RANEY® Catalysts The Standard of Excellence in 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 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.

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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

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® 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

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The RANEY® Difference

RANEY® catalysts start as alloys and maintain their metallic The primary catalytic metal (e.g. Ni) “sponge” holds in/ properties through the life cycle of the catalysts. They do on its structure. The catalyst is stored underwater to protect it from not include an inert support such as alumina, silica, or oxidation, which means it is ready to use right out of the package. carbon. A RANEY® catalyst is made by leaching Al from an Unlike supported metal catalysts, it does not require reduction in alloy that contains Ni, Co, or Cu to use in hydrogenation and hydrogen before use. dehydrogenation applications. Promoters such as Cr, Mo, or Fe ® can be added to the catalyst either during manufacturing or after Grace offers a broad portfolio of RANEY catalysts that are activation to enhance the activity and selectivity. effective for a variety of reactions.

Hydrogenation Catalysts

Homogeneous Heterogeneous

Precious Metal Base Metal

Unsupported Supported RANEY® catalysts Supported e.g. Pt black e.g. Pt/C e.g. RANEY® Ni e.g. Ni/Al O 2 3

RANEY® Catalyst Offerings To accommodate dynamic industries, RANEY® catalysts are Often the hydrogenation processes require modifying or expanding available in a granular form for fixed-bed applications (also fixed- the capabilities of RANEY® catalysts. Grace helps customers to bed alloy), as well as the traditional fine-sized slurry form to allow improve processes and end product by tailoring catalysts to meet customers to design processes which best meet their unique specific demands. In a typical joint catalyst development program, needs. RANEY® catalysts have proven highly efficient in fixed-bed catalyst samples with modified properties are prepared by Grace continuous operation and Grace chemists work extensively with and tested at your site. customers in developing and perfecting fixed-bed applications.

Grace works closely with its customers, helping to improve processes and end product by tailoring catalysts to meet specific demands.

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RANEY® Nickel Slurry Catalysts RANEY® Fixed-bed Catalysts ® Multi-purpose A number of hydrogenation catalysts offer high activity in a applications require a fixed-bed variety of applications, plus rapid operation for better performance settling in most liquids, facilitating and economics. Grace offers a catalyst-product separations. Our range of fixed-bed catalysts based nickel grades differ from one another on nickel, cobalt or copper with primarily in particle size distributions, a range of particle sizes to meet aluminum content, and internal pore customer requirements. The fixed- structures. Such distinctions often bed catalysts are unique with an favor the use of one catalyst type activated surface and dense core over another in a given application. providing high particle strength and Customers can request a customized lower attrition along with optimum Slurry catalyst Fixed-bed catalyst catalyst, tailored for specific needs. activity for the reaction. Grace offers a wide range of unpromoted nickel slurry catalyst. Grace also offers a range of promoted RANEY® catalysts containing one or more promoters to improve performance in chemical reactions in which unusual demands are placed on the catalyst’s activity or selectivity or in a particularly harsh reaction medium.

For example, in the use of iron and chromium promoted nickel for reduction of nitriles to amines, and the use of molybdenum promoted nickel for conversion of dextrose to sorbitol, the promoted catalysts far surpass the performance of unpromoted nickel.

RANEY® Cobalt Slurry Catalysts Similar to nickel catalysts, cobalt-based compositions can be Fixed-bed alloys in different particle sizes promoted or unpromoted, with similarly improved selectivity through promoters. Cobalt catalysts are useful when the high activity RANEY® Fixed-bed Alloys of nickel leads to unwanted side reactions such as hydrogenolysis. Examples of cobalt catalysts demonstrating outstanding Grace also supplies unactivated fixed-bed alloy for applications performance in specific reactions include an unpromoted version such as butanediol where the customer does the activation in-situ. in partial hydrogenation of cyclic diolefins to olefins, and a Cr-Ni We can supply alloys of any standard composition with particle promoted version in nitrile-to-amine conversions. sizes that meet customer requirements. The advantages of a Fixed-bed catalysts are continuous processing; RANEY® Copper Slurry Catalysts high activity; effectivness at low reaction temperatures; short Copper-based catalysts extend to even more specialized and/ diffusion paths; high strength of “core” for reduced attrition; and or selective types. Forms of RANEY® copper can be used, relatively easy reactivation. for dehydrogenation, oxidation, ester hydrogenolysis, and chemoselective hydrogenation, as in the case of carbonyl reductions. Fixed-bed Conventional ® As with nickel and cobalt, copper is sometimes combined with RANEY Catalyst Fixed-bed Catalyst promoters which alter activity, selectivity, and stability.

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Customizable RANEY® Catalysts for Other Specialty Applications

Catalysts Application Examples Acetylenes to olefins 2-hexyne to 2-hexene Diolefins to olefins 2-methyl-1, 3-butadiene to 2-methyl-1-butene Alkenylaldehydes to alkylaldehydes 2-butenal to butanal Unsaturated aldehydes to unsaturated alcohols 2-butenal to 2-butene-1-ol Desulfurization of fuels Gasoline and chemicals, e.g. animal fat Ester hydrogenolysis into alcohols Dimethyl succinate to tetrahydrofuran Highly selective hydrogenations Nitrochlorobenzene to chloroaniline C-C hydrogenolysis 1-methylcyclopropylbenzene to 1-methylpropylbenzene C-O hydrogenolysis Glycerine to propylene glycol

Grace Global Capabilities

R&D and Manufacturing Grace has over 60 years of R&D experience in developing and customizing catalysts for wide range of applications globally. Grace engineers are experts at the scale up of new products and processes as well as the supervision and process control of pilot scale catalyst manufacturing. Our skilled engineers apply the troubleshooting techniques used on our own processes to solving catalyst usage and handling problems for customers.

