JPS6049178B2 - How to make amines - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the reaction of an alco, aldehyde, or ketone having up to 25 carbon atoms with ammonia, a primary or secondary amine in the presence of a catalyst in a reducing atmosphere. The present invention relates to a method for producing an amine and an amine produced by such a method.

A large number of catalyst materials for the production of amines from alcohols are disclosed in the prior art.

GB 436,414 discloses a number of catalysts, typically hydrogenation catalysts, useful in the production of amines from alcohols. US Pat. No. 3,128,311 reacts alcohol and ammonia in the presence of catalysts including nickel, copper and oxides of chromium, titanium, thorium, zinc or manganese. US Patent No. 3
No. 520,933 discloses a number of metals that are useful in converting alcohols to amines when used in conjunction with pyro or polyacids. None of the prior art disclosures points out that the special combination of copper, zinc and chromium of the present invention produces a synergistic effect to enhance selectivity or catalyst stability.

The invention thus provides a method for treating alcohols, aldehydes, or ketones having up to 2 carbon atoms by reacting them with ammonia or primary or secondary amines having 1 to 8 carbon atoms in a reducing atmosphere. , 0.5 to 90 weight percent copper, measured as metal per total catalytic metal present, in a process for producing amines;
10 to 9 measured as metal per total catalytic metal present
The above reaction is carried out in the presence of a catalyst comprising a mixture of catalytic metals and oxides having a pore weight percent zinc and 0.5 to 60 weight percent chromium, measured as metal, per total catalytic metal present. The above method includes.

The catalyst of the present invention comprises bulk metals and . Both are used as oxide mixtures and/or supported on suitable supports.

The weight percent of copper (calculated on the basis of copper metal relative to the total catalytic metal present in the catalyst) is between 0.5% w and 90
%w is preferably in the range of 30%w to 70%w; The weight percent of zinc (calculated on the basis of zinc metal relative to the total catalytic metal present in the catalyst) ranges from 10%w to 90%w, preferably from 15%w to 60%w. The weight percent of chromium (calculated on the basis of chromium 4 metal relative to the total catalytic metals present in the catalyst) is 0
．． 5%w to 60%w preferably 0.5%w to 4
0%w most preferably in the range 0.5%w to 30%w. If the catalytic metal is supported on a support, the weight percent of total active metal with respect to the total weight of catalyst and support is:
It ranges from 0.5%w to 50%w, most preferably from 2%w to 30%w. The weight percentage of copper is preferably in the range 0.0025%w to 45%w1, more preferably 0.6%w to 21%w. The weight percent of zinc is preferably between 0.05%w and 45%w1
More preferably, it is in the range of 0.3%W to 18%W. The weight percent of chromium is preferably 0.0025
%W to 30%W1, preferably) 0.01%W to 9%W. Carriers compatible with the method of the invention are:
It is selected from conventional porous, heat-resistant supports that are resistant under the reaction conditions to the starting mixtures to be used and to the products formed in the reaction. - The carrier may be natural or synthetic. Very suitable supports include those of siliceous and/or aluminous composition. Particular examples of suitable supports are aluminum oxide, charcoal, pumice, magnesia, zirconia, diatomaceous earth, Fuller's earth, silicon carbide, silica and/or
or porous conglomerate rocks containing silicon carbide, clays, artificial and natural zeolites, ceramics, etc. Refractory supports particularly useful in the preparation of catalysts include those containing siliceous and/or aluminous materials, particularly gamma-alumina. If the active catalytic metal is supported on a support, the catalyst can be prepared by any suitable method, such as by co-precipitating the metal component onto a powdered or pelleted support, or from an aqueous solution with the support, such as sodium carbonate or It can be produced by coprecipitation using sodium hydroxide.

A preferred method involves impregnating with a solution of a suitable salt of the active metal, and then sequentially drying and drying the impregnated support for 10 minutes.
Firing is performed at a temperature in the range of 0°C to 600°C. The preferred solvent is water, although certain organic solvents are also suitable. Useful salts for aqueous synthesis are chloride, bromide, nitrate, acetate or lactate. Alternatively, a solution of active metal and carrier salts can be spray dried and calcined at temperatures of 100°C to 600°C. Unsupported catalysts are prepared from solutions of salts of active metals by co-precipitation with, for example, sodium carbonate or sodium hydroxide, or by spray drying solutions of salts of active metals.

The resulting product is calcined at a temperature of 100°C to 500'C to produce the catalyst in the form of a bulk oxide of the active metal. The catalyst used in the invention is activated before use by heating in a reducing atmosphere, for example in hydrogen or ammonia.

