CA2552744A1 - Use of modifiers in a dinitrile hydrogenation process at high pressures - Google Patents
Use of modifiers in a dinitrile hydrogenation process at high pressures Download PDFInfo
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- CA2552744A1 CA2552744A1 CA002552744A CA2552744A CA2552744A1 CA 2552744 A1 CA2552744 A1 CA 2552744A1 CA 002552744 A CA002552744 A CA 002552744A CA 2552744 A CA2552744 A CA 2552744A CA 2552744 A1 CA2552744 A1 CA 2552744A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
Catalytic process for hydrogenating a dinitrile to produce both aminocapronitrile and hexamethylenediamine in which the dinitrile is contacted with hydrogen in the presence of a catalyst and a modifier selected from the group consisting of quaternary ammonium hydroxides, cyanides, fluorides and thiocyanides; quaternary phosphonium hydroxide; carbon monoxide; and hydrogen cyanide.
Description
USE OF MODIFIERS IN A DINITRILE HYDROGENATION PROCESS AT HIGH PRESSURES
FIELD OF THE INVENTION
The present invention concerns the hydrogenation of aliphatic s dinitriles to produce diamines and/or aminonitriles, e.g. adiponitrile to produce hexamethylenediamine and/or 6-aminocapronitrile.
BACKGROUND OF THE INVENTION
Dinitriles are common feedstocks to the chemical, pharmaceutical, and agrochemical industries. Through hydrogenation they can be io converted to diamines and/or aminonitriles, which are used in or as polymer intermediates, surfactants, chelatirig agents, and chemical synthesis intermediates. As a particular example, adiponitrile can be converted to 6-aminocapronitrile and/or hexamethylenediamine by .hydrogenation. Hexamethylenediarnine is an intermediate in the is pr~duc~oon.of'f~yldi~"66.'"0-~=~di:nin~o~aproriitrsoe'~a~ii~e use'd'~a~
ate' ,;;, intermediate in_the production of Nvlon 6. ..
Traditional methods of producing hexamethylenediamine include hydrogenation of adiponitrile over a reduced iron oxide or cobalt oxide catalyst at high pressures and temperatures. US6110856 describes the 2o use of cobalt and iron based catalysts in a process for the ~hydrogenafiion of adiponitrile to a mixture of aminocapronitrile and ' hexamethylenediamine. The process does not produce aminocapronitrile with high selectivity, yielding 37% aminocapronitrile at 75% adiponitrile conversion. Low-pressure processes are known for the simultaneous' as production of aminocapronitrile and hexamethylenediamine. US5,151,543 describes the hydrogenation of dinitriles, including adiponitrile in the presence of a solvent. US6,258,745, US6,566,297, US6,376,714, W099/47492 and W003/000651A2 all describe the hydrogenation of dinitriles to aminonitriles in the presence of selectifying agents for low 3o pressure reactions, i.e. less than about 13.89 MPa (2000 psig).
For simultaneous production of aminonitrile and diamines, it would be advantageous to employ a commercial equipment that is currently used for hexamethylenediamine production and that operates at high pressures, i.e. greater than 13.89 MPa (2000 psig). Additionally, it would be adv~tx~~~~eous~ to oipe~°'f~ese pfo~eas~I;i'h ~orre~~ea~etevti~~ity,~fo aminocapronitrile than is possible under operating conditions taught in the art.
SUMMARY OF THE INVENTION
The present invention is, therefore, a process of hydrogenating a dinitrile for the simultaneous production of aminocapronitrile and hexamethylenediamine, said process comprising:
treating the dinitrile with hydrogen in the present of a'catalyst and a modifier at a pressure at least about 15.27 MPa (2200 psig), wherein said 1o catalyst comprises an element selected from the group consisting of~Fe, Ru, Co, and Ni and said modifier is at least one member selected from the group consisting of quaternary ammonium hydroxides, quaternary ammonium cyanides, quaternary ammonium fluorides, quaternary ammonium thiocyanides, quaternary phosphonium, hydroxides, carbon is monoxide, and hydrogen cyanide.
DETAILED DESCRIPTION OF THE INVENTION
In~thev present. invention, an aliphatic or alicyclic dinitrile can be hydrogenated to a diamine or a mixture of a diamine and an aminonitrile using a catalyst at pressures greater than 15.27 MPa (2200 psig). For 2o example, adiponitrile can be hydrogenated to hexamethylenediamine or a mixture of hexamethylenediamine and 6-aminocapronitrile. The process employs one or more modifiers to maintain or improve the selectivity of the process for the production of aminonitrile. These modifiers may react with the catalyst surface or may modify the reactivity of the dinitrile and/or 2s aminonitrile. The modifiers may comprise quaternary ammonium hydroxide, cyanide, fluoride or thiocyanide salts, or quaternary phosphonium hydroxide salts or carbon monoxide or hydrogen cyanide.
Notably, the modifiers of the present invention are not expected to build-up in the incinerator firebricks, nor are they expected to require disposal via 3o deep-wells, when they or their decomposition products are removed from the crude product obtained from the said hydrogenation of dinitrile.