RANEY® Catalysts Manufacturing Process Grace’s Chattanooga, TN, RANEY® manufacturing plant. Aluminum Metal Reaction Nickel Metal • Experienced catalytic scientists R&D Center, • Extensive catalyst Cooling Columbia, MD characterization capability • Catalyst evaluations capability Crushing and Grinding • 100 Kg quantity

Scale-up, • Process engineering Fixed-bed Catalyst Slurry Catalyst Chattanooga, TN • Full-scale production simulation Activation Activation • Adjacent to manufacturing plant Fixed-bed Fixed-bed Alloys Slurry Catalysts • Flexible processing Catalysts Manufacturing, • Batch processing capability Chattanooga, TN • Expert technical staff • Superior quality

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Analytical and Characterization Tools Grace uses a variety of chemical and physical instruments to characterize RANEY® alloys and catalysts, whether produced at research or manufacturing scale. Statistical process control (SPC), product quality control (QC), and certificate of analysis (COA) tools include: • ICP-APS (bulk chemical analysis) • Laser light-scattering method for particle size distribution • Settling rate tests • Pulse-flow sorptometer for surface area and chemisorptions

In research, where feedback about possible improvements in catalyst quality is desired, or in technical service, where in-use handling characteristics or deactivation mechanisms are studied, additional non-standard techniques are sometimes used, including: • X-ray Photoelectron Spectroscopy (XPS) for chemical analysis • Scanning Election Microscopy (SEM) Fixed-bed reactor column • Electron microprobe / Auger Electron Spectroscopy (AES)

Global Technical Service Automated processes have been implemented, and all customer representatives are thoroughly trained. We focus on the details, so In addition to developing, manufacturing, and delivering catalyst, that our customers can concentrate on the more important aspects Grace plays a critical role in: of their business.

A Commitment to Quality Custom On-site Catalyst Catalyst Reactor Grace is committed to being a competent, reliable, and high- Selection Development Loading quality partner. Since 1995, this commitment to quality has been continuously recognized by maintaining ISO 9001 certification for RANEY® catalysts. And we maintain quality systems to ensure customer satisfaction and continual improvement.

Bench-scale Catalyst Spent Catalyst Testing for Screening Analysis International Standards, Manufacturing Evaluations Processes, and Regulations Certified RANEY® catalysts comply with all major international standards including stringent adherence to manufacturing Grace’s technical service capacity extends across catalysts’ life processes and regulations. Certifications include: cycles. Grace will advise on the use and handling of catalysts; make recommendations for the deactivation and proper disposal • ISO 9001 • Kosher of spent catalyst; and perform post-mortem studies to determine • HALAL • REACH causes of catalyst poisoning or deactivation. Health and Safety Customer Service Solutions Responsive, personal service, individualized to each customer, Our activities are coordinated through an EHS Management is the benchmark of Grace’s customer service philosophy. Our System that has been audited and certified by a third-party comprehensive service facilitates communication and problem registrar for meeting the requirements of the American Chemistry solving and makes it easy to obtain accurate information on pricing, Council, the gold standard for the industry. The management product, and availability quickly. system serves as the framework for Grace’s global EHS activities.

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A Global Technology Leader Grace Sales by Region Latin America Built on talent, technology, and trust, Grace high-performance specialty chemicals and materials improve the products and Europe Asia processes of our customer partners around the world. Middle East Pacific $1.6 Africa Grace is a recognized global leader in fluid catalytic cracking billion1 (FCC) catalysts, hydroprocessing catalysts, and specialty catalysts. Grace’s specialty catalysts portfolio includes polyolefin catalysts, RANEY® catalysts, and DAVICAT® catalysts. North America

1 Sales based on FY2016

Global Headquarters Columbia, MD, USA

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* Planned Site Manufacturing R&D and Technical Service 22 facilities in 11 countries 9 facilities in 7 countries grace.com

Grace Corporate Headquarters Regional Locations W. R. Grace & Co.-Conn Latin America Asia/Pacific Europe 7500 Grace Drive São Paulo, Brasil Shanghai, China Worms, Germany Columbia, MD 21044 USA Tel: +55.11.4197.7540 Tel: +86.21.3325.8288 Tel: +49.6241.40300 Tel: +1.410.531.4000 For more information about RANEY® catalysts, visit: grace.com/chemical-processing/en-us/chemical-catalysts

The information presented herein is derived from our testing and experience. It is offered for your consideration and verification. Since operating conditions vary significantly, and are not under our control, we disclaim all warranties on the results that may be obtained from the use of our products. W. R. Grace & Co.-Conn. and its subsidiaries can not be held responsible for any damage or injury occurring as a result of improper installation or use of its products. Grace reserves the right to change prices and/or specifications without prior notification. GRACE®, RANEY®, and DAVICAT® are trademarks, registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. TALENT TECHNOLOGY TRUST™ is a trademark of W. R. Grace & Co.-Conn. This trademark list has been compiled using available published information as of the publication date of this brochure and may not accurately reflect current trademark ownership or status. © Copyright 2017 W. R. Grace & Co.-Conn. All rights reserved.

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