CRYOSIV Desiccants for Refrigerant Drying. Grace Davison Materials & Packaging Technologies. Enriching Lives, Everywhere.

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1 CRYOSIV Desiccants for Refrigerant Drying Grace Davison Materials & Packaging Technologies Enriching Lives, Everywhere.

2 Index Product Range 2 The Company 3 Safety First You Keep It Cool. We Keep It Dry. 4 A Look at the Desiccant s Backstage Grace Makes the Difference Make the Right Choice 5 Product Portfolio CRYOSIV Desiccants Main Properties 6 Technical Service, 7 Our Experience Your Success Our Support Innovation and Quality 8 Research & Development Quality Management The Lean Six Sigma Advantage Manufacturing at Grace Quality Guaranteed 9 REACH Product Range CRYOSIV Desiccants for Refrigerant Drying PHONOSORB Beaded adsorbents for insulating glass SAFETYSORB Desiccants for the pharmaceutical and diagnostic applications SYLOSIV Molecular sieve powder for the polyurethane industry SYLOBEAD Adsorbent for OEM Industry SYLOID Matting agents for coatings DARACLAR Beer stabilisers TriSyl Silica gel for refining edible oil SYLOBLANC /SYLODENT Abrasive and thickening agents for toothpaste SHIELDEX Non-toxic anti-corrosion pigments SYLOJET Pigments for Ink Jet Coatings LUDOX Colloidal Silica SYLOWHITE Titanium dioxide extenders for paints and printing inks ELFADENT Thickeners/mild abrasives for the toothpaste industry You Keep It Cool. We Keep It Dry. PERKASIL Reinforcing agents for the tyre and rubber industry DURAFILL Special pigments and fillers for the paper and pulp industry APPERTA Can Coatings DAREX Can and Closure Sealants Sistiaga Can Coatings Celox Oxygen Scavengers Sincera Closure Sealants 2 GRACE, GRACE DAVISON, APPERTA, CELOX, CRYOSIV, DAREX, DARACLAR, LUDOX, PHONOSORB, SAFETYSORB, SHIELDEX, SINCERA, SYLOBLANC, SYLODENT, SYLOID, SYLOJET, SYLOSIV, TRISYL and ENRICHING LIVES, EVERYWHERE. are trademarks, registered in the United States and/or other countries, of W. R. Grace & Co.-Conn. SISTIAGA is a trademark, registered in the United States and/or other countries of Grace, S.A., Grace, S.A. is a wholly owned subsidiary of W. R. Grace & Co.-Conn. SYLOWHITE is a trademark of W. R. Grace & Co.-Conn. ELFADENT, DURAFILL, and PERKASIL are trademarks, registered in the United States and/or other countries, of Grace Silica GmbH. Grace Silica GmbH is a wholly owned subsidiary of W. R. Grace & Co.-Conn. SIX SIGMA is a trademark, registered in the United States and/or other countries of Motorola, Inc. This brochure is an independent publication and is not affiliated with, nor has it been authorized, sponsored, or otherwise approved by Motorola, Inc. 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 2010 W. R. Grace & Co.-Conn. All rights reserved.

3 The Company Grace Davison is a business division of W.R. Grace & Co. one of the world s largest companies for specialty chemicals. Grace Davison has a focus on silica technology and silica/ aluminium oxide technology products. We produce a wide range of products including synthetic amorphous silica gel, colloidal and precipitated silicas, zeolites, silicic acid and materials for chromotography. This extensive material portfolio has contributed to Grace Davison's position as a leading global supplier of silica and zeolite adsorbents and catalysts. These specialty chemicals improve product performance or enhance manufacturing processes within a wide range of industrial applications. Our key strengths lie in the development of innovative technologies through which product quality and application characteristics are improved. Manufacturing flexibility, global infrastructure and the commitment of our company to close customer relationships are factors which provide high levels of customer satisfaction. With manufacturing sites, research & development centres and sales offices around the globe, we are well prepared to meet the challenges of global market requirements. When it comes to sales, marketing and technical customer services, our business structure combines the strengths of a globally operating company with the flexibility and ability to adjust to regional infrastructure. In order to guarantee a constantly high level of product quality, all of Grace s sites are ISO certified and carry out Quality Management Systems. With our sales offices in all key countries, we are able to quickly react to the needs of our customers. Safety and environmental considerations are the main points that our company focuses on. Products which are tailored to the needs of the customer, punctual deliveries, specialist technical support at a high level and a reliable customer service department are all factors that go to make Grace a preferred supplier within the industry. Safety First Our first priority is to ensure the safety of all those who work with us or come into contact with our products. Safety data sheets and information concerning the way in which Grace s products adhere to application-related provisions are available on request. At Grace Davison, the environment is a major issue and we are proud to maintain an outstanding record of leadership in safety standards and good corporate citizenship. Through the Responsible Care Program, every Grace Davison facility worldwide fulfills both stringent health and safety requirements as well as environmental requirements. It demonstrates the high priority of work safety within the organisation, which has led to a substantial reduction in workplace injuries, bringing the company close to the goal of zero. 3 European Headquarters Worms, Germany

