Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
1999-11-17
2001-02-20
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S480000
Reexamination Certificate
active
06191310
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to hydroamination. In particular this invention is related to a process for the selective hydroamination of a hydrocarbon having from two to six carbons and characterized by two hydroxy groups , preferably separated by at least one or more carbons to yield a diaminoalkane. The reactants would include diols having two to four carbons, and mixtures of same. Examples could include ethylene glycol, 1,2-propanediol, and 1,3-propanediol. In the preferred embodiment this invention provides a process for the selective hydroamination of 1,3-propanediol to yield 1,3-propanediamine and its homologues in one step. Greater than 95% conversions of 1,3-propanediol (PDO) and 38% effluent concentrations of 1,3-propanediamine (PDA) are demonstrated per pass.
BACKGROUND
The hydroamination of commodity and specialty alcohols, aldehydes and ketones to manufacture the corresponding aliphatic amines is known in the art. The selection of a catalyst with optimal advantages has also been the focus of much research. Aliphatic amines are of considerable industrial importance and find applications in many facets of modern technology, agriculture and medicine. Lower aliphatic amines (C
1
to C
6
) are particularly important for both the chemical and pharmaceutical industries.
In an article titled “Equilibrium Conditions for Amination of Alcohols and Carbonyl Compounds”,
Ind. Eng. Chem. Prod. Res. Develop.,
11, 3, 333-337 (1972), Josef Pasek et al. described the influence of pressure, temperature, and initial composition on the equilibrium content of primary, secondary, and tertiary amines and unsaturated compounds.
Alfons Baiker et al., in an article titled “Catalytic Amination of Long Chain Aliphatic Alcohols”,
Ind. Eng. Chem., Prod. Res. Dev.,
16, 3, 261-266 (1977), indicate a preference for the use of a copper catalyst in the amination of dodecanol with dimethylamine.
In
Catalysis of Organic Reactions
, Blackburn, D. W., ed., 1990, at Chapter 14, M. Ford et al. review the selective synthesis of mixed alkyl amines by amine-alcohol reactions over hydrogen phosphate.
The amination of alcohols, aldehydes, and ketones using catalysts containing nickel, copper, or both, has been also been described, for example, in U.S. Pat. Nos. 3,520,933; 4,153,581; 4,152,353; and 4,409,399. These patents do not appear to contemplate the selective production of diamines.
The process disclosed in U.S. Pat. No. 4,683,336 employs catalysts comprising carbonates of copper, nickel, and cobalt, or mixtures thereof to produce amines from aliphatic alcohols or aliphatic aldehydes.
U.S. Pat. No. 4,806,690 discloses a method of preparing amines from an alcohol, aldehyde, ketone or mixture thereof, in the presence of a catalyst containing about 1 to 20% cobalt, 75 to 95% copper, 1 to 16% of a third component selected from iron, zinc, zirconium, and mixtures thereof. The preferred embodiment demonstrates the reductive amination of MEA.
U.S. Pat. No. 3,270,059 discloses the production of diaminoalkanes by passing an alkanediol, alkanolamine, alkylene oxide, or alkyleneimine along with either ammonia or an alkylamine in the presence of hydrogen and at an elevated temperature over a catalyst which contains sintered cobalt or nickel. The sintering process requires extra steps and high temperatures.
From the foregoing references it appears there is a need in the art for an improved method of selectively producing shorter chain diaminoalkanes. There does not appear to be a disclosure of the amination a short chain diol, such as, for example, 1,3-propanediol to 1,3-propanediamine in one step with greater than 90% conversions of 1,3-propanediol per pass. It would be very desirable in the art if a process were available for aminating a diol which is available in large volumes. This would provide an attractive route to an added-value commodity chemical. These diamines could find large volume applications in polyamide resins as monomer/comonomers, as well as price-competitive usage in lube oils, epoxies, hot melt adhesives, and surfactants. They might also be useful in fuel additives, chelating agents, fungicides, and plastic lubricants.
SUMMARY
In accordance with the foregoing, there is disclosed a hydroamination process which comprises reacting a diol characterized by two to six carbons, preferably 1,3-propanediol with excess ammonia and sufficient hydrogen to stabilize a catalyst which comprises at least one metal selected from the group consisting of nickel and cobalt, or mixtures thereof, optionally supported, or as a bulk-metal catalyst, and optionally in the presence of one or more promoters, at a temperature of at least 150° C. and a pressure of at least 500 psig until there is substantial formation of the desired diaminoalkane. Said hydroamination exhibits good selectivity for the desired diaminoalkanes and may be conducted batchwise or in a continuous reactor system.
REFERENCES:
patent: 3270059 (1966-08-01), Winderl et al.
patent: 3520933 (1970-07-01), Adam et al.
patent: 4152353 (1979-05-01), Habermann
patent: 4153581 (1979-05-01), Habermann
patent: 4409399 (1983-10-01), Swift et al.
patent: 4622428 (1986-11-01), Merger et al.
patent: 4683336 (1987-07-01), Blackhurst
patent: 4806690 (1989-02-01), Bowman
Josef Pa{haeck over (s)}ek et al, “Equilibrium Conditions for Amination of Alcohols and Carbonyl Compounds,”Ind. Eng. Chem. Prod. Res. Develop.,11, 3, 333-337 (1972). Month unavailable.
Alfons Baiker et al., “Catalytic Amination of Long Chain Aliphatic Alcohols,”Ind. Eng. Chem., Prod. Res. Dev.,16, 3, 261-266 (1977). Month unavailable.
Michael E. Ford et al., Selective Catalytic Synthesis of Mixed Alkylamines and Polyfunctional Amines,Catalysis of Organic Reactions,D. W. Blackburn, ed., Ch. 14, pp. 219-240 (1990) month unavailable.
J. F. Knifton and D. J. Janitor, “Diaminoalkane Syntheses Via Selective Amination of Hydroxy Aldehydes,” Patent Application Serial No. 60/109,572, filed Nov. 23, 1998 (Docket No. TH-1160).
Janitor Daniel John
Knifton John Frederik
Barts Samuel
Shell Oil Company
LandOfFree
Diaminoalkane syntheses via selective amination of dihydric... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Diaminoalkane syntheses via selective amination of dihydric..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Diaminoalkane syntheses via selective amination of dihydric... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2596264