RANEY® Catalysts The Standard of Excellence in Hydrogenation RANEY® Catalyst Leader in Hydrogenation RANEY® catalysts from Grace are integral in the processing of Grace has over 60 years of experience innovating with superior petroleum and food products and the production of an extensive RANEY® catalysts. In 1963, Grace acquired the manufacturing site, array of pharmaceuticals, fibers, fragrances, and personal care. technology, and registered trademark of RANEY® catalysts from the original inventor. In these fast-paced industries, you need efficiency and speed to adapt to the demands of the ever-changing consumer demands and regulatory standards. Grace is a global catalysts leader and a major supplier of RANEY® hydrogenation and dehydrogenation catalysts. Our base metal RANEY® products provide unmatched performance in the synthesis of organic compounds. When you partner with Grace, you get longer lasting, more efficient, and more reliable catalysts. Grace RANEY® catalysts are the most efficient class of catalysts available for many hydrogenation processes. With distinctively high activity, selectivity, and handling characteristics, RANEY® catalysts significantly increase throughput while decreasing the formation of undesirable by-products. Through advances in surface chemistry and by specifically tailoring catalysts to meet a demanding and In 1926, Murray RANEY developed RANEY® catalysts for the unique range of industrial requirements, Grace consistently hydrogenation of vegetable oils. They were found to be 5x more provides solutions that are both flexible and lasting. Adding active than the best catalysts used in the hydrogenation of promoters can modify the surface characteristics of RANEY® cottonseed oil. catalyst for a variety of applications. Advantages of Partnering with Grace Advantages of RANEY® Catalysts Pioneer of RANEY® catalysts with over 60 years of experience Highly active (high metal surface area) and ready-to-use R&D / technical service to continually improve performance Versatile for various hydrogenations and dehydrogenations Flexible assets for scale-up and commercial production Low cost compared to precious metal catalysts Range of analytical tools for product and process improvement Ease of separation from product (high density and magnetic separation) Consistency of quality Efficiency; longer catalyst life Global footprint to support local demands Durability in wide range of environments Customized catalysts to meet specific customer requirements Customizable and offers the ability to add promoters Flexibility to customize particle size ranges With distinctively high activity, selectivity, and handling characteristics, RANEY® catalysts significantly increase throughput while decreasing the formation of undesirable by-products. grace.com | 1 RANEY® Catalyst Grace Catalysts Portfolio Grace catalysts are used in a wide range of hydrogenation and dehydrogenation applications. Hydrogenation Functional Group Product Type Product Example Grace Catalyst Benefits Aromatic Nitro Aromatic Amine TDA 6800 (Ni) • Higher productivity Ar-NO2 Ar-NH2 Aniline 2400 (promoted Ni) • Good settling properties 4200 (promoted Ni) • Less extensive cleanups • Less down time Aliphatic Nitro Aliphatic Amine Alkylamines 4200 (Ni) • Long lifetime R-NO2 R-NH2 Amino alcohols 2800 (Ni) • High activity 3201, 3111 (promoted Ni) Carbonyl: Aldehyde Primary Alcohol Sorbitol 3111/3110 (promoted Ni) • Lower overall cost RCHO RCH2OH Butanol 5831 (fixed-bed Mo/Ni) • Better settling times Butanediol • Lower losses • Consistent performance • Superior for different grades of dextrose Carbonyl: Ketone Secondary Alcohol Isopropanol 3111/3110 (promoted Ni) • Better settling times RR’C=O RR’CH2OH • Better filterability • Resistance of poisons Nitrile Amine HMDA and isomers 2400 (Ni) • Improved selectivity RCN RCH2NH2 Fatty Amines 2724 (promoted /Co) • Consistent performance (e.g. C4-C6 diamines) 2786 (fixed-bed promoted /Co) • Improved settling times 2400 (promoted/Ni) • Less use of NH3 (2724) 2800 (Ni) • Longer life for Co catalyst Alkene (Olefin) (Saturated derivative) Sulfolane 5601 (Ni) • Higher performance RCH=CHR’ Rosin-esters 4200 (Ni) • Consistency 2400 (promoted Ni) • Better usage of catalysts 2800 (Ni) Alkyne (Acetylene) (Saturated derivative) Butanediol 4200 (Ni) • Unique fixed-bed catalyst RC≡CR’ 2800 (Ni) • Next generation activated catalyst 5886 (Ni) • Catalyst shelf stable Reductive Alkylation Functional Group Product Type Product Example Grace Catalyst Benefits Carbonyl + amine 2°, 3° Amines Methyl Propylamine 2800 (Ni) • Higher selectivity 4200 (Ni) • Longer life 2724 (Co) Dehydrogenation/Oxidation Functional Group Product Type Product Example Grace Catalyst Benefits Alcohol (1° or 2°) Acid, aldehyde, ketone Glycine 2800 (Ni) • Higher selectivity RCH2OH or RCOOH, RCHO, or Cyclohexanone 4200 (Ni) • Longer life RR’CH2OH RR’C=O 2900 (Cu) Amino Alcohol AMINO ACID Glycine 2900 (Cu) • Higher selectivity H2NRCH2OH H2N-RCOOH • Longer life Reductive Amination Functional Group Product Type Product Example Grace Catalyst Benefits Carbonyl + ammonia Primary Amine Propylamine 2800 (Ni) • Higher selectivity RCHO+NH3 4200 (Ni) Alcohol + ammonia Primary Amine i-propylamine 2724 (Co) RCH2OH+NH3 grace.com | 2 RANEY® Catalyst ® RANEY Catalysts Add Value RANEY® superior metal catalysts offer extremely high activity, Greater Overall Economy Increases Profits excellent selectivity, a high degree of versatility, ease of filtration, and RANEY® catalysts offer the lowest initial cost per pound of catalytic excellent settling characteristics. More importantly, RANEY® catalysts metal particularly when compared to precious metal catalysts. offer genuine savings in both low initial cost and low ultimate cost RANEY® catalysts also offer manufacturing flexibility to use many per pound of end product. metals, providing overall economics to the process. Superior Selectivity Reduces By-Product Recyclability Lowers Cost RANEY® catalyst formulations can be fine-tuned to meet the Spent catalyst can be recycled to recover some of the initial metal performance requirements of specific applications. RANEY® investment. Metal recycling is a well-established process and there catalysts provide consistent and reliable performance. They many global companies who have expertise in this segment. Grace selectively hydrogenate a wide variety of functional organic can provide regional contacts to help you recycle spent catalyst. compounds under mild to severe reaction conditions. The low by-product formation substantially reduces environmental waste Typical RANEY® 5% Platinum on disposal costs and increases the effective usage of raw materials Nickel Catalyst Carbon Catalyst providing significant value to the process. “Sticker” Price $30/kg $1,600/kg Recovery Value ($5/kg) ($1,425/kg) High Activity Increases Production Rates Net Cost $25/kg $175/kg Grace works closely with customers to optimize the performance of RANEY® catalysts helping increase throughput in large-scale Additional savings are possible in amount of working capital required. hydrogenation processes. The RANEY® catalysts have higher activity due to higher active site density as compared to supported base metal Ready-to-Use Convenience catalysts and, in some cases, supported precious metal catalysts. The active RANEY® catalysts are supplied ready-to-use under water and do not require preactivation. This will reduce batch startup In an aromatic nitrile-to-amine application, for example: times and labor, facilitating improved economics. • Yield improved from 98.4% to 98.8%, saving the customer over $2.5 million in raw materials. Ease of Settling Increases Plant Capacity • The improved yield also reduced high boilers which reduced Settling rates of RANEY® catalysts in slurry form are superior waste disposal costs. to those of finely divided supported catalysts. High density RANEY® catalysts helps separate the catalyst quickly from the Longer Life Improves Economics reaction medium. Shorter processing times result in increased plant capacity and economics. The shorter contact times after the Extremely efficient, RANEY® catalysts last longer in reaction reaction would potentially minimize the side reactions providing mixtures and thus contribute to reduced net costs. RANEY® enhanced selectivity for desired products. catalysts are useful in systems containing many aqueous solutions, especially bases, where other catalysts are not. Value Added with Grace Catalysts Resistance to Poisons Provides Greater Flexibility $13.5 The high metal content in RANEY® catalysts provides protection FASTER SETTLING LEADS against severe catalyst poisoning. This high resistance to catalytic $12.5 TO GREATER THROUGHPUT poisons allows for greater flexibility in the selection of raw material. Grace switched a customer from a supported nickel fixed-bed $11.5 catalyst to a RANEY® fixed-bed cobalt catalyst and doubled the Revenue, $M lifetime from six months on-stream to over 12 months on-stream. $10.5 Not only did the customer cut their catalyst consumption in Competitor Grace half; they eliminated a second shut-down, saving hundreds of thousands of dollars per year. • 12,000 MT/YR Sorbitol Plant • RANEY® cut total cycle time and increased batches per day from 7.8 to 8.5 • Plant gained additional 1,000 MT/YR of capacity • Added $1M in additional revenue grace.com | 3 RANEY® Catalyst The RANEY® Difference RANEY® catalysts start as alloys and maintain their metallic The primary catalytic metal (e.g. Ni) “sponge” holds hydrogen in/ properties through