The preferred atmosphere is hydrogen. Activation temperature is 250°C
The temperature ranges from 600°C to 600°C. The time required for activation is
Depending on the temperature, the higher the temperature, the shorter the time. We find that typically useful times range from 0.1 hour to 24 hours, and although times outside these ranges are also useful, economic considerations tend to dictate their use. be. Preferred reactant hydrocarbon materials are aliphatic, cycloaliphatic, arylaliphatic or aromatic alcohols, ketones or aldehydes having no more than 2 carbon atoms, preferably no more than 1 carbon atom. These starting materials may be unsaturated, for example those containing one or two olefin double bonds. They may also contain substituents which are inert under the reaction conditions, for example alkyl groups having 1 to 4 carbon atoms attached via an ether bridge. Of particular industrial importance are bonded to aliphatic or cycloaliphatic alcohols having no more than one carbon atom. Examples of suitable alcohols/aldehydes are:
Ethanol/al, propanol/al, isopropanol, butanol/al, isobutanol/al, 2-
Ethylhexanol/al, decanol/al, dodecanol/al, hexadecanol/al, cyclopentol, cyclohexanol, cyclooctanol, cyclododecanol, benzyl alcohol/aldehyde, phenylethyl alcohol/aldehyde, 1,4-butanediol /Al, 1,6-hexanediol/Al, 1
, 5-pentadiol/Al, and 1,8-octanediol/Al. Examples of suitable ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone, phenyl methyl ketone, phenylethyl ketone, 3-decanone, 5-dodecanone, cyclopentanone, cyclohexanone, cyclooctanone and cyclododecanone. Preferred reactant amine materials are primary or secondary amines.

Alkylamines having 1 to 12 carbon atoms,
cycloalkylamines or aralkylamines, especially 1
Alkylamines having from to 4 carbon atoms and one amine group in the molecule are preferred.

Examples of suitable amines are monomethylamine, dimethylamine, methylethylamine, monoethylamine and diethylamine. Preferred reactant amines are monomethylamine and dimethylamine. The reactant alcohol, aldehyde or ketone is advantageously reacted with at least an equivalent amount of ammonia or reactant amine, and also in excess, for example up to 50 moles, preferably up to 20 moles per reactant hydroxyl or carbonyl group. It can also be used advantageously.

The reaction is advantageously carried out at a temperature of 160°C to 350°C.

Preferred temperatures are in the range 180°C to 300'C. The response is in the range of 1 to 300 k9/CIL, preferably 10 to 75 k9/CIL. Preferably, the reaction is carried out in the presence of hydrogen. 0.7 to 220k9
It is advantageous to use a hydrogen partial pressure of /d, preferably 7 to 75k9/d.

It is advantageous to use a hydrogen to alcohol, aldehyde or ketone ratio of greater than 1.

The reaction system may also be partially pressurized with an inert gas such as nitrogen, argon. The reaction can be carried out batchwise or in continuous operation.

To explain the batch method, use a high-pressure stirring autoclave,
The alcohol, aldehyde or ketone, reactant amine or ammonia, and catalyst are charged, pressurized with hydrogen and heated to reaction temperature. After the reaction has run for the desired time, the autoclave is cooled, excess hydrogen is vented and the product is worked up by conventional methods. To explain continuous operation, a catalyst is placed in a vertical high-pressure column, and then a
The alcohol and reactant amine are fed from the top. At the same time, hydrogen is metered into the column in the same or opposite direction. Hydrogen is advantageously recycled. Appropriate temperature and pressure conditions are maintained during the reaction. The reaction products are removed from the bottom of the column, liberated from theta hydrogen and worked up by conventional methods. Another continuous process involves trickling the reaction mixture in which the catalyst is dispersed over a packing or bubbling in a column. The invention is further illustrated by the following examples. Example 1 Part A: Alumina supported catalyst solution was 163V copper nitrate CU(NO3)2.3H20
, 120y zinc nitrate Zn(NO3)2-6H2014
5g of chromium nitrate Cr(NO3)2.9H20 and 2
50ml of distilled water was produced.

17 ml of this solution was diluted with 3 ml of water and 48 ml of
．． 5y 18x32 mesh alumina. Impregnation was carried out with good mixing to ensure uniform distribution of metal salts on the alumina. After 30 minutes, the impregnated alumina was placed in a vertical tube and 400TrL1/Mi
n of air was passed over it, while the temperature was gradually increased to the following temperature series in 3 increments: 80°C, 100°C.
°C, 125 °C,. 150°C1175°C12000
C1250℃, 300℃, 400℃ and 500℃C0
The catalyst was then reduced in stages from 125 to 500 °C over 2 hours using a nitrogen diluted hydrogen gas mixture.