Suitable aliphatic or alicyclic dinitriles, for use herein, have the general formula R(CN)2, wherein R~is a saturated hydrocarbylene group.
A saturated hydrocarbylene group~contains carbon and hydrogen atoms in branched or straight chains or rings and does not contain a double or triple bond between any pair of carbon atoms. Preferred hydrocarbylene groups contain from 2 to 25, more preferably 2 to 15, and most preferably 2 to 10 carbon atoms per group. In other words, preferred dinitriles contain from 4 s to 27, more preferably 4 to about 17, and most preferably 4 to 12, carbon atoms per dinitrile molecule. The preferred type of hydrocarbylene group is a linear alkylene group.
Examples of suitable dinitriles include, but are not limited to, adiponitrile; methylglutaronitrile; succinonitrile; glutaronitrile; alpha, io omega-heptanedinitrile; alpha, omega-octanedinitrile, alpha, omega decanedinitrile, alpha, omega-dodecanedinitrile; and combinations of two or more thereof. The preferred embodiment is adiponitrile (ADN).
The catalyst in the process is a hydrogenation catalyst suitable for hydrogenating a dinitrile to a diamine or a mixture of diamine and is aminonifirile. Preferred are cafalysts~based on the elements iron, cobalt-nickel,,.or: ruth_e.nium and.combinations._there_of in. which the said elements,.
can exist as metals or their~compounds. Most preferred is a catalyst comprising iron. The catalytic element may comprise about 1 to 99 % of the total catalyst weight, preferably about 50 to 85 wt%. The catalyst may 20 further comprise one or more promoters selected from the group consisting of aluminum, silicon, titanium, vanadium, magnesium, chromium, sodium,, potassium and manganese. The promoters may be present in concentrations up to about 15% based on the total weight of the catalyst, preferably. about 0.05 to 2 wt%.
2s While the degree of beneficial effects of this invention may vary with the structure of the dinitrile, the identity of the catalytic element, and the identity of the modifier, it is important to realize that even small improvements in selectivity can have large economic impact for large-scale industrial processes.
3o The catalytic element can also be supported on an inorganic support~such as...~lum~na, magnesium oxide, and combinations thereof.
The element can be supported on an inorganic support by any means known to one skilled in the art such as, for example, impregnation, coprecipitation, ion exchange, and combinations of two or more thereof. If the catalytic element is supported on an inorganic support or is a component of an alloy or a solid solution, the catalytic element is generally present in the range of about 0.1 to about 60 wt% and preferably about 1 to about 50 weight percent, based on the total catalyst weight.
The catalyst can be present in any appropriate physical shape or form. It can be in fluidizable forms, extrudates, tablets, spheres, or combinations of two or more thereof. When employing the process using a fixed bed catalyst, the catalyst is in the form of granules having a particle size in the range of about 0.76 to 10.2 mm (0.03 to 0.40 inch). When io employing the process using a slurry-phase catalyst, the catalyst is in finely divided form, preferably less than about 100 Nm in size, most preferred range being about 20 to 75 Nm.
The molar ratio of catalyst.to. dinitrile can be any ratio as long as the ratio can catalyze the selective hydrogenation of a dinitrile. The weight us ratio of catalyst to dinitrile i~:g~ners~ly in the range: ~f frort~about O:,OD'I~.1 ~1,,~~~~
to about 1:1, preferably about OJ001:1 to about 0.5:1.
The modifiers of the present invention can be selected from the group consisting of quaternary ammonium hydroxide, quaternary ammonium cyanide, quaternary ammonium fluoride, quaternary 2o ammonium thiocyanides, quarternary phosphonium hydroxide,~carbon monoxide and hydrogen cyanide. The term quaternary describes a nitrogen or phosphorous atom with four bonds to it and bearing a formal charge of +1. The ammonium ion (NH4+) and tetraalkylammonium ions are included within the definition of quaternary ammonium. More than one 2s modifier can be used in the reaction. Examples of suitable modifiers are tetramethylammonium hydroxide, tetrabutylammonium cyanide, tetraethylammonium fluoride, tetrabutylammonium thiocyanide and tetrabutylphosphonium hydroxide. Preferred modifiers are quaternary ammonium hydroxide and quaternary ammonium cyanide. Examples~of 3o suitable tetraalkylammonium hydroxide compounds are tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
Examples of suitable tetraalkylammonium cyanide compounds are tetramethylammonium cyanide, tetraethylammonium cyanide and tetrabutylammonium cyanide. It should be noted that various hydrated forms such as, for example, tetramethylammonium hydroxide pentahydrate, are included within the meaning of tetraalkylammonium hydroxide and tetraalkylphosphonium hydroxide.
The hydrogenation reaction can be conducted at a temperature about 50 to 250°C and preferably about 90 to 180°C and at a pressure about 15.27 to 55.26 MPa (2200 to 8000 psig) total pressure with hydrogen and preferably at about 20.78 to 34.58 MPa (3000 to 5000 psig).
