Chemical Processing-August 2008

IN PROCESS Catalyst Simpliﬁes Amine Production Direct reaction of ammonia with allenes promises low cost synthesis A NOVEL catalyst may revolutionize the way amines are commercially made, hope researchers at the University of California, Riverside, Calif. eir laboratory trials indicate that the catalyst — a gold atom linked to a cyclic alkyl amino carbene (Figure 1) — provides high yields and good selectivity for the reaction of ammonia and allenes under mild conditions. Moreover, adjusting the ammonia/allene ratio allows signiﬁcant control over selectivity, notes Guy Bertrand, distinguished professor of chemistry at the school, who heads the team of researchers. e catalyst also is suitable for reacting alkynes and can be used to produce most amines. Current commercial processes rely on hydrochloric acid and generate three times as much waste as product. “Our ‘green chemistry’ method, however, produces no waste, which makes it inexpensive. Moreover, the reaction is a quick, one-step reaction, and you need a tiny amount of catalyst to do the trick,” he says. e researchers have used the catalyst to react ammonia with 1,2 propadiene to form mono, di- and triallylamine. e gram-scale tests took place at 110° to 180°C and atmospheric pressure, usually ran for 10 to 16 hours, and gave amine yields of around 80% to 90%, says Bertrand, who stresses that yields haven’t been optimized. Fine-tuning of reactant ratio provided selectivities for allylamine and triallylamine of 86% and 91%, respectively, with further improvements possible, he adds. Unreacted ammonia can be recycled. Catalyst Economic Snapshot 58,500 58,000 57,500 57,000 56,500 56,000 $ Million 55,500 55,000 54,500 54,000 53,500 53,000 Shipments (NAICS S325) Capacity utilization 86.0 85.0 84.0 83.0 82.0 81.0 80.0 79.0 78.0 77.0 76.0 75.0 74.0 June 07 July 07 Aug 07 Sept 07 Oct 07 Nov 07 Dec 07 Jan 08 Feb 08 Mar 08 Apr 08 May 08 The catalyst is thermally stable and used at low concentrations (1 mol%), he notes. At the small scale of the trials, it hasn’t been worth trying to recover the material. However, in a commercial process — where the catalyst likely would be put on a support — its recovery certainly is possible, he says. e ultimate goal is to use such a catalyst to add NH3 to alkenes. “ is process is widely considered to be one of the 10 greatest challenges for catalytic chemistry,” notes Bertrand. It would open up even more important industrial applications. He has developed new ligands with that in mind and expects to run trials with alkenes over the summer. e university has applied for a patent on the catalyst and now is seeking partners to commercially develop it. e school already has granted an exclusive license for the carbene to Rhodia, Paris and Cranbury, N.J. Both shipments and capacity utilization rose slightly. Source: American Chemistry Council. Nanorods Boost Boiling Depositing copper nanorods on a copper surface significantly enhances boiling, say researchers at Rensselaer Polytechnic Institute, Troy, N.Y. “The increased boiling efficiency seems to be the result of an interesting interplay between the nanoscale and microscale surfaces of the treated metal,” notes Nikhil Koratkar, associate profes13 CHEMICALPROCESSING.COM AUGUST 2008 Figure 1. Carbene-based catalyst contains gold (yellow), nitrogen (blue), hydrogen (gray) and carbon (black). Source: University of California, Riverside. % http://CHEMICALPROCESSING.COM

Table of Contents Feed for the Digital Edition of Chemical Processing-August 2008

Chemical Processing- August 2008 Contents From the Editor ChemicalProcessing.com Field Notes In Process Energy Saver Compliance Advisor Protect your Plant What’s on Tap for Water? Keep Operations Safe Polystyrene Plant Gains Extra Output and More Process Puzzler Plant InSites Equipment & Services Adlits Product Spotlight/Classifieds Ad Index End Point

For optimal viewing of this digital publication, please enable JavaScript and then refresh the page. If you would like to try to load the digital publication without using Flash Player detection, please click here.