Part B: Bulk Oxide Catalyst 181.7y of copper nitrate CU(NO3)2 at 90°C in 2 liters of distilled water.

01134y zinc nitrate Znl(NO3)2.6H20
and 50q of chromium nitrate Cr(NO3)3.9H20
was dissolved.

The hot metal salt solution was added to 3 liters of a 90°C aqueous solution containing 153y of sodium carbonate. Mixing of the two solutions was done with vigorous stirring for 2 minutes.

A blue-green precipitate was formed. The mixture was stirred one more time and then filtered. The solid was
Washed with 0 liters of distilled water, suction dried and 1
00'C and left in vacuum open overnight. The dried material was calcined for 3 times in a Matsufuru oven for 2 batches at approximately 265°C. It was then reduced in hydrogen below 250°C.
Examples (1) Catalysts not according to the invention were prepared by impregnating an alumina support with a 50% w aqueous solution of copper nitrate and then reducing the impregnated support in hydrogen at below 500°C. .

The catalyst contained 10% W copper. Catalyst (10
cc) in a trickle phase reactor (Tr
monomethylamine and 1-dodecanol were fed to the reactor at a liquid hourly space velocity (LHSV) of 1.1 and a molar ratio of amine to alcohol of 3. The reactor is 20
The temperature was maintained at 0°C. Hydrogen was metered into the reactor at a rate of 100 cc/min and the pressure was 27 k9/c! l
was maintained. After 5 hours of operation, the conversion of dodecanol was 92.7%, the selectivity to methyldodecylamine was 85.9%, and the selectivity to C24 and C25 amines was 14.1%.

The above experiment was repeated and after 3 hours of operation, the alcohol conversion was 86.8% and the selectivity to methyldodecylamide was 72.
．． 1%, and the selectivity to C24 and C25 amines was 21.3%. The stability of this catalyst was poor. (2) Catalysts not according to the invention were prepared by impregnating an alumina support with a 55% w aqueous solution of nickel nitrate and then reducing the impregnated support in hydrogen at 500°C.

The catalyst contained 10% w nickel. Catalyst (1
0 cc) was placed in the trickle phase reactor. Monomethylamine and 1-dodecanol were fed to the reactor at a liquid hourly space velocity of 1.1 and a molar ratio of amine to alcohol of 3. The reactor was maintained at a temperature of 190'C. 100
Hydrogen flow rate of cc/Min was maintained at 27k9/c#i. After 3 hours of operation, the conversion of dodecanol was 58.
4%, selectivity to methyldodecylamine is 30.9%, selectivity to dimethyldodecylamine is 16.8%
, the selectivity to C24 and C25 amines was 51.6%.

:3) Catalysts not according to the invention were prepared by coprecipitating the metal salts with sodium carbonate to obtain a mixture of metal carbonates, followed by calcination to obtain a bulk metal oxide mixture.

The catalyst contained 41% WCUll 6%% WZn and 13
% WAg. Catalyst (10 cc) was placed in a trickle phase reactor and monomethylamine and 1-dodecanol were fed to the reactor at a liquid hourly space velocity of 1.1 and a molar ratio of amine to alcohol of 3. 20 reactors
A temperature of 0°C was maintained. Hydrogen was metered into the reactor at a rate of IOOcc/Min and the pressure was 27k9/Cr.
i was maintained. After 3 hours of operation, the conversion of dodecanol was 65.7%, and the selectivity to methyldodecylamine was 54.1%, and the selectivity to C2, and C25 amines was 43.4%. It was hot.

1) A catalyst not according to the invention was prepared by impregnating an alumina support with an aqueous solution of copper nitrate and chromium nitrate.

The impregnated support was calcined in air at 500°C for 1 hour and then heated at 27 kg/Cjl for 1.5 hours below 300°C.
Reduced in hydrogen. The catalyst contained 5.5% WCu and 1.2% WCr. Catalyst (10cc)
was placed in a trickle phase reactor and monomethylamine and 1-dodecanol were fed to the reactor at a liquid hourly space velocity of 1.1 and a molar ratio of amine to alcohol of 5 to 3. The reactor was maintained at a temperature of 190°C. Hydrogen is 1
It was metered into the reactor at a rate of 00 cc/Mjn and the pressure was maintained at 27k9/Clt. After 3 hours of operation, the conversion of dodecanol was 88.2%, the selectivity to methyldodecylamine was 76.6%, and the selectivity to C24 and C25 amines was 20.3%. .