In a preferred mode of operation, the process~is conducted continuously in io a continuous stirred tank reactor (CSTR), a plug flow reactor (PFR); a slurry bubble column reactor (SBCR),~or a trickle bed reactor. A
continuous stirred tank reactor, also known as a back-mixed reactor, is a vessel in which the reactants are added in a continuous fashion and a flow of product stream is continuously withdrawn from it. There is adequate t~s <rvii~ing in tlie.>vesseb'~rovid~~i ~b:~~a :rnia~i<nyzd~5ice;.~ e.ig:;;.a ~echa~icar agitator,ao that.~the composition.inside.the reactor is uniform and is the.
same as that in the product stream withdrawn. A plug flow reactor is a tubular reactor in which the reactants' are added in a continuous fashion in one end of the tubular reactor and the product is withdrawn in a 2o continuous fashion from the other end of the tube. There is no back-mixing, i.e: the composition inside the reactor tube is not uniform. It is possible to incorporate backmixing in PFRs by recycling a part of the product flow back to the inlet of the reactor. It is also possible to achieve plug flow reactor behavior by using multiple CSTRs is series. A slurry 2s bubble column reactor is a vessel, in which liquid reactants and gas are continuously fed to the bottom of the reactor, while product is continuously withdrawn from the top of the reactor. The gas is present in the reactor as bubbles, which rise and simultaneously provide mixing for a solid powdered catalyst (20 to 200 pm average particle sizes). The catalyst 3o may be removed continuously with the product and added continuously by addition with the liquid feed. A trickle bed reactor is a tubular reactor in which the catalyst is fixed while the reactants are added at the top of the reactor and flow to the bottom where the product is continuously withdrawn. Gaseous reactants may flow cocurrently with the liquid or may flow countercurrently from the bottom to the top of the reactor.
The preference for reactor is not meant to limit the invention, which can also be conducted in batch mode.
The process can be operated in the absence or presence of a solvent. In this invention, a solvent is defined as a substance that is added to a reaction mixture and that serves to solvate one or more reaction components, increases the volume of the reaction mixture, provides a medium for transferring (or removing) the heat of reaction, and is either to not incorporated in the final product or does not alter the properties of the final product. While not comprehensive, a list of solvents includes ammonia; amines such as triethylamine; alcohols such as methanol, ethanol; propanol, and butanol; ethers such as tetrahydrofuran and dioxane; amides such diethylacetamide and N-methylpyrolidinone; and S 1; J .,g t.~ ~,.= 3 W~,f :, p. ~. " 'k is °este~~~°sucn~~ ~t~~l~ acei~~~~a1"nd ditzieth~ilaidip~te ~'he 'pr~fierred 's~iv~~t~i ammonia., ~:~The solvent can. be present in. the. reaction mixture. in, about~20.
to 90% by weight, preferably about ~30 to 50%~.
The modifier and ainitrile may be introduced to a reactor, which contains catalyst, separately or as a premixed solution with a diamine, an 2o aminonitrile, water, a solvent or any combination thereof. The modifier can be added in a weight ratio to dinitrile from about 1:5000 to 1:30, preferably from about 1:2000 to 1:500.
The yields of diamine and/or aminonitrile, e.g.
hexamethylenediamine and/or 6-aminocapronitrile; depend on operating 2s conditions including temperature; pressure, hydrogen flow rate, amount and kind of catalyst, amount of modifier and space velocity and the like.' For the purpose of this invention, the term "space velocity" is defined as the unit weight of dinitrile fed into the reactor per hour, per unit weight of the catalyst. Typically, the dinitrile should be added to the reactor such 3o that the space velocity of the dinitrile is within the range of about 0.5 to 20 h''. Most preferred space velocities may be readily determined by those skilled in the art using conventional techniques.
While not meant to limit the invention by any theory, it is possible that the modifier reacts with the el~ement(s) of the catalyst forming a, modifier/catalytic element complex. The resulting~complex may contain the Group VIII element in its metallic state or perhaps in an oxidized state.
The reaction of modifier with the catalytic element may be irreversible but more likely is a reversible equilibrium reaction. The interaction of the modifier with the catalyst may alter the reactivity of the catalyst, improve the selectivity for aminonitrile production, suppress secondary amine oligomer formation and, perhaps, increase the lifetime of the catalyst.
The catalyst and modifier can be separately introduced into a reactor to contact the.dinitrile; however, the catalyst may be precontacted io with the modifier. This may be done in water and/or a solvent such as, for example, an alcohol, ether, ester, ammonia, or combinations of two or more thereof.
The molar ratio of hydrogen to dinitrile is not critical as long as sufficient hydrogen is present to produce an aminonitriie and/or a diamine, ;i~~~ e:g fi-ahnino~~~prc~rDat~iIWa~id/h~fh~xa~n~ethylenddiamine °Hyd~oger~vs~
generally used in.excess.