4 You Keep It Cool. We Keep It Dry. Grace, a major producer of molecular sieves, has for many years supplied desiccants for drying of refrigerants. Although we don t influence the functionality of the refrigerant cycle, Grace Davison CRYOSIV desiccants can ensure that you can maximize the lifetime of your closed loop desiccant system. Grace Davison desiccants are de signed to offer low dusting, mechanical strength and selec tive adsorption of moisture which could result in ice for ma tion in expansion valves, capillary tubes and evaporators, corrosion, hydrolysis of lubricants and sludge formation leading to early failure of your refrigerant system. The transition from the use of CFC refrigerants to chlorinefree alternatives at the end of the last century, as required by the Montreal Protocol, led to the introduction of a great variety of new refrigerants, refrigerant blends, and lubricants with different chemistries. Meanwhile even more stringent requirements regarding environmentally safe refrigerants were put in place. Europe is taking the lead here. From 2011 on, the European Union will phase out refrigerants with a Global Warming Potential (GWP) of more than 150 for automotive air conditioning. A Look at the Desiccant s Backstage There are several products available for adsorbing water including alumina and silica gel. But synthetic zeolites, also called molecular sieves, are the most selective type of desiccants. Zeolites are crystalline alumosilicates with a unique structure. Their defined structure and pore size ensures the adsorption of some molecules and the occlusion of other molecules. Since they work as a screen, we refer to this as the molecular sieve effect. The zeolites which are used to dry refrigerants are strongly hydrophilic. They have a high affinity towards water molecules. The most selective and efficient zeolites for water adsorption have a maximum pore size of 3Å. Grace s strategy has always been to offer universal desiccants, which are compatible with all refrigerants. The projects Grace initiated regarding the development of new desiccants for refrigerant drying are oriented on common standards, given by European organizations like VDA, as well as North American organizations like ASHRAE. CRYOSIV Beads, Zeolite Crystals, Crystal Structure Grace Makes the Difference CRYOSIV molecular sieves are designed to fulfill all requirements for usage in a refrigerant cycle. 4 Development 1929 First commercial Production of CFC s 1987 Montreal Protocol 1998 Phase-out of CFC s, e.g. R 12 in Germany 2000 Phase-out of CFC s in Europe 2000 Phase-out of HCFC s, e.g. R 22 in Germany 2008 Phase-out of HCFC s in Europe 2011 Refrigerants with GWP < 150 are required in Europe The main task of the desiccant is to keep the refrigerant dry, at all times independent of whether the dryer is installed in the liquid or in the gas phase of the refrigerant system. Targeting a high adsorptivity, Grace s universal CRYOSIV desiccants guarantee compatability with all common refrigerant types and have an extraordinary high selectivity for moisture. By minimizing co-adsorption of the refrigerant by the zeolite, any side reactions of the refrigerant or lubricants catalyzed by the zeolite lattice can be prevented. CRYOSIV desiccants satisfy the highest quality demands in the applications of refrigerant drying: < High adsorptivity for water, to ppm levels < Long system lifetime < Excellent chemical compatibility with common refrigerants and lubricants.