(5) A catalyst not according to the invention was prepared *15 by impregnating alumina with an aqueous solution of copper nitrate and zinc nitrate.

The impregnated support was fired at 500°C. The catalyst is 5
% WCu and 3% WZn. Catalyst (10
cc) was placed in a trickle phase reactor and monomethylamine and 1-dodecanol were fed at a liquid hourly space velocity of 1.1 and a molar ratio of amine to alcohol of 3. The reactor temperature was 197C. Reactor pressure is 27k9/Cl
t and was maintained with a hydrogen flow rate of 100 cc/Mln. After 4 hours of operation, the conversion of dodecanol was 83.
3%, and the selectivity to methyldodecylamine was 65.
9%, selectivity to C24 and C25 amines is 31.4
It was %.

3) A series of catalysts according to the invention were prepared in a manner analogous to that described in Example 1.

The properties of the catalyst and support are listed in Table 1. Catalyst (10
cc) were individually charged into a trickle phase reactor, and monomethylamine and 1-dodecanol were charged at a liquid hourly space velocity of 1.14 and a molar ratio of amine to alcohol of 3:
1 was supplied.

Reactor X reactor temperatures are listed in Table ■. The reactor pressure is 2
7k9/Crl and maintained with a hydrogen flow rate of 100cc/Mjn. The conversion and selectivity after an operating time of 2 hours are listed in Table ■.

was produced by impregnating ReynOldsRAI aluminum with a solution containing copper nitrate and zinc nitrate.

The material was then calcined and reduced with hydrogen at 500°C. The catalyst contained 4.9% WCu and 3
%WZn. Catalyst (10 cc) was placed in a trickle phase reactor and monomethylamine and 1 dodecanol were fed to the reactor at a liquid hourly space velocity of 1 and a molar ratio of amine to alcohol of 3:1. Hydrogen is 100
It was metered into the reactor at a rate of cc/Min and the pressure was maintained at 30k9/CTi. The results are shown in Table ■. (8) Life tests were conducted on Cu/Cr catalysts made not according to the present invention.

The results are shown in Table 2 below. The product was contaminated with metals leached from the catalyst during use.

(9) The life test was conducted on the Cu/Zn fabricated according to the present invention.
/Cr catalyst.

The catalyst was prepared by a method similar to Example 1, Part A. The catalyst product is 5%WCUl3%Wzn
1 and 0.7% WCr. Catalyst/Medium (10
cc) in a trickle phase reactor and containing a mixture of monomethylamine and a 14 and b carbon alcohol.
alcohol. The reactants at a molar ratio of amine to neodol alcohol of 3 were fed to the reactor at a liquid hourly space velocity of 1. Hydrogen was metered into the reactor at a rate of 220cc/Min and 24k9/CFl! pressure was maintained. The results are shown in Table ■. Table ■Cu/Zn/C
r Life test of catalyst 1Cj The catalyst according to the present invention was tested using NH3 for 4
It was prepared in a manner similar to that described in Example 11 Part A, except that the stepwise reduction was carried out below 00° C. for 90 minutes.

The final catalyst contained 4.4% WCUl, 3.2% WZn and 0.6% WCr. Catalyst (10 cc) was placed in a trickle phase reactor and monomethylamine and n
-Butanol was fed to the reactor at a liquid hourly space velocity of 1 and a molar ratio of 2:1. Hydrogen was metered into the reactor at a rate of 100 cc/Min and the pressure was maintained at 27 kg/Crl. Reactor temperature was maintained at approximately 190'C.
After an operating time of 2.5 hours, the analysis of the product was 48 mol%.
It showed an alcohol conversion of 89.6 mol% and a selectivity to methylbutylamine of 89.6 mol%.

11) A series of catalysts according to the invention were prepared in Example 1, Part A.
Manufactured by a method similar to that described in .

Catalyst (10 cc) was placed individually in a trickle phase reactor and dimethylamine and 1-dodecanol were fed to the reactor at a liquid hourly space velocity of 1 and a molar ratio of 3:1. The reactor pressure was 27k9/C7lf and was maintained with a hydrogen flow rate of 100cc/Min. The results after 3 hours of operation time are shown in the wall (■) below.

(12) A catalyst according to the invention was prepared in a manner analogous to that described in Example 11 Part A.