Diamine and/or aminonitrile, e.g. hexamethylenediamine and/or 6-aminocapronitrile, can be recovered from the reaction products by typical purification procedures such as. recrystallization or preferably, distillation.
2o The unreacted dinitrile can be recycled back to the hydrogenation reactor to obtain additional diamine and/or aminonitrile.
EXAMPLES
The hydrogenation of adiponitrile (ADN) may be described using a kinetic 2s model in which ADN is first converted to aminocapronitrile (ACN) andlthe ACN is then converted to hexamethylenediamine (HMD), e.g., ADN ~ ACN ~ HMD
where each reaction step is a first order reaction, and the first step has a rate constant 2k~ and the second step has a rate constant k2. In this 3o model a k~/k2=1 value describes a' non-selective catalyst and the maximum yield of ACN will be 50°/a.,in a well-mixed batch reaction. It is desirable to maximize the k~/k2 value.
Comparative Example 1. A 1-L stainless steel pressure vessel was charged with 216 g of adiponitrile and 20g of a powdered, reduced iron catalyst. The vessel was sealed, purged with hydrogen and charged with 225g ammonia. It was heated to 150°C and pressurized to 4500 psig (31 s MPa). As hydrogen was consumed, it was constantly replenished from a pressurized cylinder to maintain an operating pressure of 4500 psig (31 MPa). After 70 min the reaction was stopped, and a sample was analyzed via gas chromatography. The analysis showed that the reaction product comprised 12 wt% adiponitrile (ADN), 45wt% 6-aminocapronitrile (ACN), ~o and 36wt% hexamethylenediamine. The k~/k2 value was 1.1.
Examples 2 to 4. The experiment of Example 1 was repeated except ~.2g of a modifier chemical was added to the reaction mixture with the ADN.
The results are presented in Table 1. TBACN = tetrabutylammonium la~ ,.cyaniae,eT~AI~~= re~raetr~yi~'mo~oni-um cydrtid~sri'l'~AFIP~=
tetramethylammonium hydroxide,pentahydrate..
Example ModifierTime Wt% Wt% Wt% k~/k~
of ~ ADN in ACN in HMD in Reactionreactionreactionreaction (min) product product product 1 None 70 12 45 36 1.1 2 TBACN 315 21 57 17 1.8 3 TEAF 180 21 54 21 1.4 4 TMAHP 120 M 11 51 ' 28 1.6 s
FIELD OF THE INVENTION
The present invention concerns the hydrogenation of aliphatic s dinitriles to produce diamines and/or aminonitriles, e.g. adiponitrile to produce hexamethylenediamine and/or 6-aminocapronitrile.
BACKGROUND OF THE INVENTION
Dinitriles are common feedstocks to the chemical, pharmaceutical, and agrochemical industries. Through hydrogenation they can be io converted to diamines and/or aminonitriles, which are used in or as polymer intermediates, surfactants, chelatirig agents, and chemical synthesis intermediates. As a particular example, adiponitrile can be converted to 6-aminocapronitrile and/or hexamethylenediamine by .hydrogenation. Hexamethylenediarnine is an intermediate in the is pr~duc~oon.of'f~yldi~"66.'"0-~=~di:nin~o~aproriitrsoe'~a~ii~e use'd'~a~
ate' ,;;, intermediate in_the production of Nvlon 6. ..
Traditional methods of producing hexamethylenediamine include hydrogenation of adiponitrile over a reduced iron oxide or cobalt oxide catalyst at high pressures and temperatures. US6110856 describes the 2o use of cobalt and iron based catalysts in a process for the ~hydrogenafiion of adiponitrile to a mixture of aminocapronitrile and ' hexamethylenediamine. The process does not produce aminocapronitrile with high selectivity, yielding 37% aminocapronitrile at 75% adiponitrile conversion. Low-pressure processes are known for the simultaneous' as production of aminocapronitrile and hexamethylenediamine. US5,151,543 describes the hydrogenation of dinitriles, including adiponitrile in the presence of a solvent. US6,258,745, US6,566,297, US6,376,714, W099/47492 and W003/000651A2 all describe the hydrogenation of dinitriles to aminonitriles in the presence of selectifying agents for low 3o pressure reactions, i.e. less than about 13.89 MPa (2000 psig).
For simultaneous production of aminonitrile and diamines, it would be advantageous to employ a commercial equipment that is currently used for hexamethylenediamine production and that operates at high pressures, i.e. greater than 13.89 MPa (2000 psig). Additionally, it would be adv~tx~~~~eous~ to oipe~°'f~ese pfo~eas~I;i'h ~orre~~ea~etevti~~ity,~fo aminocapronitrile than is possible under operating conditions taught in the art.
SUMMARY OF THE INVENTION
The present invention is, therefore, a process of hydrogenating a dinitrile for the simultaneous production of aminocapronitrile and hexamethylenediamine, said process comprising:
treating the dinitrile with hydrogen in the present of a'catalyst and a modifier at a pressure at least about 15.27 MPa (2200 psig), wherein said 1o catalyst comprises an element selected from the group consisting of~Fe, Ru, Co, and Ni and said modifier is at least one member selected from the group consisting of quaternary ammonium hydroxides, quaternary ammonium cyanides, quaternary ammonium fluorides, quaternary ammonium thiocyanides, quaternary phosphonium, hydroxides, carbon is monoxide, and hydrogen cyanide.