5 Make the Right Choice Using molecular sieves in refrigerant drying requires a number of properties to ensure a long lifetime and the best performance. The CRYOSIV product portfolio from Grace offers several products, developed by experts taking not only in account the chemical/physical properties of zeolites but also the application related requirements. Refrigeration Circuit Driers may be installed in the liquid line (compression line) or in the vapor line (suction line). When applying desiccants in refrigerant drying the following questions need to be answered: < Which refrigerant and lubricant is/are used? < Is the dryer installed in gas or in liquid phase? < How much water needs to be adsorbed over a certain time period? < What pressure/temperature conditions are present in the refrigerant cycle? < Are there other mechanical demands with regard to the dryer? Compression Line Drier Compressor < How is the desiccant incorporated: < In a cartridge? < As a solid core? < As a multifunctional part? Expansion Valve Suction Line < What is the required lifetime of the drying system? Evaporator < Are there any parts with a higher water vapor transmission rate (e.g. plastic pipes) which could require higher adsorption capacity? Product Portfolio CRYOSIV Desiccants Zeolite Grade Bead Size (mm) Main Usage 3A 4A loose fill solid core Application Comment MS Standard grade compatible with all common refrigerants, high mechanical strength, high water adsorption, excellent compatibility, avoids co-adsorption. MS Standard grade compatible with all common refrigerants, high mechanical strength, high water adsorption, excellent compatibility, avoids co-adsorption, reduces pressure drop. MS Premium grade for R744, high mechanical strength, excellent water adsorption kinetics, excellent compatibility. MS Highest water adsorption capacity per volume unit, good compatibility with binder systems in solid core manufacturing. MS 511H (EU) High water adsorption capacity per volume unit, MS 422S (US) good compatibility with binder systems in solid core manufacturing, pre-wetted grade. MS C High water adsorption capacity per volume, good compatibility with binder systems in solid core manufacturing, avoids co-adsorption, chloride reduced. 5

6 CRYOSIV Desiccants Main Properties CRYOSIV products are especially designed to be highly compatible with the components used in a refrigerant cycle and therefore have the following properties: < High water adsorption capacity and kinetics, per volume unit < Excellent dry down behavior in liquid or gas phase < Good moisture selectivity < Superior mechanical properties in terms of crush strength and attrition < Excellent compatibility with all common refrigerants and lubricants H 2 O R152a R134a R744 R22 R125 R143 R32 R410a The Molecular Sieve Effect High Water Adsorption To meet the dryer specifications of our customers and to ensure the highest possible adsorption capacity per volume unit, the bulk density of the product has been optimized to provide the best ad sorption properties. A well defined bead size distribution guarantees efficient filling of the molecular sieve in dryer cartridges. Uniform zeolite crystals in the molecular sieve beads manufactured in a well established process ensure consistent adsorption properties. Mechanical Properties Desiccants in air conditioning systems are exposed to two mechanical forces. The first is pressure caused by the flow rate in the systems. The second are vibrations, for example in car air conditioning systems while driving. Dry Down Behavior No matter whether the desiccant is installed in liquid or gas phase of the cycle, the water uptake has to be fast within a given stream. The clay bound granules in bead shape have a smooth surface yet possess a certain macro- and micro-porous structure which ensures a fast transportation of the water molecules towards the adsorption sites in the zeolite lattice. Selectivity Selectivity means avoiding co-adsorption of refrigerant. Even if water molecules will always win in competitive adsorption compared to the refrigerant molecules when using hydrophilic molecular sieves, there can be concerns of unwanted co-adsorption of small molecule refrigerants, and a certain reactivity at the adsorption sites. Therefore, the pore openings are designed to have the appropriate size to allow water molecules to enter and to exclude larger, less polar substance. Grace controls these properties by applying tests according to ASHRAE standards for analyzing crush strength and attrition. Compatibility Grace ensures the compatibility of all CRYOSIV products with the most common refrigerants and lubricants by inhouse experiments, and by tests at authorized external institutes, especially in the case of new refrigerants released within the refrigerant industry. Our products are tested regarding European and US standards to prove compatibility. 6