The final catalyst contained 5% WCu, 3% WZn and 0.7
It contained %M medicine. Catalyst (10cc) trickle reciprocal 2
0 reactor and ammonia and isopropyl alcohol were fed at a liquid hourly space velocity of 1 and a molar ratio of 10:1. Hydrogen was metered into the reactor at a rate of 100 cc/Min and the pressure was maintained at 27 k9/Clt. The reactor temperature was maintained at approximately 25025°C. After 1 hour of operation time, analysis of the product showed 92.5 mol% alcohol conversion and 74.8 mol% selectivity to isopropylamine, 22.5 mol% selectivity to di-isopropylamine. showed that.

3θ The supply to the above catalyst is
The molar ratio of ammonia to alcohol was changed to 20:1 and the liquid hourly space velocity to 1. The temperature was adjusted to approximately 237C. After an operating time of 2 hours, the conversion of alcohol was 92.
7 mol%, and the selectivity to isopropylamine is 3! :
, 76.9 mol%, the selectivity to di-isopropylamine was 18.5 mol%, and the selectivity to tri-isopropylamine was 4.6 mol%.

The reactor temperature was then adjusted to 290° C. and after 2 hours of operation time the conversion to alcohol was 98.2 mol% 4C and the selectivity to isopropylamine was 87.5 mol% diisopropylamine. The selectivity for tri-isopropylamine is 9.7 mol% and 2.8 for tri-isopropylamine.
It was mol%. The feed to the above catalyst is then carried out in a molar ratio of 3
:1 of dimethylamine and lauric aldehyde and a liquid hourly space velocity of 1.

Reactor temperature was adjusted to 192'C. After 2 hours of operation time, the aldehyde conversion was virtually complete and the selectivity to dimethyldodecylamine was 69.7 mol%, 1.0 mol% to methyldodecylamine and to higher amines. The selectivity was 29.4 mol%.

13) A catalyst according to the invention was prepared in a manner analogous to that described in Example 11 Part A.

The final catalyst contained 4.4% WCU1, 3.2% WZn and 6.6% WCr. The catalyst (10 cc) was placed in a trickle phase reactor and the ammonia and n-dodecanol were mixed at a liquid time space velocity of 1 and a molar ratio of 12.5:1.
and supplied to the reactor.

Hydrogen was metered into the reactor at a rate of 100 cc/Min and the pressure was maintained at 27k9/CFl.
For three separate operations at temperatures of 206° C., 215° C. and 202° C., the analysis of the products gave alcohol conversions of 85.4 mol%, 97.3 mol% and 76.9 mol% and 41.9 mol%, respectively. 4 mol%, 21.9 mol% and 7
．． It showed a selectivity to dodecylamine of 4 mol% and a selectivity to dodecylamine of 58.6 mol%, 76.0 mol% and 89.2 mol%, respectively.

Claims (1)

[Scope of Claims] 1 Alcohols, aldehydes, or ketones having up to 25 carbon atoms are combined with ammonia or 1 to 8 carbon atoms.
A process for preparing amines by reacting them in a reducing atmosphere with a primary or secondary amine having 100 carbon atoms containing from 0.5 to 90 percent by weight, measured as metal, of the total catalytic metal present. Copper, a mixture of catalytic metals and oxides having 10 to 90 weight percent zinc, measured as metal per total catalytic metal present, and 0.5 to 60 weight percent chromium, measured as metal per total catalytic metal present. The above method is characterized in that the above reaction is carried out in the presence of a catalyst. 2 Claim 1 in which the catalyst is supported on a carrier
The method described in. 3. The method according to claim 2, wherein the support is alumina. 4. The method according to claim 3, wherein the support is gamma alumina. 5. The method according to any one of claims 1 to 4, wherein the reducing atmosphere is hydrogen. 6. The method according to any one of claims 1 to 5, wherein the reaction pressure is 1 to 300 kg/cm^2. 7. Process according to any one of claims 1 to 6, wherein the reaction is carried out at a temperature of 160°C to 350°C. 8. The method of claim 1, wherein the weight percent of copper is from 30 to 70, the weight percent of zinc is from 15 to 60 and the weight percent of chromium is from 0.5 to 40. 9. The method according to any one of claims 1 to 8, wherein alcohol is reacted with monomethylamine or dimethylamine. 10. The method of claim 9, wherein the molar ratio of monomethylamine or dimethylamine to alcohol ranges from 1:1 to 50:1. 11. The method according to claim 9 or 10, wherein the alcohol is an aliphatic or cycloaliphatic alcohol having up to 20 carbon atoms.