DETAILED DESCRIPTION OF THE INVENTION
In~thev present. invention, an aliphatic or alicyclic dinitrile can be hydrogenated to a diamine or a mixture of a diamine and an aminonitrile using a catalyst at pressures greater than 15.27 MPa (2200 psig). For 2o example, adiponitrile can be hydrogenated to hexamethylenediamine or a mixture of hexamethylenediamine and 6-aminocapronitrile. The process employs one or more modifiers to maintain or improve the selectivity of the process for the production of aminonitrile. These modifiers may react with the catalyst surface or may modify the reactivity of the dinitrile and/or 2s aminonitrile. The modifiers may comprise quaternary ammonium hydroxide, cyanide, fluoride or thiocyanide salts, or quaternary phosphonium hydroxide salts or carbon monoxide or hydrogen cyanide.
Notably, the modifiers of the present invention are not expected to build-up in the incinerator firebricks, nor are they expected to require disposal via 3o deep-wells, when they or their decomposition products are removed from the crude product obtained from the said hydrogenation of dinitrile.
Suitable aliphatic or alicyclic dinitriles, for use herein, have the general formula R(CN)2, wherein R~is a saturated hydrocarbylene group.
A saturated hydrocarbylene group~contains carbon and hydrogen atoms in branched or straight chains or rings and does not contain a double or triple bond between any pair of carbon atoms. Preferred hydrocarbylene groups contain from 2 to 25, more preferably 2 to 15, and most preferably 2 to 10 carbon atoms per group. In other words, preferred dinitriles contain from 4 s to 27, more preferably 4 to about 17, and most preferably 4 to 12, carbon atoms per dinitrile molecule. The preferred type of hydrocarbylene group is a linear alkylene group.
Examples of suitable dinitriles include, but are not limited to, adiponitrile; methylglutaronitrile; succinonitrile; glutaronitrile; alpha, io omega-heptanedinitrile; alpha, omega-octanedinitrile, alpha, omega decanedinitrile, alpha, omega-dodecanedinitrile; and combinations of two or more thereof. The preferred embodiment is adiponitrile (ADN).
The catalyst in the process is a hydrogenation catalyst suitable for hydrogenating a dinitrile to a diamine or a mixture of diamine and is aminonifirile. Preferred are cafalysts~based on the elements iron, cobalt-nickel,,.or: ruth_e.nium and.combinations._there_of in. which the said elements,.
can exist as metals or their~compounds. Most preferred is a catalyst comprising iron. The catalytic element may comprise about 1 to 99 % of the total catalyst weight, preferably about 50 to 85 wt%. The catalyst may 20 further comprise one or more promoters selected from the group consisting of aluminum, silicon, titanium, vanadium, magnesium, chromium, sodium,, potassium and manganese. The promoters may be present in concentrations up to about 15% based on the total weight of the catalyst, preferably. about 0.05 to 2 wt%.
2s While the degree of beneficial effects of this invention may vary with the structure of the dinitrile, the identity of the catalytic element, and the identity of the modifier, it is important to realize that even small improvements in selectivity can have large economic impact for large-scale industrial processes.
3o The catalytic element can also be supported on an inorganic support~such as...~lum~na, magnesium oxide, and combinations thereof.
The element can be supported on an inorganic support by any means known to one skilled in the art such as, for example, impregnation, coprecipitation, ion exchange, and combinations of two or more thereof. If the catalytic element is supported on an inorganic support or is a component of an alloy or a solid solution, the catalytic element is generally present in the range of about 0.1 to about 60 wt% and preferably about 1 to about 50 weight percent, based on the total catalyst weight.
The catalyst can be present in any appropriate physical shape or form. It can be in fluidizable forms, extrudates, tablets, spheres, or combinations of two or more thereof. When employing the process using a fixed bed catalyst, the catalyst is in the form of granules having a particle size in the range of about 0.76 to 10.2 mm (0.03 to 0.40 inch). When io employing the process using a slurry-phase catalyst, the catalyst is in finely divided form, preferably less than about 100 Nm in size, most preferred range being about 20 to 75 Nm.
The molar ratio of catalyst.to. dinitrile can be any ratio as long as the ratio can catalyze the selective hydrogenation of a dinitrile. The weight us ratio of catalyst to dinitrile i~:g~ners~ly in the range: ~f frort~about O:,OD'I~.1 ~1,,~~~~
to about 1:1, preferably about OJ001:1 to about 0.5:1.