7 Technical Service Our Experience Your Success Grace has a long history in supporting desiccant usage in the refrigerant drying application. Our technical experts accompanied the development of refrigerants from the Montreal Protocol 1987 on, including the phase-out of CFC s as well as the later phase-out of HCFS s at the beginning of this century. The active participation in associations like ASHRAE give us the opportunity to better understand the requirements of our customers and to serve them with relevant results within all stages of the refrigerant history. In a closed loop, under defined pressure and temperature, using a defined amount of refrigerant and molecular sieve, certain amounts of water are injected. After dosing the water the dry down behavior is measured and the time registered until the moisture content of the refrigerant is below 60 ppmw. This is repeated several times until a moisture increase is observed in the refrigerant. The cooperation with specialized institutes and independent laboratories enables us to provide our customers with independent analytical results for compatibility testing and dry-down behavior. The most recent environmental targets have lead to the usage of green refrigerants, having a Global Warning Potential (GWP) lower than150 which require a number of investigations and lab testing. We strive to have the best compatibility with all components in the system, including oil and metal parts. Following are just two examples of the services Grace is offering to customers, and we can do more. 1 Compatibility is tested in a sealed tube test according to the ASHRAE standard and is done either in-house or together with a major German institute. In the compatibility studies we test and analyze the following: < moisture content of the refrigerant < trace metals in the lubricant by ICP < total acid number < appearance of the metal strips before and after testing < functionality of the CRYOSIV Desiccant 2 When all compatibility criteria are met we than test the adsorption kinetics and adsorption capacity of our CRYOSIV Desiccant in a dry-down test. Line Diagram of Test Ring for Dynamic Measurements This is a typical drying-down behavior of CRYOSIV Desiccants and can be influenced by selecting the right CRYOSIV Desiccants type for your requirements. The main parameters for the right choice are compatibility, adsorption kinetics and mechanical strength. Our Support < Complete analysis of molecular sieves < Support in defect search (trouble-shooting) in case of field problems by using analytical tests including SEM or ICP < Gas phase adsorption tests for specific substances < Drying-out tests in static systems < Compatibility tests of desiccants under customized conditions < Determination of water adsorption isotherms < Sealed tube test according to ASHRAE standard < Dynamic drying-out tests (defined water injection, quantify the kinetics) Grace stays on top of requirements and developments on the market by participating in regional as well as ASHRAE meetings. A typical drying-down process flow chart 7

8 Innovation and Quality Research & Development Grace Davison is a firm believer in driving innovation. Our researchers are continuously working to improve the quality of existing products and seeking ways to broaden our product range in order to fulfill the increasing requirements of our customers. In order to meet the needs and expectations of our customers, the Quality Management program includes the functional divisions of sales and marketing, research and development as well as customer service. Our dedicated work force is our most important asset and customer satisfaction is our most important objective. With R&D centers in Columbia, MD/USA and Worms/ Germany, Grace has over 80 years of experience and expertise in the development of adsorbents for numerous industries. Modern laboratory facilities enable us to carry out a range of chemical/ physical characterization experiments and we are able to carry out application testing in our technical center. Being familiar with refrigerant drying processes, our technical experts can develop sophisticated solutions for different technologies. Besides several beading materials, we can offer powder products or zeolites bound in polymers. Those products open the door for new applications and show zeolites/desiccant in a new light. The usage of them in a multifunctional way is quite new and unique. Grace considers itself as an idea creator and driver, always with the target to find new solutions in customer applications and to increase the added value of our customer s products. The Lean Six Sigma Advantage At Grace Davison, Lean Six Sigma is part of the company s culture for more than 10 years. To maintain Grace Davison s high process standards, we employ the Lean Six Sigma tools as an integral component of continuous improvement. These were designed to investigate process parameters, quantify their effects and optimize them in order to achieve the best possible results. Our Lean Six Sigma initiative aims at improving both product consistency as well as production flexibility using advanced statistical methods and evaluation procedures. Our customers benefit from products of the highest quality. Quality Management Our Quality Management System takes a customer centric approach and is based on Grace Davison s philosophy of continuous improvement in every area of the organization. < All our facilities are ISO 9001 certified (our Worms plant is also ISO certified) and we implement internal and external audits to find ways to improve our services and processes. < We employ the latest Statistical Process Controls (SPC) to monitor and analyse production and related work processes. < We continuously monitor and improve our processes by using Six Sigma & Lean Management tools < Our well-equipped Quality Control department works around the clock to ensure constant product quality. < We continuously collect and assess customer information and feedback as an important factor in our QM program. 8

