Three Novel Wax Removal Methods for Wax Containing

Three Novel Wax Removal Methods for Wax Containing Old Corrugated Containers: Carbon Dioxide Extraction, Kraft Pulping and Agglomeration Richard A. Venditti, John F. Kadla, Richard D. Gilbert, Hasan Jameel, Hou-min Chang North Carolina State University Department of Wood and Paper Science

Background • Waxboard products are a $3 billion a year business • Currently wax containers are separated from OCC and landfilled • Problems associated with wax products in recycling Wax deposits on paper machine – Lower paper physical properties –

Important Characteristics of Waxes: Main Component is paraffin wax Based on hydrocarbons and as such are hydrophobic. Are soluble in organic solvents. Are not strong/tough materials. Have low viscosity. Melt at temperatures around 125 F. Often have higher molecular weight modifiers Serve to strengthen the wax film. Increase melting point. Decrease solubility in organic solvents.

Strategy of the Research: • Wax and fibers are significantly different in their properties and these differences can be exploited for separation purposes – (1) Dispersion/emulsification tendency in a water based phase: Can this be exploited to wash the wax away in kraft cooking liquors? – (2) Hydrophobicity: Can this be exploited to agglomerate and screen the wax in the water phase? – (3) Solubility: Can this be exploited to extract the wax by supercritical CO 2?

Can Wax-OCC be Processed in a Kraft Digester • Hypothesis: The high temperatures and presence of fatty acids in a kraft digester will stabilize wax in the liquor. • Approach: use a pilot plant digester to compare the pulping performance and resulting pulps from – Control: 100% Hardwood Chips – Trial: 90% Hardwood Chips and 10% Wax-OCC

Kraft Pulping of Hardwood Chips and Waxed OCC Blends 100% HW or 90% HW 10% WOCC M&K Digester AA % = 18 S% = 25 L/W=4 T= 335 F H-factor= 800 Rinsed with 40 liters of 180 F Water Disintegrated Screened 0. 014 inch slots Screened Pulp for Testing

Kraft Pulping HW-WOCC Blends Pulping Results: 100% HW 90/10 HW/WOCC Screening Accepts (%) 46 47 Kappa Number 16. 2 14. 8 Viscosity 30. 4 26. 2 Hexane Extractives in Accepts(%) 1. 4 0. 5 Black Liquor Solids (g/l) 177 183

Kraft Pulping HW-WOCC Blends Paper Properties : 100% HW 90/10 HW/WOCC CS Freeness (ml) 650 635 Density (g/cm 3) 0. 63 0. 70 Breaking Length (Km) 5. 4 6. 0 STFI (klbf ft/lb) 9. 1 9. 9 Slide Angle (degrees) 20. 5 22. 5

Summary of Processing Wax-OCC in a Kraft Digester • Comparison of 10% level of Wax-OCC in HW chips to a 100% HW chips control – The resulting pulp extractives % were similar – The paper properties were similar – No operating difficulties were experienced in the pulper, disintegrator or screen

Can Wax-OCC be Agglomerated in a Re-pulper and Screened? • Approach: use lab-scale pulper to evaluate pulping conditions on the agglomeration and dispersion of the wax in the pulper. Investigate: – – – Time Temperature Consistency p. H Agglomerating Agents

Agglomeration Process Curtain Coated Waxboard (16. 5% Wax, m. p. = 64 C) Tap Water Pulmac Screen (0. 006 inch slots) Collection Screen (150 mesh) Rejects (Fisher Filter Paper - P 8) Filtrate Accepts

Material Balance around Pulmac Screen and Collection Basket Pulmac Screen Collection Basket Feed Accepts Fiber Wax Rejects Fiber Wax Filtrate Fiber and fines Wax Losses (filtrate) = Feed - Rejects - Accepts

Effect of Pulping Temperature on Wax Distribution 5% K, 30 min.

Effect of Pulping Consistency on Wax Distribution 70 C, 30 min

Summary of Pulping and Agglomeration • Wax detachment is promoted by low consistency and temperatures greater than the mp of wax (less than 1% remaining on fiber) • Agglomeration is promoted by low consistency • Dispersion is promoted by high consistency • Simple lab air flotation removed 80% of the wax from the wash filtrates • The addition of “agglomerating” chemicals did not enhance agglomeration (octadecanol, non-ionic surfactant, polyethylene, polystyrene)

Can wax be extracted from Wax-OCC by supercritical CO 2? • Proposed Process: Wax is removed from dry Wax-OCC in a high pressure extraction vessel. The dewaxed OCC is then pulped and recycled. The wax is sold as a valuable by-product. • Approach: Extraction of pre-consumer wax-OCC with CO 2 in a lab-scale high pressure extraction vessel has been conducted and evaluated.

Advantages and Attributes of Supercritical CO 2 • Solvating characteristics similar to many organic solvents • Tunable solvating properties • Gas-like viscosity • Gas-like diffusivity • Inexpensive • Non-toxic • Environmentally benign P PC s Super Critical Region l g TC T PC = 72. 2 atm; TC = 31 o. C

SC-CO 2 Extraction Process 500 m. L Extractor CO 2 Source Cyclone Separator Wax Chiller Pump Heater Waxed OCC CO 2

Extractions of Saturated and Curtain-Coated Corrugated Containers Saturated Containers Wax Extraction Efficiency with CO 2 Residual Wax as % Board Weight after CO 2 Extraction (determined by Soxhlet-hexane) Curtain-Coated Containers 99% 70% 0. 5% 2. 0% 300 Atm, 100 °C, 1 hour, ~50 g CO 2 / min *Total and residual wax content determined by Soxhlet extraction with hexane for 24 hours.

Effect of Time-Temperature-Pressure on the Extraction Efficiency of Saturated Containers Bar / ºC

SEM of Soxhlet and SC-CO 2 Extracted OCC Images are 250 microns wide at 500 X magnification Waxed Untreated Unwaxed Untreated Waxed Soxhlet Extracted Unwaxed Soxhlet Extracted Waxed SC-CO 2 Extracted Unwaxed SC-CO 2 Extracted

Effects of SC-CO 2 Extraction on the Papermaking Properties of Recycled OCC

Summary of CO 2 Wax Extraction • Wax removal efficiencies can be greater than 99%. Extractive levels in the fibers can be reduced to less than 1%. • Paper properties of the SC-CO 2 extracted material are slightly lower than a control (unwaxed, recycled board) and are attributed to a small amount of residual wax. • The SC-CO 2 extracted wax may be recovered as a recyclable wax product. • The cost of capital for implementation is prohibitive under the current price structure.

Acknowledgements • The careful work of Li Wang, Qing-min Chen and Thad Stauffer is greatly appreciated. • We would like to thank SCA, Ecosynthetix, Weyerhaueser, Nippon Paper and Shell for supporting the agglomeration research. • We would like to thank the AF&PA Containerboard Technical Group for supporting the CO 2 extraction research. • We would like to thank Pulmac and Apogee for their generous donations of equipment to NCSU.