The modifiers of the present invention can be selected from the group consisting of quaternary ammonium hydroxide, quaternary ammonium cyanide, quaternary ammonium fluoride, quaternary 2o ammonium thiocyanides, quarternary phosphonium hydroxide,~carbon monoxide and hydrogen cyanide. The term quaternary describes a nitrogen or phosphorous atom with four bonds to it and bearing a formal charge of +1. The ammonium ion (NH4+) and tetraalkylammonium ions are included within the definition of quaternary ammonium. More than one 2s modifier can be used in the reaction. Examples of suitable modifiers are tetramethylammonium hydroxide, tetrabutylammonium cyanide, tetraethylammonium fluoride, tetrabutylammonium thiocyanide and tetrabutylphosphonium hydroxide. Preferred modifiers are quaternary ammonium hydroxide and quaternary ammonium cyanide. Examples~of 3o suitable tetraalkylammonium hydroxide compounds are tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
Examples of suitable tetraalkylammonium cyanide compounds are tetramethylammonium cyanide, tetraethylammonium cyanide and tetrabutylammonium cyanide. It should be noted that various hydrated forms such as, for example, tetramethylammonium hydroxide pentahydrate, are included within the meaning of tetraalkylammonium hydroxide and tetraalkylphosphonium hydroxide.
The hydrogenation reaction can be conducted at a temperature about 50 to 250°C and preferably about 90 to 180°C and at a pressure about 15.27 to 55.26 MPa (2200 to 8000 psig) total pressure with hydrogen and preferably at about 20.78 to 34.58 MPa (3000 to 5000 psig).
In a preferred mode of operation, the process~is conducted continuously in io a continuous stirred tank reactor (CSTR), a plug flow reactor (PFR); a slurry bubble column reactor (SBCR),~or a trickle bed reactor. A
continuous stirred tank reactor, also known as a back-mixed reactor, is a vessel in which the reactants are added in a continuous fashion and a flow of product stream is continuously withdrawn from it. There is adequate t~s <rvii~ing in tlie.>vesseb'~rovid~~i ~b:~~a :rnia~i<nyzd~5ice;.~ e.ig:;;.a ~echa~icar agitator,ao that.~the composition.inside.the reactor is uniform and is the.
same as that in the product stream withdrawn. A plug flow reactor is a tubular reactor in which the reactants' are added in a continuous fashion in one end of the tubular reactor and the product is withdrawn in a 2o continuous fashion from the other end of the tube. There is no back-mixing, i.e: the composition inside the reactor tube is not uniform. It is possible to incorporate backmixing in PFRs by recycling a part of the product flow back to the inlet of the reactor. It is also possible to achieve plug flow reactor behavior by using multiple CSTRs is series. A slurry 2s bubble column reactor is a vessel, in which liquid reactants and gas are continuously fed to the bottom of the reactor, while product is continuously withdrawn from the top of the reactor. The gas is present in the reactor as bubbles, which rise and simultaneously provide mixing for a solid powdered catalyst (20 to 200 pm average particle sizes). The catalyst 3o may be removed continuously with the product and added continuously by addition with the liquid feed. A trickle bed reactor is a tubular reactor in which the catalyst is fixed while the reactants are added at the top of the reactor and flow to the bottom where the product is continuously withdrawn. Gaseous reactants may flow cocurrently with the liquid or may flow countercurrently from the bottom to the top of the reactor.
The preference for reactor is not meant to limit the invention, which can also be conducted in batch mode.
The process can be operated in the absence or presence of a solvent. In this invention, a solvent is defined as a substance that is added to a reaction mixture and that serves to solvate one or more reaction components, increases the volume of the reaction mixture, provides a medium for transferring (or removing) the heat of reaction, and is either to not incorporated in the final product or does not alter the properties of the final product. While not comprehensive, a list of solvents includes ammonia; amines such as triethylamine; alcohols such as methanol, ethanol; propanol, and butanol; ethers such as tetrahydrofuran and dioxane; amides such diethylacetamide and N-methylpyrolidinone; and S 1; J .,g t.~ ~,.= 3 W~,f :, p. ~. " 'k is °este~~~°sucn~~ ~t~~l~ acei~~~~a1"nd ditzieth~ilaidip~te ~'he 'pr~fierred 's~iv~~t~i ammonia., ~:~The solvent can. be present in. the. reaction mixture. in, about~20.
to 90% by weight, preferably about ~30 to 50%~.
The modifier and ainitrile may be introduced to a reactor, which contains catalyst, separately or as a premixed solution with a diamine, an 2o aminonitrile, water, a solvent or any combination thereof. The modifier can be added in a weight ratio to dinitrile from about 1:5000 to 1:30, preferably from about 1:2000 to 1:500.
The yields of diamine and/or aminonitrile, e.g.
hexamethylenediamine and/or 6-aminocapronitrile; depend on operating 2s conditions including temperature; pressure, hydrogen flow rate, amount and kind of catalyst, amount of modifier and space velocity and the like.' For the purpose of this invention, the term "space velocity" is defined as the unit weight of dinitrile fed into the reactor per hour, per unit weight of the catalyst. Typically, the dinitrile should be added to the reactor such 3o that the space velocity of the dinitrile is within the range of about 0.5 to 20 h''. Most preferred space velocities may be readily determined by those skilled in the art using conventional techniques.
