtained by: which is coated with nickel and / or cobalt in metal or oxide form, is impregnated with a solution of ruthenium halide and b) the catalyst xelane product is dried, the ruthenium halide compound is reduced at elevated temperature in a hydrogen stream to ruthenium metal, and if necessary and / or the cobalt oxides are finally reduced in hydrogen to finely divided nickel and / or cobalt metal. 2. A process according to claim 1, characterized in that ethylene glycols or ethanolamines are aminated with aramoniac.