PEP Review CONTINUOUS SAP PRODUCTION VIA DOUBLE KNEADER REACTOR By Anthony Pavone (November 2011)

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1 PEP Review CONTINUOUS SAP PRODUCTION VIA DOUBLE KNEADER REACTOR By Anthony Pavone (November 2011) ABSTRACT Superabsorbent polymer (SAP) is a partially neutralized homo-polymer of glacial acrylic acid (with internal and surface cross-linking) that has found widespread commercial use as a liquid absorbent in baby diapers, adult incontinence products, feminine hygiene products, electric cable wrap protection, fire fighting, planting soils, and as a thickener in cosmetics and coatings. As global demand for SAP has increased to 2 million metric tons per year in 2011, production plants have gotten larger in capacity, bulk customers have demanded more consistent product composition, and buyers have naturally demanded product at lower cost. In response to these market inputs, the major SAP producers (Evonik, Nippon Shokubai, BASF) have developed process technology to convert the manufacturing operation from bulk production to continuous production. As glacial acrylic acid is polymerized to produce SAP, it forms a sticky, wet gel with very high viscosity that is impossible to pump, As a result, historically, batch polymerization was conducted in shallow, horizontal trays on a flat conveyor belt that was processed through a modest temperature air furnace to complete the conversion of monomer to polymer, and conduct the separate unit operations for internal and surface cross-linking. While in process, the SAP gel was sliced into manageable chunks (1 3 cm) to enhance the drying operation. Once dry, the SAP chunks are pulverized to a fine powder product with an average size range of microns. In this review we develop an alternate, continuous SAP production process that relies on BASF s patent estate for kneader-reactor technology. The technology employs a horizontal, kneader-reactor design by LIST AG (Switzerland) whose internals contain two or more interleaved and counter-rotating shafts along the horizontal axis of the reactor. The shafts are fitted with blades for slicing the SAP gel into small particles, and T or L shaped arms for kneading the polymer gel such that it flows with a nearly plug flow profile through the reactor operating between C, and 500 millibar operating pressure. Estimated capital investment and production costs are summarized below. Capacity (mt/y) Investment ($ million) Total Fixed Capital Production Cost ($/mt) At 100% Capacity 3, , ,145.1 SRI Consulting, IHS Inc. PEP Review

2 A private report by the Process Economics Program Review No CONTINUOUS SAP PRODUCTION VIA DOUBLE KNEADER REACTOR by Anthony Pavone November 2011 Menlo Park, California 94025

3 SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client s use of the reports or other deliverables produced by SRIC pursuant to this agreement. For detailed marketing data and information, the reader is referred to one of the SRI Consulting programs specializing in marketing research. THE CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons and their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.

4 CONTENTS INTRODUCTION... 1 VALUE PROPOSITION... 2 SCOPE OF REPORT... 2 SAP INDUSTRY STATUS... 3 SAP CHEMISTRY AND PROCESS TECHNOLOGY... 5 SAP Product Chemistry... 5 SAP Polymerization Chemistry... 6 Choice of Solvent... 9 Conventional, Commercial SAP Manufacturing Sequence Reaction Initiators Reaction Start-Up Reaction Kinetics Cross-Linking Agents Chain Transfer Agents Chelating Agents Dispersing Agents Residual Monomer Conversion Reactor Cooling Neutralization Reactor Product Washing Extractable Polymer Content Polymer Gel Size Reduction Polymer Drying Solvent Recovery Polymer Milling DESIGN BASIS FOR BASF PROCESS TECHNOLOGY SAP Product Specifications BASF KNEADER-REACTOR PROCESS TECHNOLOGY SRI Consulting, IHS Inc. iii PEP Review

5 CONTENTS (Concluded) Rationale for Continuous SAP Production First Commercial Migration to Continuous SAP Processing BASF Migration to Continuous SAP Processing BASF Continuous Horizontal Kneader-Reactor SAP Technology Chemicals Mixed and Reacted Conditions under Which Reaction Occurs Means for Managing Exothermic Heat of Reaction SAP Reactor Apparatus Composition of SAP Reactor Product Post Reactor Processing BASF KNEADER-REACTOR PROCESS DESIGN Block Flow Diagram Process Flow Diagram and Process Description Material Balance Equipment List PRODUCTION ECONOMICS Itemized Capital Cost Estimate Total Fixed Capital Cost Variable Production Costs Fixed Production Costs Measures of Profitability REFERENCES SRI Consulting, IHS Inc. iv PEP Review

6 FIGURES 1 SAP Producer Global Market Share Posted U.S. Historic SAP Prices Chemical Structure of Polyacrylic Acid Structure of Partially Neutralized Polyacrylic Acid with Cross-Linking Agents Collapsed (Dry) and Expanded (Gel) State of Water Soluble Polymer Chains Free Radical Polymerization of Acrylic Acid Monomer Impact of ph on SAP Absorption Rate The Commercial Manufacture of Superabsorbent Polymer Block Flow Diagram Polyacrylic Acid Relative Reaction Rate as a Function of ph Use of N 2 Sealed Endless Screw Conveyors BASF Continuous Reactor SAP Process Block Flow Diagram BASF Horizontal Continuous SAP Reactor (USP 4,769,427) LIST AG Kneader-Reactor Internals (USP 6,039,469) LIST AG Kneader-Reactor Shaft Attachments (USP 6,039,469) LIST AG Kneader-Reactor Vessel (USP 6,039,469) Kneader Reactor Block Flow Diagram Continuous SAP Production via Double Kneader Reactor (1 of 2) Process Flow Diagram Continuous SAP Production via Double Kneader Reactor (2 of 2) Process Flow Diagram SRI Consulting, IHS Inc. v PEP Review

7 TABLES 1 Major SAP Producers Taylor Screen Size versus Particle Size Representative SAP Product Specifications BASF Patents for SAP Continuous Horizontal Kneader Reactor Producing Superabsorbent Polymer by Continuous SAP Kneader-Reactor Polymerization Stream by Stream Material Balance Equipment List with Duty Specifications Itemized Capital Cost Estimate Total Fixed Capital Cost Estimate Unit Pricing Used in Economic Analysis Continuous Process SAP Unit Variable Costs Assumptions for Fixed Cost Calculations SAP Production Cost Estimate SAP Profitability Estimate SRI Consulting, IHS Inc. vi PEP Review

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