While not meant to limit the invention by any theory, it is possible that the modifier reacts with the el~ement(s) of the catalyst forming a, modifier/catalytic element complex. The resulting~complex may contain the Group VIII element in its metallic state or perhaps in an oxidized state.
The reaction of modifier with the catalytic element may be irreversible but more likely is a reversible equilibrium reaction. The interaction of the modifier with the catalyst may alter the reactivity of the catalyst, improve the selectivity for aminonitrile production, suppress secondary amine oligomer formation and, perhaps, increase the lifetime of the catalyst.
The catalyst and modifier can be separately introduced into a reactor to contact the.dinitrile; however, the catalyst may be precontacted io with the modifier. This may be done in water and/or a solvent such as, for example, an alcohol, ether, ester, ammonia, or combinations of two or more thereof.
The molar ratio of hydrogen to dinitrile is not critical as long as sufficient hydrogen is present to produce an aminonitriie and/or a diamine, ;i~~~ e:g fi-ahnino~~~prc~rDat~iIWa~id/h~fh~xa~n~ethylenddiamine °Hyd~oger~vs~
generally used in.excess.
Diamine and/or aminonitrile, e.g. hexamethylenediamine and/or 6-aminocapronitrile, can be recovered from the reaction products by typical purification procedures such as. recrystallization or preferably, distillation.
2o The unreacted dinitrile can be recycled back to the hydrogenation reactor to obtain additional diamine and/or aminonitrile.
EXAMPLES
The hydrogenation of adiponitrile (ADN) may be described using a kinetic 2s model in which ADN is first converted to aminocapronitrile (ACN) andlthe ACN is then converted to hexamethylenediamine (HMD), e.g., ADN ~ ACN ~ HMD
where each reaction step is a first order reaction, and the first step has a rate constant 2k~ and the second step has a rate constant k2. In this 3o model a k~/k2=1 value describes a' non-selective catalyst and the maximum yield of ACN will be 50°/a.,in a well-mixed batch reaction. It is desirable to maximize the k~/k2 value.
Comparative Example 1. A 1-L stainless steel pressure vessel was charged with 216 g of adiponitrile and 20g of a powdered, reduced iron catalyst. The vessel was sealed, purged with hydrogen and charged with 225g ammonia. It was heated to 150°C and pressurized to 4500 psig (31 s MPa). As hydrogen was consumed, it was constantly replenished from a pressurized cylinder to maintain an operating pressure of 4500 psig (31 MPa). After 70 min the reaction was stopped, and a sample was analyzed via gas chromatography. The analysis showed that the reaction product comprised 12 wt% adiponitrile (ADN), 45wt% 6-aminocapronitrile (ACN), ~o and 36wt% hexamethylenediamine. The k~/k2 value was 1.1.
Examples 2 to 4. The experiment of Example 1 was repeated except ~.2g of a modifier chemical was added to the reaction mixture with the ADN.
The results are presented in Table 1. TBACN = tetrabutylammonium la~ ,.cyaniae,eT~AI~~= re~raetr~yi~'mo~oni-um cydrtid~sri'l'~AFIP~=
tetramethylammonium hydroxide,pentahydrate..
Example ModifierTime Wt% Wt% Wt% k~/k~
of ~ ADN in ACN in HMD in Reactionreactionreactionreaction (min) product product product 1 None 70 12 45 36 1.1 2 TBACN 315 21 57 17 1.8 3 TEAF 180 21 54 21 1.4 4 TMAHP 120 M 11 51 ' 28 1.6 s
Claims (7)
1. A process of hydrogenating a dinitrile for the simultaneous production of an aminonitrile and a diamine, said process comprising: contacting the dinitrile with hydrogen in the presence of a catalyst and a modifier at a pressure of at least about 15.27 MPa (2200 psig), wherein said catalyst comprises an element selected from the group consisting of Fe, Ru, Co, and Ni and said modifier is at least one member selected from the group consisting of quaternary ammonium hydroxides, quaternary ammonium cyanides, quaternary ammonium fluorides, quaternary ammonium thiocyanides, quaternary phosphonium hydroxides, and hydrogen cyanide.
2. The process of claim 1 wherein the temperature is in the range of about 50°C
to 250°C.
to 250°C.
3. The process of claim 1 wherein the pressure is in the range of about 20.7 to 34.5 MPa (3000 to 5000 psig).
4. The process of claim 1 wherein the catalyst comprises iron.
5. The process of claim 1 wherein the modifier comprises a quaternary ammonium cyanide or quaternary ammonium hydroxide salt.