9 Manufacturing at Grace Quality Guaranteed In order to ensure quality and consistency, Grace Davison uses state-of-the-art technologies and processes in the manufacturing of adsorbents. Our operations are committed to a Quality Management System and we have set ourselves the target of exceeding environmental and work safety requirements. Molecular sieves are manufactured by crystallisation of aluminium hydroxide, sodium hydroxide and sodium silicate. Under carefully controlled conditions, the crystallisation process produces the required sodium aluminium silicate structure. In a subsequent step, the zeolite crystals undergo an ion ex change through which the desired pore dimension is set. After drying the molecular sieve crystals, a small quantity of binder is added, forming the material into beads. These beads are then dried and calcined, and at the final stage, any dust is removed and they are screened to the required particle size prior to packaging. Grace s desiccants are permanently subject to the strict control of our quality department, which operates around the clock to ensure a high level of product quality. In our production operations, we employ the latest statistical process control (SPC) techniques in order to monitor and analyse production and related work processes, as well as strive for continuous process improvement using Grace s Six Sigma tools. These were designed to investigate process parameters, quantify their effects and to optimize these in order to achieve the best possible results. As a premier specialty chemicals company, it is one of Grace's utmost priorities to comply with all relevant legislation, including REACH. Therefore, in November of 2008 we undertook extensive efforts to achieve compliance of all our products, substances and formulations. Since the beginning of 2010 our main products including synthetic amorphous silica, zeolites and synthetic amorphous silicates are all registered under REACH. Regardless of which product you buy from us in the EU, you can be assured that all necessary steps have been taken to ensure continuous and smooth supply of your products. REACH Information Portal To better answer the increasing number of customer requests, we have established an interactive internet web - page On this website you will find our standardized statements regarding the implementation status for REACH, as well as the registration status of our manufactured substances. Please follow the given guidelines so that you will receive an access code for the individual search portal of Grace pre-registration/reference numbers. The search function is based on the CAS no., which is provided in Chapter 3 of the product MSDS. Grace has committed itself to further using these methods in order to continually improve the production processes. Our customers benefit from our endeavors by obtaining products of the highest quality. Quality you can count on. 3 Ion-exchange Tank 5 Filter 1 Crystallisation Tank 6 Silo 8 Screening 9 Drier 10 Activator 2 Vacuum Filter 4 Drier CRYOSIV Desiccant Packaging Production of CRYOSIV Molecular Sieve 7 Granulation 9

10 Grace is a premier specialty chemical and materials company with more than 6000 employees located around the world. Our products are used by millions of people each day. Among many other things, we ensure the integrity of some of the world s major buildings and bridges, enhance the performance of your petroleum products and preserve the safety of your food. Grace Davison has successfully pre-registered all REACH relevant substances. The next step is the ongoing preparation of the required registration dossiers and final registration of our substances. Grace Davison has already fully registered its synthetic amorphous silica and zeolites. Now our customers can have confidence in REACH compliance and supply security beyond Non-EU customers should contact us about their import needs. World Headquarters W. R. Grace & Co.-Conn Grace Drive Columbia, Maryland 21044/USA Tel.: NA Toll Free: Fax: North America Latin America Europe Asia/Pacific W. R. Grace & Co.-Conn. Grace Brasil Ltda Grace GmbH & Co. KG Grace China Ltd. 62 Whittemore Ave. Rua Albion, o andar, cj 104 In der Hollerhecke 1 19th Floor, K Wah Centre Cambridge, MA 02140/USA Lapa, São Paulo - SP/Brasil Worms/Germany 1010 Huai Hai Zhong Road Tel.: Cep Tel.: Shanghai, / China Fax: Tel.: Fax: Tel.: Fax: Fax: The information contained herein is based on our testing and experience and is offered for the user's consideration, investigation and verification. WARRANTIES EXPRESSED OR IMPLIED, regarding results obtained from the use of our products, MUST BE DISCLAIMED since customer operating and use conditions vary and are beyond our control. Test methods are available on request W. R. Grace & Co.-Conn. All rights reserved. Printed in Germany / June 2010 / Ref: cryosiv_br_e / studiohauck Enriching Lives, Everywhere.