US007547805B2 (12) United States Patent (10) Patent No.: US 7,547,805 B2 Malek et al. (45) Date of Patent: Jun. 16, 2009 (54) CATALYTIC PREPARATION OF SEVERELY (56) References Cited STERICALLY HINDEREDAMNO-ETHER U.S. PATENT DOCUMENTS ALCOHOLS USINGAMETAL LOADED CATALYST 4,112,051 A 9, 1978 Sartori et al. 4,112,052 A 9, 1978 Sartori et al. 4.405,585 A 9, 1983 Sartori et al. (75) Inventors: Andrzej Malek, Baton Rouge, LA (US); 4.417,075 A 1 1/1983 Stogryn Christine Nicole Elia, Bridgewater, NJ 4,471,138 A 9/1984 Stogryn (US); Adeana Richelle Bishop, Baton 4.487,967 A 12/1984 Stogryn et al. Rouge, LA (US); Edmund John 4,508,692 A 4, 1985 Savage et al. Mozeleski, Califon, NJ (US); Michael 4,618,481 A 10, 1986 Heinzelmann et al. Siskin, Randolph, NJ (US) 4,665,195 A 5/1987 Stogryn et al. 4,762.934 A 8/1988 Stogryn 4,892,674. A 1/1990 Ho et al. (73) Assignee: Exxonmobil Research and 4,894, 178 A 1/1990 Ho et al. Engineering Company, Annandale, NJ 4,961,873. A 10, 1990 Ho et al. 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Winsor, "Binary and Multicomponent Solutions of Amphiphilic Compounds', Chemical Reviews, Jan. 25, 1968, pp. 1-40, vol. 68, (65) Prior Publication Data No. 1. US 2007/0276.162 A1 Nov. 29, 2007 Ulrike Ciesla, Ferdi Schuth, “Ordered mesoporous materials”, 1999, pp. 131-149, 27. Elsevier Science B.V., Microporous and Related U.S. Application Data Mesoporous Materials. (60) Provisional application No. 60/545,197, filed on Feb. Primary Examiner Brian J Davis 17, 2004. (57) ABSTRACT (51) Int. Cl. The present invention relates to a process for the production CD7C 209/6 (2006.01) of severely sterically hindered amino-ether alcohols using a C07C 209/18 (2006.01) catalyst based on the combination of one or more catalytically (52) U.S. Cl. ....................... 564/402:564/403: 564/474; active metals Supported in a dispersed form on one or more 564/478: 564/479;564/480 ordered mesoporous materials as Support. (58) Field of Classification Search ....................... None See application file for complete search history. 39 Claims, 1 Drawing Sheet US 7,547,805 B2 1. 2 CATALYTIC PREPARATION OF SEVERELY hols by the reaction of a primary amino compound with a STERICALLY HINDEREDAMNO-ETHER polyalkenyl ether glycol over a catalyst comprising one or ALCOHOLS USING AMETAL LOADED more catalytically active highly dispersed metals Supported CATALYST on one or more Support materials. The catalyst Support material can comprise one or more This application is the U.S. National Phase filing of PCT ordered mesoporous Support materials. Application No. PCT/US2005/003059 filed Feb. 1, 2005, The catalytic Support material can also comprise one or which claims priority to U.S. Provisional Patent Application more ordered mesoporous Support materials matrixed or Ser. No. 60/545,197 filed Feb. 17, 2004. bound with the one or more additional materials selected 10 from the group consisting of conventional amorphous Support FIELD OF THE INVENTION material, crystalline Support material, and mixtures thereof. The catalyst Support material can also comprise one or The present invention relates to the production of severely more ordered mesoporous Support materials combined in sterically hindered amino-ether alcohols, diaminopolyalk admixture with the one or more mixed porosity mesoporous enyl ethers, and mixtures thereof, using a mixture of primary 15 Support materials. amino and polyalkenyl ether glycol reacted over a catalyst The catalyst Support material can also comprise one or comprising one or more catalytically active metal compo more Support materials selected from the group consisting of nents deposited on a Support, the catalytic process being conventional amorphous Support material, crystalline Support conducted at elevated temperature and pressure. materials, and mixtures thereof. The catalytically active metal comprises at least one metal DESCRIPTION OF RELATED ART of transition group VIII of the Periodic Table, excluding plati num and palladium (e.g., iron, cobalt, nickel, ruthenium, The catalytic production of severely sterically hindered rhodium, osmium, iridium), either alone or together with at amino-ether alcohols is already established in the literature. least one additional metal selected from the group consisting Such severely sterically hindered amino-ether alcohols