6. The process of claim 1 wherein the dinitrile is adiponitrile.
7. A process for hydrogenating a dinitrile in the presence of a catalyst and a modifier at a pressure of at least about 15.27 MPa (2200 psig) and simultaneously producing an ammonitrile and a diamine, characterized in that the catalyst is an element selected from the group consisting of Fe, Ru, Co, and Ni and the modifier is at least one member selected from the group consisting of quaternary ammonium hydroxides, quaternary ammonium cyanides, quaternary ammonium fluorides, quaternary ammonium thiocyanides, quaternary phosphonium hydroxides, and hydrogen cyanide whereby selection of aminonitrile is preferred over diamine,
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2004/036662 WO2006062496A1 (en) | 2004-12-07 | 2004-12-07 | Use of modifiers in a dinitrile hydrogenation process at high pressures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2552744A1 true CA2552744A1 (en) | 2006-06-15 |
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| CA002552744A Abandoned CA2552744A1 (en) | 2004-12-07 | 2004-12-07 | Use of modifiers in a dinitrile hydrogenation process at high pressures |
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| Country | Link |
|---|---|
| EP (1) | EP1819665A1 (en) |
| JP (1) | JP2008522969A (en) |
| KR (1) | KR101129878B1 (en) |
| CN (1) | CN101068775B (en) |
| CA (1) | CA2552744A1 (en) |
| WO (1) | WO2006062496A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110318066A (en) * | 2019-06-20 | 2019-10-11 | 青岛鼎海电化学科技有限公司 | A kind of preparation method of tetra-alkyl ammonium hydroxide |
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| EP1900428B1 (en) | 2006-08-09 | 2016-01-06 | Mitsubishi Gas Chemical Company, Inc. | Production method of primary amines and catalysts for producing primary amines |
| CN106824038A (en) * | 2017-03-17 | 2017-06-13 | 濮阳市盛源能源科技股份有限公司 | A kind of synthetically produced use reaction unit of sebacic dinitrile and sebacic dinitrile synthetic process |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB728599A (en) * | 1951-07-28 | 1955-04-20 | Du Pont | Catalytic hydrogenation of nitriles to amines |
| US3773832A (en) * | 1970-01-16 | 1973-11-20 | Du Pont | Hydrogenation of adiponitrile over alkali-modified cobalt catalyst |
| US3758584A (en) * | 1970-12-23 | 1973-09-11 | Du Pont | Hydrogenation of adiponitrile |
| DE4446893A1 (en) * | 1994-12-27 | 1996-07-04 | Basf Ag | Process for the preparation of aliphatic alpha, omega-aminonitriles |
| DE19614154C1 (en) * | 1996-04-10 | 1997-09-25 | Basf Ag | Process for the simultaneous production of 6-aminocapronitrile and hexamethylenediamine |
| DE19636768A1 (en) * | 1996-09-10 | 1998-03-12 | Basf Ag | Catalysts suitable for the production of aliphatic alpha, omega-aminonitriles by partial hydrogenation of aliphatic dinitriles |
| DE19742221A1 (en) * | 1997-09-24 | 1999-03-25 | Basf Ag | Production of aliphatic alpha ,w-amino-nitrile compounds |
| US6258745B1 (en) * | 1999-04-28 | 2001-07-10 | E. I. Du Pont De Nemours And Company | Aminonitrile production |
| DE60013286T2 (en) * | 1999-04-28 | 2005-09-15 | Invista Technologies S.A.R.L., Wilmington | PROCESS FOR HYDROGENATION OF DINITRILES TO AMINONITRILES |
| US6566297B2 (en) * | 2000-03-10 | 2003-05-20 | E. I. Du Pont De Nemours And Company | Aminonitrile production |
| US6376714B1 (en) * | 2001-05-31 | 2002-04-23 | E. I. Du Pont De Nemours And Company | Environmentally friendly process for the hydrogenation of dinitriles |
| FR2826364B1 (en) * | 2001-06-22 | 2005-01-14 | Rhodia Polyamide Intermediates | PROCESS FOR THE HEMIHYDROGENATION OF DINITRILES OF AMINONITRILES |
-
2004
- 2004-12-07 JP JP2007544315A patent/JP2008522969A/en active Pending
- 2004-12-07 CA CA002552744A patent/CA2552744A1/en not_active Abandoned
- 2004-12-07 WO PCT/US2004/036662 patent/WO2006062496A1/en active Application Filing
- 2004-12-07 CN CN2004800442035A patent/CN101068775B/en not_active Expired - Fee Related
- 2004-12-07 EP EP04810293A patent/EP1819665A1/en not_active Ceased
- 2004-12-07 KR KR1020067011311A patent/KR101129878B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110318066A (en) * | 2019-06-20 | 2019-10-11 | 青岛鼎海电化学科技有限公司 | A kind of preparation method of tetra-alkyl ammonium hydroxide |
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| Publication number | Publication date |
|---|---|
| KR20070100854A (en) | 2007-10-12 |
| KR101129878B1 (en) | 2012-03-28 |
| CN101068775B (en) | 2011-04-13 |
| WO2006062496A1 (en) | 2006-06-15 |
| JP2008522969A (en) | 2008-07-03 |
| EP1819665A1 (en) | 2007-08-22 |
| CN101068775A (en) | 2007-11-07 |
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