are 25 of transition group 1B (e.g., copper), group IIA (e.g., mag made by reacting a primary amino compound. Such as ter tiary-butylamine (TBA), with a polyalkenyl etherglycol such nesium), and mixtures thereof, preferably nickel and cobalt, as diethylene glycol (DEG) in the presence of a catalytically most preferably nickel. effective amount of a Group VIII metal containing supported DETAILED DESCRIPTION OF THE INVENTION hydrogenation catalyst at elevated temperatures and pressure, 30 such as about 160° C. to about 425°C. and about 50 to about In the process of the present invention, a primary amino 3,000 psig, as described in U.S. Pat. No. 4,487.967. The compound is reacted with a polyalkenyl ether glycol in the reaction of tertiary-butyl amine with diethylene glycol pro presence of a catalyst comprising one or more catalytically duces ethoxyethanol-tertiary-butyl amine, known as EETB. active metals dispersed on one or more Support materials. The EETB is useful in gas treating processes for the selective 35 class of Support materials identified as ordered mesoporous removal of HS from gas streams containing mixtures of HS materials which have a high pore Volume, high Surface area and CO. The use of such severely sterically hindered amino and controlled pore openings of at least 2 nm are useful for the ether alcohols in Such a separation process is described in production of severely sterically hindered amino-ether alco U.S. Pat. Nos. 4,894.178; 4,405,585; 4,508,692; 4,618,481; hols. Such mesoporous Support materials can be used as such, 4,112,052: 4,961,873; 4,892,674; 4,417,075. 40 or combined with additional materials as matrix/binder mate There is a need, however, for a new process for the produc rials such as macroporous materials, e.g., conventional silica tion of severely sterically hindered amino-ether alcohols or alumina, or combined with mixed porosity materials as which produce lower level of undesirable by-products and maxtrix/binder materials. Other useful supports for the highly have improved selectively for the desired products. It is an dispersed catalytically active metal are the conventional object of the present invention to provide a new catalytic 45 amorphousand/or crystalline Support materials. process for the production of severely sterically hindered amino-ether alcohols using a specific class of catalyst which The process comprises the batch or continuous production is marked by a high level of conversion of starting materials of severely sterically hindered amino ether alcohols by react and selectivity for the desired end product. ing 50 (a) a primary amino compound of the general formula DESCRIPTION OF THE FIGURE R" NH, FIG. 1 is a plot of the level of diethylene glycol conversion wherein R' is selected from the group consisting of second versus the EETB/TBM molar ratio for a process run using a ary- and tertiary-alkyl radicals having 3 to 8 carbon atoms, catalyst made using an organic dispersion aid and represen 55 cycloalkyl radicals having 3 to 8 carbon atoms, and mixtures tative of those useable in the present invention as compared thereof, preferably secondary or tertiary alkyl radicals having against three other process runs which utilize catalysts made 4 to 6 carbon atoms, more preferably tertiary alkyl radicals without the use of an organic dispersion aid and representa having 4 to 6 carbon atoms, with tive of those outside the present invention. TBM is an unde (b) a polyalkenyl ether glycol of the general formula sirable side product (N-tertiary-butylmorpholine). 60 SUMMARY OF THE INVENTION R2 R4 The present invention is directed to a process for the pro Ho-info-firion duction of severely sterically hindered amino-ether alcohols, 65 R3 R5 2 diaminopolyalkenyl ethers, and mixtures thereof, preferably predominantly severely sterically hindered amino-ether alco US 7,547,805 B2 3 4 wherein R. R. R. and Rare each independently selected encased in a basket. Alternatively, the reactants can be passed from the group consisting of hydrogen, C-C alkyl radicals, over a fixed bed of the catalyst, either co-currently or counter and C-C cycloalkyl radicals, with the proviso that if the currently. Other reactors suitable for use include moving bed carbon atom of R' directly attached to the nitrogen atom is a reactors and continuously stirred reactors.